catalytic nanowires and methods for their preparation and use

专利摘要:
SUMMARY"CATALYTIC NANOFITS AND METHODS FOR THEIR PREPARATION AND USE"This document presents nanowires useful as heterogeneous catalysts. Catalytic nanowires are useful in a variety of catalytic reactions, for example, the oxidative coupling of methane to C2 hydrocarbons. Related methods for the use and manufacture of nanowires are also revealed.
公开号:BR112014012795A2
申请号:R112014012795-6
申请日:2012-11-29
公开日:2020-10-20
发明作者:Fabio R. Zurcher；Jarod McCormick；Anna Merzlyak；Marian Alcid；Daniel Rosenberg；Erik-Jan Ras；Erik C. Scher；Joel M. Cizeron；Wayne P. Schammel；Alex Tkachencko；Joel Gamoras；Dmitry KARSHTEDT；Greg NYCE；Anja Rumplecker
申请人:Siluria Technologies, Inc.；
IPC主号:

专利说明:

[002] [002] The sequence listing associated with that request is provided in text format, instead of a hard copy, and is incorporated into this document as a reference in the specification. The name of the text file containing the String Listing is 860158 _420WO _SEQUENCE_ LISTING.txt. The text file is 19 KB and was created on November 29, 2012 and was submitted electronically via EFS-Web.
[005] [005] Catalysts are generally characterized as heterogeneous or homogeneous. Heterogeneous catalysts exist in a different phase than reactants (for example, a solid metal catalyst and gas phase reagents), and the catalytic reaction generally occurs on the surface of the heterogeneous catalyst. Thus, for the catalytic reaction to occur, the reagents must propagate and / or adsorb on the surface of the catalyst. This transport and adsorption of the reagents is often the limiting step of the heterogeneous catalysis reaction rate. Heterogeneous catalysts are also, in general, easily separable from the reaction mixture by means of common techniques, such as filtration or distillation.
[006] [006] In contrast to a heterogeneous catalyst, a homogeneous catalyst exists in the same phase as the reactants (for example, a soluble organometallic catalyst and reagents dissolved in solvent). In this way, the reactions catalyzed by a homogeneous catalyst are controlled by different kinetics of a heterogeneous catalyzed reaction. In addition, homogeneous catalysts can be difficult to separate from the reaction mixture.
[007] [007] Although catalysis is involved in a number of technologies, a particularly important area is the petrochemical industry. At the base of the modern petrochemical industry is high energy intensity endothermic steam cracking of crude oil. Cracking is used to produce almost all of the fundamental chemical intermediates in use today.
[008] [008] Although there are multi-stage paths for converting methane into certain specific chemicals using, first, high temperature steam from the synthesis gas reform (a mixture of H2 and CO), followed by adjustment of stoichiometry and conversion to methanol or, through Fischer-Tropsch (FT) synthesis, in liquid hydrocarbon fuels, such as diesel or gasoline, this does not allow the formation of certain intermediate chemical compounds of high value. This indirect multi-step method also requires a large capital investment in facilities and is expensive to operate, partly due to the energy-intensive endothermic reform step. (For example, in the methane reform, approximately 40 ° / o of methane is consumed as fuel for the reaction). It is also inefficient in that a substantial part of the carbon fed into the process ends up as GHG CO2, both directly from the reaction and, indirectly, by burning fossil fuels to heat the reaction. Thus, in order to better exploit natural gas resources, direct methods, which are more efficient, economical and environmentally responsible, are mandatory.
[009] [009] One of the reactions of direct activation of natural gas and its transformation into a chemical of high useful value, is the oxidative coupling of methane ("OCM") to ethylene: 2CH4 "O, -" "C2H4 + 2H2O. , for example, Zhang, Q., Journal of Natural Gas Chem, 12:81, 2003; Olah, G. "Hydrocarbon Chemistry", Ed. 2, John Wiley & Sons (2003). This reaction is exothermic (L H = -67 kcal / mol) and has typically been shown to occur at very high temperatures ("700 ° C). Although the detailed reaction mechanism is not fully characterized, experimental evidence suggests that free radical chemistry is involved. (Lunsford, J. Chem. Soc., Chem. Comm, 1991; H. Lunsford, Angew.
[0010] [0010] Since the CMO reaction was first reported more than thirty years ago, it has been the target of intense scientific and commercial interest, but the fundamental limitations of the conventional approach to activate CH binding seem to limit the yield of this attractive reaction. Specifically, several publications from industrial and academic laboratories have consistently demonstrated characteristic performance of high selectivity in low methane conversion or low selectivity in high conversion (J.A. Labinger, Gat.
[0012] [0012] In order to result in a commercially viable CMO process, a catalyst optimized for the activation of the methane CH bond at lower temperatures (eg 500-700 ° C), the higher activities and higher pressures are needed. Although the above discussion focused on the CMO reaction, several other catalytic reactions (as discussed in more detail below) could benefit significantly from catalytic optimization.
[0013] [0013] In summary, the nanowires and related methods are revealed. Nanowires find use in a number of applications, including use as heterogeneous catalysts in petrochemical processes, such as OCM. In one embodiment, the disclosure provides a catalytic nanowire comprising a combination of at least four different doping elements, in which the doping elements are selected from a metallic element, a semi-metallic element and a non-metallic element.
[0014] [0014] In other embodiments, the present description refers to a catalltic nanowire comprising at least two different doping elements, in which the doping elements are selected from a metallic element, a semi-metallic element and a non-metallic element, and in which at least one of the doping elements is K, Sc, Ti, V, Nb, Ru, Os, lr, Cd, ln, Tl, S, Se, Po, Pr, Tb, Dy, Ho, Er, Tm, Lu or an element selected from any of groups 6, 7, 10, 11, 14, 15 or 17.
[0015] [0015] In yet another aspect, the present description provides a catalytic nanowire comprising at least one of the following combinations of dopants: Eu / Na, Sr / Na, Na / Zr / Eu / Ca, Mg / Na, Sr / Sm / Ho / Tm, Sr / VV, Mg / La / k, Na / k / Mg / Tm, Na / Dy / k, Na / La / Dy, Sr / HF / K, Na / La / Eu, Na / La / Eu / ln, Na / La / k, Na / La / Li / Cs, K / La, K / La / S, K / Na, Li / Cs, Li / Cs / La, Li / Cs / La / Tm, Li / Cs / Sr / j "m, Li / Sr / Cs, Li / Sr / Zn / k, Li / Ga / Cs, Li / K / Sr / La, Li / Na, Li / Na / Rb / Ga, Li / Na / Sr, Li / Na / Sr / La, Sr / Zr, Li / Sm / Cs, Ba / Sm / Yb / S, Ba / Tm / k / La, Ba / 1 "m / Zn / k, Sr / Zr / k, Cs / K / La, Cs / La / Tm / Na, Cs / Li / k / La, Sm / Li / Sr / Cs, Sr / Cs / La, Sr / Tm / Li / Cs, Zn / k, Zr / Cs / K / La, Rb / Ca / ln / Ni, Sr / Ho / Tm, La / Nd / S, Li / Rb / Ca, Li / k, Tm / Lu / Ta / P, Rb / Ca / Dy / P, Mg / La / Yb / Zn, Rb / Sr / Lu, Na / Sr / Lu / Nb, Na / Eu / Hf, Dy / Rb / Gd, Sr / Ce, Na / Pt / 8i, Rb / Hf, Ca / Cs, Ca / Mg / Na, HF / B1, Sr / Sn, Sr / VV, Sr / Nb, Sr / Ce / k, Zr / VV, YNV, Na / VV, Bi / VV, Bi / Cs, Bi / Ca,
[0016] [0016] In still other embodiments, the disclosure provides a catalytic nanowire comprising Ln14-, Ln2xO6 and a dopant containing a metallic element, a semi-metallic element, a non-metallic element or combinations of these elements, in which Lnl and Ln2 are each, independently , a lanthanide element, in which Lnl and Ln2 are not the same, ex is a number ranging from more than 0 to less than 4.
[0017] [0017] In other embodiments, the development provides a nanowire comprising a mixed oxide of Y-La, Zr-La, Pr-La, Ce-La or their combinations and at least one dopant chosen from a metallic element, a semi-metallic element and a non-metallic element.
[0018] [0018] In still other embodiments, the invention provides a catalytic nanowire comprising a mixed oxide of a rare earth element and an element of Group 13, wherein the catalytic nanowire further comprises one or more elements of group 2.
[0019] [0019] The present disclosure is also directed to a catalytic nanowire, in which the conversion of single-stage methane into a nanowire catalyzed COM reaction is greater than 20 ° / o.
[0020] [0020] In still other modalities the development provides a catalytic nanowire presenting a C2 selectivity greater than 10% in the OCM reaction, when the reaction is carried out with an oxygen source other than air or O2. For example, the catalytic nanowire may have activity in the OCM reaction, in the presence of CO2, H2O, SO2, SO3 or combinations thereof. In some previous embodiments, the catalytic nanowire comprises La2O3 / ZnO, CeO2 / ZnO, CaO / ZnO, CaO / CeO2, CaO / Cr, O3, CaO / MnO ,, SRO / ZnO, SrO / CeO ,, SrO / Cr, O3 , SrO / MnO ,, SrCO, / MnO ,, BaO / ZnO, BaO / CeO ,, BaO / Cr2O3, BaO / MnO ,, CaO / MnO / CeO ,, Na, WO4 / Mn / SiO ,, Pr2O3, Tb2O3 or combinations thereof.
[0021] [0021] In yet other modalities of any of the preceding catalytic nanowires, the catalytic nanowire is polycrystalline and has a ratio between the effective length to actual length less than one and an aspect ratio greater than ten, measured by TEM, in luminous field at 5 keV, in which the catalytic nanowire comprises one or more elements from any of groups 1 to 7, lanthanides, actinides or combinations thereof.
[0022] [0022] Still in other embodiments of any of the preceding catalytic nanowires, the catalytic nanowire has a curved morphology, and in other embodiments of the catalytic nanowire it has a straight morphology. In yet other embodiments of any of the preceding catalytic nanowires, the catalytic nanowire comprises a metal oxide, metal oxy-hydroxide, a metal oxycarbonate, a metal carbonate or combinations thereof, for example, in some embodiments the catalytic nanowire comprises a metal oxide .
[0023] [0023] The present disclosure also provides a catalytic material which comprises a plurality of catalytic nanowires in combination with a diluent or support agent, wherein the diluent or support comprises an alkaline earth metal compound. In some embodiments, the alkaline earth metal compound is MgO, MgCO3, MgSO4, Mg3 (po4) 2, MgAl, O ,, CaO, CaCO3, CaSO4, Ca3 (PO4) 2, CaA | 2O4, SrO, SrCO3, SrSO4, Sr3 (PO4) 2, SrA | 2O4, BaO, BaCO3, BaSO4, Ba3 (PO4) 2, BaAl2O4 or combinations thereof. For example, in some embodiments the alkaline earth metal compound is MgO, CaO, SrO, MgCO3, CaCO3, SrCO3, or combinations thereof. In other embodiments, the catalytic material appears in the structural form of a pressed, extruded or monolithic microsphere. Ç
[0024] [0024] In other embodiments, the present disclosure relates to a catalytic material comprising a plurality of catalytic nanowires and a sacrificial binder, and in other embodiments the present disclosure is directed to a catalytic material in the form of pressed microspheres (for example , pressure treatment), wherein the catalytic material comprises a plurality of catalytic nanowires and substantially no binding material.
[0025] [0025] In other embodiments, the development provides a catalytic material in the form of pressed or extruded microspheres, wherein the catalytic material comprises a plurality of pore catalytic nanowires with a diameter greater than 20 nm. For example, in some modalities the catalytic material is in the form of a wafer, and in other modalities, the catalytic material is in the form of an extrudate.
[0026] [0026] In still other embodiments of the present description, a catalytic material is provided which comprises a plurality of catalytic nanowires supported on a structured support. For example, the structured support can comprise a foam, foil structure or is in the form of aromatics. In other embodiments, the structured support comprises silicon carbide or alumina, and in still other embodiments, the support comprises a meta-foam structure, silicon carbide or alumina foam, corrugated metal sheet arranged to form channel dies or in the form of extruded ceramic aromatics.
[0027] [0027] Other modalities provide a catalytic material comprising a catalytic nanowire, in which the catalytic material is in contact with a reactor. For example, in some embodiments, the reactor is used to perform OCM, and in other embodiments, the catalytic material comprises silicon carbide. In other embodiments, the reactor is a fixed bed reactor, and in other examples, the reactor comprises an internal diameter of at least 2.54 cm.
[0028] [0028] In another embodiment, the disclosure provides a catalytic material that comprises at least one O2-OCM catalyst and at least one CO2-OCM catalyst. For example, in some ways, at least one O2-OCM catalyst or the CO2-OCM catalyst is a catalytic nanowire.
[0029] [0029] In another embodiment, the disclosure provides a catalytic material that comprises at least one O2-OCM catalyst and at least one CO2 -ODH catalyst. For example, in some respects, at least one O2-OCM catalyst or the CO2 -ODH catalyst is a catalytic nanowire.
[0030] [0030] In other embodiments of any of the preceding catalytic materials, the catalytic material comprises any of the catalytic nanowires described in this document.
[0031] [0031] Other embodiments of the present description include a method for preparing a catalytic material, the method comprising mixing a plurality of catalytic nanowires with a sacrificial binder and removing the sacrificial binder to obtain a catalytic material that comprises substantially none. bonding material and shows an increase over the microporosity of catalytic material prepared without the sacrificial binder. For example, the catalytic material can be any of the preceding catalytic materials.
[0032] [0032] In still other embodiments, the present disclosure is directed to a method for purifying a phage solution, the method comprising: a) a microfiltration step comprising filtering a phage solution through a membrane comprising pores ranging from 0.1 to 3 µm to obtain a microfiltration retentate and a microfiltration permeate; and b) an ultrafiltration step comprising filtering the microfiltration permeate through a membrane comprising pores ranging from 1 to 1,000 kDa and recovering an ultrafiltration retentate, comprising a purified phage solution.
[0033] [0033] In some modalities, the ultrafiltration stage is performed by means of tangential flow filtration. In other embodiments, the method further comprises diafiltration of a purified phage solution for buffer exchange media.
[0034] [0034] In some modalities, the microfiltration stage and the ultrafiltration stage are performed using tangential flow filtration, while in other modalities the microfiltration stage is performed by means of depth filtration.
[0035] [0035] In other embodiments, the disclosure provides a method for the preparation of a catalytic nanowire comprising a metal oxide, a metal oxy-hydroxide, a metal oxycarbonate or a metal carbonate, the method comprising: a) providing a solution comprising a plurality of models; b) introducing at least one metal ion and at least one anion into the solution under conditions and for a time sufficient to allow the nucleation and development of a nanowire, comprising a plurality of metal salts
[0036] [0036] In still other embodiments, the disclosure provides a method for the preparation of catalytic nanowires of metal oxide, metal oxy-hydroxide, metal oxycarbonate or metal carbonate in a central core / shell structure, the method comprising: (a) provision of a solution that includes a plurality of models; (b) introduction of a first metal ion and a first anion to the solution, under conditions and for a time sufficient to allow nucleation and the development of a first nanowire (M1m1X1n1 Zp1) on the model; and (c) introduction of a second metal ion and, optionally, a second anion to the solution, under conditions and for a time sufficient to allow the nucleation and development of a second nanowire (M2m2X2n2 Zp2) on the surface of the first nanowire (M1m1X1n1 Zp1); (d) conversion of the first nanowire (M1m1X1n1Zp1) and the second nanowire
[0037] [0037] In still other embodiments, the disclosure provides a method for preparing a catalytic nanowire, the method comprising treating at least one metal compound with an ammonium salt with the formula NR4X, where each R is independently H , alkyl, alkenyl, alkynyl or aryl, and X is an anion.
[0038] [0038] In still other embodiments, a method is provided for the preparation of a nanowire, comprising a metal oxide, a metal oxy-hydroxide, a metal oxycarbonate or a metal carbonate. The method comprising: a) providing a solution comprising a plurality of multifunctional coordination ligands; b) introduction of at least one metal ion to the solution, thus forming a metal-ligand ion complex; and
[0039] [0039] Other embodiments include a method for preparing a catalytic nanowire, the method comprising: mixing (A) with a mixture comprising (B) and (C): mixing (B) with a mixture comprising (A) and ( Ç); or mixture (C) with a mixture comprising (A) and (B) to obtain a mixture comprising (A), (B) and (C), wherein (A), (B) and (C) comprise, respectively: A) a model; B) one or more salts comprising one or more elements selected from Groups 1 to 7, lanthanides and actinides and their hydrates; and C) one or more anion precursors.
[0040] [0040] Nanowires are also provided, prepared according to any of the described methods, as well as the catalytic materials that comprise the nanowires.
[0041] [0041] In another embodiment, the disclosure provides a method for the oxidative coupling of methane, the method which comprises the conversion of methane into one or more C2 hydrocarbons in the presence of a catalytic material, wherein the catalytic material comprises at least one catalyst O2-OCM and at least one CO2-OCM catalyst. In some embodiments, at least one of the O2-OCM catalysts or the CO2-OCM catalyst is a catalytic nanowire, for example, any of the nanowires disclosed herein. In some embodiments, the catalytic material comprises a bed of alternating layers of O2-OCM catalysts and alternating CO2-OCM catalysts, while in other embodiments the catalytic material comprises a homogeneous mixture of O2-OCM catalysts and CO2-catalysts. CMO.
[0042] [0042] In even more embodiments, the disclosure provides a method for the preparation of ethane, ethylene or combinations thereof, the method comprising the conversion of methane to ethane, ethylene or combinations thereof, in the presence of a catalytic material, wherein the materia! catalytic comprises at least one O2-OCM catalyst and at least one CO2 ODH catalyst. For example, in some embodiments, at least one of the O2-OCM catalysts or the CO2-OCM catalyst is a catalytic nanowire, for example, any of the catalytic nanowires described in this document, such as metal oxide, oxy hydroxide metallic, metallic oxycarbonate or a metallic carbonate nanowire or combinations thereof. These and other aspects of the invention will be evident upon reference to the following detailed description.
[0043] [0043] For this purpose, several references are presented in this document, which describe in more detail certain information of fundamentals, procedures, compounds and / or compositions, and are incorporated in this document as a reference in its entirety. BRIEF DESCRIPTION OF THE DRAWINGS
[0044] [0044] In the drawings, the dimensions and relative positions of the elements of the drawings are not necessarily provided in scale. For example, the various elements and angles are not drawn to scale, and some of these elements are arbitrarily enlarged and positioned to improve the readability of the drawing. In addition, the particular shapes of the elements, according to the project, are not intended to convey any information regarding the actual shape of the determined elements, and were selected only for ease of recognition of the drawings.
[0045] [0045] Figure 1 schematically represents a first part of an OCM reaction on the surface of a metal oxide catalyst.
[0046] [0046] Figure 2 shows a high performance spreadsheet to generate and synthetically test the nanowire libraries.
[0047] [0047] Figures 3A and 3B illustrate a nanowire in one embodiment.
[0048] [0048] Figures 4A and 4B illustrate a nanowire in a different modality.
[0049] [0049] Figures 5A and 5B illustrate a plurality of nanowires.
[0050] [0050] Figure 6 illustrates a filamentous bacteriophage.
[0051] [0051] Figure 7 is a flowchart of an exemplary nucleation process for the formation of a metal oxide nanowire.
[0052] [0052] Figure 8 is a flowchart of an exemplary sequential nucleation process to form a nanowire with a central core / shell configuration.
[0053] [0053] Figure 9 schematically describes a carbon dioxide reform reaction on a catalytic surface.
[0054] [0054] Figure 10 is a flow chart for the collection and processing of data in order to evaluate the catalytic performance.
[0055] [0055] Figure 11 illustrates a certain number of products downstream of ethylene.
[0056] [0056] Figure 12 illustrates a representative process for preparing a lithium doped MgO nanowire.
[0057] [0057] Figure 13 shows an X-ray diffraction pattern of Mg (OH) 2 nanowires and MgO nanowires.
[0058] [0058] Figure 14 shows a number of MgO nanowires each synthesized in the presence of a different phage sequence.
[0059] [0059] Figure 15 illustrates a representative process for the growth of a central core / ZrO2 / La2O3 nanowire structure with strontium doping.
[0060] [0060] Figure 16 is a gas chromatograph that shows the formation of OCM products at 700 ° C when passed through a La2O3 nanowire doped with Mr.
[0061] [0061] Figures 17A-17C are graphs showing the conversion of methane, C2 selectivity and C2 yield, in an OCM reaction catalyzed by Sr2-doped La2O3 nanowires versus the corresponding volume material, in the same temperature range reaction.
[0062] [0062] Figures 18A-18B are graphs showing the comparative results of C2 selectivity in a CMO reaction catalyzed by the La2O3 catalytic nanowires wired with Sr prepared by different synthetic conditions.
[0063] [0063] Figure 19 is a graph comparing the conversions of ethane and propane in ODH reactions catalyzed by either Li-doped MgO phage nanowires or Li-doped MgO volume catalyst.
[0064] [0064] Figure 20 is a TEM image showing La2O3 nanowires prepared under conditions not directed at the model.
[0065] [0065] Figure 21 illustrates CMO and ethylene oligomerization modules.
[0066] [0066] Figure 22 shows the conversion of methane, C2 selectivity and C2 yield in a reaction catalyzed by representative nanowires.
[0067] [0067] Figure 23 shows the conversion of methane, C2 selectivity and C2 yield in a reaction catalyzed by representative nanowires.
[0068] [0068] Figure 24 is a graph showing the conversion of methane, C2 selectivity and C2 yield in a reaction catalyzed by representative nanowires. DETAILED DESCRIPTION OF THE INVENTION
[0069] [0069] In the description that follows, certain specific details are established, in order to provide a complete understanding of the various modalities. However, one skilled in the art will understand that the invention can be practiced without these details. In other cases, well-known structures have not been presented or described in detail to avoid unnecessarily obscuring the descriptions of the modalities. Unless the context provides otherwise, throughout the entire specification and claims that follow, the term "understands" and variations thereof, such as, "understand, understand" must be interpreted in an open inclusive sense, that is , such as "including but not limited". In addition, the headings provided in this document are for convenience only and do not interpret the scope or meaning of the claimed invention.
[0070] [0070] The reference throughout this specification to "the modality" or "a modality" means that a particular resource, structure or characteristic described in connection with the modality is included in at least one modality. Thus, the phrases "in the modality" or "in a modality" in various places throughout this specification are not necessarily all referring to the same modality. In addition, the particular aspects, structures, or characteristics can be combined in any suitable way, in one or more modalities. In addition, as used in this specification and the appended claims, the singular forms "one," "one," and "o", "a" include references to the plural, unless the context clearly indicates otherwise.
[0071] [0071] As discussed above, heterogeneous catalysis takes place between several phases. Generally, the catalyst is a solid, the reactants are gases or liquids, and the products are gases or liquids. Thus, a heterogeneous catalyst provides a surface that has multiple active sites for the adsorption of one or more gas or liquid reagents. Once absorbed, certain bonds within the reactive molecules are weakened and dissociate, creating reactive fragments of the reactants, for example, in the form of free radicals. One or more products are generated as new links between the resulting reactive fragments form, in part, due to their proximity to each other on the catalytic surface.
[0072] [0072] As an example, figure 1 schematically shows the first part of a CMO reaction that occurs on the surface of a metal oxide catalyst 10, which is followed by coupling of the methyl radical in the gas phase.
[0073] [0073] It is generally recognized that the catalytic properties of a catalyst correlate strongly with its surface morphology.
[0074] [0074] Nano-size catalysts have relatively increased surface areas compared to their volume counterpart materials. The catalytic properties are expected to be increased as more surface active sites are exposed to the reagents. Typically in traditional preparations, a top-down approach (for example, grinding) is adopted to reduce the size of the material by volume. However, the surface morphologies of such catalysts remain largely the same as those of the material in original volume.
[0075] [0075] Several modalities described in this document are directed to nanowires with controllable or adjustable surface morphologies.
[0076] [0076] In contrast to a catalyst by volume of a certain elementary composition, which is likely to have a corresponding surface morphology in particular, several nanowires with different surface morphologies can be generated, despite having the same elementary composition.
[0077] [0077] In contrast to the volume catalyst of a given elementary composition, which probably has a corresponding specific surface morphology, several nanowires with different surface morphologies can be generated despite having the same elementary composition. In this way, morphologically different nanowires can be created and classified according to their performance and catalytic activity parameters in any given catalytic reaction. Advantageously, the nanowires disclosed in this document and their production methods have general applicability for a wide variety of heterogeneous catalysts, including without limitation: oxidative methane coupling (for example, figure 1), oxidative dehydrogenation of alkanes in its corresponding alkenes, selective oxidation of alkanes to alkenes and alkynes, oxidation of carbon monoxide, dry reforming of methane, selective oxidation of aromatic compounds, Fischer-Tropsch reaction, hydrocarbon fractionation and the like.
[0078] [0078] Figure 2 schematically shows a high yield workflow for synthetic generation of libraries of morphological or diverse composition nanowires and classification of their catalytic properties. An initial phase of the workflow involves a primary classification, which is designed to classify a broad and diverse set of nanowires in a broad and efficient way that, logically, could accomplish the desired catalytic transformation.
[0079] [0079] More specifically, workflow 100 starts with designing synthetic experiments based on solution phase model formations (block 110). The synthesis, treatments and subsequent exams can be manual or automated. As will be discussed in more detail in this document, by varying the synthesis conditions, nanowires can be prepared with different surface morphologies and / or the compositions in the respective microwells (block 114). The nanowires are then calcined and then optionally doped (block 120). Optionally, the doped and calcined nanowires are further mixed with a catalyst support (block 122). In addition to the optional support step, all subsequent steps are performed in a "wafer" format, in which the catalytic nanowires are deposited on a quartz wafer that has been etched to create an ordered model of microwells.
[0080] [0080] Nanowires obtained under various synthesis conditions are then deposited in the respective microwells of a wafer (140) to evaluate their respective catalytic properties in a given reaction (blocks 132 and 134). The catalytic performance of each member of the library can be classified in series by several known primary classification technologies, including scanning mass spectroscopy (SMS) (Symyx Technologies lnc., Santa Clara, California). The classification process is fully automated and the SMS tool can determine whether a nanowire is catalytically active or not, as well as its relative power as a catalyst at a particular temperature. Typically, the wafer is placed over a motion control phase capable of positioning a single well below a probe that drains the feed of the starting material over the surface of the nanowire and removes the reaction products from a mass spectrometer and / or other detector technologies (biocos 134 and 140). The individual nanowire is heated to a predefined reaction temperature, for example, using a CO2 IR laser from the rear side of the quartz wafer and an infrared chamber to monitor the temperature and a preset mixture of reagent gases. The SMS tool collects data regarding the consumption of reagent (s) and the generation of the product (S) of the catalytic reaction, in each well (block 144), and for each temperature and flow rate.
[0081] [0081] The SMS data obtained, as described above, provide information on the relative catalytic properties among all members of the library (block 150).
[0082] [0082] In order to obtain more quantitative data on the catalytic properties of nanowires, possible aspects that meet certain criteria are subjected to a secondary classification (bioco 154). Typically, secondary classification technologies include a single or alternatively multiple fixed channel beds or fluidized bed reactors (as described in more detail herein). In parallel reactor systems or a multi-channel fixed bed system, a single supply system provides reagents for a set of circulation restrictors. Circulation restrictors divide flows evenly between parallel reactors. Care is taken to achieve a uniform reaction temperature between the reactors, so that the different nanowires can be differentiated based solely on their catalytic performance. The secondary classification allows the precise determination of catalytic properties, such as selectivity, yield and conversion (block 160). These results serve as feedback for the design of new nanowire libraries.
[0083] [0083] The secondary classification is also schematically illustrated in figure 10, which shows a flow chart for the collection and processing of data for the evaluation of the catalytic performance of the catalysts according to the invention.
[0084] [0084] Thus, according to various modalities described in this document, the nanowires of composition and morphologically different can be rationally synthesized to satisfy the criteria of catalytic performance.
[0085] [0085] As used herein and unless the context otherwise indicates, the following terms have the meanings as specified below.
[0086] [0086] "Catalyst" means a substance that changes the rate of a chemical reaction. A catalyst either increases the rate of chemical reaction (that is, a "positive catalyst") or slows down the reaction rate (that is, a "negative catalyst"). Catalysts participate in a reaction in a cyclic manner, so that the catalyst is regenerated cyclically. "Catalytic" means that it has the properties of a catalyst.
[0087] [0087] "Nanoparticle" means a particle that has a diameter at least on the order of nanometers (for example, between about 1 and 100 nanometers).
[0088] [0088] "Nanowire" means a nanowire structure that has at least a diameter on the order of nanometers (for example, between about 1 and 100 nanometers) and an aspect ratio greater than 10: 1. The "aspect ratio" of a nanowire is the ratio of the actual length (L) of the nanowire to the diameter (D) of the nanowire. The aspect ratio is expressed as L: D.
[0090] [0090] "Effective length" of a nanowire means the shortest distance between the two distal ends of a nanowire as measured by transmission electron microscopy (TEM) in bright field mode at 5 keV. "Average effective length" refers to the average of the effective lengths of individual nanowires within a plurality of nanowires.
[0091] [0091] "Actual length" of a nanowire means the distance between the two distal ends of a nanowire as traced through the nanowire structure, measured by TEM, in bright field mode, at 5 keV. "Average actual length"
[0092] [0092] The "diameter" of a nanowire is measured on an axis perpendicular to the axis of the actual length of the nanowire (that is, perpendicular to the structure of the nanowires). The diameter of a nanowire will vary from narrow to wide, measured at different points along the structure of the nanowire. As used in this document, the diameter of a nanowire is the predominant diameter (ie, the mode).
[0093] [0093] The "ratio between the effective length and the actual length" is determined by dividing the effective length by the actual length. A nanowire having a "folded morphology" will have a ratio between the effective length and the actual length of less than one, as described in more detail in this document. A straight nanowire will have a ratio between the effective length and the actual length equal to one, as described in more detail in this document.
[0094] [0094] "Polymer" refers to a molecule made up of two or more structural repeating units (ie, "monomers"). Structural units are typically joined by covalent bonds. The structural units are, in each occurrence, independently, the same or different and can be linked in any order (for example, random, repetition, bi-glass cup, etc.). An exemplary polymer is polyethylene, which can be prepared using a process that uses the disclosed nanowires. Certain modalities of the polymers described in this document are suitable for use as a model for forming the disclosed nanowires. Polymers in this regard include, but are not limited to, PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol), PEl (polyethyleneimine), PEG (polyethylene glycol), polyethers, polyesters, polyamides, dextran, sugar polymers, hydrocarbon polymers, hydrocarbon polymers, hydrocarbon polymers functionalized, polylactic acid, polycaprolactone, polyglycolic acid, po | i (ethyl | enogen |) -po | i (propylene glycol), poly (ethyl | en | g | ico |), copolymers and combinations of the foregoing and similar.
[0095] [0095] "Functionalized" when used in reference to a polymer, means that the polymer can be replaced with one or more functional groups. In general, functional groups are groups capable of interacting with metal ions (for example, through coordination or other interaction) and are useful for initiating the nucleation of the nanowires. Representative functional groups include, but are not limited to, amine, carboxylic acid, sulfate, alcohol, halogen (e.g., F, Cl, Br or I) and / or thiol fractions. Unless specifically indicated otherwise, the polymers described in this document are optionally functionalized (i.e., they may or may not be functionalized with one or more functional groups).
[0096] [0096] "Inorganic" means a substance that comprises a metallic element or semi-metallic element. In certain embodiments, it refers to an inorganic substance that comprises a metallic element. An inorganic compound can contain one or more metals, in its elemental state, or more typically, a compound formed by a metal ion (M '", where n 1, 2, 3, 4, 5, 6 or 7) and a anion (X "", m is 1, 2, 3 or 4), which balance and neutralize the positive charges of the metal ion through electrostatic interactions. Non-limiting examples of inorganic compounds include oxides, hydroxides, halides, nitrates, sulfates , carbonates, phosphates, acetates, oxalates, and combinations thereof, of metallic elements Other non-limiting examples of inorganic compounds include Li2CO3, Lj2po4, L1OH, Li2O, LiCl, Li8r, Lil, Li2C2O4, Li2SO4, Na2CO3, Na2PO4, NaOH , Na, O, NaCl, Na8r, Nal, Na2C2O4, Na2SO4, K2CO3, K2PO4, KOH, K2O, Kci, K8r, Ki, K, C2O4, K2SO4, CS, CO2, CSPO ,, CSOH, CS2O, CsCl, CsBr CSL, CsC2O4, CSSO4, Be (OH) 2, BeCO3, BePO4, BeO, BeC | 2, BeBr2, Be | 2, BeC2O4, BeSO ,, Mg (OH) 2, MgCO ,, MgPO ,, MgO, MgCl ,, Mg8r ,, Mg | 2, MgC, O ,. MgSO ,,
[0097] [0097] "Salt" means a compound comprising positive and negative ions. Salts are generally composed of cations and counterions. Under appropriate conditions, for example, the solution also comprises a model, the Metal Ion (M '") and the anion (X" ") attach to the model to induce the nucleation and growth of an MmX nanowire in the model "Anion precursor", therefore, is a compound comprising an anion and a cationic counterion, which allows the anion (X "") to dissociate from the cationic counterion in a solution. Specific examples of metal salt precursors and precursors anions are described in more detail in this document.
[0098] [0098] "Oxide" refers to a metal compound that comprises oxygen.
[0099] [0099] "Mixed oxide" or "mixed metal oxide" refers to a compound comprising two or more oxidized metals and oxygen (ie, M1, M2yO ,, where Ml and M2 are the same or different metallic elements, O is oxygen ex, y and z are numbers from 1 to 100). A mixed oxide can comprise metallic elements in various oxidation states and can include more than one type of metallic element.
[00100] [00100] "Rare earth oxide" refers to an oxide of an element in group 3 of the lanthanides or actinides. Rare earth oxides include mixed oxides containing a rare earth element. Examples of rare earth oxides include, but are not limited to, La2O3, Nd2O3, Yb2O3, Eu2O3, Sm2O3, Y2O3, Ce2O3, Pr2O3, Ln14-xLn2, O6, La4-xLn1xO6, La4-, NdxO6, where Lnl and Ln each, independently, a lanthanide element, in which Lnl and Ln2 are not the same, ex is a number that varies between more than 0 and less than 4, La3NdO6, LaNd3O6, La1.5Nd2. 5O6, La2.5Nd1.5O6, La3,2Ndo.eO6, La3.5Nd0.5O6, La3.8Nd0.2O6, Y-La, Zr-La, Pr-La and Ce-La.
[00102] [00102] "Single-crystalline nanowires" means a nanowire with a single crystal domain.
[00103] [00103] "Mold" is any synthetic and / or natural material that provides at least one nucleation site, where the ions can nuclear and grow to form nanoparticles. In certain embodiments, the models may be a multi-molecular biological structure comprising one or more biomolecules. In certain other embodiments, the models comprise non-biomolecule polymers.
[00104] [00104] "Biomolecule" refers to an organic molecule of biological origin. Biomolecule includes modified and / or degraded molecules of a biological origin. Non-limiting examples of biomolecules include peptides, proteins (including cytokines, growth factors, etc.), nucleic acids, polynucleotides, amino acids, antibodies, enzymes and single-stranded or double-stranded nucleic acid, including any modifications and / or degraded forms of the same.
[00105] [00105] "Amyloid fibers" refers to protein filaments about 1 - nm in diameter.
[00106] [00106] A "bacteriophage" or "phage" is any one of a number of viruses that infect bacteria. Normally, bacteriophages consist of an outer protein layer or "main coat protein" encapsulating genetic material. A non-limiting example of a bacteriophage is bacteriophage M13.
[00107] [00107] A "capsid" is the protein shell of a virus. A capsid comprises several oIigomeric structural subunits made of proteins.
[00108] [00108] "Nucleation" refers to the process of forming a solid from solubilized particles, for example forming a nanowire in situ through the conversion of a soluble precursor (for example, metal and hydroxide ions) into nanocrystals in the presence of a model.
[00109] [00109] "Nucleation site" refers to a location in a model, for example, a bacteriophage, where Ion nucleation can occur. Nucleation sites include, for example, amino acids having carboxylic acid (-COOH), amino (-NH3 "or - NH2), hydroxyl (-OH), and / or thiol (-SH) functional groups.
[00110] [00110] A "peptide" refers to two or more amino acids joined by peptide (amide) bonds. The building blocks of naturally occurring amino acids (subunits) include α-amino acids and / or unnatural amino acids, such as β-amino acids and homoamino acids. An unnatural amino acid can be a chemically modified form of a natural amino acid. The peptides can consist of 2 or more, 5 or more, 10 or more, 20 or more, or 40 or more amino acids.
[00111] [00111] "Peptide sequence" refers to the sequence of amino acids within a peptide or protein.
[00112] [00112] "Protein" refers to a natural or manufactured macromolecule with a primary structure, characterized by peptide sequences. In addition to the primary structure, proteins also exhibit secondary and tertiary structures, which determine their final geometric shapes.
[00113] [00113] "Polynucleotide" means a molecule made up of two or more nucleotides ligated through an internucleotide bond (for example, a phosphate bond). Polynucleotides can consist of either ribose and / or deoxyribose nucleotides. Examples of nucleotides include guanosine, adenosine, thiamine and cytosine, as well as their unnatural analogs. ~ 3
[00114] [00114] "Nucleic acids" means a macromolecule composed of polynucleotides. Nucleic acids can be both single-stranded and double-stranded, and, like proteins, can have secondary and tertiary structures that determine their final geometric shapes.
[00115] [00115] "Nucleic acid sequence" of the "nucleotide sequence" refers to the nucleotide sequence and a polynucleotide or nucleic acid.
[00116] [00116] "Anisotropic" means having an aspect ratio greater than one.
[00117] [00117] "Anisotropic biomolecule" means a biomolecule, as defined in this document, having an aspect ratio greater than 1.
[00118] [00118] "Number of turnover" is a measure of the number of molecules that the catalyst reagent can convert into product molecules per unit time.
[00119] [00119] "Active" or "catalytically active" refers to a catalyst that has substantial activity in the reaction of interest. For example, in some embodiments, a catalyst that is active OCM (ie has an activity in the OCM reaction) has a C2 septivity of 5% or more and / or a methane conversion of 5 ° / 0 or more, when the catalyst is used as a heterogeneous catalyst in oxidative methane coupling at a temperature of 750 ° C or less.
[00120] [00120] "Inactive" or "catalytically inactive" refers to a catalyst that has no substantial activity in the reaction of interest. For example, in some embodiments a catalyst that is inactive OCM has a C2 selectivity of less than 5% and / or a methane conversion of less than 5 ° / 0 when the catalyst is used as a heterogeneous catalyst in the oxidative coupling of methane to a 750 ° C or less.
[00121] [00121] "Activation temperature" refers to the temperature at which a catalyst becomes catalytically active.
[00122] [00122] "OCM activity" refers to the ability of a catalyst to catalyze the OCM reaction.
[00123] [00123] A catalyst having "high OCM activity" refers to a catalyst with a C2 selectivity of 50% or more and / or a methane conversion of 20% or more, when the catalyst is used as a heterogeneous catalyst in oxidative coupling methane at a specific temperature, for example 750 ° C or less.
[00124] [00124] A catalyst having "moderate OCM activity" refers to a catalyst that has a C2 selectivity of about 20-50% and / or a methane conversion of about 10-20% or more, when the catalyst is used as a heterogeneous catalyst in the oxidative coupling of methane at a temperature of 750 ° C or less.
[00125] [00125] A catalyst having "low OCM activity" refers to a catalyst that has a selectivity of about C2 of 5-20% and / or a methane conversion of about 5-10% or more, when the catalyst is used as a heterogeneous catalyst in the oxidative coupling of methane at a temperature of 750 ° C or less.
[00126] [00126] "Dopante" or "dopante" is an impurity added or incorporated to a catalyst to optimize the catalytic performance (for example, to increase or decrease the catalytic activity). In comparison to the non-doped catalyst, a doped catalyst can increase or decrease the selectivity, conversion, and / or yield of a reaction catalyzed by the catalyst.
[00127] [00127] "Atomic percentage" (° / 0 atm. Or atm./atm.) Or "atomic ratio" when used in the context of nanowire dopants refers to the relationship between the total number of doping atoms to the total number of atoms of metal in the nanowire. For example, the atomic percentage of the dopant in a lithium-doped Mg6MnO8 nanowire is determined by calculating the total number of lithium atoms and dividing by the sum of the total number of magnesium and manganese atoms, and multiplying by 100 (ie, percentage dopant atomic = [Li atoms / (Mg atoms + Mn atoms)] x 100).
[00128] [00128] "Percent weight" (w / w) "when used in the context of nanowire dopants refers to the ratio of the total dopant weight to the combined total weight of the doping agent and the nanowire. For example, the percentage weight of doping agent in a Mg6MnO8 nanowire doped with is determined by calculating the total weight of lithium and dividing by the sum of the combined total weight of lithium and
[00129] [00129] An "extrudate" refers to a material (for example, catalytic material) prepared by forcing a semi-solid material comprising a catalyst through a suitable model or opening. Extrudates can be prepared in a variety of shapes and structures by common means known in the art.
[00130] [00130] A "microsphere" or "pressed microspheres" refers to a material (for example, the catalytic material), prepared by applying pressure (ie, compression) to a material that comprises a catalyst in a desired shape. Microspheres having various dimensions and shapes, can be prepared according to techniques common in the art.
[00131] [00131] "Monolith" or "monolith support" is generally a structure formed from a single structural unit, preferably having passages arranged through it in any irregular or regular pattern with porous or non-porous walls that separate adjacent passages. Examples of such monolithic supports include, for example, porous structures made of foam-like metal or ceramic. The single structural unit can be used in place of or in addition to conventional particles, or granular catalysts (for example, microspheres or extrudates). Examples of such irregular stamped monolith substrates include fillers used for molten metals. Monoliths generally have a porous fraction ranging from about 6 ° / o to 9 ° / o and a flow resistance substantially less than the flow resistance of a similarly filled bed (for example, about 10 ° / o to 3 ° °) / o flow resistance of a packaged bed of similar volume).
[00132] [00132] Examples of regular standardized substrates include supports in the form of monolith aromatics used to purify exhaust from motor vehicles and used in various chemical processes and ceramic foam structures with irregular passages. Many types of monolith support structures made from conventional refractory materials or ceramics, such as alumina, zirconia, yttrium oxide, silicon carbide, and mixtures thereof, are well known and commercially available from, among others, Corning, Iac; Vesuvius Hi-Tech Ceramics lnc .; and Porvair Advanced Materials, lnc. and SICAT (Sicatalyst.com). Monoliths include foams, aromatics, leaves, mesh, gauze and the like.
[00133] [00133] Elements of "Group 1" include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr).
[00134] [00134] Elements of "Group 2" include beryl (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra).
[00135] [00135] Elements of "Group 3" include scandium (Sc) and Yttrium (Y).
[00136] [00136] Elements of the "Group, 4" include titanium (Ti), zirconium (Zr), hafnium (Hf), and ruterphorium (Rf).
[00137] [00137] Elements of "Group 5" include vanadium (V), niobium (Nb), tantalum (Ta) and dubnium (Db).
[00138] [00138] Elements of "Group 6" include chromium (Cr), molybdenum (Mo), tungsten (W), and seaborium (SG).
[00139] [00139] Elements of "Group 7" include manganese (Mn), technetium (Tc), rhenium (Re), and borium (Bh).
[00140] [00140] Elements of "Group 8" include iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs).
[00141] [00141] Elements of "Group 9" include cobalt (Co), rhodium (Rh), iridium (lr), and meitnerium (Mt).
[00142] [00142] Elements of "Group 10" include nickel (Ni), palladium (Pd), platinum (Pt) and darmistadium (Ds).
[00143] [00143] Elements of "Group 11" include copper (Cu), silver (Ag), gold (Au), and roentgenium (Rg).
[00144] [00144] Elements of "Group 12" include zinc (Zn), cadmium (Cd), mercury (Hg) and copernicium (Cn).
[00145] [00145] "Lanthanides" include Ianthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb) ), dysprosium (Dy), hóimio (Ho), erbium (Er), thulium (Tm), iterbium (Yb) and lutetium (Lu).
[00146] [00146] "Actinides" include actinium (Ac), thorium (Th), protatinium (Pa), uranium (U), neptunium (Np), plutonium (Pu), americium (Am), curium (Cm), berklelio (Bk ), californium (Cf), einsteinium (Es), fermium (Fm), Mendelevium (Md), Nobelium (No) and iawrencio (LR).
[00147] [00147] Elements of "rare earth" include Group 3, lanthanides and actinides.
[00148] [00148] "Metallic element" or "metals" is any element, except hydrogen, selected from Groups 1 to 12, lanthanides, actinides, aluminum (Al), gallium (Ga), Indium (In), tin (Sn ), thallium (T1), lead (Pb), and bismuth (Bi).
[00149] [00149] "Semi-metallic element" refers to an element selected from boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po) .
[00150] [00150] "Non-metallic element" refers to an element selected from carbon (C), nitrogen (N), oxygen (O), fluorine (F), phosphorus (P), sulfur (S), chlorine (Cl ), selenium (Se), bromine (Br), iodine (I) and astatine (At).
[00151] [00151] "C2" refers to a hydrocarbon (for example, the compound consisting of carbon and hydrogen atoms), having only two carbon atoms, for example, ethane and ethylene. Likewise, "C3" refers to a hydrocarbon with only 3 carbon atoms, for example, propane and propylene.
[00152] [00152] "Conversion" means the molar fraction (ie, percent) of a reagent converted into a product or products.
[00153] [00153] "Selectivity" refers to the percentage of reagent that has been converted to a specified product, for example, C2 selectivity is the ° / 0 of converted methane that formed ethane and ethylene, C3 selectivity is at ° /) converted methane that formed propane and propylene, the selectivity of CO is the ° / 0 of converted methane that formed CO.
[00154] [00154] "Yield" is a measure (for example, percent) of the product obtained in relation to that of the maximum theoretical product obtainable. The yield is calculated by dividing the quantity of the product obtained in mol by theoretical yield in mol.
[00155] [00155] "Catalyst by volume" or "material by volume" means a catalyst prepared by traditional techniques, for example, by grinding or grinding large particles of catalysts to obtain smaller particles of smaller / larger surface area. Voiume materials are prepared with minimal control over the size and / or morphology of the material.
[00156] [00156] "Alkane" means a saturated linear or branched aliphatic hydrocarbon, non-cyclic or cyclic. Alkanes include linear, branched and cyclic structures. Representative straight chain alkanes include methane, ethane, n-propane, n-butane, n-pentane, n-hexane, and the like; while branched alkanes include isopropane, sec-butane, isobutane, t-butane, isopentane, and the like. Representative cyclic alkanes include cyclopropane, cyclobutane, cyclopentane, cyclohexane, and the like. "Alkene" means a straight or branched chain aliphatic, unsaturated, acyclic or cyclic hydrocarbon having at least one carbon-carbon double bond. Alkenes include linear, branched and cyclic structures. Representative straight and branched chain alkenes include ethylene, propylene, l-butene, 2-butene, isobutylene, l-pentene, 2-pentene, 3-methyl-1-butene, 2-methyl-2-butene, 2,3- dimethyl -2-butene e.
[00157] [00157] "Alkines" means straight or branched chain aliphatic, unsaturated, acyclic or cyclic hydrocarbon having at least one carbon-carbon triple bond. Alkines include linear, branched and cyclic structures. Representative straight and branched chain alkines include acetylene, propine, l-butino, 2-butino, l-pentino, 2-pentino, 3-methyl-1-butino and the like. Representative cyclic alkines include cycloheptin and the like.
[00158] [00158] "Alkyl", "alkenyl" and "alkynyl" refer to an alkane, aicene or alkaline radical, respectively.
[00159] [00159] "Aromatic" means a carbocyclic fraction with a cyclic system of conjugated p orbitals that form a delocalized conjugate system 1t and a number of electrons tt equal to 4n + 2 with n = 0, 1, 2, 3, etc. Representative examples of aromatic compounds include benzene, naphthalene and toluene.
[00160] [00160] "Arila" refers to an aromatic radical. Examples of aryl groups include, but are not limited to, phenyl, naphthyl and the like.
[00161] [00161] "Carbon-containing compounds" are compounds that comprise carbon. Non-limiting examples of carbon-containing compounds include hydrocarbons, CO and CO2.
[00162] [00162] As noted above, nanowires useful as catalysts are described herein. Catalytic nanowires and methods for their preparation are also described in PCT Publication number 2011/149996, the complete disclosure of which is incorporated into this document as a reference in its entirety. Figure 3A is a TEM image of a polycrystalline nanowire 200 having two distal ends 210 and 220. As shown, an actual length 230 traces essentially along the structure of nanowire 200, considering that an effective length 234 is the shortest distance between the two distal ends. The ratio of the effective length to the actual length is an indicator of degrees of kinks, curves and / or folds in the overall morphology of the nanowire. Figure 3B is a schematic representation of nanowire 200 of figure 3A.
[00163] [00163] Compared with nanowire 200 in figure 3A, nanowire 250 in figure 4A has a different morphology and does not have as many twists, curves and folds, which suggests a different base crystalline structure and a different number of defects and / or stacking failures. As shown for nanowire 250, the ratio between the effective length 270 and the real length 260 is greater than the ratio between the effective length 234 and the actual length 240 nanowire 200 of Figure 3A. Figure 4B is a schematic representation of nanowire 250, showing non-uniform diameters (280 a, 280b, 280C and 280d).
[00164] [00164] As noted above, in some embodiments nanowires presenting "folded" morphology (ie "folded nanowires") are provided. The "folded" morphology means that the folded nanowires comprise various twists, curves and / or folds in their general morphology as illustrated in general in figures 3A and 3B and discussed above. Folded nanowires have a ratio of effective length to actual length less than one. Therefore, in some embodiments of the present disclosure, it provides nanowires having an effective length to actual length ratio of less than one. In other modalities, nanowires may have an effective length to actual length ratio between 0.99 and 0.01, between 0.9 and 0.1, between 0.8 and 0.2, between 0.7 and 0, 3, or between 0.6 and 0.4. In other modalities, the ratio between effective length to actual length is less than 0.99, less than 0.9, less than 0.8, less than 0.7, less than 0.6, less than 0.5 , less than 0.4, less than 0.3, less than 0.2 or less than 0.1. In other modalities, the ratio between the effective length to actual length is less than 1.0 and greater than 0.9, less than 1.0 and greater than 0.8, less than 1.0 and greater than 0.7, less 1.0 and more than 0.6, less than 1.0 um and greater than 0.5, less than 1.0 and greater than 0.4, less than 1.0 and greater than 0.3, less at 1.0 esuperiora0.2, ouinferiora1, OesuperioraO, 1.
[00165] [00165] The relationship between the effective length to the real length of a nanowire with a curved morphology can vary depending on the angle of observation. For example, one skilled in the art will recognize that the same nanowire, when viewed from different perspectives, can have a different effective length, as determined by TEM. In addition, not all nanowires having a curved morphology will have the same ratio between effective length to actual length. Therefore, in a population (that is, the plurality) of nanowires having a curved morphology, a series of proportions of effective length to actual length is predicted. Although the ratio of effective length to actual length can vary from nanowire to nanowire, nanowires having a curved morphology will always have an effective length to actual length ratio of less than one from any angle of observation.
[00166] [00166] In several embodiments, a substantially linear nanowire is provided. A substantially linear nanowire has an effective length to reactive length ratio of one. Therefore, in some embodiments, the nanowires of the present description have an effective length to actual length ratio of one.
[00167] [00167] The actual lengths of the nanowires disclosed in this document may vary. For example, in some embodiments, nanowires can have an actual length between 100 nm and 100 µm. In other embodiments, nanowires can have a reactive length between 100 nm and 10 µm. In other embodiments, nanowires can have an actual length between 200 nm and 10 µm.
[00168] [00168] The diameter of the nanowires may be different at different points along the nanowire structure. However, nanowires comprise a mode diameter (that is, the most frequent diameter). As used in this document, the diameter of a nanowire refers to the mode diameter. In some embodiments, nanowires have a diameter between 1 nm and 10 µm, between 1 nm and 1 µm, between 1 nm and 500 nm, between 1 nm and 100 nm, between 7 nm and 100 nm, between 7 nm and 50 nm , between 7 nm and 25 nm, or between 7 nm and 15 nm. In other embodiments, the diameter is greater than 500 nm. As indicated below, the diameter of the nanowires can be determined by TEM, for example, in the light field mode, at 5 keV.
[00169] [00169] Several embodiments of the present disclosure provide nanowires with different aspect ratios. In some embodiments, nanowires have an aspect ratio greater than 10: 1. In other embodiments, nanowires have an aspect ratio greater than 20: 1. In other embodiments, nanowires have an aspect ratio greater than 50: 1. In other embodiments, nanowires have an aspect ratio greater than 100: 1.
[00171] [00171] The morphology of a nanowire (including length, diameter, and other parameters) can be determined by transmission electron microscopy (TEM). Transmission electron microscopy (MET) is a technique by which an electron beam is transmitted through an ultrathin specimen that interacts with the sample it passes through. An image is formed from the interaction of the transmission electrons through the sample. The image is enlarged and focused on an imaging device, such as a fluorescent screen, on a layer of photographic film or detected by a sensor, such as a CCD camera. TEM techniques are well known to those skilled in the art.
[00172] [00172] A TEM image of nanowires can be obtained, for example, in bright field mode, at 5 keV [for example, as shown in figures 3A and 4A).
[00173] [00173] The nanowires of the present disclosure can be further characterized by X-ray diffraction (XRD). XRD is a technique capable of revealing information about the crystallographic structure, chemical composition and physical properties of materials, including nanowires. XRD is based on the observation of the diffracted intensity of an x-ray beam that strikes a sample as a function of the incident and diffraction angle, polarization and wavelength or energy.
[00174] [00174] The crystal structure of the composition and phase including the size of the nanowire crystalline domain can be determined by XRD. In some embodiments, nanowires comprise a single crystal (i.e., single crystalline) domain. In other embodiments, nanowires comprise several crystal domains (i.e., polycrystalline). In some other embodiments, the average crystal domain of the nanowires is less than 100 nm, less than 50 nm, less than 30 nm, less than 20 nm, less than 10 nm, less than 5 nm, or less than 2 nm.
[00175] [00175] Typically, a catalytic material described in this document comprises a plurality of nanowires. In certain embodiments, the plurality of nanowires forms a mesh of interconnected nanowires distributed at random and to varying degrees. Figure 5A is a TEM image of a nanowire magnet 300 which comprises a plurality of nanowires 310 and a plurality of pores 320. Figure 5B is a schematic representation of the nanowire mesh 300 of Figure 5A.
[00176] [00176] The total surface area per gram of a nanowire or plurality of nanowires can have an effect on catalytic performance. The pore size distribution can also affect the catalytic performance of the nanowires. The surface area and pore size distribution of the nanowires or plurality of nanowires can be determined by BET measurements (Brunauer, Emmett Teller) measurements. BET techniques use nitrogen adsorption at various temperatures and partial pressures to determine the surface area and pore size of catalysts. BET techniques for determining the surface area and pore size distribution are well known in the art.
[00177] [00177] In some embodiments, the nanowires have a surface area between 0.0001 and 3.000 m '/ g, between 0.0001 and 2.000 m' / g, between 0.0001 and
[00178] [00178] In some embodiments, the nanowires have a surface area between 0.001 and 3,000 m '/ g, between 0.001 and 2,000 m' / g, between 0.001 and 1,000 m '/ g, between 0.001 and 500 m' / g, between 0.001 and 100 m '/ g, between 0.001 and 50 m2 / g, between 0.001 and 20 m' / g, between 0.001 and 10 m '/ g or between 0.001 and 5 m' lg.
[00182] [00182] In one embodiment, the development provides a catalyst comprising an inorganic catalytic polycrystalline nanowire, the nanowire having an effective length to actual length ratio less than one and an aspect ratio greater than ten, measured by TEM, in field mode luminous, at 5 keV, in which the nanowire comprises one or more elements from any of groups 1 to 7, lanthanides, actinides or combinations thereof.
[00183] [00183] In some embodiments, nanowires comprise one or more metallic elements from any of groups 1-7, lanthanides, actinides or combinations thereof, for example, the nanowires can be monometallic, bimetallic, trimetallic, etc. (that is, they contain one, two, three, or more metallic elements). In some modalities, the metallic elements are present in the nanowires in elementary form, while in other modalities the metallic elements are present in the nanowires in oxidized form. In other embodiments, the metallic elements are present in the nanowires, in the form of a compound that comprises a metallic element. The metallic element or compound comprising the metallic element can be in the form of oxides, hydroxides, oxyhydroxides, salts, hydrated oxides, carbonates, oxycarbonates, sulfates, phosphates, acetates, oxalates and the like. The metallic element or compound comprising the metallic element can also be in the form of any of a number of different crystalline or polymorphic structures.
[00184] [00184] In certain examples, metal oxides may be hygroscopic and may change shape, once exposed to air they may absorb carbon dioxide, they may be subject to incomplete calcination or any combination thereof. Therefore, although nanowires are often referred to as metal oxides, in certain embodiments nanowires also comprise hydrated oxides, oxyhydroxides, hydroxides, oxycarbonates (or oxide carbonates), carbonates or combinations thereof. jo0185] In other modalities, the nanowires comprise one or more Group 1 metallic elements. In other modalities, the nanowires comprise one or more Group 2 metallic elements. In other modalities, the nanowires comprise one or more Group metallic elements.
[00186] [00186] In another embodiment, the nanowires comprise one or more metallic elements of Group 1, in the form of an oxide. In another embodiment, the nanowires comprise one or more Group 2 metallic elements, in the form of an oxide. In another embodiment, the nanowires comprise one or more Group 3 metallic elements, in the form of an oxide. In another embodiment, the nanowires comprise one or more Group 4 metallic elements, in the form of an oxide. In another embodiment, the nanowires comprise one or more metallic elements of Group 5, in the form of an oxide. In another embodiment, the nanowires comprise one or more Group 6 metallic elements, in the form of an oxide. In another embodiment, the nanowires comprise one or more Group 7 metallic elements, in the form of an oxide. In another embodiment, nanowires comprise one or more metallic elements of lanthanides, in the form of an oxide. In another embodiment, the nanowires comprise one or more metallic elements of the actinides, in the form of an oxide.
[00187] [00187] In other embodiments, the nanowires comprise oxides, hydroxides, sulfates, carbonates, oxides, acetates, oxalates, phosphates (including hydrogenated phosphates and dihydrogenated phosphates), oxy, hydroxyalides, oxisulfate oxydroxides, or combinations thereof of one or more elements metals from any of Groups 1-7, lanthanides, actinides or combinations thereof. In some other embodiments, the nanowires comprise oxides, hydroxides, sulfates, carbonates, oxides, oxalates or combinations thereof of one or more metallic elements from any of Groups 1-7 of lanthanides, actinides or combinations thereof. In other embodiments, the nanowires comprise oxides, and in other embodiments, the nanowires comprise hydroxides. In other embodiments, the nanowires comprise carbonates, and in other embodiments, the nanowires comprise oxycarbonates.
[00188] [00188] In other embodiments, the nanowires comprise Li2CO3, L1OH, Li, O, Li, C, O ,, Li, SO4, Na, CO ,,, NaOH, Na, O, Na, C, O4, Na, SO4 , K, CO ,, KOH, K, O, K, C, O4, K, SO4, CS, CO ,, CSOH, CS, O, CSC, O4, CSSO4, Be (OH) 2, BeCO ,, BeO, Alley,. BeSO4, Mg (OH) 2, MgCOm MgO, MgC, O4. MgSO ,, Ca (OH) 2, CaO, CaCO3, CaC, O ,, CaSO4, Y2O3, Y3 (CO3) 2, Y (OH) 3, Y2 (C2O4) 3, Y2 (SO4) 3, Zr (OH) 4, ZrO (OH) 2, ZrO2, Zr (C2O4) 2, Zr (SO4) 2, Ti (OH) 4, TiO (OH) 2, TiO2, Ti (C2O4) 2, Ti (SO4) 2, BaO, Ba (OH) 2, BaCO3, BaC2O4, BaSO4, La (OH) 3, La2O3, La2 (C2O4) 3, La2 (SO4) 3, La2 (CO3) 3, Ce (OH) 4, CeO2, Ce2O3, Ce ( C2O4) 2, Ce (SO4) 2, Ce (CO3) 2, ThO2, Th (OH) 4, Th (C2O4) 2, Th (SO4) 2, Th (CO3) 2, Sr (OH) 2, SrCO, , SrO, SrC2O4, SrSO4, Sm2O3, Sm (OH) 3, Sm2 (CO3) 3, Sm2 (C2O3) 3, Sm2 (SO4) 3, LiCa2Bi3O4C | 6, NaMnO4, Na2WO4, NaMnNVO4, COWO4, CuWO4, K / SrCo ,, K / Na / SrCoO3, Na / SrCoO ,, Li / SrCoO ,,
[00189] [00189] In other embodiments, the nanowires comprise Li2O, Na2O, K, O, CS, O, BeO MgO, CaO, ZrO (OH) 2, ZrO2, TiO ,, TiO (OH) 2, BaO, Y2O3, La2O3, CeO2, Ce2O3, ThO2, SrO, Sm2O3, Nd2O3, Eu2O3, Pr2O3, LiCa2Bi3O4C | 6, NaMnO4, Na, WO4, Na / MnNVO4, Na / MnWO ,, Mn / VVO4, K / SrCoO ,, K / Na / SrCoO ,, K / Na / SrCoO ,, K / Na / SrCoO ,, , K / SrCoO ,,, Na / SrCoO3, Li / SrCoO ,, SrCoO3, Mg6MnO8, Na / B / Mg6MnO8, Li / B / Mg6MnO8, Zr2Mo2O8, molybdenum oxides, Mn2O3, Mn3O4, manganese oxides, oxides, oxides tungsten oxides, neodymium oxides, rhenium oxide, chromium oxide, or combinations thereof.
[00190] [00190] Still other aspects, the nanowires comprise lanthanides containing perovskites. Perovskite is any material with the same type of crystal structure as titanium oxide and calcium (CaTiO3). Examples of perovskites, within the context of the present description include, but are not limited to, LaCoO3 and La / SrCoO3.
[00191] [00191] In other embodiments, the nanowires comprise TiO2, Sm2O3, V2O ,, MOO3, BeO, MnO2, MgO, La2O3, Nd2O ,, Eu, O3, ZrO ,, Sro, Na2WO4, MnNVO4, BaO, Mn2O3, Mn3O8, Mg6Mnn , Na / B / Mg6MnO8, Li / B / Mg6MnO8, NaMnO4, CaO or combinations thereof. In the additional embodiments, the MgO nanowires comprise, La2O3, Nd2O3, Na2WO4, MnNVO4, Mn2O3, Mn3O4, Mg6MnO8, Na / B / Mg6MnO8, Li / B / Mg6MnO8 or combinations thereof.
[00192] [00192] In some embodiments, the nanowires comprise Mg, Ca, Sr, Ba, Y, La, W, Mn, Mo, Nd, Sm, Eu, Pr, Zr or combinations thereof, and in other embodiments the nanowire comprises MgO , CaO, SrO, BaO, Y2O3, La2O3, Na2WO4, Mn2O3, Mn3O4, Nd2O3, Sm2O3, Eu2O3, Pr2O3, Mg6MnO8, NaMnO4, Na / MnNV / O, Na / MnWO4, MnWO4 or combinations of the same.
[00193] [00193] In more specific modalities, the nanowires comprise MgO.
[00196] [00196] In still other modalities, the nanowires comprise an oxide of an anterior lanthanide element. For example, in some embodiments, the nanowires comprise a lanthanum oxide. In other embodiments, the nanowires comprise a cerium oxide. In other embodiments, the nanowires comprise a praseodymium oxide. In other embodiments, the nanowires comprise a neodymium oxide. In other embodiments, the nanowires comprise a promethium oxide. In other modalities, nanowires comprise samarium oxide. In other embodiments, the nanowires comprise a europium oxide. In other embodiments, the nanowires comprise a gadolinium oxide.
[00200] [00200] In some embodiments, nanowires or a catalytic material comprising a plurality of nanowires comprise a combination of one or more of the metallic elements from any of Groups 1-7, lanthanides or actinides and one or more metallic elements , semi-metallic or non-metallic elements. For example, in one embodiment, nanowires comprise combinations of Li / Mg / O, Ba / Mg / O, Zr / La / O, Ba / La / O, Sr / La / O, Zr / V / P / O , Mo / V / Sb / O, V, O, / Al, O ,, MON / O, V / Ce / O, V / Ti / P / O, V, O, / TiO ,, V / P / O /Uncle,,
[00201] [00201] In some other specific embodiments, the nanowires comprise the Li / MgO combination. In other specific embodiments, the nanowires comprise the Ba / MgO combination. In other specific embodiments, the nanowires comprise the Sr / La2O3 combination. In other specific embodiments, the nanowires comprise the Ba / La2O3 combination. In other specific embodiments, the nanowires comprise the Mn / Na2WO4 combination. In other specific embodiments, the nanowires comprise the combination of Mn / Na2 NO / SiO2. In other specific embodiments, the nanowires comprise the Mn2O3 / Na2WO4 combination. In other specific embodiments, the nanowires comprise the Mn3O4 / Na2WO4 combination. In other specific embodiments, the nanowires comprise the MnNVO4 / Na2WO4 combination. In other specific embodiments, the nanowires comprise the Li / B / Mg6MnO8 combination. In other specific embodiments, the nanowires comprise the Na / B / Mg6MnO8 combination. In other specific embodiments, the nanowires comprise the NaMnO4 / MgO combination.
[00202] [00202] Polyoxometalates (POM) constitute a class of metal oxides that varies in terms of molecular structure for the micrometric scale. The unique physical and chemical properties of POM agglomerates, and the ability to tune these properties through synthetics, have attracted great interest from the scientific community to create "designer" materials. For example, heteropolianions, such as the well-known Keggin anion [XM12O40] "and Wells-Dawson anions [X2M18O62]" (where M = W or Mo, and X = a tetrahedral model, such as, but not limited to Si, Ge , P) and isopolyanions with metal oxide structures with the general formulas [MOJ n, where M = Mo, W, V and Nb and x = 4-7 are ideal candidates for OCM / ODH catalysts. Thus, in one embodiment, the nanowires comprise anions [XM12O40] "or [X2M18O62]" (where M = W or Mo, and X = a tetrahedral model, such as, but not limited to Si, Ge, P) and isopolyanions with metal oxide structures with general formulas [MOJ n where M = Mo, W, V, and Nb and x = 4-7. In some modalities, X is P or Si.
[00203] [00203] These POM clusters have "lacunous" sites, which can accommodate first bivalent and trivalent transition metals, the metal oxide clusters acting as binders. These lacunous sites are essentially "doping" sites allowing the dopant to be dispersed at the molecular level, rather than in large quantities which can create pockets of unevenly dispersed doped material. Since POM clusters can be manipulated using standard synthetic techniques, POMS are highly modular and a vast library of materials can be prepared with different compositions, cluster size, and dopant oxidation status. These parameters can be adjusted to produce the desired OCM / ODH catalytic properties.
[00205] [00205] In some embodiments, the nanowire comprises a combination of two or more metal compounds, for example, metal oxides. For example, in some embodiments, the nanowire comprises Mn2O3 / Na2WO4, Mn3O4 / Na2WO4 MnWO4 / Na2WO4 / Mn2O3, MnWO4 / Na2WO4 / Mn3O4 or NaMnO4 / MgO.
[00206] [00206] Certain rare earth compositions have been considered as useful catalysts, for example, as catalysts in the CCE reaction. Thus, in one embodiment, the catalytic nanowires comprise lanthanide oxides such as La2O3, Nd2O3, Yb2O3, Eu2O3, Sm2O3, Y2O3, Ce2O3 or Pr2O3. In other embodiments, the nanowires comprise mixed oxides of lanthanide metals. Such mixed oxides are represented by Ln14-, Ln2, O6, where Lnl and Ln2 are each, independently, a lanthanide element and x is a number ranging from more than 0 to less than 4. In other more specific embodiments, oxides mixed lanthanide comprise La-xLn14-xO6, where Lnl is a lanthanide element and x is a number ranging from more than 0 to less than 4. For example, in some embodiments, mixed lanthanide oxides are mixed lanthanide oxides and neodymium and nanowires comprise La4-, NdxO6, where x is a number ranging from more than 0 to less than 4, has also been found to be useful in the OCM reaction. For example La3NdO6, LaNd3O6, La1.5Nd2.5O6, La2.5Nd1.5O6, La3.2Nd0.8O6, La3.5Nd0.5O6, La3.8Nd0,2O6, or combinations thereof have been considered as. useful OCM catalyst compositions.
[00208] [00208] In other modalities, the nanowires are in a central core / shell arrangement (see below) and the nanowires comprise: I in an MgO core; La in an MgO core; Nd in an MgO core; Sm in an MgO core; Y-Ce in a MgO core doped with Na; Ce-Y doped with Na in MgO core.
[00209] [00209] In one aspect of the invention, nanowires and the materials comprising them are provided, with the empirical formula M4wM5, M6yO ,, in which each M4 is independently one or more elements selected from groups 1 to 4, each M5 is independently one or more elements selected from Group 7 and M6 is independently one or more elements selected from Groups 5 to 8 and 14 to 15 groups ew, x, y and z are integers, such that the global load is balanced.
[00210] [00210] In some modalities, M4 comprises one or more elements selected from Group 1, such as sodium (Na), while M6 includes one or more elements selected from Group 6, such as tungsten (W) and M5 is Mn. In another modality, M4 is Na, M5 is Mn, M6 is W, the ratio of w: x is 10: 1, and the ratio of w: y is 2: 1. In ta! In this case, the general empirical formula for the nanowire is Na10MnW5O ". When Na is in the oxidation state +1, W is in the oxidation state +6, and Mn is in the oxidation state +4, z must be equal to 17, so to fulfill the Na, ' N and Mn valence requirements. As a result, the general empirical form of the nanowire in this modality is Na10MnW5O17.
[00213] [00213] In certain embodiments, the catalytic material comprises a support or vehicle. The support is preferably porous and has a high surface area. In some modalities the support is active (that is, it has a catalytic activity). In other modalities, the support is inactive (that is, not catalytic). In some embodiments, the support comprises an inorganic oxide, AI, O ,, SiO ,, TiO ,, MgO, CaO, SrO, ZrO ,, ZnO, LjAIo2, MgAl, O ,, MnO, MnO2, Mn3O4, La2O3, A | PO4, SiO2 / Al2O3, activated carbon, silica gel, zeolites, activated clays, activated A | 2O3, SiC, diatomaceous earth, magnesia, aluminum silicates, calcium aluminate, supporting nanowires or combinations thereof. In some embodiments, the support is composed of silicon, for example, SiO2. In other embodiments, the support comprises magnesium, for example, MgO. In other modalities, the support comprises zirconium, for example, ZrO2- In still other modalities, the support comprises Ianthanum, for example, La2O3. In yet other embodiments, the support comprises lanthanum, for example, Y2O3. In yet other modalities, the support comprises hafnium, for example, HfO2. In yet other modalities, the support comprises aluminum, for example, A | 2O3. In yet other embodiments, the support comprises gallium, for example, Ga2O3.
[00214] [00214] In yet other embodiments, the support material comprises an inorganic oxide, A | 2O3, SiO2, TiO2, MgO, ZrO2, HfO2, CaO, SrO, ZnO, LiA | O2, MgA | 2O4, MnO, MnO2, Mn2O4 , Mn3O4, La2O3, activated carbon, silica gel, zeolites, activated clays, activated A | 2O3, diatomaceous earth, magnesium oxide, aluminum silicates, calcium aluminate, support nanowires or their combinations. For example, the support material can comprise SiO2, ZrO2, CaO, La2O3 or MgO.
[00215] [00215] In yet other embodiments, the support material comprises a carbonate. For example, in some embodiments the support material comprises MgCO3, CaCO3, SrCO3, BaCO3, Y2 (CO3) 3, La2 (CO3) 3, or a combination thereof.
[00216] [00216] In yet other modalities, a nanowire can serve as a support for another nanowire. For example, a nanowire can be composed of non-catalytic metallic elements and adhered to or incorporated into the support, the nanowire is a catalytic nanowire. For example, on. in some embodiments, the support nanowires are made up of SiO2, MgO, CaO, SrO, TiO2, ZrO2, A | 2O3, ZnO, MgCO3, CaCO3, SrCO3, or combinations thereof. The preparation of supported catalytic nanowires (i.e., core / shell nanowires) is discussed in more detail below. The ideal amount of nanowires present in the support depends, among other things, on the nanowire's catalytic activity. In some embodiments, the amount of nanowire present in the support is 1 to 100 parts by weight of nanowires per 100 parts by weight of support or 10 to 50 parts by weight of nanowires per 100 parts by weight of support. In other embodiments, the amount of nanowires present in the support ranges from 100-200 parts of nanowires per 100 parts by weight of support, or 200-500 parts of nanowires per 100 parts by weight of support, or 500-1,000 parts of nanowires per 100 parts by weight of support. Typically, heterogeneous catalysts are employed either in their pure form or in a mixture with inert materials, such as silica, alumina, etc. The mixture with the inert material is used in order to reduce and / or control non-uniformities at high temperatures inside the reactor bed, often observed in the case of strongly exothermic (or endothermic) reactions. In the case of complex multi-step reactions, such as the methane to ethylene (OCM) reaction, typical mixing materials can selectively reduce or saturate one or more reactions in the system and promote unwanted side reactions. For example, in the case of oxidative coupling of methane, silica and alumina can saturate methyl radicals and thus prevent the formation of ethane. In certain aspects, the present disclosure provides a catalytic material that solves these problems generally associated with the catalyst support material. Consequently, in certain embodiments, the catalytic activity of the catalytic material can be adjusted by mixing two or more catalysts and / or catalyst support materials. The mixed catalytic material may comprise a catalytic nanowire as described herein and a volume catalyst material and / or inert carrier material.
[00217] [00217] Mixed catalytic materials comprise metal oxides, hydroxides, oxyhydroxides, carbonates, group 1-16 oxalates, lanthanides, actinides or combinations thereof. For example, the combined catalytic materials may comprise a pIurality of inorganic, polycrystalline catalytic nanowires, as disclosed herein, and any one or more of the linear nanowires, nanoparticles, bulk materials and inert carrier materials. Bulk materials are defined as any material in which any attempt to control size and / or morphology was made during their synthesis. Catalytic materials may not be doped or may be doped with any of the dopants described in this document.
[00218] [00218] In one embodiment, the catalyst mixture comprises at least one type 1 component and at least one type 2 component. Type 1 components comprise catalysts with high OCM activity at moderately low temperatures and type 2 components comprise catalysts having little or no OCM activity at these moderately low temperatures, but are OCM active at higher temperatures. For example, in some embodiments the type 1 component is a catalyst (for example, nanowires) having high OCM activity at moderately low temperatures. For example, the type 1 component may comprise a C2 yield greater than 5 ° / 0 or greater than 10% at temperatures below 800 ° C, below 700 ° C or below 600 ° C. The type 2 component may comprise a C2 yield of less than 0.1%, less than 1 ° / 0 or less than 5 ° / 0 at temperatures below 800 ° C, below 700 ° C or below 600 ° C. The type 2 component may comprise a C2 yield greater than 0.1%, greater than 1 ° / 0, greater than 5 ° / 0, or greater than 10 ° / 0, at temperatures greater than 800 ° C, greater than 700 ° C or higher than 600 ° C. Typical type 1 components include nanowires, for example, polycrystalline nanowires as described in this document, while typical type 2 components include OCM catalysts in volume and catalytic nanowires that only have good OCM activity at higher temperatures, for example above 800 ° C. Examples of . Type 2 components can include catalysts comprising MgO. The catalyst mixture may further comprise inert support materials, as described above (for example, silica, alumina, silicon carbide, etc.)
[00219] [00219] In certain embodiments, the type 2 component acts as a diluent in the same way that an inert material does and, therefore, helps to reduce and / or control the heated points in the catalyst bed caused by the exothermic nature of the OCM reaction. However, since the type 2 component is a CMO catalyst, although not particularly active, it can prevent the occurrence of unwanted side reactions, for example, saturation of the radial methyl. In addition, the control of heated points has the benefit of extending the life of the catalyst.
[00220] [00220] For example, it has been found that diluting the OCM catalysts of active lanthanide oxide (eg nanowires) with as much as a 10: 1 ratio of MgO, which in itself is not an active catalyst in OCM at temperature in which the lanthanide oxide operates, it is a good way to minimize the "hot spots" in the reactor catalyst bed, while maintaining the catalyst selectivity and yield performance. On the other hand, performing the same dilution with quartz SiO2 is not effective because it seems to saturate the methyl radicals that serve to decrease selectivity for C2.
[00221] [00221] In yet another modality, type 2 components are good oxidative dehydrogenation (ODH) catalysts at the same temperature as type 1 components are good OCM catalysts. In this embodiment, the ethylene / ethane ratio of the resulting gas mixture can be adjusted in favor of higher ethylene. In another embodiment, type 2 components are not only good ODH catalysts at the same temperature as type 1 components are good OCM catalysts, but they also limit moderate OCM activity at these temperatures.
[00222] [00222] In related modalities, the catalytic performance of the catalytic material is adjusted by selecting the specific type 1 and type 2 components of a catalyst mixture. In another modality, the catalytic performance is adjusted by adjusting the proportion between the type 1 and type 2 components in the catalytic material. For example, the type 1 catalyst can be a catalyst for a specific step in the catalytic reaction, while the type 2 catalyst can be specific for a different step in the catalytic reaction. For example, the type 1 catalyst can be optimized for the formation of methyl radicals and the type 2 catalyst can be optimized for the formation of ethane or ethylene.
[00224] [00224] Thus, in one embodiment the present disclosure provides for the use of a catalytic material comprising a first catalytic nanowire and a catalyst by volume and / or a second catalytic nanowire in a catalytic reaction, for example, the catalytic reaction can be OCM or ODH. In other embodiments, the first catalytic nanowire and the volume catalyst and / or the second catalytic nanowire are each catalytic with respect to the same reaction, and in other examples, the first catalytic nanowire and the volume catalyst and / or second catalytic nanowire has the same chemical composition.
[00225] [00225] In some specific embodiments of the foregoing, the catalytic material comprises a first catalytic nanowire and a second catalytic nanowire. Each nanowire can have completely different chemical compositions, or it can have the same basic composition and differ only in the doping elements.
[00226] [00226] In a related modality, the catalytic material comprises a first catalytic nanowire and a volume catalyst. The first nanowire and the volume catalyst can have completely different chemical compositions or can have the same basic composition and differ only in the doping elements. In addition, the first catalytic nanowire and the volume catalyst can each be catalytic with respect to the same reaction, but have different activity. Alternatively, the first nanowire and the volume catalyst can catalyze different reactions.
[00227] [00227] Still in other modalities of the above, the catalytic nanowire has a catalytic activity in the catalytic reaction, which is superior to a catalytic activity of the catalyst in volume in the catalytic reaction, at the same temperature.
[00228] [00228] OCM catalysts can be prone to hot spots, due to the very exothermic nature of the OCM reaction. The dilution of such catalysts helps to manage the hot spots. However, the diluent needs to be carefully chosen so that the overall performance of the catalyst is not degraded. Silicon carbide, for example, can be used as a diluent, with little impact on the OCM selectivity of the mixed catalytic material, considering that the use of silica as a diluent significantly reduces the selectivity of OCM. The good thermal conductivity of SiC is also beneficial for minimizing hot spots. As noted above, the use of a catalyst diluent or support material that is properly active in OCM has significant advantages over more traditional diluents, such as silica and alumina, which can saturate methyl radicals and thus reduce the performance of Catalyst CMO. An OCM active thinner is not expected to have any negative impact on the generation and lifetime of the methyl radicals and therefore the dilution should not have any negative impact on the performance of the catalyst.
[00229] [00229] In some embodiments, the above diluent comprises an alkaline earth metal compound, for example, alkali metal oxides, carbonates, sulfates or phosphates. Examples of diluents useful in various embodiments include, but are not limited to, MgO, MgCO3, MgSO4, Mg3 (PO4) 2, MgA | 2O4, CaO, CaCO3, CaSO4, Ca3 (PO4) 2, CaA! 2O4, SrO, SrCO3, SrSO4, Sr3 (PO4) 2, SrA! 2O4, BaO, BaCO3, BaSO4, Ba3 (PO4) 2, BaAl2O4 and the like. Most of these compounds are very inexpensive, especially MgO, CaO, MgCO3, CaCO3, SrO, SrCO3 and are therefore very attractive for use as diluents from an economic point of view. In addition, magnesium, calcium and strontium compounds are environmentally friendly. Accordingly, an embodiment of the invention provides a catalytic material comprising a catalytic nanowire, in combination with a diluent selected from one or more of MgO, MgCO3, MgSO4, Mg3 (PO4) 2, CaO, CaCO3, CaSO4, Ca3 (PO4 ) 2, SRO, SrCOs, SrSO4, Sr3 (PO4) 2, BaO, BaCO3, BaSO4, Ba3 (PO4) 2. In some specific configurations the diluents are MgO, CaO, Sro, MgCO3, CaCO3, SrCO3 or a combination of these. Methods for using the preceding catalytic materials in an OCM reaction are also provided. The methods include the conversion of methane and ethane or ethylene in the presence of catalytic materials.
[00230] [00230] The diluents and supports above can be used in any number of methods. For example, in some modalities a support (for example, MgO, CaO, CaCO3, srCog can be used in the form of a tablet or monolith (for example , in the form of aromatic) of structure, and catalytic nanowires can be impregnated or supported in it. In other embodiments, a central core / shell arrangement is provided and the support material can form part of the core or shell. MgO, CaO, CaCO3 or SrCO3 core can be coated with a shield from any of the disclosed nanowire compositions.
[00231] [00231] In some modalities, the diluent has a morphology selected from large quantities (for example, commercial type), nano (nanowires, nanobonds, nanoparticles, etc.), or combinations thereof.
[00232] [00232] In some embodiments, the diluent has no activity until a moderate catalytic activity at the temperature at which the OCM catalyst is operated. In some other embodiments, the diluent has moderate to great catalytic activity at a higher temperature than the temperature at which the OCM catalyst is operated. Still in some other embodiments, the diluent has no activity until moderate catalytic activity at the temperature at which the OCM catalyst is operated and moderate to great catalytic activity at higher temperatures than at the temperature at which the OCM catalyst is operated. Typical operating temperatures for an OCM reaction according to the present disclosure are 800 ° C or less, 750 ° C or less, 700 ° C or less, 650 ° C or less, 600 ° C or less at 550 ° C or any less.
[00233] [00233] For example, CaCO3 is a relatively good OCM catalyst at T> 750 ° C (50 ° / o selectivity,> 20 ° / o conversion), but essentially has no activity below 700 ° C. Experiments carried out in support of the present invention showed that diluting linear nanowires of Nd2O3 with CaCO3 or SrCO3 (volume) did not show any degradation in the performance of OCM and, in some cases, even better performance than the pure catalyst.
[00234] [00234] In some embodiments, the diluent portion in the catalyst / diluent mixture is 0.01 ° / 0, 10 ° / 0, 3 ° / 0, 5 ° / j, 7 ° / 0, 90% or 99 , 99% (percentage by weight) or any other value between 0.01% and 99.9%. In some embodiments, dilution is carried out with the OCM catalyst ready to work, for example, after calcination. In some other embodiments, the dilution is carried out before the final calcination of the catalyst, that is, the catalyst and the diluent are calcined together. Still in some other modalities, dilution can be done during synthesis, as well, so that, for example, a mixed oxide is formed.
[00235] [00235] In some embodiments, the catalyst / diluent mixture consists of more than one catalyst and / or more than one diluent.In some other embodiments, the catalyst / diluent mixture is micronized and sized, or obtained in the form of extremes or deposited on a monolith, or foam, or is used as is. The methods of the invention include taking advantage of the very exothermic nature of OCM by diluting the catalyst with another catalyst that is (almost) inactive in the OCM reaction at the operating temperature of the first active catalyst, but at a higher temperature. In these methods, the heat generated by the heated points of the first catalyst will provide the necessary heat for the second catalyst to become active.
[00236] [00236] For ease of illustration, the above description of catalytic materials often refers to the CMO; however, such catalytic materials find use in other catalytic reactions, including, but not limited to: oxidative dehydrogenation (ODH) of alkanes from their corresponding alkenes, selective oxidation of alkanes and alkenes and alkynes, Co oxidation, dry methane reform , selective oxidation of aromatics, Fischer-Tropsch, combustion of hydrocarbons, etc.
[00237] [00237] Catalytic materials can be prepared according to any number of methods known in the art. For example, catalytic materials can be prepared after the preparation of the individual components by mixing the individual components in dry form, for example, mixing of powders, and, optionally, a ball mill can be employed to reduce the particle size and / or increase the mixture. Each component can be added together or one after the other, to form layered particles.
[00238] [00238] In other examples, catalytic materials are prepared by mixing the individual components with one or more solvents, in a suspension or paste, and the optional mixture and / or a ball mill can be used to maximize uniformity and reduction of the particle size.
[00239] [00239] Catalytic materials may optionally comprise a dopant, as described in more detail below. In this respect, the doping material (S) can be added during the preparation of the individual components, after the preparation of the individual components, but before drying them, after the drying step, but before calcination or after calcination.
[00240] [00240] Doping material (s) can also be added as dry components and, optionally, a ball mill can be employed to increase the mixture. In other embodiments, the doping material (S) is added as a liquid (e.g., solution, suspension, paste, etc.) to the individual dry components of the catalyst or to the combined catalytic material. The amount of liquid can optionally be adjusted to optimize the catalyst wetting, which can result in a better coverage of catalyst particles by doping material. Ball blending and / or grinding can also be used to maximize doping coverage and uniform distribution. Alternatively, the doping material (S) is added as a liquid (e.g., solution, suspension, paste, etc.), to a suspension or paste of the catalyst in a solvent. Mixing and / or ball milling can be used to maximize doping coverage and uniform distribution. Incorporation of dopants can also be achieved using any of the methods described in this document.
[00241] [00241] As noted below, an optional calcination step generally follows an optional drying step at T <200 ° C (typically 60-120 ° C) in a regular oven or a vacuum oven. The calcination can be carried out on the individual components of the catalytic material or on the combined catalytic material. Calcination is normally carried out in an oven at a temperature above the minimum temperature in which at least one of the components decomposes or undergoes a phase transformation and can be carried out in an inert atmosphere (for example, N2, Ar, He, etc.) , oxidizing atmosphere (air, O2, etc.) or reducing atmosphere (H2, H2 / N2, H2 / Ar, etc.). The atmosphere can be a static atmosphere or a gas flow and can be carried out at ambient pressure, at p <1 atm, in a vacuum or at p> 1 atm. High pressure treatment (at any temperature) can also be used to induce phase transformation, including from amorphous to crystalline. Calcination can also be carried out by means of microwave heating.
[00242] [00242] Calcination is generally carried out in any combination of steps comprising elevation, residence time and decline. For example, elevation to 500 ° C, residence at 500 ° C for 5 h, elevation to room temperature (RT). Another example includes elevation to 100 ° C, residence at 100 ° C for 2 h, elevation to 300 ° C, residence at 300 ° C for 4 h, elevation to 550 ° C, residence at 550 ° C for 4 h, elevation to RT. Calcination conditions (pressure, type of atmosphere, etc.) can be changed during calcination. In some embodiments, calcination is carried out before preparing the material! mixed catalytic (ie the individual components are calcined) after the preparation of the mixed catalytic material, but before doping, after doping the individual components or the mixed catalytic material. The calcination can also be carried out several times, for example, after the preparation of the catalyst and after doping.
[00243] [00243] Catalytic materials can be incorporated into a bed reactor to perform any number of catalytic reactions (eg, OCM, ODH and the like). Thus, in one embodiment, the present disclosure provides a catalytic material, as disclosed in this document in contact with a reactor and / or a bed reactor. For example, the reactor can be used to carry out a CMO reaction, it can be a fixed bed reactor and it can have a diameter greater than 1 cm. In this regard, the catalytic material can be packaged neat (without diluents) or diluted with an inert material (for example, sand, silica, alumina, etc.). The catalyst components can be packaged evenly to form a homogeneous reactor bed.
[00244] [00244] The particle size of the individual components within a catalytic material can also alter the catalytic activity, and other properties, of the same. Thus, in one embodiment, the catalyst is ground to an average target particle size or the powdered catalyst is sieved to select a particular particle size. In some aspects, the powdered catalyst can be pressed into tablets and the catalyst tablets can optionally be ground and sieved or to obtain the desired particle size distribution.
[00245] [00245] In some embodiments, the catalyst materials, alone or with binding agents and / or diluents, can be configured in forms of larger aggregates, such as microspheres, ends, or other aggregates of catalyst particles. For ease of discussion, such larger forms are generally referred to here as "microspheres". Such microspheres can optionally include a binding agent and / or support material; however, the present inventors have surprisingly found that the disclosed nanowires are particularly suitable for use in the form of a microsphere without a binder and / or support material. Therefore, one embodiment of the present review provides catalytic material in the absence of a binder. In this respect, it is believed that the morphology of the described nanowires (both curved and linear) contributes to the nanowires' ability to be pressed into inserts without the need for a binder. Catalytic materials without binders are simpler, less complex and cheaper than the corresponding materials with binders and thus offer some advantages.
[00246] [00246] In some cases, catalytic materials can be prepared using a "sacrificial binder" or support. Due to their special properties, nanowires allow the preparation of forms of catalytic materials (for example, microspheres), without the use of a binder. A "sacrificial" binder can be used in order to create the unique microporosity in microspheres or ends. After removing the sacrificial binder, the structural integrity of the catalyst is ensured by the special bonding properties of the nanowires and the materia! The resulting catalytic has unique microporosity as a result of the removal of the binder. For example, in some embodiments, a catalytic nanowire can be prepared with a bonding agent, and then the binder is removed by any number of techniques (for example, combustion, calcination, acid erosion, etc.). design and preparation of catalytic materials having a unique microporosity (ie microporosity is a function of the size, etc., of the sacrificial binder). The ability to prepare various forms (for example, microspheres) of nanowires, without the use of a binder is not only useful for the preparation of catalytic materials from nanowires, but also allows the nanowires to be used as support material (or both catalytic material and support).
[00248] [00248] As the reaction of OCM is very exothermic, it may be desirable to reduce the conversion rate per unit volume of the reactor, in order to avoid the leakage of temperature rise in the catalyst bed, which can result in spots that affect the performance and life of the catalyst. One way to reduce the OCM reaction rate per unit volume of the reactor is to spread the active catalyst on an inert support with large interconnected pores as in ceramic or metal foams (including metal alloys having reduced reactivity with hydrocarbons under OCM reaction conditions) or with rows of the channel as in ceramics structured in aromatics or goal setting !.
[00249] [00249] In one embodiment, a catalytic material comprising a catalytic nanowire is provided as reviewed in the present document supported on a structured support. Examples of such structure supports include, but are not limited to, metal foams, silicon carbide or alumina foams, corrugated metal foil arranged to form rows of cane !, ultra-plated ceramic scents, for example, Cordierite (available from Corning or NGK ceramics, USA), Silicon Carbide or Alumina.
[00250] [00250] Load of active catalyst in the structured support ranges vary from 1 to 500 mg per ml of support component, for example from 5 to 100 mg per ml of support structure. Cell densities in aromatic structured support materials can range from 100-900 CPSI (cells per square inch), for example, 200 to 600 CPSI. Foam densities can vary from 10 to 100 pp] (pores per inch), for example, 20 to 60 PPl. .
[00251] [00251] In other modalities, the exotherm of the OCM reaction can be at least partially controlled by mixing the active catalytic material with. a catalytically inert material, and pressing or extruding, the mixture formed into microspheres or ends. In some embodiments, these mixed particles can then be loaded into a packaged bed reactor. Extruded or microspheres comprise between 30 ° / o to 7 ° / o of the pore volume with 5% to 50% of the active catalyst by weight fraction. Inert materials useful in this regard include, but are not limited to, MgO, CaO, A | 2O3, SiC and cordierite.
[00252] [00252] In addition to reducing the potential for heated spots inside the catalytic reactor, another advantage of using a structured pore ceramic with a large volume of pores as a catalytic support is reduced flow resistance, with the same hourly spatial gas speed in comparison with a packed bed containing the same amount of catalyst.
[00253] [00253] Yet another advantage of using these supports is that the structured support can be used to provide characteristics that are difficult to obtain in a packed bed reactor. For example, the support structure can improve mixing or allow standardization of deposits of active catalyst across the reactor volume. Such standardization may consist of depositing multiple layers of catalytic materials on the support, in addition to the active component of OCM, in order to affect the transport to the catalyst or combination of catalytic functions such as the addition of O2-ODH activity, CO2-OCM activity or CO2-ODH activity for the system, in addition to the O2-OCM active material. Another standardization strategy may be to create deviation within the catalyst structure, essentially free of an active catalyst to limit the overall conversion within a given volume of supported catalyst.
[00254] [00254] Yet another advantage is the reduced heating capacity of the structured catalyst bed over a packed bed of a similar active catalyst load, therefore reducing the start-up time.
[00255] [00255] Catalysts conformed in nanowires are specifically well adapted for incorporation into microspheres or extremes or deposition in structured supports. Aggregated nanowires forming a mesh-like structure can have good adhesion on rough surfaces.
[00256] [00256] The mesh-like structure can also provide a better cohesion in the ceramic composite, improving the mechanical properties of the microspheres or ends containing the catalyst particles in the form of nanowires.
[00257] [00257] Alternatively, such nanowires on the support or in microsphere-shaped approaches can be used for other reactions, in addition to OCM, such as ODH, dry methane reform, FT, and all other catalytic reactions.
[00259] [00259] In still other embodiments, the development provides a catalytic material that comprises one or more different catalysts. The catalysts can be a nanowire as disclosed herein and a different catalyst, for example, a volume catalyst. Mixtures of two or more catalytic nanowires are also contemplated. The catalytic material may comprise a catalyst, for example, a catalytic nanowire, having one.
[00260] [00260] Those skilled in the art will recognize that various alternative combinations or methods above are possible and such variations are also included within the scope of the present disclosure.
[00261] [00261] In other embodiments, the development provides nanowires comprising a doping agent (ie, doped nanowires). As noted above, dopants or dopants are impurities added or incorporated into a catalyst to optimize the performance of the catalyst (for example, increasing or decreasing catalytic activity). In comparison to the non-doped catalyst, a doped catalyst can increase or decrease the selectivity, conversion, and / or yield of a catalytic reaction. In one embodiment, dopants of nanowires comprise one or more metallic elements, semimetallic elements, non-metallic elements or combinations thereof. Although oxygen is included in the group of non-metallic elements, in certain modalities oxygen is not considered a dopant. For example, certain modalities are directed at nanowires comprising two, three or even four or more dopants, and dopants are different oxygen dopants. Thus, in these modalities, a metal oxide nanowire is not considered as an oxygen-doped metal nanowire.
[00262] [00262] The dopant can be present in any form and can be derived from any suitable source of the element (for example, chlorides, bromides, iodides, nitrates, oxynitrates, oxalides, acetates, formats, hydroxides, carbonates, phosphates, sulfates, alkoxides , and the like.). In some embodiments, the nanowire dopant is in elementary form. In other embodiments, the nanowire dopant is in reduced or oxidized form. In other embodiments, the nanowire dopant comprises an oxide, hydroxide, carbonate, nitrate, acetate, sulfate, format, oxynitrate, oxyhalide, oxyhalide or hydroxyalide of a metallic element, semimetallic element or non-metallic element or combinations thereof.
[00263] [00263] In one embodiment, the nanowires comprise one or more metallic elements selected in Groups 1-7, lanthanides, actinides or combinations thereof, in the form of an oxide and further comprise one or more dopants, in which one or more dopants , comprise metallic elements, semi-metallic elements, non-metallic elements or combinations thereof.
[00264] [00264] For example, in one embodiment, the nanowire dopan comprises Li, Li2CO3, L1OH, Li, O, LiCl, LiNO3, Na, Na, CO ,, NaOH, Na, O, NaCl, NaNO ,, K, K , CO ,, KOH, K, O, KCl, KNO ,, Rb, Rb, CO ,, RbOH, Rb, O, RbCl, RbNO ,, Cs, CS, CO ,, CSOH, CS, O, CsCl, CSNO, , Mg, MgCO3, Mg (OH) 2, MgO, MgCl ,, Mg (NO3) 2, Ca, CaO, CaCO3, Ca (OH) 2, CaCl ,, Ca (NO3) 2, Sr, SrO, SrCO ,, Sr (OH) z SrC | 2, Sr (NO3) 2, Ba, BaO, BaCO3, Ba (OH) 2, BaC! 2, Ba (NO3) 2, La, La2O3, La2 (CO3) 3, La (OH ) 3, LaC | 3, La (NO3) 2, Nd, Nd2O3, Nd2 (CO3) 3, Nd (OH) 3, NdC | 3, Nd (NO3) 2, Sm, Sm2O3, Sm2 (CO3) 3, Sm (OH) 3, SmCb, Sm (NO3) 2, Eu, Eu2O3, Eu2 (CO3) 3, Eu (OH) 3, EuC | 3, Eu (NO3) 2, Gd, Gd2O3, Gd2 (CO3) 3, Gd (OH) 3, GdCl ,, Gd (NO3) 2, Ce, Ce (OH) 4, CeO2, Ce2O3, Ce (CO3) 2, CeC | 4, Ce (NO3) 2, Th, ThO ,, ThC | 4 , Th (OH) 4, Zr, ZrO2, ZrC | 4, Zr (OH) 4, ZrOC | 2, Zr (CO3) 2, ZrOCO3, ZrO (NO3) 2, P, phosphorus oxides, phosphorus chlorides, carbonates phosphorus, Ni, nickel oxides, nickel chlorides, nickel carbonates, nickel hydroxides, Nb, niobium oxides, niobium chlorides, carbon niobium oxides, niobium hydroxides, Au, gold oxides, gold chlorides, gold carbonates, gold hydroxides, Mo, molybdenum oxides, molybdenum chlorides, molybdenum carbonates, molybdenum hydroxides, tungsten chlorides, carbonates tungsten, tungsten hydroxides, Cr, chromium oxides, chromium chlorides, chromium hydroxides, Mn, manganese oxides, manganese chlorides, manganese hydroxides, Zn, ZnO, ZnCl2, Zn (OH) 2, B, borates, BCl ,,, N, nitrogen oxides, nitrates, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, ln, Y, Sc, Al, Cu, Cs, Ga, Hf, Fe, Ru, Rh, Be, Co, Sb, V, Ag, Te, Pd, Tb, lr, Rb or combinations thereof. In other embodiments, the nanowire dopant comprises Li, Na, K, Rb, Cs, Mg, Ca, Sr, Eu, Na, Nd, Sm, Ce, Gd, Tb, Er, Tm, Yb, Y, Sc, or combinations thereof. In other embodiments, the nanowire dopant comprises Li, Li, O, Na, Na2O, K, K, O, Mg, MgO, Ca, CaO, Sr, SrO, Ba, BaO, La, La2O3, Ce, CeO2, Ce2O3 , Th, ThO2, Zr, ZrO ,, P, phosphorus oxides, Ni, nickel oxides, Nb, niobium oxides, Au, gold oxides, Mo, molybdenum oxides, Cr, chromium oxides, Mn, oxides of manganese, zinc, ZnO, B, borates, N, nitrogen oxides or combinations thereof. In other embodiments, the nanowire dopant comprises Li, Na, K, Mg, Ca, Sr, Ba, La, Ce, Ta, Zr, P, Ni, Nb, Au, Mo, Cr, Mn, Zn, B, N or combinations thereof. In other embodiments, the nanowire dopant comprises Li2O, Na2O, K2O, MgO, CaO, SrO, BaO, La2O3, CeO2, Ce2O3, ThO2, ZrO2, phosphorus oxides, nickel oxide, niobium oxide, gold oxide, oxides molybdenum, chromium oxides, manganese oxides, ZnO, borates, nitrogen oxides, or combinations thereof. In other embodiments, the nanowire dopant comprises Sr or Li. In other specific embodiments, the nanowire dopant comprises La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb , Lu, ln, Y, Sc, or combinations thereof. In other specific embodiments, the nanowire dopant comprises Li, Na, K, Mg, Ca, Ba, Sr, Eu, Sm, Co or Mn.
[00265] [00265] In certain embodiments, the dopant comprises an element of group 1. In some embodiments, the dopant comprises lithium. In some embodiments, the dopant comprises sodium. In some embodiments, the dopant comprises potassium. In some modalities, the dopant comprises rubidium.
[00266] [00266] In some embodiments the nanowires comprise a lanthanide element and are doped with a group 1, group 2 doping agent or combinations thereof. For example, in some embodiments, nanowires comprise a lanthanide element and are doped with lithium. In other embodiments, the nanowires comprise a lanthanide element and are doped with sodium. In other embodiments, the nanowires comprise a lanthanide element and are doped with potassium. In other embodiments, the nanowires comprise a lanthanide element and are doped with rubidium. In other embodiments, the nanowires comprise a lanthanide element and are doped with cesium. In other embodiments, the nanowires comprise a lanthanide element and are doped with beryllium. In other embodiments, the nanowires comprise a lanthanide element and are doped with magnesium. In other embodiments, the nanowires comprise a lanthanide element and are doped with calcium. In other embodiments, nanowires comprise a lanthanide element and are doped with strontium. In other embodiments, nanowires comprise a lanthanide element and are doped with barium.
[00267] [00267] In some embodiments the nanowires comprise a transition metal tungstate (for example, Mn / VV and the like) and are doped with a group 1, group 2 doping agent or combinations thereof. For example, in some embodiments, nanowires comprise a transition metal tungstate and are doped with lithium. In other embodiments, the nanowires comprise a transition metal tungstate and are doped with sodium. In other embodiments, the nanowires comprise a transition metal tungstate and are doped with potassium. In other embodiments, the nanowires comprise a transition metal tungstate and are doped with rubidium. In other embodiments, the nanowires comprise a transition metal tungstate and are doped with cesium. In other embodiments, the nanowires comprise a transition metal tungstate and are doped with beryllium. In other embodiments, the nanowires comprise a transition metal tungstate and are doped with magnesium.
[00268] [00268] In some embodiments the nanowires comprise Mn / Mg / S and are doped with a doping agent from group 1, group 2, group 7, group 8, group 9 or group 10 or combinations thereof. For example, in some embodiments, nanowires comprise Mn / Mg / S and are doped with lithium. In other embodiments, the nanowires comprise Mn / Mg / S and are doped with sodium.
[00270] [00270] As mentioned above, the present inventors have determined that certain catalytic nanowires comprising rare earth elements (for example, rare earth oxides), are useful as catalysts in various reactions, for example, the OCM reaction. In certain modalities the element of rare earth is La, Nd, Eu, Sm, Yb, Gd or Y. In some modalities, the element of rare earth is La. In other modalities, the element of rare earth is Nd. In other embodiments, the element of rare earth is I. In other modalities, the element of rare earth is Sm. In other modalities, the element of rare earth is Yb. In other modalities, the element of rare earth is Gd. In other embodiments, the rare earth element is Y.
[00271] [00271] In certain modalities of catalytic nanowires comprising rare earth elements, the catalyst may further comprise a dopant selected from the elements of alkaline earth (Group 2). For example, in some modalities the dopant is selected from Be, Mg, Ca, Sr and Ba. In other modalities, the dopant is Be. In other modalities, the dopant is Ca. In other modalities, the dopant is Sr., in other modalities, the dopant is Ba.
[00272] [00272] In some embodiments, these rare earth compositions comprise La2O3, Nd2O3, Yb2O3, Eu2O3, Sm2O3, Y2O3, Ce2O3, Pr2O3, Ln14-, Ln2, O6, La4-, Ln1, Q6, La4-, NdxO6, La3NdO6, La3NdO6, La3NdO6 LaNd3O6, La1.5Nd2.5O6, La2. 5Nd1.5O6, La3.2Ndo.eO6, La3.5Nd0.5O6, La3.8Nd0.2O6, Y-La, Zr-La, Pr-La or Ce-La or combinations thereof, where Lnl and Ln2 are each , independently, a lanthanide element, in which Lnl and Ln2 are not the same, ex is a number ranging from more than 0 to less than 4.
[00273] [00273] In addition, Depositors have found that certain combinations of dopants, when confined to the rare earth compositions above, serve to increase the catalytic activity of nanowires in certain catalytic reactions, for example, OCM. Doping agents can be present at various levels (for example, w / w), and nanowires can be prepared by any number of methods. Various aspects of the nanowires above are provided in the following paragraphs and in Tables 9-12.
[00274] [00274] In certain embodiments, the rare earth compositions above comprise a strontium dopant and at least one more dopant adds! selected from groups 1, 4-6, 13 and lanthanides. For example, in some embodiments the additional doping agent is Hf, K, Zr, Ce, Tb, Pr, W, Rb, Ta,. B or combinations thereof.
[00275] [00275] In other modalities, the dopant comprises Sr / Hf, Sr / Hf / k, Sr / Zr, Sr / Zr / k, Sr / Ce, Sr / Ce / k, Sr / Tb, Sr / Tb / k, Sr / Pr, Sr / Pr / k, Sr / W, Sr / HF / Rb, Sr / Ta or Sr / 8. In some other embodiments, the preceding rare earth nanowires may comprise La2O3 or La3NdO6.
[00276] [00276] In other embodiments, catalytic nanowires comprise a rare earth oxide and dopants selected from at least one of the following combinations: Eu / Na, Sr / Na, Mg / Na, Sr / W, K / La, K Na, Li / Cs, Li / Na, Zn / k, Li / k, Rb / HF, Ca / Cs, Hf / 8i, Sr / Sn, Sr / W, Sr / Nb, Zr / W, YNV, Na / VV, Bi / VV, Bi / Cs, Bi / Ca, Bi / Sn, Bi / Sb, Ge / Hf, Hf / Sm, Sb / Ag, Sb / 8i, Sb / Au, Sb / Sm, Sb / Sr, Sb / VV, Sb / Hf, Sb / Yb, Sb / Sn, Yb / Au, Yb / Ta, Yb / W, Yb / Sr, Yb / Pb, Yb / VV, Yb / Ag, Au / Sr, W / Ge, Ta / Hf, W / Au, Ca / W, Au / Re, Sm / Li, La / k, Zn / Cs, Zr / Cs, Ca / Ce, LilSr, Cs / Zn, Dy / K, La / Mg, Na / Sr, Sr / Cs, Ga / Cs, Lu / Fe, Sr / Tm, La / Dy, Mg / k, Zr / k, Li / Cs, Sm / Cs, Na / k, Lu / Tl, Pr / Zn, Lu / Nb, Na / Pt, Na / Ce, Ba / Ta, Cu / Sn, Ag / Au, Al / 8i, AI / MO, Al / Nb, Au / Pt, Ga / 8i, Mg / W, Pb / Au, Sn / Mg, Zn / 8i, Gd / Ho, Zr / 8i, Ho / Sr, Ca / Sr, Sr // Hf Pb and Mr.
[00277] [00277] In yet other modalities, catalytic nanowires comprise a rare earth oxide and dopants selected from at least one of the following combinations: La / Nd, La / Sm, La / Ce, La / Sr, Eu / Na, Eu / Gd, Ca / Na, Eu / Sm, Eu / Sr, Mg / Sr, Ce / Mg, Gd / Sm, Sr / VV, Sr / Ta, Au / Re, Au / Pb, Bi / Hf, Sr / Sn or Mg / N, Ca / S, Rb / S, Sr / Nd, Eu / Y, Mg / Nd, Sr / Na, Nd / Mg, La / Mg, Yb / S, Mg / Na, Sr / VV, K / La, K Na, Li / Cs, Li / Na, Zn / k, Li / k, Rb / HF, Ca / Cs, HF / B1, Sr / Sn, Sr / VV, Sr / Nb, Zr / VV, YNV, Na / VV, BilVV, Bi / Cs, Bi / Ca, Bi / Sn, Bi / Sb, Ge / HF, HF / Sm, Sb / Ag, Sb / 8i, Sb / Au , Sb / Sm, Sb / Sr, Sb / VV, Sb / Hf, SbfVb, Sb / Sn, Yb / Au, Yb / Ta, Yb / W, Yb / Sr, Yb / Pb, Yb / VV, Yb / Ag , Au / Sr, W / Ge, Ta / Hf, W / Au, Ca / VV, Au / Re, Sm / Li, La / k, Zn / Cs, Zr / Cs, Ca / Ce, Li / Sr, Cs / Zn, Dy / k, La / Mg, Na / Sr, Sr / Cs, Ga / Cs, Lu / Fe, Sr / Tm, La / Dy, Mg / k, Zr / k, Li / Cs, Sm / Cs , Na / k, Lu / Tl, Pr / Zn, Lu / Nb, Na / Pt, Na / Ce, Ba / Ta, Cu / Sn, Ag / Au, Al / 8i, AI / MO, Al / Nb, Au / Pt, Ga / 8i, Mg / W, Pb / Au, Sn / Mg, Zn / 8i, Gd / Ho, Zr / 8i, Ho / Sr, Ca / Sr, Sr // Hf Pb and Sr.
[00278] [00278] In other embodiments of the preceding rare earth oxide nanowire catalysts, catalytic nanowires comprise a combination of two doping elements. In some embodiments, the combination of two doping elements is La / Nd. In other modalities, the combination of two doping elements is La / Sm. In other modalities, the combination of two doping elements is La / Ce. In other modalities, the combination of two doping elements is La / Sr. In other modalities, the combination of two doping elements is Eu / Na. In other modalities, the combination of two doping elements is Eu / Gd. In other modalities, the combination of two doping elements is Ca / Na. In other modalities, the combination of two doping elements is Eu / Sm. In other modalities, the combination of two doping elements is Eu / Mr. In other modalities, the combination of two doping elements is Mg / Sr. In other modalities, the combination of two doping elements is Ce / Mg. In other modalities, the combination of two doping elements is Gd / Sm. In other modalities , the combination of two doping elements is Sr / W. In other embodiments, the combination of two doping elements is Sr / Ta.
[00279] [00279] In yet other modalities, catalytic nanowires comprise a rare earth oxide and dopants selected from at least one of the following combinations Mg / La / k, Na / Dy / k, Na / La / Dy, Na / La / Eu, Na / La / k, K / La / S, Li / Cs / La, Li / Sr / Cs, Li / Ga / Cs, Li / Na / Sr, Li / Sm / Cs, Cs / K / La, Sr / Cs / La, Sr / Ho / Tm,
[00280] [00280] In more embodiments, catalytic nanowires comprise a rare earth oxide and dopants selected from at least one of the following combinations Nd / Sr / CaO, La / Nd / Sr, La / 8i / Sr, Mg / Nd / Fe, Mg / La / k, Na / Dy / k, Na / La / Dy, Na / La / Eu, Na / La / k, K / La / S, Li / Cs / La, Li / Sr / Cs, Li / Ga / Cs, Li / Na / Sr, Li / Sm / Cs, Cs / K / La, Sr / Cs / La, Sr / Ho / Tm, La / Nd / S, Li / Rb / Ca, Rb / Sr / Lu, Na / Eu / Hf, Dy / Rb / Gd, Na / Pt / 8i, Ca / Mg / Na, Na / k / Mg, Na / Li / Cs, La / Dy / k, Sm / Li / Sr, Li / Rb / Ga, Li / Cs / Tm, Li / k / La, Ce / Zr / La, Ca / A1 / La, Sr / Zn / La, Cs / La / Na, La / S / Sr, Rb / Sr / La, Na / Sr / Lu, Sr / Eu / Dy, La / Dy / Gd, Gd / Li / k, Rb / k / Lu, Na / Ce / Co, Ba / Rh / Ta, Na / Al / Bi, Cs / Eu / S, Sm / Tm / Yb, Hf / Zr / Ta, Na / Ca / Lu, Gd / Ho / Sr, Ca / Sr / W, Na / Zr / Eu / Tm, SrNV / Li or Ca / Sr / VV.
[00281] [00281] In other embodiments of the preceding rare earth oxide catalytic nanowires, the catalytic nanowires comprise a combination of at least three doping elements. In some embodiments, the combination of at least three different doping elements is Nd / Sr / CaO. In other embodiments, the combination of at least three different doping elements is La / Nd / Sr. In other embodiments, the combination of at least three different doping elements is La / 8i / Sr. In other embodiments, the combination of at least three different doping elements is Mg / Nd / Fe. In other embodiments, the combination of at least three different doping elements is Mg / La / k. In other embodiments, the combination of at least three different doping elements is Na / Dy / k. In other embodiments, the combination of at least three different doping elements is Na / La / Dy. In other modalities, the combination of at least three different doping elements is Na / La / Eu.
[00282] [00282] As noted above, certain combinations of dopants have been found to be useful in several catallactic reactions, such as OCM.
[00283] [00283] In other embodiments, the catalytic nanowire comprises lanthanide oxide, for example, a mixed lanthanide oxide, for example, in some embodiments of the catalytic nanowire comprises Ln14-, Ln2xO6, in which Lnl and Ln2 are each, independently, a lanthanide element, where Lnl and Ln2 are not the same and x is a number ranging from more than 0 to less than 4. In other embodiments, the catalytic nanowire comprises La4-, NdxO6, where x is a number that varies from more than 0 and less than 4, and in yet other modalities, the catalytic nanowire comprises La3NdO6, LaNd3O6, La1.5Nd2.5O6, La2.5Nd1.5O6, La3.2Nd0.8O6,
[00284] [00284] In other modalities, the doping elements are selected from Eu, Na, Sr, Ca, Mg, Sm, Ho, Tm, W, La, K, Dy, Na, Li, Cs, S, Zn, Ga , Rb, Ba, Yb, Ni, Lu, Ta, P, Hf, Tb, Gd, en, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, B, Re, Fe, A !, Zr, T1, Pr, Co, Ce, Rh, and Mo. For example, in some modalities, the combination of at least four different doping elements is: Na / Zr / Eu / Ca, Sr / Sm / Ho / Tm, Na / k Mg / Tm, Na / La / Eu / ln , Na / La / Li / Cs, Li / Cs / La / Tm, Li / Cs / Sr / Tm, Li / Sr / Cs, Li / Sr / Zn / k, Li / k Sr / La, Li / Na / Rb / Ga, Li / Na / Sr / La, Ba / Sm / Yb / S, Ba / Tm / k / La, Ba / Tm / Zn / k, Cs / La / Tm / Na, Cs / Li / k / La, Sm / Li / Sr / Cs, Sr / Tm / Li / Cs, Zr / Cs / K / La, Rb / Ca / ln / Ni, Tm / Lu / Ta / P, Rb / Ca / Dy / P, Mg / La / Yb / Zn, Na / Sr / Lu / Nb, Na / Nd / ln / K, Rb / Ga / Tm / Cs, K / La / Zr / Ag, Ho / Cs / Li / La, K / La / Zr / Ag, Na / Sr / Eu / Ca, K / Cs / Sr / La, Na / Mg / Tl / P, Sr / La / Dy / S, Na / Ga / Gd / l l, Sm / Tm / Yb / Fe, Rb / Gd / Li / k, Gd / Ho / Al / P, Na / Zr / Eu / Tm Sr / Ho / Tm / Na or Rb / Ga / Tm / Cs or La / Bi / Ce / Nd / Mr.
[00285] [00285] In other modalities, the combination of at least four different doping elements is Sr / Sm / Ho / Tm. In other embodiments, the combination of at least four different doping elements is Na / k Mg / Tm. In other modalities, the combination of at least four different doping elements is Na / La / Eu / ln. In other embodiments, the combination of at least four different doping elements is Na / La / Li / Cs. In other embodiments, the combination of at least four different doping elements is Li / CS / LA / Tm. In other embodiments, the combination of at least four different doping elements is Li / Cs / Sr / Tm. In other embodiments, the combination of at least four different doping elements is Li / Sr / Zn / k. In other embodiments, the combination of at least four different doping elements is Li / Ga / Cs. In other embodiments, the combination of at least four different doping elements is Li / k Sr / La. In other embodiments, the combination of at least four different doping elements is Li / Na / Rb / Ga. In other embodiments, the combination of at least four different doping elements is Li / Na / Sr / La. In other modalities, the combination of at least four different doping elements is Ba / Sm / V'b / S. In other embodiments, the combination of at least four different doping elements is Ba / Tm / k / La.
[00286] [00286] In other embodiments, the catalytic nanowire comprises at least two different doping elements, in which the doping elements are selected from a metallic element, a semi-metallic element and a non-metallic element, and in which at least one of the doping elements is K, Sc, Ti, V, Nb, Ru, Os, lr, Cd, ln, Tl, S, Se, Po, Pr, Tb, Dy, Ho, Er, Tm, Lu or an element selected from any one of groups 6, 7, 10, 11, 14, 15 or 17. In some embodiments, at least one of the doping elements is K, Ti, V, Nb, Ru, Os, lr, Cd, ln, Tl, S, If, Po, Pr, Tb, Dy, Ho, Er, Tm, Lu or an element selected from any of the groups of 10, 11, 14, 15 or 17. In certain other modalities of the previous catalytic nanowire, the nanowire catalytic comprises a metal oxide, and in other embodiments the catalytic nanowire comprises a lanthanide metal. In yet other embodiments, the catalytic nanowire comprises La2O3, Nd2O3, Yb2O3, Eu2O3, S1Tl2O3, Y2O3, Ce2O3, Pr2O3 or combinations thereof.
[00287] [00287] In other embodiments of the previous catalytic nanowire, the catalytic nanowire comprises lanthanide oxide, for example, a mixed lanthanide oxide, for example, in some embodiments the catalytic nanowire comprises Ln14-, Ln2, O6, where Lnl and Ln2 are each, independently, a lanthanide element, in which Lnl and Ln2 are not the same and x is a number ranging from more than 0 to less than 4. In other embodiments, the catalytic nanowire comprises La-xNd, O6, where x is a number that varies from more than 0 to less than 4, and in other modalities, the catalytic nanowire comprises La3NdO6, LaNd3O6, La1.5Nd2.5O6, La2.5Nd1.5O6, La3.2Nd0.8O6, La3.5Nd0 .5O6, La3.8Nd0.2O6 or combinations thereof. In certain other modalities the mixed oxide comprises Y-La, Zr-La, Pr-La, Ce-La or combinations thereof.
[00288] [00288] In other modalities of the nanowire comprising at least two doping elements, the doping elements are selected from Eu, Na, Sr, Ca, Mg, Sm, Ho, Tm, W, La, K, Dy, Na, Li, Cs, S, Zn, Ga, Rb, Ba, Yb, Ni, Lu, Ta, P, Hf, Tb, Gd, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, B, Re, Fe, Al, Zr, Tl, Pr, Co, Ce, Rh, and Mo.
[00289] [00289] In yet another aspect, the present description provides a catalytic nanowire comprising at least one of the following combinations of dopants: Eu / Na, Sr / Na, Na / Zr / Eu / Ca, Mg / Na, Sr / Sm / Ho / Tm, Sr / VV, Mg / La / k, Na / k / Mg / Tm, Na / Dy / k, Na / La / Dy, Sr / Hf / k, Na / La / Eu, Na / La / Eu / ln, Na / La / k, Na / La / Li / Cs, K / La, K / La / S, K / Na, Li / Cs, Li / Cs / La, Li / Cs / La / Tm, Li / Cs / Sr / Tm, Li / Sr / Cs, Li / Sr / Zn / k, Li / Ga / Cs, Li / k / Sr / La, Li / Na, Li / Na / Rb / Ga, Li / Na / Sr, Li / Na / Sr / La, Sr / Zr, Li / Sm / Cs, Ba / Sm / Vb / S, Ba / Tm / k / La, Ba / Tm / Zn / k, Sr / Zr / k, Cs / K / La, Cs / La / Tm / Na, Cs / Li / K / La, Sm / Li / Sr / Cs, Sr / Cs / La, Sr / Tm / Li / Cs, Zn / k, Zr / Cs / K / La, Rb / Ca / ln / Ni,
[00290] [00290] In other modalities of the preceding catalytic nanowire, the dopant is selected from Cs / Eu / S, Sm / Tm / Yb / Fe, Sm / Tm / Yb, Hf / Zr / Ta, Rb / Gd / Li / k, Gd / Ho / Al / P, Na / Ca / Lu, Cu / Sn, Ag / Au, A! / 8i, AI / Mo, Al / Nb, Au / Pt, Ga / 8i, Mg / VV, Pb / Au , Sn / Mg, Zn / 8i, Gd / Ho, Zr / 8i, Ho / Sr, Gd / Ho / Sr, Ca / Sr, Ca / Sr / VV, Na / Zr / Eu / Tm, Sr / Ho / Tm / Na, Sr / Pb, Ca, SrNV / Li, Ca / Sr / VV, Sr / Hf, Eu / Na, Sr / Na, Na / Zr / Eu / Ca, Mg / Na, Sr / Sm / Ho / Tm , Sr / VV, Mg / La / k, Na / k / Mg / Tm, Na / Dy / k, Na / La / Dy, Na / La / Eu, Na / La / Eu / ln, Na / La / K , Na / La / Li / Cs, K / La, K / La / S, K / Na, Li / Cs, Li / Cs / La, Li / Cs / La / Tm, Li / Cs / Sr / Tm, Li / Sr / Cs, Li / Sr / Zn / k, Li / Ga / Cs, Li / k / Sr / La, Li / Na, Li / Na / Rb / Ga and Li / Na / Sr.
[00291] [00291] Still in other modalities of the preceding catalytic nanowire the dopant is selected from Li / Na / Sr / La, Li / Sm / Cs, Ba / Sm / Yb / S, Ba / Tm / k / La, Ba / Tm / Zn / k, Cs / K / La, Cs / La / Tm / Na, Cs / Li / K / La, Sm / Li / Sr / Cs, Sr / Cs / La, Sr / Tm / Li / Cs,
[00292] [00292] Still in other modalities of the preceding catalytic nanowire, the dopant is selected from Ta / Hf, W / Au, Ca / VV, Au / Re, Sm / Li, La / k, Zn / Cs, Na / k / Mg , Zr / Cs, Ca / Ce, Na / Li / Cs, Li / Sr, Cs / Zn, La / Dy / k, Dy / k, La / Mg, Na / Nd / ln / k, ln / Sr, Sr / Cs, Rb / Ga / Tm / Cs, Ga / Cs, K / La / Zr / Ag, Lu / Fe, Sr / Tm, La / Dy, Sm / Li / Sr, Mg / k, Li / Rb / Ga , Li / Cs / Tm, Zr / k, Li / Cs, Li / k / La, Ce / Zr / La, Ca / Al / La, Sr / Zn / La, Sr / Cs / Zn, Sm / Cs, ln / k, Ho / Cs / Li / La, Cs / La / Na, La / S / Sr, K / La / Zr / Ag, Lu / Tl, Pr / Zn, Rb / Sr / La, Na / Sr / Eu / Ca, K / Cs / Sr / La, Na / Sr / Lu, Sr / Eu / Dy, Lu / Nb, La / Dy / Gd, Na / Mg / Tl / P, Na / Pt, Gd / Li / k , Li / Sr / Cs, Li / Sr / Zn / K, Li / Ga / Cs, Li / k / Sr / La, Li / Na, Li / Na / Rb / Ga, Li / Na / Sr, Li / Na / Sr / La, Li / Sm / Cs, Ba / SmfVb / S, Ba / Tm / k / La, Ba / Tm / Zn / k, Cs / K / La, Cs / La / Tm / Na, Cs / Li / k / La, Sm / Li / Sr / Cs, Sr / Cs / La, Sr / Tm / Li / Cs, Zn / k, Zr / Cs / K / La, Rb / Ca / ln / Ni, Sr / Ho / Tm, La / Nd / S, Li / Rb / Ca, Li / k, Tm / Lu / Ta / P, Rb / Ca / Dy / P, Mg / La / Yb / Zn, Rb / Sr / Lu, Na / Sr / Lu / Nb, Na / Eu / Hf, Dy / Rb / Gd, Na / Pt / 8i, Rb / Hf, Ca / Cs, Ca / Mg / Na, Hf / 8i, Sr / Sn, Sr / VV , Sr / Nb, Zr / W, YNV, Na / VV, Bi / W, Bi / C s, Bi / Ca, Bi / Sn, Bi / Sb, Ge / Hf, Hf / Sm, Sb / Ag, Sb / 8i, Sb / Au, Sb / Sm, Sb / Sr, Sb / VV, Sb / H ' f, Sb / Vb, Sb / Sn, Yb / Au, Yb / Ta, Yb / W, Yb / Sr, Yb / Pb, Yb / W, Yb / Ag, Au / Sr and W / Ge.
[00293] [00293] For example, in certain preceding embodiments of the catalytic nanowire, the catalytic nanowire comprises a metal oxide, and in other embodiments the catalytic nanowire comprises a lanthanide metal. Still other modalities, the catalytic nanowire comprises La2O3, Nd2O3, Yb2O3, Eu2O3, Sm2O3,
[00294] [00294] In other embodiments of the exposed nanowire, the catalytic nanowire comprises a lanthanide oxide, for example, a mixed lanthanide oxide, for example, in some embodiments the catalytic nanowire comprises Ln14-, Ln2, O6, where Lnl and Ln2 are each, independently, a lanthanide element, in which Lnl and Ln2 are not the same, ex is a number ranging from more than 0 to less than 4. In other embodiments, the catalytic nanowire comprises La4-, NdxO6, where x is a number that varies from more than 0 to less than 4, and in other modalities, the catalytic nanowire comprises La3NdO6, LaNd3O6, La1.5Nd2.5O6, La2.5Nd1.5O6, La3.2Nd0.8O6, La3.5Nd0 .5O6, La3.eNd0.2O6 or combinations thereof. In certain other embodiments, the mixed oxide comprises Y-La, Zr-La, Pr-La, Ce-La or combinations thereof.
[00295] [00295] In yet other embodiments, the disclosure provides a catalltic nanowire comprising Ln14-, Ln2, O6 and a dopant containing a metallic element, a semimetallic element, an element or combinations of these non-metallic elements, where Lnl and Ln2 are each , independently, a lanthanide element, in which Lnl and Ln2 are not the same, ex is a number ranging from more than 0 to less than 4. For example, in certain embodiments the catalytic nanowire comprises La4-, Ln1xO6, where Lnl is a lanthanide element and x is a number that ranges from more than 0 to less than 4, and in other specific embodiments, the catalytic nanowire comprises La4-, Nd, 06, where x is a number ranging from more than 0 to less than 4.
[00296] [00296] Still other preceding modalities of the nanowire include modalities in which the catalytic nanowire comprises La3NdO6, LaNd3O6, La1.5Nd2.5O6, La2.5Nd1.5O6, La3.2Ndo.8O6, La3.5Nd0.5O6, La3.8Nd0.2O6 or combinations thereof.
[00297] [00297] In other modalities, the dopant is selected from: Eu, Na,
[00298] [00298] In other embodiments, the development provides a nanowire comprising a mixed oxide of Y-La, Zr-La, Pr-La, Ce-La or combinations thereof and at least one dopant selected from a metallic element, a semimetallic element and a non-metallic element.
[00299] [00299] In still other embodiments, the invention provides a catalytic nanowire comprising a mixed oxide of a rare earth element and a Group 13 element, wherein the catalytic nanowire further comprises one or more elements of group 2. In some embodiments , the element of Group 13 is B, Al, Ga or ln. In other modalities, the element of Group 2 is Ca or lr. In still other modalities the element of rare earths is La, Y, Nd, Yb, Sm, Pr, Ce or Eu.
[00300] [00300] Examples of preceding catalytic nanowires include catalytic nanowires comprising CaLnBO ,, CaLnAlO ,, CaLnGaO ,, CaLnlnO ,, CaLnAlSrO, and CaLnAlSrO ,, where Ln is a lanthanide or Yttrium and x is the number such that the charges are balanced. For example, in some embodiments, the catalytic nanowire comprises CaLaBO4, CaLaA | O4, CaLaGaO4, CaLalnO4, CaLaA | SrO5, CaLaA | SrO5, CaNdBO4, CaNdAlO ,,. CaNdGaO4, CaNdlnO ,, CaNdA | SrO4, CaNdA | SrO4, CaYbBO4, CaYbAlO ,, CaYbGaO4, CaYblnO ,, CaYbAlSrO ,, CaYbA | SrO5, CaEuBO4, CaEuA | O4, CaEuO5 CaSmBO4, CaSmA | O4, CaSmGaO4, CaSm | nO4, CaSmA | SrO5, CaSmAlSrO ,, CaYBO ,, CaYA | O4, CaYGaO ,, CaY | nO4, CaYAlSrO ,, CaYA | SrO5, CaCeBO4, CaCeG4 | nO4, CaCeA | SrO5, CaCeA | SrO5, CaPrBO4, CaPrA | O4, CaPrGaO4, CaPrlnO4, CaPrA | SrO5 or CaPrA | SrO5.
[00301] [00301] In other embodiments, the invention is directed to a catalytic nanowire comprising a rare earth oxide, in which the nanowires are doped with a dopant (or dopants) selected from Eu / Na, Sr / Na, '] Na / Zr / Eu / Ca, Mg / Na, Sr / Sm / Ho / Tm, Sr / VV, Mg / La / k, Na / k / Mg / Tm, Na / Dy / k, Na / La / Dy, Sr / H'f / k, Na / La / Eu, Na / La / Eu / ln, Na / La / k, Na / La / Li / Cs, K / La, K / La / S, K / Na, Li / Cs, Li / Cs / La, Li / Cs / La / Tm, Li / Cs / Sr / Tm, Li / Sr / Cs, Li / Sr / Zn / k, Li / Ga / Cs, Li / k / Sr / La, Li / Na, Li / Na / Rb / Ga, Li / Na / Sr, Li / Na / Sr / La, Sr / Zr, Li / Sm / Cs, Ba / SmWb / S, Ba / Tm / k / Over there,
[00302] [00302] In other embodiments, the nanowires comprise La2O3, Yb2O3, Eu2O3, Sm2O3, Y2O3, Ce2O3, Pr2O3, Ln14-, Ln2, O6, La4-, Ln1, O6, La4-xNdxO6, where L, 1 and L, 2 are each, independently, a lanthanide element, where L, 1 and L, 2 are not the same and x is a number ranging from more than 0 to less than 4,
[00303] [00303] Furthermore, the present inventors have found that Ianthanide oxides doped with alkali metals and / or alkaline earth metals and at least one other doping agent selected from Groups 3-16 have desirable catalytic properties and are useful in a variety of catalytic reactions, such as CMO. Thus, in one embodiment the catalytic nanowires comprise a lanthanide oxide doped with an alkali metal, an alkaline earth metal or combinations thereof, and at least one other dopant from groups 3-16. In some embodiments, the catalytic nanowire comprises lanthanide oxide, a dopant of a meta! alkaline and at least one other doping agent selected from Groups 3-16. In other embodiments, the catalytic nanowire comprises lanthanide oxide, an alkaline earth metal dopant and at least one other doping agent selected from Groups 3-16.
[00304] [00304] In some more specific embodiments of the foregoing, the catalytic nanowire comprises a lanthanide oxide, a lithium dopant and at least one other dopant selected from Groups 3-16. In still other embodiments, the catalytic nanowire comprises lanthanide oxide, a sodium dopant and at least one other dopant agent selected from Groups 3-16. In other embodiments, the catalytic nanowire comprises lanthanide oxide, a potassium dopant and at least one other dopant agent selected from Groups 3-16. In other embodiments, the catalytic nanowire comprises lanthanide oxide, a rubidium dopant and at least one other dopant agent selected from Groups 3-16. In more embodiments, the catalytic nanowire comprises lanthanide oxide, a cesium dopant and at least one other dopant agent selected from Groups 3-16.
[00305] [00305] In yet other modalities of the above, the catalytic nanowire comprises lanthanide oxide, a beryllium dopant and at least one other dopant agent selected from Groups 3-16. In other embodiments, the catalytic nanowire comprises lanthanide oxide, a magnesium dopant and at least one other dopant agent selected from Groups 3-16. In still other embodiments, the catalytic nanowire comprises lanthanide oxide, a calcium dopant and at least one other dopant agent selected from Groups 3-16. In more embodiments, the catalytic nanowire comprises lanthanide oxide, a strontium dopant and at least one other dopant agent selected from Groups 3-
[00306] [00306] In some embodiments of the preceding lanthanide oxide catalytic nanowires, the catalysts comprise La2O3, Nd2O3, Yb2O3, E112O3, Sm2O3, Ln14-, Ln2, O6, La4-xLn1, O6, La4-xNdxO6, where Lnl and Ln are each, independently, a lanthanide element, where Lnl and Ln2 are not the same and x is a number ranging from more than 0 to less than 4, La3NdO6, LaNdsO6, La1.5Nd2.5O6, La2.5Nd1.5O6, La3.2Ndo.8O6, La3.5Nd0.5O6, La3 0.8 Nd0.2O6, Y-La, Zr-La, Pr-La or Ce-La or combinations thereof. In other embodiments, the .. lanthanide oxide catalytic nanowire comprises a C2 selectivity of more than 5 ° / o and a methane conversion greater than 20%, when the lanthanide oxide catalytic nanowire is employed as a heterogeneous catalyst in the oxidative coupling methane, at a temperature of 750 ° C or less.
[00307] [00307] In various embodiments, of any of the above catalytic nanowires, the catalytic nanowire comprises a C2 selectivity greater than 50% and a methane conversion greater than 20 ° / o, when the catalytic nanowire is employed as a heterogeneous catalyst in the coupling oxidative of methane at a temperature of 750 ° C or less, 700 ° C or less, 650 ° C or less, or even 600 ° C or less.
[00308] [00308] In more embodiments, of any of the above catalytic nanowires, the catalytic nanowire comprises a C2 selectivity greater than 50 ° / o, greater than 55%, greater than 6Õ ° / o, greater than 65%, greater than 70% , or even greater than 75%, and a methane conversion greater than 20%, when the catalytic nanowire is employed as a heterogeneous catalyst in the oxidative coupling of methane, at a temperature of 750 ° C or less.
[00309] [00309] In other embodiments, of any of the above mentioned catalysts, the catalyst comprises a C2 selectivity greater than 50 ° / o, and a methane conversion greater than 2 ° ° / o, greater than 25%, greater than 30 ° / o, greater than 35%, greater than 40%, greater than 45 ° / o, or even greater than 50%, when the rare earth oxide catalyst is used as a heterogeneous catalyst in the oxidative coupling of methane at a temperature 750 ° C or less. In some of the above, methane conversion and C2 selectivity are calculated based on a single base of passage (ie, the percentage of converted methane or C2 selectivity when a single passage in the catalyst or catalytic bed, etc.).
[00310] [00310] In some embodiments, the preceding doped nanowires comprise 1, 2, 3 or four doping elements. In other embodiments, nanowires comprise more than four doping elements, for example, 5, 6, 7, 8, 9, 10 or even more doping elements. In this regard, each dopant may be present in the nanowires (for example, any of the nanowires described in Tables 9-12), up to 75% by weight. For example, in one embodiment, the concentration of a first doping element ranges from 0.01 ° / 0 to 1 ° / 0 weight / weight, 1 ° / 5% weight / weight, 5% to 10 ° / weight / weight . 10 ° / 0 to 2 ° / weight / weight, 20 ° / 0 to 30 ° / weight / weight, 30% to 40% weight / weight or 40 ° / 0 to 5 ° ° / weight / weight, for example, about i ° / weight / weight, about 2 ° / 0 weight / weight, about 3 ° / 0 weight / weight, about 4 ° / 0 weight / weight, about 5 ° / 0 weight / weight, about 6 ° / 0 weight / weight, about 7 ° / 0 weight / weight, about 8% weight / weight, about 9 ° / 0 weight / weight, about 10 ° / weight / weight, about 11% weight / weight, about 12% weight / weight, about 13% weight / weight, about 14% weight / weight, about 15% weight / weight, about 16 ° / weight / weight, about 17% weight / weight, about 18% weight / weight, about 19% weight / weight or about 20 ° / weight / weight.
[00312] [00312] In other modalities, the concentration of a third doping element (when present) ranges from 0.01% to 1 ° / 0 weight / weight, i ° / o to 5% weight / weight, 5% to 10 ° / o weight / weight, 10% to 20% weight / weight, 20 ° / o to 30 ° / weight / weight, 30% to 40 ° /, weight / weight or 40 ° to 50% weight / weight, for example, about about 1 ° / 1 weight / weight, about 2% weight / weight, about 3 ° / 0 weight / weight, about 4% weight / weight, about 5% weight / weight, about 6 ° / 0 weight / weight, about 7 ° / 0 weight / weight, about 8 ° /, weight / weight, about 9 ° / 0 weight / weight, about 10 ° 6 weight / weight, about 11% weight / weight, about about 12% weight / weight, about 13% weight / weight, about 14% weight / weight, about 15% weight / weight, about 16% weight / weight, about 17% weight / weight, about 18% weight / weight, about 19% weight / weight or about 20% weight / weight.
[00314] [00314] In other modalities, the dopant concentration is measured in terms of atomic percentage (a /%). In some of these modalities, each dopant can be present in the nanowires (for example, any of the nanowires described in Tables 1-12), up to 75% / y. For example, in one embodiment, the concentration of a first doping element ranges from 0.01 ° / 0 to 1% / a, 1 ° / 0 to 5% / a, 5 ° / 0 to 10 ° / 0 in / no. 10 ° / 0 to 20% / a, 20 ° / 0 to 30% / a, 3 ° / 0 to 40% / a, or 40 ° / 0 to 50% / a, for example, about 1% / a, about 2% / a, about 3% / a, about 4% / a, about 5% / a, about 6 ° / ja, about 7 ° / Ja, about 8% / a, about 9 % / a, about 10% / a, about 11% / a, about 12% / a, about 13% / a, about 14% / a, about 15% / a, about 16 % / w, about 17% / w, about 18 ° / w, about 19% / w or about 20% / w.
[00316] [00316] In other modalities, the concentration of a third doping element (when present) is comprised between 0.01% to 1% / a, 1 ° / 0 to 5% / a, 5 ° / 0 of 10% / a , 10 ° / 0 to 2 ° / weight / weight, 20% to 30 ° / ja, 30 ° / 0 to 40 ° / ja or 40% to 50% / a, for example, about 1% / a, about 2% / a, about 3% / a, about 4% / a, about 5% / a, about 6 ° / ja, about 7% / a, about 8% / a, about 9% / a, about 10% / a, about 2% / a, about 12% / a, about 13% / a, about 14% / a, about 15% / a, about 16% / a, about 17% / a, about 18% / a, about 19% / a or about 20% / a.
[00318] [00318] Consequently, any of the doped nanowires described above or in Tables 1-12, can comprise any of the preceding dopant concentrations.
[00319] [00319] In addition, different catalytic characteristics of the doped nanowires above can vary or be "adjusted" based on the method used to prepare them. For example, in one embodiment the nanowires above (and the nanowires in Tables 1-12) are prepared using a biological modeling approach, for example, phage. In other embodiments, nanowires are prepared using a hydrothermal or sol gei approach (ie, an unmodelated approach). Some modalities for the preparation of the nanowires (for example, the rare earth nanowires), comprise the preparation of the nanowires directly from the corresponding oxide or by means of a metal hydroxide gel approach. Such methods are described in more detail in the present document and other methods are known in the art. In addition, the above dopants can be incorporated either before or after (or combinations thereof) of an optional calcination step as described in this document.
[00320] [00320] In other embodiments, the nanowires comprise a mixed oxide selected from a mixed Y-La oxide doped with Na. (Y varies from 5 to 20% of La mol / mo!); a mixed Zr-La oxide doped with Na (Zr ranges from 1 to 5% La
[00321] [00321] Some types of metal oxides described in this document may be in the form of oxides, hydroxides, oxy-hydroxides, oxycarbonates, or a combination thereof, after being exposed to the action of moisture, carbon dioxide, subject to calcination incomplete or combination thereof.
[00322] [00322] It is contemplated that any one or more of the dopants disclosed in this document can be combined with any of the nanowires described in this document to form doped nanowires comprising one, two, three or more dopants. Tables 1-12 below show the exemplary doped nanowires, according to several specific modalities. Dopants (Dop) are shown in the horizontal lines and base catalytic nanowire (NW) in vertical columns in Tables 1-8, and dopants are shown in the vertical columns and base catalytic nanowire in the horizontal lines in Tables 9-12. The resulting doped catalysts are shown in cells that intersect in all Tables. In some embodiments, the doped nanowires shown in tables 1-12 are doped with one, two, three or more additional dopants.
[00324] [00324] Okay! as used in Tables 1-12 and throughout the specification, a nanowire composition represented by E1 / E2 / E3, etc., in which EÍ E2 and E3 are each, independently, an element or a compound comprising one or more elements, refers to a nanowire composition consisting of a mixture of E1, E2 and ÊZ E1 / E2 / E3 etc., are not necessarily present in equal amounts and do not need to form a bond with one another. For example, a nanowire comprising Li / MgO refers to a nanowire comprising Li and MgO, for example, Li / MgO may refer to a MgO nanowire doped with Li. By way of another example, a nanowire comprising NaMnO4 / MgO refers to to a nanowire composed of a mixture of NaMnO4 and MgO. Doping agents can be added in the appropriate way. For example, in a magnesium oxide nanowire doped with lithium (Li / MgO), Li dopant can be incorporated in the form of Li2O, Li2CO3, L1OH, or other appropriate forms. Li can also be fully incorporated into the MgO crystalline network (for example, (Li, Mg) O). Dopants for other nanowires can be incorporated in a similar way.
[00325] [00325] In some more specific modalities, the dopant is selected from Li, Ba and Sr. In other specific modalities, the nanowires comprise Li / MgO, Ba / MgO, Sr / La2O3, Ba / La2O3, Mn / Na2WO4, Mn2O3 / Na2WO4, Mn3O4 / Na2WO4, Mg6MnO8, Li / B / Mg6MnO8, Na / B / Mg6MnO8, Zr2MO2O8 or NaMnO4 / MgO.
[00326] [00326] In some other specific embodiments, the nanowire comprises a mixed oxide of Mg and Mn with or without B and with or without Li. Additional dopants for these nanowires may include doping elements selected from Groups 1 and 2 and Groups 7-13. The dopants can be present as dopants, singly or in combination with other dopants. In certain specific nanowire modalities comprising a mixed oxide of Mg and Mn with or without B and with or without Li, the dopant comprises a combination of elements from Group 1 and Groups 8-11.
[00327] [00327] Nanowires comprising mixed oxides of Mg and Mn are well suited for the incorporation of dopants because magnesium atoms can be easily replaced by other atoms, as long as their size is.
[00328] [00328] Examples of nanowires that make up Li / Mn / Mg / B and an additional dopant include; Li / Mn / Mg / B doped with Co; Li / Mn / Mg / B doped with Na, Li / Mn / Mg / B doped with BE; Li / Mn / Mg / B doped with AI; Li / Mn / Mg / B doped with lC; Li / Mn / Mg / B doped with Zr; Li / Mn / Mg / B doped with Zn; Rh doped Li / Mn / Mg / B and Ga doped Li / Mn / Mg / B. Nanowires comprising Li / Mn / Mg / B doped with different combinations of these dopants are also provided. For example, in some embodiments, Li / Mn / Mg / B nanowires are doped with Na and Co. In other embodiments, Li / Mn / Mg / B nanowires are doped with Ga and Na.
[00329] [00329] In other embodiments, nanowires comprising Mn / VV, with or without dopants are provided. For example, the present inventors have discovered through high performance tests that nanowires comprising Mn / VV and various dopants are good catalysts in the OCM reaction. Therefore, in some embodiments, the Mn / VV nanowires are doped with Ba. In other modalities, MNNV nanowires are doped with Be. In other modalities, the Mn / VV nanowires are doped with Te.
[00330] [00330] In any of the above modalities, MNNV nanowires can comprise a SiO2 support. Alternatively, the use of different supports, such as ZrO2, HfO2 and | n2O3 in any of the above modes, has been shown to promote OCM activity at a reduced temperature compared to the same silica-supported catalyst, with limited reduction in selectivity.
[00331] [00331] The nanowires that make up rare earth oxides doped with various elements are also effective catalysts in the OCM reaction. In certain specific embodiments, rare earth oxide or oxy-hydroxide can be any rare earth, preferably La, Nd, Eu, Sm, Yb, Gd. In certain types of nanowires comprising elements of rare earth or Yttrium, the dopant comprises alkaline earth elements (Group 2). The degree of effectiveness of a specific dopant is a function of the rare earths used and the concentration of alkaline earth dopants. In addition to alkaline earth elements, other modalities of rare earth or yttrium nanowires include modalities in which the nanowires comprise alkaline elements as dopants, which further promote the selectivity of the catalytic activity in OCM of the doped material. In yet other embodiments of the above, nanowires comprise both an alkaline and alkaline earth element and doping element. In yet other modalities, an additional dopant can be selected from rare earths and from additional Groups 3, 4, 8, 9, 10, 13, 14.
[00334] [00334] In other modalities, the nanowires comprise Nd2O3 or NdOy (OH) ,, emqueyvariade0a1,5, xvariade0a3e2y + x = 3, dopadocomSr,
[00335] [00335] In still other examples of doped nanowires, the nanowires comprise Yb2O3 or YbOy (OH) ,, where y varies from 0 to 1, 5, x ranges from 0 to 3 and 2y + x = 3, doped with Sr, Ca, Ba, Nd or combinations thereof. In certain other embodiments, the OCM nanowires Yb2O3 or YbOy (OH) X are doped with a binary combination, for example Sr / Nd.
[00336] [00336] Still other examples of doped nanowires, the nanowires comprise Eu2O3 or EuOy (OH) x, where y varies from 0 to 1, 5, x ranges from 0 to 3 and 2y + x = 3, doped with Sr, Ba , Sm, Gd, Na or combinations or a binary doping combination, for example Sr / Na or Sm / NA.
[00337] [00337] Examples of dopants for Sm2O3 or SmOy (OH) nanowires, where x and y are each independently an integer from 1 to 10, include Sr, and examples of dopants for Y2O3 or YOy (OH) X nanowires, where y ranges from 0 to 1.5, x ranges from 0 to 3 and 2y + x = 3, comprise Ga, La, Nd or combinations thereof. In certain other embodiments, the Y2O3 or YOy (OH) X nanowires comprise a binary dopant combination, for example Sr / Nd, Eu / V or Mg / Nd or a tertiary dopant combination, for example Mg / Nd / Fe.
[00338] [00338] In other modalities, the nanowires comprise Ln2O3 or LnZOy (OH) x, where Ln is, in each occurrence, independently, a lanthanide, xvariadeOa3e2y + x = 3, yvariadeOa1,5, ezé1,2ou3, eonanofioss doped with Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Mn, Ni, Pd, Pt, Cu, Ag, Au, Zn, Al, Ga, ln, Tl, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te, or combinations thereof.
[00339] [00339] Rare earth nanowires, which without dopants often have low OCM selectivity, can be greatly improved by doping to reduce their combustion activities. In particular, nanowires, comprising CeO2 and Pr2O3 tend to have a strong total oxidation activity of methane, however, doping with additional rare earth elements can significantly slow combustion activity and increase the overall usefulness of the catalyst. Examples of dopants to improve selectivity for Pr2O3 or PrOy (OH) nanowires, where y ranges from 0 to 1.5, x ranges from 0 to 3 and 2y + x = 3, comprise binary dopants, for example, Nd / Mg, La / Mg or Yb / Sr.
[00340] [00340] In some modalities, dopants are present in nanowires, for example, in less than 50%, in less than 25%, in less than 10%, in less than 5 ° / 0, in less than 1 or in% .
[00341] [00341] In other nanowire modalities, the atomic proportion of (weight / weight) of one or more metallic elements chosen from Groups 1-7 and lanthanides and actinides, in the form of an oxide and the dopant varies from 1: 1 up until
[00342] [00342] In the additional modalities, the nanowires comprise one or more metallic elements from Group 2, in the form of an oxide and a dopant from Group 1. In other modalities, the nanowires comprise magnesium and lithium. In other embodiments, the nanowires comprise one or more metallic elements from Group 2 and a dopant from Group 2, for example, in some embodiments, the nanowires comprise magnesium oxide and barium. In other embodiments, the nanowires comprise one or more metallic elements from Group 2, a dopant from Group 2 and an additional dopant, for example, in some embodiments, nanowires comprise magnesium oxide and are doped with strontium and tungsten dopants ( i.e., SrNV / MgO). In another embodiment, the nanowires comprise a lanthanide element, in the form of an oxide and a dopant from Group 1 or Group 2. In other embodiments, the nanowires comprise lanthanum and strontium.
[00343] [00343] Various methods are provided for the preparation of doped nanowires. In one embodiment, the doped nanowires can be prepared by co-precipitation of a metal oxide precursor to the nanowire and a doping precursor.
[00344] [00344] In some embodiments, nanowires can be prepared in. a solution phase, using an appropriate model. In this context, an appropriate model can be any natural or synthetic material, or a combination of these, which provides nucleation sites for the binding ions (for example, metal element and / or hydroxide ions or other anions) and promoting growth of a nanowire. The models can be selected in such a way that the determined control of the nucleation sites, in terms of their composition, quantity and location can be achieved in a statistically significant way. The models are generally linear or anisotropic in shape, thus directing the growth of a nanowire. The models described in the following embodiments include biological models, such as phage, and non-biological models, such as non-biological polymers.
[00345] [00345] In contrast to other preparations of the targeted model of nanostructures, the nanowires of the invention are generally not prepared from nanoparticles deposited on a model in a reduced state, which are then heat treated and fused into an elongated nanoporous nanostructure . In particular, these methods are generally not applicable to continuous nanowires comprising one or more elements from any of Groups 1 to 7, lanthanides, actinides or combinations thereof. Instead of forming a plurality of catalyst nanoparticles, nanocrystals, or nanocrystallites on the model surface (for example, phage or non-biological polymers), the nanowires of the invention are preferably prepared by nucleating an oxidized metal element (for example, in the form of a metal ion) and subsequent growth of a nanowire. After nucleation of the oxidized metallic element, the nanowires are usually calcined to produce the desired oxide, however annealing of nanoparticles is not necessary to form the nanowires.
[00346] [00346] Consequently, the nanowires used in the context of the invention have several properties that differentiate them from other nanostructures, such as those created as fused aggregates of nanoparticles. In particular, nanowires are characterized as having one or more of: a substantially non-nanoporous structure, an average size of the crystal domain, either before and / or after calcination, of more than 5 nm, and a habit of anisotropic crystals.
[00347] [00347] In the context of non-nanoporous nanowires, the preferred compositions are differentiated from elongated nanostructures formed as nanoporous nanoparticle aggregates due to their substantially non-nanoporous structures. Such substantially non-nanoporous nanowire structures will preferably have a surface area of less than 150 m2 / g, more preferably less than 100 m2 / g, less than 50 m2 / g, less than 40 m2 / g, less than 30 m2 / g , less than 25 m2 / g, less than 20 m2 / g, less than 15 m 2 / g, less than m2 / g, or between 1 m2 / g and any of the foregoing. As will be appreciated, nanowires created by modeling processes, where additional aggregates can fuse to a non-nanoporous or substantially non-nanoporous nanowire core, will typically have elevated surface areas, for example, the surface areas for the upper end of the gap, while nanowires created from other processes, for example, by hydrothermal processes, will typically have lower surface areas.
[00348] [00348] In certain respects, the nanowires of the invention are characterized by relatively large crystal domain sizes in the context of nanowire structures of relatively high surface area. In particular, and as noted above, for those nanowires of the invention having an average crystal domain size in at least one crystal dimension that is greater than 5 nm, the preferred nanowires of the invention will typically have an average crystal domain size in at least one crystal dimension that is greater than 10 nm, and in more preferred aspects, greater than 20 nm.
[00349] [00349] In certain embodiments, the nanowires of the invention can also be characterized by their additional structural properties. For example, in certain aspects, the nanowires of the invention can be characterized by a continuous crystalline structure within the nanowire, excluding stacking failures.
[00350] [00350] In some embodiments, methods for forming the nanowires that have the empirical formula M4wM5, M6yO, are provided, where M4 comprises one or more elements selected from groups 1 to 4, M5 comprises one or more elements selected from the Group 7 and M6 comprises one or more elements selected from Groups 5 to 8 and Groups 14 to 15 and w, x, y and z are integers such that the overall load is balanced. The methods comprise combining one or more sources of M4, one or more sources of M5, and one or more sources of M6, in the presence of a modeling agent and a solvent to form a mixture.
[00351] [00351] In certain embodiments, M4 includes one or more elements selected from Group 1, such as Na, while M6 includes one or more elements selected from Group 6, such as W and M3 is Mn. In one embodiment, M4 is Na and the source of M4 is NaCl, M5 is Mn and the source of M5 is Mn (NO3) 2, M6 is W and the source of M6 is WO3, the solvent is water, and the agent model is a bacteriophage. In other embodiments, the modeling agent is a non-biological polymer.
[00352] [00352] In several embodiments, the source of M4 can be one or more of chloride, bromide, iodide, oxychloride, oxybromide, oxiodide, nitrate, oxynitrate, sulfate or phosphate salt of any element in Group 1, Group 2, Group 3, or a Group 4.
[00353] [00353] In yet other embodiments, the modeling agent may include a surfactant, such as tetraoctylammonium chloride, ammonium lauryl sulfate or lauri! glucoside. For any model agent or any source of M4, M6 or Mn, the solvent can include an organic solvent, such as ethanol, diethyl ether, or acetonitrile. In addition, any embodiment of the method for forming a nanowire described above can include any additional component in the reaction mixture, such as a base.
[00354] [00354] Methods of forming nanowires of various embodiments of the invention comprise the combination of a source of M4, a source of M5, a source of M6, a model agent, and a solvent in a reaction mixture. In other embodiments, however, the nanowire forming methods of the present invention comprise the combination of two from an M4 source, M5 source and an M6 source in the presence of a model agent and a solvent to form an intermediate and then the nanowire combining a remnant of the M4 source, M5 source and the M6 source with the intermediate nanowire, where M4 includes one or more elements selected from Group 1, Group 2, Group 3 and Group 4 , in which the M5 elements include one or more elements selected from Group 7 and where M6 includes one or more elements selected from the elements of Group 5, Group 6, Group 7, Group 8, Group 14 and Group 15. In one modality, one intermediate nanowire is formed by combining the source of M5 and the source of M6, in the presence of the model agent and the solvent, followed by combination of the intermediate nanowire with the source of M4.
[00355] [00355] Since the peptide sequences have been shown to have a specific and selective binding affinity for many different types of ions of metal elements, biological models that incorporate peptide sequences such as nucleation sites are preferred. In addition, biological models can be modified to include predetermined nucleation sites in predetermined spatial relationships (for example, separated by a few tens of nanometers).
[00356] [00356] Wild type (that is, naturally occurring) and genetically modified biological models can be used. As discussed in this document, biological models such as proteins and bacteriophages can be manipulated based on genetics to ensure control over the type of nucleation sites (for example, by controlling peptide sequences), their locations in models and the their respective density and / or proportion to other nucleation sites. See, for example, Mao, CB et al., (2004) Science, 303, 213-217 .; Belcher, A. et al., (2002) Science 296, 892-895 .; Belcher, A. et al., (2000) Nature 405 (6787) 665-668 .; Reiss et al., (2004) Nanoletters, 4 (6), 1 127-1 132, Flynn, C. et al., (2003) J. Mater. Sci., 13, 2414-2421 .; Mao, CB et al., (2003) PNAS, 100 (12), 6946-6951, whose references are incorporated into this document as a reference in their entirety. This allows the ability to control the composition and distribution of nuclear sites in the biological model.
[00357] [00357] Thus, biological models can be particularly advantageous for controlled growth of nanowires. Biological models can be biomolecules (for example, proteins), as well as multimolecular structures of biological origin, including, for example, bacteriophages, viruses, amyloid fiber, and capsid.
[00358] [00358] In certain modalities, biological models are biomolecules.
[00359] [00359] Since protein synthesis can be genetically driven, proteins can be easily manipulated and functionalized to contain desired peptide sequences (i.e., nucleation sites) at the desired locations within the primary structure of the protein. The protein can then be assembled to provide a model.
[00360] [00360] Thus, in various modalities, the models are biomolecules, native proteins or proteins that can be modified to have nucleation sites for specific ions.
[00361] [00361] In a particular embodiment, the biological model comprises a bacteriophage M13 that has or can be modified to have one or more specific peptide sequences to be expressed in the coating proteins. The bacteriophage M13 is a filamentous bacterial virus that is produced by amplification using E.coli bacteria. It is 880 nm long and 6.7 nm in diameter. The filamentous phage surface is mainly composed of its main coating protein, pV111. 2,700 copies of this protein pack the phage's DNA to form a tight, cylindrical envelope. The N terminal of pVlll forms a dense periodic display spaced at 2.7nm. The last five pVlll residues are structurally unrestricted and exposed to the solvent, thus presenting an ideal target for substrate engineering, manipulation and interaction.
[00362] [00362] Figure 6 schematically shows a filamentous bacteriophage 400, in which a single strand of DNA from nucleus 410 is surrounded by a protein layer 420. The coating is composed mainly of pV111 proteins
[00363] [00363] For example, in another embodiment, peptide sequences having one or more particular nucleation sites specific to several ions are expressed in the coating proteins. For example, in one embodiment, the coating protein is pV111 with peptide sequences that have one or more particular nucleation sites specific to several Ions attached thereto. In other additional embodiments, the peptide sequences linked to the coating protein comprise two or more amino acids, 5 or more amino acids, 10 or more amino acids, 20 or more amino acids, or 40 or more amino acids. In other embodiments, the peptide sequences expressed in the coating protein comprise between 2 and 40 amino acids, between 5 and 20 amino acids or between 7 and 12 amino acids.
[00364] [00364] One of the approaches for obtaining different types of bacteriophage M13 is to modify the genetic code of the virus, in order to change the amino acid sequence of the main coat pV111 protein. The changes in the sequence affect only the N-ending amino acids of the pV111 protein, which are the only ones that form the surface of the M13 phage, while the first 45 amino acids are left unchanged, so that the packaging of the pVlll proteins around the phage does not. is compromised. By changing the N-terminating amino acids of the pVlll protein, the characteristics of the phage surface can be adapted to the higher affinities for specific metal ions, thus promoting the selective growth of specific inorganic materials on the phage surface.
[00365] [00365] Many short amino acid sequences can be manipulated at the N-terminus of pVlll to precipitate different materials or combinations thereof. Typical functional groups on amino acids that can be used to adapt phage surface affinity to metal ions include: carboxylic acid (-COOH), amino (-NH3 "or-NH2), hydroxyl (-OH), and / or groups functional thiol (-SH) .Table 13 summarizes a number of exemplary phages used in the present invention for the preparation of inorganic metal oxide nanowires. In a given embodiment, the present description refers to any of the peptide sequences in Table 13. Sequences in Table 13 refer to the amino acid sequence of the pV111 protein (single Ietra amino acid code). Underlined portions indicate the terminal sequence that has varied to match the phage surface affinity to metal ions. SEQ ID NO 30 represents the protein wild-type pV111, while SEQ ID NO 31 represents wild-type pV111, including the signaling peptide part (bold).
[00366] [00366] The amino acid side chains have assorted chemical properties that can be used for material synthesis. Glutamic acid (E) and aspartic acid (D) have side chains of carboxylic acid and are therefore negative at neutral pH. Negative residues are attractive for positively charged metal cations and, therefore, can nuclear biomineralization.
[00367] [00367] Consequently, in certain embodiments the present disclosure provides phage sequences useful for catalytic nanowire models. In some embodiments, the engineered pV111 sequence comprises at least one containing amino acid (e.g., P) and a repeat of 2 negative amino acids (e.g., E and D). Alanine is one of the smallest side chain amino acids, and in some embodiments it can be included as a spacer. Negative charges can be spread on both D and E amino acids as to avoid an excess of repetitions of the same amino acid which can contribute to lower phage yield. In a variation of the above sequence, Lysine (K) can be included in the terminal phage sequence. Lysine has an active amine group, and therefore can be potentially attractive to the transition metals of the upper group (for example, Pt, Pd, Au), which exist as negatively charged ions in solution.
[00369] [00369] In other embodiments, a degenerate library approach is employed to detect other viable sequences, that is, the amino acids of interest can be restricted and others can be left to be chosen for what is biologically favorable for the production of bacteria phages . For example, alternative libraries based on negative AEXEXEX or ADXDXDX residues can be prepared using a degenerate library approach. In some embodiments, restricted histidine or restricted tryptophan libraries (for example, AHXHXHX, AWXWXWX, AXXWHWX) are useful for identifying hydrophobic and aromatic interactions. Other modalities include changing the position and order of amino acids (for example, ADDXEE), and yet other modalities include restriction of sequences with proline amino acids (for example, AEPEPEP, ADPDPDP), to explore the effect of the structure of the peptide on synthesis. Any combination of the above options can be designed and explored for biological viability and model behaviors.
[00370] [00370] In one embodiment, the present disclosure provides methods for the preparation and purification of the filamentous bacteriophage. Purification methods can be based on conventional methods or on the new filtration methods described below. Such filtration methods can be advantageous in the practice of certain embodiments of the invention, since the methods are conducive to large-scale preparations. Standard methods for purifying the virus, bacteriophages, DNA and recombinant proteins from the raw material solution usually include several steps. For example, the heavier components of the raw material, such as bacterial cells and cellular debris, are first separated by centrifugation. In addition, the particles of interest are then precipitated from the remaining supernatant using a solution of polyethylene-gHcol and salt.
[00371] [00371] Although not wishing to be limited by theory, it is believed that po | ieti | enog | ico | (PEG) as a large inert molecule adds osmotic stress to the solution by steric hindrance and increased agglomeration, although the high salt concentration filters the repulsion of charges between the particles. The concentration of PEG, type and quantity of salts, as well as the subsequent processing steps depend on the particular application. In the example of the filamentous bacteriophage, its long-stemmed anisotropic geometry allows the minimum amount of PEG to selectively precipitate these particles from the remaining supernatant, after centrifugation, and may contain components of the nutrient medium used for amplification, as well as proteins and DNA excreted by bacteria during amplification and potential cell lysis. After precipitation, the solution is usually centrifuged again to settle the particles of interest, such as bacteriophage, and then resuspended in the desired volume of buffer solution.
[00372] [00372] The standard process described above works well on a small scale, however, it can be limited by the centrifugal capacity as it is staggered. Often, the final solution needs to be further clarified from the remaining bacteria, by additional centrifugation or filtration. In addition, the purified product may contain small amounts of polyethylene glycol, as well as the salt used for precipitation, in quantities that are difficult to quantify, still potentially influencing additional chemical processing. In the case of bacteriophage, the solution can be further purified by a CsC gradient! and ultracentrifugation, however, these steps are sometimes difficult to scale, due to the volumes that can be processed, as well as the time and costs involved. Therefore, there remains a need to improve phage preparation methods, which are amenable to large-scale production of purified phage.
[00373] [00373] The new methods described in this document are useful for large-scale phage preparation. In one embodiment, the method comprises two-step filtration to purify bacteriophage from a raw material solution. In the following description, these two filtration steps are sometimes referred to as the first filtration step and the second filtration step, respectively. In some embodiments, the types of filtration employed comprise 'tangential flow' filtration! (TFF) and / or deep filtration.
[00374] [00374] Tangential flow filtration is a technique that separates the solution based on a principle of size exclusion dictated by the pore size of the membrane used. The solution to be filtered flows through the membrane, with the pressure applied through the membrane. One aspect of TFF is that the solvent is divided into two parts, the materia! retained and permeated; therefore, the particles in both the retentate and the permeate remain in the solution. Particles smaller than the pore size of the filter pass through the permeate side, and larger particles are trapped in the solution on the retentate side of the membrane. Clogging of the membrane is minimized by continuous flow and recirculation of the solution on the retentate side of the membrane. Depending on the particular application, the particles of interest can be collected, either in the retentate or in the permeate, since both are still in the solution.
[00375] [00375] Deep filtration also separates the solution based on a principle of size exclusion dictated by the pore size of the membrane used, however the solution to be filtered flows through the membrane, instead of flowing along it tangentially as in TFF. Unlike TFF, the entire solution is drained through the membrane. Particles smaller than the pore size of the filter through the permeate side, and larger particles are retained in the solution on the retentate side of the membrane. Therefore, the main difference between TFF and depth filtration is the nature of the retentate, which is a solution in TFF and a solid ("pie") in depth filtration. Typically, in depth filtration the particles of interest will be collected in the permeate and not in the retentate, which is trapped in the membrane.
[00376] [00376] In one embodiment, a two-stage TFF process is provided for the purification of bacteriophage. In the first stage, microfiltration is performed, and in the second stage, ultrafiltration is performed. In this regard, a microfiltration comprises the filtration of a solution containing the phage, through membranes of larger pore size (for example, 0.1 to 3 µm). During this stage, the larger particles of the raw material, such as cells and cell fragments, are clarified from the solution and retained in the retentate, while the particles of interest (for example, phages) are filtered through the permeate. Ultrafiltration refers to filtration using smaller pore size filtration membranes (for example, 1 to 1,000 kDa), the size of which depends on the specific application. During this filtration the particles of interest are retained while the smaller particles, such as components of the medium and small proteins are filtered out. In certain embodiments, the ultrafiltration step can also be used to concentrate the solution, filtering the water. In an optional third step, diafiltration can be used to exchange the remaining concentrated media for buffer solution. Diafiltration can be performed on the same ultrafiltration membrane.
[00377] [00377] Various parameters of the filtration process described above can be varied to obtain optimal purification results. In some embodiments, both microfiltration and ultrafiltration, the parameters that control the flow of material throughout and through the membrane are important and can be varied.
[00378] [00378] One embodiment of the present description provides a tangential flow filtration process that is easily scalable. In this modality, the volume of the raw material that can be processed at any given time, is in direct scale with the surface area of the membrane used. As the surface area is increased and the flow rate adjusted accordingly, the other process parameters can remain the same. This allows the manufacturing process to be initially designed and optimized using laboratory scale equipment and, subsequently, directly scaled to larger scales.
[00379] [00379] In one embodiment of the preceding purification and filtration process for M13 phage, both microfiltration and ultrafiltration are performed using TFF. For microfiltration, a flat sheet nylon membrane cartridge with pore sizes ranging from 0.1 to 3 µm, 0.1 to 1 µm or 0.2-0.45, µm can be used. In some modalities, the flow in microfiltration varies from 100 to 3,500 l / h / m ', 300 to 3,000 l / h / m' or 500 to 2,500 l / h / m '. In some embodiments, the flow rate in microfiltration is around 550 | / h / m2. In other modalities, the transmembrane pressure, in microfiltration, ranges from 6.89 kPa to 206.84 kPa, or from 13.78 kPa to 137.89 kPa, and in some modalities the transmembrane pressure is around 103.42 kPa .
[00380] [00380] For the ultrafiltration and diafiltration steps, a polyethersulfone flat sheet membrane cartridge can be used having pore sizes ranging from 100 to 1,000 kDa. In some embodiments, the cartridge comprises pores with sizes of about 500 kDa. Flow parameters of approximately 100 to 3,500 l / h / m ', 300-3,000 l / h / m' or 500-2,500 l / h / m ', for example, about 2,200 L / hr / m' can be used . Transmembrane pressures range from 6.89 kPa to 206.84 kPa, from 13.78 to 137.89 kPa, and in some embodiments the transmembrane pressure is around 41.36 kPa. In some embodiments, the solution can be diafiltered with between 1 and 20 volumes of water, for example, 10 volumes of water. The optimum number of volumes depends on the desired purity for the final product. Any of the above parameters, including the membrane material and configuration, as well as the flow parameters can be changed, depending on the application, the particle of interest and the desired purity and yield in the final product.
[00381] [00381] In another modality, the microfiltration step is performed with depth filtration, instead of TFF to eliminate bacterial cells and cell residues. In-depth filtration can be performed using two filters connected in series. In some embodiments, the first filtering device comprises a fiberglass capsule with a nominal porosity of 0.5 to 3 µm, for example, about 0.2 1 µm and followed by a double membrane filter capsule each having membrane filter capsule with a pore size of 0.1 to 1 µm, for example, about 0.8 µm and about 0.45 µm, respectively.
[00382] [00382] Any of the above parameters can be modified to obtain other modalities. For example, in the initial step of clarifying the cell solution and cell fragments either the TFF or depth filtration can be. used. For the second stage of purification of the filamentous bacteriophage from the remaining solution, TFF or depth filtration can also be used; however, in certain embodiments, TFF is used. ,
[00383] [00383] The described purification and filtration methods can be applied to any other biological particles that are currently purified using a combination of centrifugation and precipitation methods. Such biological particles include, but are not limited to, other bacteriophages (i.e., not just M13), viruses, proteins, etc. The geometry of the filter membrane can be a flat sheet or hollow fiber.
[00384] [00384] In some embodiments, the membranes used for TFF are chemically activated, by means of charge or affinity molecules, and such membranes may exhibit preferential binding of particles of interest or be filtered or retained. In other embodiments, the filter materials used for in-depth filtration can be activated, using charge or affinity molecules, and can exhibit a preferential bonding of particles to be filtered. In addition, some modalities use membranes for TFF that are mechanically activated by vibration to reduce fouling and improve filtration.
[00385] [00385] In another modality, amyloid fibers can be used as a biological model in which metal ions can be nuclear and be grouped in a catalytic nanowire. Under certain conditions, one or more normally soluble proteins (ie, a precursor protein) can fold and group into a filamentous structure and become insoluble. Amyloid fibers are typically composed of aggregated β-ions, regardless of the origin of the precursor protein structure. As used herein, the precursor protein may contain natural or unnatural amino acids. The precursor protein can be further modified with a fatty acid tail. (D) Capsule Viruses
[00386] [00386] In other embodiments, a virus or a capsid can be used as a biological model. Similar to a bacteriophage, a virus also comprises a protein layer and a nucleic acid nucleus. In particular, viruses of anisotropic forms, such as viral fibers, are suitable for the nucleation and growth of the catalytic nanowires described herein. In addition, a virus can be genetically engineered to express specific peptides on its coat for desirable binding to ions. Viruses that have filamentary or elongated structures include those that are described in, for example, Christopher Ring, Genetic / Engineered Virus, (Ed) Bios Cientifica (2001).
[00387] [00387] In certain modalities, the virus can have its genetic materials removed and only the outer coat of protein (capsid) remains as a biological model.
[00388] [00388] As discussed above, the present disclosure provides methods and nanowires for preparing them using polymer model methods. Polymer or "soft" models have been widely used in the synthesis of materials to prepare materials with unique nano and microstructures.
[00389] [00389] Polymers can be used to prepare OCM catalysts for textured and shaped metal oxide, for example, in the form of nanowires. This application describes a simple method of preparing mixed metal and metal oxide OCM catalysts using polymer models. In one embodiment, the disclosed methods employ polymers (for example, water-soluble polymers) with a wide range of molecular weights, as the modeling source. Examples of polymers include PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol), PEl (polyethyleneimine), PEG (polyethylene glycol), polyether, polyesters, polyamides, dextran and other sugar polymers, functionalized hydrocarbon polymers, functionalized polystyrene acid, polystyrene acid , poIicaprolactone, polyglycolic acid, po! i (ethylene glycol) -poly (propylene glycol), poly (ethylene-glycol) and copolymers and combinations thereof. In some embodiments, the polymer model is functionalized with at least one of the amine, carboxylic acid, sulfate,
[00390] [00390] Briefly, a metal and polymer precursor are dissolved in water to produce a viscous solution. The solution is dried and calcined (oven or microwave) to remove the polymer model. In some embodiments, several metal precursors (for example, M1, M2, etc.) are dissolved in a polymer solution. The solution is dried and calcined as described above, to obtain mixed metal oxide systems for OCM catalysis. Another modality uses lyophilization to dry the polymer / metal solution in order to prepare a more controllable porosity in mixed metallic and metal oxide materials.
[00391] [00391] Some modalities include the use of polymers that easily form gels to prepare metal oxides and mixed metal oxides for OCM catalysts. For example, agarose readily forms a gel that can be.
[00392] [00392] In another embodiment, the disclosed methods comprise treating a metal-polymer gel composite (e.g., agarose), with a base to precipitate metal precursors within the gel structure. The precipitated metals can optionally be calcined. Another embodiment uses lyophilization to remove water from the metal-polymer gel composition. Agarose is removed by calcination in an oven or microwave to obtain metal and mixed metal OCM catalysts.
[00393] [00393] The "Pechini" method is a convenient method for preparing uniformly dispersed mixed metal oxides. The general procedure comprises the use of a multifunctional coordination binder that binds the metal in solution to create a metal coordination complex, which can be polymerized in situ, using a poHalcohol, to prepare a metal / organic compound. Typically, an alpha-hydroxycarboxylic acid, such as citric acid, is used to form a stable metal complex and can be esterified / cross-linked with a polyhydroxy alcohol, such as ethylene | or glycerol, to form a polymeric resin. The immobilization of the metal complexes in the resin reduces metal segregation and facilitates compositional homogeneity.
[00394] [00394] Nucleation is the process of forming an inorganic nanowire in situ through the conversion of soluble precursors (for example, metal salts and anions) into nanocrystals in the presence of a model. Typically, nucleation and growth takes place from multiple attachment sites along the length of the model in parallel. Growth continues until a structure surrounding the model is formed. In some embodiments, this structure is monocrystalline. In other modalities the structure is amorphous, and in other modalities the structure is polycrystalline. If desired, after completion of the synthesis, the model can be removed by heat treatment (-300 ° C) in air or oxygen, without significantly affecting the structure or shape of the inorganic material. In addition, dopants can be incorporated, either simultaneously, during the growth process or, in another embodiment, dopants can be incorporated through impregnation techniques. (a) Nanowire Growth Methods
[00395] [00395] Figure 7 shows a flowchart of a nucleation process for the formation of a nanowire, comprising a metal oxide. A modeling solution is prepared first (block 504), to which a metal salt precursor comprising metal ions is added (block 510). After that, an anion precursor is added (block 520). Note that, in various modalities, the addition of metal ions and precursor anions can be simultaneous or sequentially in any order. Under appropriate conditions (for example, pH, model molar ratio and metal salt, molar ratio of metal ions and anions, addition rate, etc.), metal ions and anions bind to a model, nuclei and grow in a nanowire of the MmX composition, Zp (block 524). After calcination, the nanowires that make up MmX, are transformed into metallic oxide nanowires that comprise (MXOy) (block 530). An optional doping step (block 534) incorporates a dopant (Dp ") in the nanowires comprising metal oxide (MXOy, where x and y are each independently, and a number from 1 to 100. For ease of illustration, figure 7 shows calcination before doping, however, in certain modalities doping can be performed before calcination.
[00396] [00396] In one embodiment, a method is provided for the preparation of inorganic, polycrystalline, catalytic nanowires, the nanowires of each having an effective length to actual length ratio of less than one and an aspect ratio greater than ten, measured by MET, in luminous field mode, at 5 keV, where the nanowires comprise, individually, one or more elements selected from Groups 1 to 7, Ianthanides, actinides or combinations thereof. The method comprises: mixing (A) with a combination comprising (B) and (C); mixing (B) with a combination comprising (A) and (C); or mixture of (C) with a combination comprising (A) and (B) to obtain a mixture comprising (A), (B) and (C), wherein (A), (B) and (C) comprise , respectively:
[00397] [00397] In some of the above, the models are biological models, such as the phage. In other embodiments, the models are non-biological polymers, for example, the non-biological polymers described in this document.
[00398] [00398] In certain embodiments, the mixture comprising (B) and (C) was prepared by combining (B) and (C), the mixture comprising (A) and (C), was prepared by combining (A ) and (C) or the mixture comprising (A) and (B) was prepared by combining (A) and (B).
[00400] [00400] In even more modalities, one or more salts comprise Mgc | 2, LaC | 3, ZrC | 4, WC | 4, MOC | 4, MnC | 2 MnC | 3, Mg (NO3) 2, La (NO3) 3, ZrOCl2, Mn (NO3) 2, Mn (NO3) 3, ZrO (NO3) 2, Zr (NO3) 4 or mixtures thereof.
[00401] [00401] In other modalities one or more salts comprise Mg, Ca, Mg, W, La, Nd, Sm, Eu, W, Mn, Zr or mixtures thereof, while in different modalities, one or more anion precursors comprise hydroxides alkali metal hydroxides, alkaline earth metal hydroxides, carbonates, bicarbonates, ammonium hydroxides or mixtures thereof. For example, in some embodiments, one or more anion precursors comprise L1OH, NaOH, KOH, Sr (OH) 2, Ba (OH) 2, Na2CO3, K2CO3, NaHCO3, KHCO3, and NR4OH, where R is selected from H , and C1-C6 alkyl.
[00402] [00402] In other embodiments, the non-biological polymer model comprises PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol), PEl (polyethyleneimine), PEG (polyethylene | polyethylene, polyamides, dextran, sugar polymers, functionalized hydrocarbon polymers, functionalized polystyrene, polylactic acid, poIicaprolactone, polyglycolic acid, poly (ethylene glycol) -po1i (propylene glycol), poly (ethylene glycol) or copolymers or combinations thereof.
[00403] [00403] In other examples, the method further comprises leaving the mixture comprising (A), (B) and (C) standing at a temperature of about 4 ° C to about 80 ° C for a sufficient period of time to allow the nucleation of the catalytic nanowires.
[00404] [00404] In some other modalities, the method further comprises the addition of a doping element, comprising metallic elements, semimetallic elements, non-metallic elements or combinations thereof, to the mixture comprising (A), (B) and (C).
[00405] [00405] In even more modalities, the method also comprises the calcination nanowires. In some embodiments, the calcination of the nanowires comprises heating the nanowires at 450 ° C or more for at least 60 minutes. In yet other modalities, the method also comprises the doping nanowires, in which the doping of the nanowires comprises contacting the nanowires with a solution comprising a doping agent and evaporating any excess liquid, in which the doping comprises a metallic element, a semimetallic element , a non-metallic element or combinations thereof.
[00406] [00406] Another embodiment provides a method for preparing a nanowire comprising a metal oxide, a metal oxy-hydroxide, a metal oxycarbonate or a metal carbonate, the method comprising: a) providing a solution comprising a plurality of models;
[00407] [00407] In some embodiments of the preceding models are biological models, such as phage. In other embodiments, the models are non-biological polymers, for example, the non-biological polymers described in this document.
[00408] [00408] In some embodiments of the foregoing, the non-biological polymer model comprises PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol), PEl (polyethylenimine), PEG (po | ieti | enog | ico |), polyether, polyesters, polyamides, dextran and other sugar polymers, functionalized hydrocarbon polymers, functionalized polystyrene, polylactic acid, polycaprolactone, polyglycolic acid, poly (ethylene-glyco1) -po! i (propylene glycol), poly (ethylene glycol), copolymers or combinations thereof . In some embodiments, the non-biological polymer model is functionalized with at least one of the amine, carboxylic acid, sulfate, alcohol, or halogen thiol groups. For example, the non-biological polymer model can be a hydrocarbon or a functionalized polystyrene polymer, with at least one of the amine, carboxylic acid, sulfate, alcohol, or halogen thiol groups.
[00409] [00409] In some modalities, the nanowire is dried in an oven, while in other modalities the nanowire is lyophilized or air dried. The drying method can have an effect on the final morphology, pore size, etc., of the resulting nanowire. In addition, the solution comprising the non-biological polymer model can be in the form of a gel and at least one metal ion is impregnated in it. The gel can then be dried, as described above. In some embodiments, the metal impregnated gel is treated with a base to precipitate the metal. In some different embodiments, the model is removed from the nanowire, either by heat treatment or by other means of removal.
[00410] [00410] In certain variations of the foregoing, two or more different metal ions may be used. This produces nanowires comprising a mixture of two or more metal oxides. Such nanowires can be advantageous in certain catalytic reactions. For example, in some embodiments, catalytic nanowires may comprise at least a first and a second metal oxide, where the first metal oxide has better OCM activity than the second metal oxide and the second metal oxide has a better ODH than the first metal oxide. In certain embodiments above, applicants have found that it may be advantageous to perform several sequential additions of metal ions, this incorporation technique may be specifically applicable to the modalities in which two or more different metal ions are used to form a mixed nanowire (M1M2X, Yy, where M1 and M2 are different metallic elements), which can be converted to M1M2O ,, for example, by calcination. The slow addition can be performed in any period of time, for example, from 1 day to 1 week. In this regard, the use of a syringe plunger or an automatic (for example, robotic) liquid dispenser can be advantageous. The slow addition of the components helps to ensure that they are nucleated in the biological model, rather than precipitating non-selectively.
[00411] [00411] In other embodiments, the metal ion is supplied by adding one or more metal salts (as described in this document) to the solution. In other embodiments, the anion is provided by adding one or more anion precursors to the solution. In various modalities, the metal ion and anion can be introduced into the solution at the same time or sequentially in any order. In some embodiments, the nanowire (MmXnZp) is converted into a metal oxide nanowire by calcination, which is a heat treatment that transforms or decomposes the MmX, Zp nanowire into a metallic oxide. In yet another modality, the method additionally comprises the doping of the metal oxide nanowires with a dopant. Doping can be carried out before or after calcination. The conversion of the nanowire into a metal oxide (or oxy-hydroxide, oxycarbonate or carbonate, etc.) is usually constituted by calcination.
[00412] [00412] In a variation of the previous method, mixed metal oxides can be prepared (as opposed to a mixture of metal oxides). Mixed metal oxides can be represented by the following formula M1WM2, M3yO ,, where Ml, M2 and M3 are either absent or a metallic element and w, x, y and z are integers such that the overall charge is balanced. Mixed metal oxides, comprising more than three metals, are also contemplated and can be prepared using an analogous method. Such mixed metal oxides find use in a variety of revealed catallotic reactions. An exemplary mixed metal oxide is Na10MnW5O17 (Example 18).
[00413] [00413] Thus, one embodiment provides a method for the preparation of a mixed metal oxide nanowire comprising a plurality of mixed metal oxides (M1WM2, M3yOZ), the method comprising: a) providing a solution comprising a plurality of models; b) introduction of metallic salts comprising Ml, M2 and M3, to the solution, under conditions and for a time sufficient to allow the nucleation and growth of a nanowire, comprising a pIurality of the metallic salts on the model; and C) conversion of the nanowire to a mixed metal oxide nanowire, comprising a plurality of mixed metal oxides (M1WM2, M3yOZ), in which: Ml, M2 and M3 are, in each occurrence, independently, a metallic element from any one of groups 1 to 7, Ianthanides or actinides; K .. n, m, x and y are each, independently, a number from 1 to 100; and p is a number from 0 to 100.
[00413] [00413] In some embodiments of the above the models are biological models, such as the phage. In other embodiments, the models are non-biological polymers, for example, the non-biological polymers described in this document.
[00414] [00414] In some embodiments of the above, the non-biological polymer model comprises PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol), PEl (polyethyleneimine), PEG (polyethylene, polyether, polyamides, polyether, polyamides, dextran and other sugar polymers, polymers of functionalized hydrocarbons, functionalized polystyrene, polylactic acid, polycaprolactone, polyglycolic acid, poly (ethylene glycol) -poI (propylene glycol), poii (ethylene glycol), copolymers or combinations thereof. In some embodiments, the non-biological polymer model is functionalized with at least one of the amine, carboxylic acid, sulfate, alcohol, or halogen or thiol groups. For example, the non-biological polymer model can be a hydrocarbon or a functionalized polystyrene polymer, with at least one of the amine, carboxylic acid, sulfate, alcohol or thiol groups.
[00415] [00415] In some embodiments, the nanowire is dried in an oven, while in other embodiments the nanowire is lyophilized or air dried. The drying method can have an effect on the final morphology, pore size, etc., of the resulting nanowire. In addition, the solution comprising the non-biological polymer model can be in the form of a gel and its salts, at least one of the metal salts are impregnated there. The gel can then be dried, as described above.
[00416] [00416] In other embodiments, the present description provides a method for the preparation of metal oxide nanowires, which do not require a calcination step. Thus, in some embodiments, the method for preparing metal oxide nanowires comprises: (a) providing a solution that includes a plurality of models; and (b) introducing a compound comprising a metal to the solution, under conditions and for a time sufficient to allow the nucleation and growth of a nanowire (MmYn) on the model; where: M is a metallic element from any of groups 1 to 7, lanthanides or actinides; Y is O; n and m are each, independently, a number from 1 to 100.
[00417] [00417] In some embodiments of the above, the models are biological models, such as the phage. In other embodiments, the models are non-biological polymers, for example, the non-biological polymers described in this document.
[00418] [00418] In some of the above, the non-biological polymer model comprises PVP (poHvinylpyrrolidone), PVA (polyvinyl alcohol), PEl (polyethylenimine), PEG (pohetilenoghcol), polyether, polyesters, polyamides, dextran and other sugar polymers , functionalized hydrocarbon polymers, functionalized polystyrene, polylactic acid, polycaprolactone, polyglycolic acid, poly (etj | enoglico |) -po | i (propylene glycol), poIi (ethylene glycol), copolymers or combinations thereof. In some embodiments, the non-biological polymer model is functionalized with at least one of the amine, carboxylic acid, sulfate, alcohol, halogen or thiol groups. For example, the non-biological polymer model can be a hydrocarbon or a functionalized polystyrene polymer, with at least one of the amine, carboxylic acid, sulfate, alcohol, halogen or thiol groups.
[00419] [00419] In some modalities, the nanowire is dried in an oven, while in other modalities the nanowire is lyophilized or air dried. The drying method can have an effect on the final morphology, pore size, etc., of the resulting nanowire. In addition, the solution comprising the non-biological polymer model can be in the form of a gel and at least one metal is impregnated.
[00420] [00420] In some specific embodiments of the previous method, M is an earlier transition metal, for example, V, Nb, Ta, Ti, Zr, Hf, W, Mo, Cr. In other embodiments, the metal oxide is WO3. In yet another modality, the method comprises the doping of metal oxide nanowires with a dopant. In some other embodiments, a reagent is added that converts the compound that comprises a metal to a metallic oxide.
[00421] [00421] In another embodiment the disclosure provides a method for the preparation of a nanowire, comprising a metal oxide, a metal oxy-hydroxide, a metal oxycarbonate or a metal carbonate, the method comprising: a) providing a solution comprising a plurality of multifunctional coordination binders; b) introduction of at least one metal ion to the solution, thus forming a metal ion binding complex; C) introduction of a polyalcohol to solution, in which the polyalcohol polymerizes with the lithium metal binding complex to form a polymerized metal ion binding complex.
[00422] [00422] In some embodiments, the multifunctional coordination linker is an alpha-hydroxycarboxylic acid, for example, citric acid. In other embodiments, the polyalcohol is ethylene glycol or glycerol. In still other embodiments, the method further comprises heating the polymerized metal ion binder complex to remove substantially all of the organic material, and optionally heating the remaining inorganic metal to convert it to a metallic oxide (i.e., calcination). In another embodiment, nanowires are prepared using salts of metals sensitive to water hydrolysis, for example, NbCl5, WCl6, TiC | 4, ZrC | 4. A polymer model can be placed in ethanol, along with the metal outlet. The water is then slowly added to the reaction in order to convert the metal salts into the metal oxide coated model.
[00423] [00423] Other embodiments of the present disclosure provide a method for the preparation of metal oxide nanowires, the method comprising: a) providing a solution comprising a plurality of models; and b) introducing a compound comprising a metal to the solution, under conditions and for a time sufficient to allow the nucleation and growth of a nanowire (MmYn) on the model; where: M is a metallic element from any of groups 1 to 7, lanthanides or actinides; Y is O, n and m are each, independently, a number from 1 to 100.
[00424] [00424] In some embodiments of the above the models are biological models, such as the phage. In other embodiments, the models are non-biological polymers, for example, the non-biological polymers described in this document.
[00425] [00425] In some exemplary embodiments, the non-biological polymer model comprises PVP (po | ivini | pyrrho | idone), PVA (polyvinyl alcohol), PEl (polyethyleneimine), PEG (polyethylene glycol), polyethers, polyesters, polyamides, dextran, sugar polymers, functionalized hydrocarbon polymers, functionalized polystyrene, polylacetic acid, polycaprolactone, poly | ig | iconic | acid, poii (ethyl | enogene |) -po | i (propylene glycol), poly ( ethylene glycol) or copolymers or combinations thereof.
[00426] [00426] In some modalities of the above methods, the non-biological polymer model is functionalized with at least one of the amine, carboxylic acid, sulfate, alcohol or thiol groups. For example, in some embodiments, the non-biological polymer model comprises a hydrocarbon polymer, or a polystyrene polymer.
[00427] [00427] In another embodiment, nanowires are prepared using metallic salts sensitive to water hydrolysis, for example NbC | 5, WC | 6, TiC | 4, ZrC | 4. A model can be placed in ethanol, along with sa! metallic. The water is then slowly added to the reaction in order to convert the metal salts into the metal oxide coated model.
[00428] [00428] Varying nucleation conditions, including (without limitation): phage and metal salt incubation time; incubation time of phage and negative ions; concentration of the model; concentration of metal ions, concentration of anions, sequence of the addition of anion ions and metal; pH: phage sequences; polymer composition, the size of the polymer, at temperature of the solution in the incubation stage and / or growth stage; types of metal precursor salt; types of anion precursor; addition rate; number of additions; amount of metal salt and / or an anion precursor per addition, time elapsed between the addition of the metal salt precursor and anions, including, for example, simultaneously (zero elapsed time) or sequential additions followed by the respective salt incubation times metallic and the precursor of the anion, the stable nanowires with different compositions and the properties of the surface, can be prepared. For example, in certain embodiments, the pH of the nuclear conditions is at least 7.0, at least 8.0, at least 9.0, at least 10.0, at least 11.0, at least less than 12.0 or at least 13.0.
[00429] [00429] As noted above, the rate of addition of reagents (for example, metal salt, metal oxide, anion precursor, etc.) is a parameter that can be controlled and varied to produce nanowires with different properties. During the addition of reagents to a solution containing an existing nanowire and / or molding material (eg, phage), a critical concentration is reached at which the rate of deposition of solids on the current nanowires and / or mold material corresponds to the rate of addition of reagents to the reaction mixture. At this point, the soluble cation concentration stabilizes and does not rise. Thus, the growth of the nanowires can be controlled and maximized by maintaining the rate of addition of the reagents so that the concentration close to the over-saturation of the cation is maintained. This helps to ensure that unwanted nucleation does not occur. If the anion over-saturation (for example, hydroxide) is exceeded, a new solid phase can begin nucleation that allows non-selective precipitation of solids, rather than the growth of the nanowire. Thus, in order to selectively deposit a layer of inorganic material onto an existing nanowire and / or mold material, the rate of addition of the reagents must be controlled to prevent over-saturation of the solution containing the suspended solid particles .
[00430] [00430] Thus, in one embodiment, the reagent is added repeatedly in small doses, to slowly form the reagent concentration in the solution containing the model. In some embodiments, the rate of addition of the reagents is such that the concentration of the reagent in the solution containing the model is close (but lower) to the saturation point of the reagent. In some other embodiments, the reagent is added in portions (that is, the addition step), rather than continuously. In these modalities, the amount of reagent in each portion, and the time between the addition of each portion, are controlled in such a way that the concentration of reagent in the solution containing the model is close (but lower) to the saturation point of the reagent. In certain embodiments of the above, the reagent is a metal cation, while in other embodiments the reagent is an anion.
[00431] [00431] The initial formation of nuclei in a model can be obtained through the same method described above, in which the reagent concentration is increased until close, but not above, the reagent supersaturation point. Such an addition method facilitates the nucleation of the solid phase on the model, instead of homogeneous non-seeding nucleation. In some embodiments, it is desirable to use a slower rate of reagent addition during the initial nucleation phase, as the supersaturation depression due to the model may be very small at this point. Since the first layer of solids (ie, the nanowire) is formed on the model, the addition speed can be increased.
[00432] [00432] In some embodiments, the rate of reagent addition is controlled, such that the rate of precipitation corresponds to the rate of reagent addition.
[00433] [00433] In some embodiments, the optimal speed of addition (and step size, if using step additions) is controlled as a function of temperature. For example, in some embodiments, the nanowire growth rate is accelerated at higher temperatures. Thus, the rate of addition of the reagents is adjusted according to the temperature of the mold solution.
[00434] [00434] In other modalities, the modeling (numerical iterative, instead of algebraic) of the nanowire growth process is used to determine the concentrations of optimal solutions and the supernatant recycling strategies.
[00435] [00435] As noted above, the rate of addition of the reagents can be controlled and modified to change the properties of the nanowires. In some embodiments, the rate of addition of a hydroxide source must be controlled in such a way that the pH of the mold solution is maintained at the desired level. This method may require specialized equipment and, depending on the rate of addition, the potential for peaks located at pH after the addition of the source hydroxide is possible. Thus, in an alternative embodiment of the present disclosure, it provides a method in which the model solution comprises a weak base which slowly generates hydroxide in situ, obviating the need for an automated addition sequence.
[00436] [00436] In the above modality, organic epoxides, such as, but not limited to propylene oxide and epichlorohydrin, are used to slowly increase the pH model solution, without the need for automatic pH control. Epoxides are proton clearers and undergo an irreversible ring opening reaction with a nucleophilic anion of the metal oxide precursor (such as, but not limited to, cr or NOi). The net effect is a slow and homogeneous increase in pH to form metallic hydroxy species in the solution that is deposited on the model's surface. In some embodiments, the organic epoxide is propylene oxide.
[00437] [00437] An interesting feature of this method is that organic epoxide can be added all at once, there is no requirement for subsequent additions of organic epoxide to develop metal oxide coatings in the course of the reaction. Due to the flexibility of "epoxide-aided" coatings, it is expected that many different modalities can be used to make new modeled materials (for example, nanowires). For example, mixed metal oxide nanowires can be prepared starting with appropriate proportions of the metal oxide and propylene oxide precursors in the presence of bacteriophage. In other embodiments, the deposition of metal oxide on the bacteriophage can be done sequentially, to prepare the materials of the central core / shell (described in more detail below).
[00438] [00438] Other modalities include nanowires prepared according to the preceding methods and use of them in catalytic reactions, such as OCM and for the preparation of ethylene and products based on them.
[00439] [00439] As noted above, nanowires are prepared by nucleating metal ions in the presence of a suitable model, for example, a bacteriophage or non-biological polymer. In this regard, any soluble metal salt can be used as a precursor to metal ions that nucleus the model. Water-soluble metal salts of Groups 1 to 7, lanthanides and actinides,
[00440] [00440] In one embodiment, the soluble metal salt comprises chlorides, bromides, iodides, nitrates, sulfates, acetates, oxides, oxy, oxinitrants, phosphates (including hydrogenated phosphate) and dihydrogenated phosphate, shapes, alkoxides or oxalates of metal elements Groups 1 to 7, lanthanides, actinides or combinations thereof. In more specific embodiments, the soluble metal salt comprises chlorides, nitrates or sulfates of metal elements from Groups 1 to 7, lanthanides, actinides or combinations thereof. This description includes all chloride, bromide, iodide, nitrate, sulfate, acetate, oxide, oxide, oxynitrates, phosphates (including hydrogenated phosphate) and dihydrogenated phosphate, formats, alkoxides and oxalate salts of groups 1 to 7 , possible lanthanides or actinides or combinations thereof.
[00441] [00441] In another embodiment, the metal salt comprises LiCl, Li8r, Lil, LiNO3, Li2SO4, LiCO2CH3, Li2C2O4, Li3PO ,, Li, HPO4, LiH2PO4, L1CO, H, L1OR, NaCl, Na8r, Nal, NaNO3, Na2SO4, NaCO2CH3, Na2C2O4, Na3PO4, Na2HPO4, NaH, PO4, NaCO, H, NaOR, KCl, K8r, K !, KNO ,, K, SO ,, KCO, CH ,, K, C, O ,, K, PO4, K , HPO ,, KH, PO ,, KCO, H, KOR, RbCl, Rb8r, Rbl, RbNO ,, Rb, SO ,, RbCO, CH ,, Rb, C, O ,, Rb, PO ,, Rb, HPO, , RbH, PO ,, RbCO2H, RbOR, CsCl, CsBr, Csl, CSNO ,, CS, SO ,, CsCO2CH3, CS2C2O4, CS3PO4, CS2HPO ,, CSH, PO4, CSCO2H, CSOR, BeCl2, BeBr2, Bel ,, Be ( NO3) 2, BeSO4, Be (CO2CH3) 2, BeC2O4, Be3 (PO4) 2, BeH PO4, Be (H2PO4) 2, Be (CO2H) 2, Be (OR) z MgCl ,, Mg8r ,, Mgl ,, Mg (NO3) 2, MgSO4, Mg (CO2CH3) 2, MgC, O4, Mg3 (PO4) 2, MgHPO4, Mg (H2pO4) 2, Mg (CO2H) 2, Mg (OR) 2, CaCl ,, Ca8r ,, Cal ,, Ca (NO3) 2, CaSO ,, Ca (CO2CH3) 2, CaC, O4, Mg3 (po4) 2, MgHPO ,, Mg (H2pO4) 2, Mg (CO2H) 2, Mg (OR) 2, SrCl, , Sr8r ,, Srl ,, Sr (NO3) 2, SrSO ,, Sr (CO2CH3) 2, SrC, O ,, Sr3 (PO4) 2, SrHPO ,, Sr (H2PO4) 2, Sr (CO2H) 2, Sr ( OR) 2, BaCl ,, Ba8r ,, Ba | 2, Ba (NO3) 2, BaSO4, Ba (CO2CH3) 2, BaC2O4, Ba3 (PO4) 2, BaHPO4, Ba (H2PO4) 2, Ba (CO2H) 2, Ba (OR) 2, ScC | 3, ScBr3, Sc | 3, Sc (NO3) 3, SC2 (SO4) 3, Sc (CO2CH3) 3, SC2 (C2O4) 3, SCPO4,
[00442] [00442] In the most specific modalities, the metallic salt comprises
[00443] [00443] In other embodiments, the metal salt comprises NdCb, NdBr3, Nd | 3, Nd (NO3) 3, Nd2 (SO4) 3, Nd (CO2CH3) 3, Nd2 (C2O4) 3, EuC | 3, EuBr3, Eu | 3, Eu (NO3) 3, Eu2 (SO4) 3, Eu (CO2CH3) 3, Eu2 (C2O4) 3, PrCh, PrBr3, Pr | 3, Pr (NO3) 3, Pr2 (SO4) 3, Pr (CO2CH3) ) 3, Pr2 (C2O4) 3 or their combinations.
[00444] [00444] In still other modalities, the metal salt comprises Mg, Ca, Mg, W, La, Nd, Sm, Eu, W, Mn, Zr or their mixtures. The salt can be in the form of (oxy), chlorides (oxy) nitrates or tungstates. (C) Anion precursor
[00445] [00445] The anions, or counterions of the metal ions that nucleise on the model are supplied in the form of an anion precursor. The anion precursor dissociates in the solution phase and releases an anion. Thus, the anion precursor can be any stable soluble salts having the desired anion. For example, bases, such as alkali metal hydroxides (for example, sodium hydroxide, lithium hydroxide, potassium hydroxides and ammonium hydroxide) are the anion precursors that provide hydroxide ions for nucleation. Alkali metal carbonates (eg, sodium carbonate, potassium carbonate) and ammonium carbonate are precursors of anions that provide carbonate ions for nucleation.
[00446] [00446] In certain embodiments, the anion precursor comprises one or more of metal hydroxide, meta carbonate, metal bicarbonate, metal sulfate, metal phosphate or metal oxalate. Preferably, the metal is an alkali metal or an alkaline earth metal. Thus, the anion precursor can comprise any of the alkali hydroxides, carbonates, bicarbonates, sulfates, phosphates or oxalate; or any of the alkaline earth metal hydroxides, carbonates, bicarbonates, sulfates, phosphates or oxalates.
[00447] [00447] In some specific embodiments, one or more anion precursors comprise L1OH, NaOH, KOH, Sr (OH) 2, Ba (OH) 2, Na2CO3, K2CO3, NaHCO3, KHCO3 (NR4) 2CO3, and NR4OH, where each R is independently selected from H, C1-C18 alkyl, C1-C18 alkenyl, C1-C18 alkynyl and C1-C18 aryl. Ammonium salts can provide certain advantages in that there is less chance of introducing unwanted metal impurities. Therefore, in another embodiment, the anion precursor comprises ammonium hydroxide or ammonium carbonate.
[00448] [00448] The dimensions of the nanowires are comparable to those of the models (for example, phage or non-biological polymer), although they can have different proportions of longer growth and can be useful to increase the diameter, while the length increases in size at a rate much slower. The spacing of the peptides on the phage surface controls the nucleation site and the size of the catalytic nanowire based on the steric impediment. The informations. specific to the peptide sequence must (or can) dictate the identity, size, shape and crystalline face of the catalytic nanowire being nucleated. Similar diversity is achieved by varying functional groups, length, sequence, etc. of a non-biological polymer.
[00449] [00449] To achieve the desired stoichiometric amount between the metal elements, supports and dopants, several specific peptides for these separate materials can be coexpressed on the same phage. Alternatively, precursors for the materials can be combined in the desired stoichiometric reaction. Techniques for phage propagation and purification are also well established, firm and scalable. Quantities of several kilos of phages can be produced easily, thus ensuring simple scale up to large industrial quantities.
[00450] [00450] In certain embodiments, the nanowires can be grown on a support nanowire that has no or a different catalytic property. Figure 8 shows an exemplary process 600 for the cultivation of a central core / shell structure. Similar to figure 7, a model solution (block 604) is prepared, to which a first metal salt and a first anion precursor are added sequentially (blocks 610 and 620), under conditions suitable to allow the nucleation and growth of a nanowire (M1m1X1n1Zp1) in the phage (block 624). Subsequently, a second metallic salt and a second anion precursor are added sequentially (blocks 630 and 634), in conditions to cause the nucleation and growth of a M2m2X2n2Zp2 coating on the MGiXlm ZpI nanowire (block 640). After calcination, the nanowires of an M1,1Oy1M2X2Oy2 core structure are formed, where xl, yl, x2 and y2 are each, independently, a number from 1 to 100, and Pl and P2 are each independently , a number from 0 to 100 (block 644). Another impregnation step (block 650) produces a nanowire comprising a dopant and comprising an M1,1Oy1 core coated with an M2.2Oy2 shell. For ease of illustration, figure 8 represents the calcination before doping; however, in certain modalities, doping can be performed before calcination.
[00451] [00451] In other modalities, M1,1Oy1 comprises La2O3, while in other modalities M2,2Oy2 comprises La2O3. In other embodiments of the above, M1,1Oy1 or M2,2Oy2 further comprises a dopant, wherein the dopant comprises Nd, Mn, Fe, Zr, Sr, Ba, Y or their combinations. Other specific combinations of core / shell nanowires are also considered to be within the scope of the present disclosure.
[00452] [00452] Thus, one embodiment provides a method for the preparation of metal oxide nanowires, metal oxy hydroxide, or metal oxycarbonate in a central core / shell structure, the method comprising: (a) providing a solution that includes a plurality of models; (b) introduction of a first metal ion and a first anion to the solution, under conditions and for a time sufficient to allow the nucleation and growth of a first nanowire (M1m1X1n1Zp1) on the model; and (C) introduction of a second metal ion and, optionally, a second anion to the solution, under conditions and for a time sufficient to allow the nucleation and development of a second nanowire (M2m2X2n2Zp2) on the surface of the first nanowire (M1m1X1n1Zp1) ; (d) conversion of the first nanowire (M1m1X1n1Zp1) and the second nanowire (M2m2X2n2Zp2) in the respective metal oxide nanowires (M1x1Oy1) and (M2x2Oy2), the respective metal oxyhydroxide nanowires (M1x1Oy1OHz1) and their oxide oxides (M2x2Hz) and (M2x2Hz) metallic (M1x1Oy1 (CO3) z1) and (M2x2Oy2 (CO3) z2) or the respective metallic carbonate nanowires (M1x1 (CO3) y1) and (M2x2 (CO3) y2), where: Ml and M2 are the same or different and independently selected from a metallic element; X1 and X2 are the same or different and, independently, hydroxide, carbonate, bicarbonate, phosphate, hydrogenated phosphate, dihydrogenated phosphate, sulphate, nitrate or oxalate; Z is O; nl, ml, n2, m2, xl, yl, zl, X2, y2 and z2 are each, independently, a number from 1 to 100; and pl and p2 are, independently, a number from 0 to 100.
[00453] [00453] In some modalities, Ml and M2 are the same or different and selected, independently, from a metallic element of any of groups 2 to 7, lanthanides or actinides.
[00454] [00454] In other modalities, M1 and M2 are different.
[00455] [00455] In other embodiments, the respective metal ion is supplied by adding one or more of the respective metal salts (as described in this document) to the solution. In other embodiments, the respective anions are provided by adding one or more of the respective anion precursors to the solution. In several modalities, the first metal ion and the first anion can be introduced into the solution simultaneously or sequentially in any order.
[00456] [00456] In some of the above, the models are biological models, such as the phage. In other embodiments, the models are non-biological polymers, for example, the non-biological polymers described in this document.
[00457] [00457] In various modalities, non-biological polymer models are selected from PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol), PEl (Polyethyleneimine), PEG (polyethylene glycol), polyether, polyesters, polyamides, dextran and others sugar polymers, functionalized hydrocarbon polymers, functionalized polystyrene, polylactic acid, polycaprolactone, polyIicylic acid, poly (ethylene | |) -po | i (propylene glycol), po | i (ethyl | eno-g | ico |) and copolymers and their combinations. In some embodiments, the non-biological polymer model is functionalized with at least one of the amine, carboxylic acid, sulfate, alcohol, halogen or thiol groups. For example, the non-biological polymer model can be a hydrocarbon or a functionalized polystyrene polymer, with at least one of the amine, carboxylic acid, sulfate, alcohol, halogen or thiol groups.
[00458] [00458] In some embodiments, the nanowire is dried in an oven, while in other embodiments the nanowire is freeze-dried or air-dried. The drying method can have an effect on the final morphology, pore size, etc., of the resulting nanowire. In addition, the solution comprising the non-biological polymer model can be in the form of a gel and the metal ions are impregnated in it. The gel can then be dried, as described above. In some different embodiments, the model is removed from the nanowire, by heat treatment or other means of removal.
[00459] [00459] In yet another modality, the method also comprises the doping of the metal oxide nanowires in a central core / shell structure with a dopant.
[00460] [00460] Varying the nucleation conditions, including the pH of the solution, the relative proportion of the metal salt precursors and the anion precursors, relative proportions of the precursors and the synthetic mixture model, stable nanowires with different compositions and properties of surface can be prepared.
[00461] [00461] In certain embodiments, the core nanowire (the first nanowire) is not catalytically active or less than the shell nanowire (the second nanowire) and the core nanowire serves as an intrinsic catalytic support for the longer shell nanowire active. For example, ZrO2 may not have high catalytic activity in an OCM reaction, whereas La2O3 doped Sr2 "does. A ZrO2 nucleus thus can serve as a support for the catalytic Sr2" doped La2O3 envelope.
[00462] [00462] In some embodiments, the present description provides a nanowire comprising a central core / shell structure, and comprising an effective length to actual length ratio of less than one. In other embodiments, nanowires that have a central core / shell structure comprise a ratio of effective length to actual length equal to one.
[00463] [00463] The nanowires in a central core / shell arrangement can be prepared in the absence of a model. For example, a nanowire comprising a first metal can be prepared according to any of the methods directed to the non-model and described in this document. A second metal can then be nucleated or coated onto the nanowire to form a core / shell nanowire. The first and second metals can be the same or different. Other methods are also envisaged for the preparation of core / shell nanowires, in the absence of a biological model.
[00464] [00464] As noted above, in some modalities, the synthesis directed to the revealed model provides nanowires with different compositions and / or morphologies.
[00466] [00466] Additional synthetic parameters, variables include growth time since both the metal and anion are present in the solution; choice of solvents (although water is normally used, certain amounts of alcohol, such as methanol, ethanol and propanol, can be mixed with water); the choice and amount of metal salts employed (for example, both LacCl3 and La (NO3) 3 can be used to provide La3 ions "); choice of or the number of anion precursors employed (eg, NaOH, then LiOl-l can be used to supply the hydroxide); choice of or the number of different sequences of phages used; choice of the number of different polymers used; the presence or absence of a buffer solution; the different stages of the growth stage (eg For example, nanowires can be precipitated and cleaned and resuspended in a second solution and perform a second growth of the same material (thicker number) or different material to form a central core / shell structure.
[00468] [00468] In some embodiments, nanowires can be synthesized in a solution phase, in the absence of a model. Typically, a hydrothermal or sunny approach! it can be used to create linear crystalline nanowires (that is, the ratio of effective length to actual length equal to one) and substantially individual. As an example, the nanowires, comprising a metal oxide can be prepared by (1), forming the nanowires of a metal oxide precursor (for example, metal hydroxide) in a solution of a metal salt and an anion precursor; (2) isolation of the nanowires from the metal oxide precursor; and (3) calcining the nanowires of the metal oxide precursor to provide nanowires of a corresponding metal oxide. In other modalities (for example, MgO nanowires), the synthesis passes through an intermediate that can be prepared as a nanowire and then converted into the desired product, maintaining its morphology. Optionally, nanowires comprising a metal oxide can be doped according to the methods described in this document. The dopant can be incorporated either before or after an optional calcination step.
[00469] [00469] In another determined modality, the nanowires, comprising a central core / shell structure are prepared in the absence of a biological model. Such methods may include, for example, the preparation of a nanowire comprising a first metal and the cultivation of an envelope on the outer surface of this nanowire, wherein the envelope comprises a second metal. The first and second metals can be the same or different.
[00470] [00470] In other respects, a central core / envelope nanowire is prepared in the absence of a biological model. Such methods comprise the preparation of a nanowire consisting of an inner core and an outer shell, wherein the inner core comprises a first metal and the outer layer comprises a second metal, the method comprising: a) preparing a first nanowire comprising the first metal; and b) treating the first nanowire with a salt comprising the second metal.
[00471] [00471] In some embodiments of the previous process, the method further comprises the addition of an anion precursor to a mixture obtained in step b). In still other examples, the first metal and the second metal are different. In still other embodiments, the salt comprising the second metal is a halide or a nitrate. In certain aspects, it may be advantageous to perform one or more sequential additions of the salt, comprising the second metal and an anion precursor. Such sequential additions help to prevent the non-selective precipitation of the second metal and favor the conditions where the second metal nucleates on the surface of the first nanowire to form a shell of the second metal.
[00474] [00474] In some embodiments, nanowires can be prepared directly from the corresponding oxide. For example, metal compounds can be treated with ammonium salts to produce nanowires. The ammonium salt comprises salts with the formula NR4X, in which each R is independently selected from H, alkyl, alkenyl, alkynyl and aryl (for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyia, pentenyl, cyclohexyl, phenyl, tolyl, benzyl, hexynyl, octyl, octenyl, octinyl, dodecyl, cetyl, oleyl, stearyl, and the like) and X is an anion, for example, halide, phosphate, hydrogenated phosphate, dihydrogenated phosphate, metatungstate, tungstate, molybdate, bicarbonate sulfate, nitrate or ethyl. In other embodiments, X is phosphate, hydrogenated phosphate, dihydrogenated phosphate, metatungstate, tungstate, molybdate, bicarbonate sulfate, nitrate or acetate.
[00475] [00475] In other modalities of the previous process, the method comprises the treatment of two or more different metal compounds, with the ammonium salt and the nanowire comprises two or more different metals. In other embodiments, the nanowire comprises a mixed metal oxide, metal oxyhalide, metal oxinitrate or metal sulfate and in other respects the ammonium salt is contacted with the metal compound in solution or in the solid state.
[00476] [00476] In yet other modalities of the previous process, the method additionally comprises the treatment of at least one meta compound! with the ammonium salt in the presence of at least one doping element, and the nanowire comprises at least one doping element. In other embodiments, at least one metal compound is an oxide of a lanthanide element. In still other modalities, R is methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentenyl, cyclohexyl, phenyl, tolyl, benzyl, hexynyl, octyl, octenyl, octinyl, dodecyl, cetyl, oleyl or stearyl.
[00477] [00477] In other embodiments of the previous method, the ammonium salt is ammonium chloride, dimethylammonium chloride, methylammonium chloride, ammonium acetate, ammonium nitrate, dimethylammonium nitrate, methylammonium nitrate or trimethylammonium cetyl bromide (CTAB) , while in other modalities the process also comprises treating metal oxide and ammonium salt at temperatures ranging from 0 ° C to reflux temperature, in an aqueous solvent for a time sufficient to produce the nanowires. Other examples include heating the metal oxide and ammonium salt under hydrothermal conditions, at temperatures ranging from the reflux temperature to 300 ° C at atmospheric pressure.
[00478] [00478] Thus, in one embodiment, the present disclosure provides a method for the preparation of a nanowire, in the absence of a biological model, the method comprising treating at least one metal compound with an ammonium salt. In certain embodiments, nanowires, comprising more than one type of metal and / or one or more dopants, can be prepared using such methods. For example, in one embodiment, the method comprises treating two or more different metal compounds with an ammonium salt and the nanowire comprises two or more different metals. The nanowire can comprise a mixed metal oxide, metal oxyhalide, metal oxinitrate or metal sulfate.
[00479] [00479] In some other embodiments of the above, the ammonium salt is in the form of NR4X, where each R is independently selected from H, alkyl, alkenyl, and aryl and X is a halide, sulfate, nitrate or acetate . Examples of the ammonium salt comprise ammonium chloride, dimethylammonium chloride, methylammonium chloride, ammonium acetate, ammonium nitrate, dimethylammonium nitrate, methylammonium nitrate. In some other embodiments, each R is, independently, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentenyl, cyclohexyl, phenyl, tolyl, benzyl, hexinyl, octyl, octenyl, octinyl, dodecyl, cetyl, oleyl or stearyl . In still other modalities, the ammonium salt is contacted with the metal compound in solution or in the solid state.
[00480] [00480] In certain embodiments, the method is useful for incorporating one or more doping elements into a nanowire. For example, the method may include treating at least one metal compound with a halide in the presence of at least one doping element, and the nanowire comprises at least one doping element. In some respects, at least one doping element is present in the nanowire in an atomic percentage ranging from 0.1 to 50 to%.
[00481] [00481] Other methods for the preparation of nanowires, in the absence of a biological model include the preparation of a metal hydroxide gel, by reacting at least one metal salt and a base. In some embodiments, the metal salt comprises a lanthanide halide and the resulting nanowire comprises a lanthanide oxide (for example, La2O3). For example, the method may further comprise aging the gel, heating the gel or combinations thereof. The aging or heating of the gel includes aging at temperatures ranging from room temperature (e.g., 20 ° C) or below to reflux for a time sufficient to produce the desired nanowires. In certain other embodiments, the method comprises the reaction of two or more different metal salts, and the nanowire comprises two or more different metals. In still other modalities, the method comprises the reaction of two or more salts of different metals, and the product comprises nanowires of two or more different metals.
[00482] [00482] Doping elements can also be incorporated using the hydroxide gel method described above, further comprising adding at least one doping element to the hydroxide gel, and wherein the nanowire comprises at least one doping element. For example, at least one doping element may be present in the nanowire in an atomic percentage ranging from 0.150 to 50%.
[00483] [00483] In some embodiments, metal oxide nanowires can be prepared by mixing a metal salt solution and an anion precursor so that a gel from a metal oxide precursor is formed. This method can work for cases where the typical morphology of the metal oxide precursor is a nanowire. The gel is heat treated so that the crystalline nanowires of the metal oxide precursor are formed. The precursor metal oxide nanowires are converted into the metal oxide nanowires, by calcination, plus chemical reaction or their combinations. In some embodiments, this method is useful for lanthanides and group 3 elements. In some embodiments, the thermal treatment of the gel is hydrothermal (or thermal solvo) at temperatures above the boiling point (at normal pressure) of the reaction mixture and at pressures above ambient pressure, in other embodiments it is carried out at ambient pressure and at temperatures equal to or below the boiling point of the reaction mixture. In some embodiments, the heat treatment is carried out under reflux conditions at a temperature equal to the boiling point of the mixture. In some specific embodiments, the anion precursor is a hydroxide, for example, ammonium hydroxide, sodium hydroxide, lithium hydroxide, tetramethyl ammonium hydroxide, and the like.
[00484] [00484] This method can be used to obtain mixed metal oxide nanowires, by mixing at least two solutions of metal salt and an anion precursor so that a mixed oxide precursor gel is formed. In such cases, the first metal can be a lanthanide or an element of group 3, and the other metals can be of other groups, including groups 1-14 and lanthanides.
[00485] [00485] In some different embodiments, metal oxide nanowires can be prepared in a similar manner to that described above by mixing a solution of metal salt and an anion precursor so that a gel from a metal hydroxide precursor is formed. This method works in cases where the typical morphology of the metal hydroxide precursor is a nanowire. The gel is treated so that the crystalline nanowires of the metal hydroxide precursor are formed. Metal hydroxide precursor nanowires are converted to metal hydroxide nanowires by base treatment and finally converted to metal oxide nanowires by calcination. In some embodiments, this method may be particularly applicable to elements in group 2, for example, Mg. In some specific embodiments, the gel treatment is a thermal treatment at temperatures in the range of 50-100 ° C, followed by hydrothermal treatment. In other modalities, gel treatment is an aging stage. In some modalities, the aging stage lasts at least one day. In some specific embodiments, the metal salt solution is a concentrated aqueous solution of metal chloride and the anion precursor is metal oxide. In some more specific modalities, the metal is Mg. In certain modalities of the above, these methods can be used to obtain mixed metal oxide nanowires. In these embodiments, the first metal is Mg and the other metal can be any other metal in groups 1-14 + Ln.
[00486] [00486] The present disclosure provides for the use of catalytic nanowires, as catalysts in catalytic reactions and related methods. In some embodiments, the catalytic reaction is any of the reactions described in this document. The morphology and composition of the catalytic nanowires are not limited and the nanowires can be prepared by any method. For example, nanowires can have a curved or linear morphology and can have any molecular composition. In some embodiments, nanowires have better catalytic properties than a corresponding catalyst in volume (that is, a catalyst that has the same chemical composition as the nanowire, but prepared from bulk material). In some embodiments, the nanowire showing better catalytic properties than a corresponding catalyst in volume has an effective length ratio to an actual length equal to one. In other embodiments, the nanowire showing better catalytic properties than a corresponding volume catalyst has a ratio between the effective length to the actual length of less than one. In other embodiments, the nanowire having better catalytic properties than a corresponding volume catalyst comprises one or more elements from Groups 1 to 7, lanthanides or actinides.
[00487] [00487] Nanowires can be useful in any number of reactions catalyzed by a heterogeneous catalyst. Examples of reactions in which nanowires that have catalytic activity can be used are revealed in Farrauto and Bartholomew, "Fundamentals of Industrial Catalytic Processes" Blackie Academic and Professional, first edition, 1997, which is incorporated here in its entirety. Other non-limiting examples of reactions in which nanowires with catalytic activity can be used include: oxidative coupling of methane
[00488] [00488] Nanowires are generally useful as catalysts in methods for converting a first carbon-containing compound (for example, a hydrocarbon, CO or CO2) into a second carbon-containing compound. In some embodiments, the methods comprise contacting a nanowire, or material comprising the same, with a gas comprising a first carbon-containing compound and an oxidizer to produce a carbon-containing compound. In some embodiments, the first carbon-containing compound is a hydrocarbon, CO, CO2, methane, ethane, propane, hexane, cyclohexane, octane or combinations thereof. In other embodiments, the second carbon-containing compound is a hydrocarbon, CO, CO2, ethane, ethylene, propane, propylene, hexane, hexene, cyclohexane, cyclohexane, bicyclohexane, octane, octene or hexadecane. In some embodiments, the oxidant is oxygen, ozone, nitrous oxide, nitric oxide, carbon dioxide, water or their combinations.
[00489] [00489] In other embodiments of the above, the method of converting a first carbon-containing compound to a second carbon-containing compound is carried out at a temperature below 100 ° C, below 200 ° C, below 300 ° C, below at 400 ° C, below 500 ° C, below 600 ° C, below 700 ° C, below 800 ° C, below 900 ° C or below 100 ° C. In other modalities, the method of covering a first carbon-containing compound in a second carbon-containing compound is carried out at a pressure above 0.5 ATM, above 1 ATM, above 2 ATM, above 5 ATM, above 10 ATM, over 25 ATM or over 50 ATM.
[00490] [00490] The catalytic reactions described in this document can be performed using laboratory equipment known to those skilled in the art, for example as described in US Patent number 6,350,716, which is incorporated herein in its entirety.
[00491] [00491] As noted above, the nanowires disclosed in this document have better catalytic activity than a catalyst in corresponding volume. In some embodiments, the selectivity, yield, conversion or combinations thereof of a reaction catalyzed by the nanowires is better than the selectivity, yield, conversion or combinations thereof of the same reaction catalyzed by the corresponding catalyst under the same conditions. For example, in some embodiments, the nanowire has a catalytic activity such that the conversion of the reagent in the product into a reaction catalyzed by the nanowire is greater than at least 1.1 times, greater than at least 1.25 times, greater than at least at least 1.5 times, greater than at least 2.0 times, greater than at least 3.0 times or greater than at least 4.0 times the conversion of the reagent into the product in the same reaction catalyzed by a catalyst prepared from the material by volume presenting the same chemical composition as the nanowire.
[00492] [00492] In other embodiments, the nanowire has a catalytic activity, such that the selectivity for the product in a reaction catalyzed by the nanowire is greater than at least 1.1 times, greater than at least 1.25 times, greater than at least 1.5 times, greater than at least 2.0 times, greater than at least 3.0 times or greater than at least 4.0 times the selectivity for the product in the same reaction, under the same conditions, but catalyzed by a catalyst prepared from the bulk material having the same chemical composition as the nanowire.
[00493] [00493] Still other modalities, the nanowire has a catalytic activity such that the yield of the product in a reaction catalyzed by the nanowire is greater than at least 1.1 times, greater than at least 1.25 times, greater than fur . less than 1.5 times, greater than at least 2.0 times, greater than at least 3.0 times or greater than at least 4.0 times the yield of the product in the same reaction, under the same conditions, but catalyzed by a catalyst prepared from the bulk material having the same chemical composition as the nanowire.
[00494] [00494] In yet other embodiments, the nanowire has a catalytic activity such that the activation temperature of a reaction catalyzed by the nanowire is at least 25 ° C lower, at least 50 ° C lower, at least 75 ° C lower, or at least 100 ° C lower than the temperature of the same reaction under the same conditions, but catalyzed by a catalyst prepared from volume material, with the same chemical composition as the nanowire.
[00495] [00495] In certain reactions (for example, OCM), production of undesirable carbon oxides (for example, CO and CO2) is a problem that reduces the overall yield of the desired product and results in an environmental responsibility. Thus, in one embodiment, the present disclosure solves this problem and provides nanowires with a catalytic activity such that the selectivity for CO and / or CO2, in a reaction catalyzed by nanowires is less than the selectivity for CO and / or CO2 in the same reaction and under the same conditions but catalyzed by a corresponding volume catalyst. Thus, in one embodiment, the present disclosure provides a nanowire that has a catalytic activity such that the selectivity for CO ,, where x is 1 or 2, in a reaction catalyzed by the nanowire is less than at least 0, 9 times, less than at least 0.8 times, less than at least 0.5 times, less than at least 0.2 times or less than at least 0.1 times the selectivity for CO, in the same reaction under the same conditions, but catalyzed by a catalyst prepared from material by volume, which has the same chemical composition as the nanowire.
[00496] [00496] In some embodiments, the absolute selectivity, yield, conversion, or combinations thereof of a reaction catalyzed by nanowires disclosed in this document are better than the absolute selectivity, yield, conversion, or combinations thereof, of the same reaction in the same conditions, but catalyzed by a corresponding volume catalyst. For example, in some embodiments the product yield in a reaction catalyzed by nanowires is greater than 20%, greater than 30%, greater than 50%, greater than 75%, or greater than 90%. In other embodiments, the selectivity for the product of a nanowire catalyzed reaction is greater than 20 ° / o, greater than 30 ° / o, greater than 50%, greater than 75%, or greater than 9 ° ° / o. In other embodiments, the conversion of the reagent to the product in a reaction catalyzed by nanowires is greater than 20%, greater than 3 ° / 0, greater than 5 ° / 0, greater than 75%, or greater than 9 ° / 0.
[00497] [00497] In addition to improving the catalytic performance of the disclosed nanowires, it is expected that the morphology of the nanowires will provide better mixing properties for the nanowires compared to standard colloidal catalyst materials (for example, by volume). The improved mixing properties are expected to improve the performance of any number of catalytic reactions, for example, in the area of heavy hydrocarbon transformation where transport and mixing phenomena are known to influence catalytic activity. In other reactions, the shape of the nanowires is expected to provide a good mix, reduce sedimentation, and provide easy separation of any solid material.
[00498] [00498] In some other chemical reactions, nanowires are useful for the absorption and / or incorporation of a reagent used in the chemical combustion cycle. For example, nanowires find use as NO traps, in unmixed combustion regimes, as oxygen storage materials, as CO2 adsorption materials (for example, cyclical reform with a high H2 yield) and in schemes for conversion of water to H2.
[00501] [00501] Cracking consumes a significant portion (about 65%) of the total energy used in the production of ethylene and the remainder is destined for separations using low temperature of distillation and compression. The total tons of CO2 emissions per ton of ethylene are estimated between 0.9 and 1.2 from the cracking of ethane and 1 to 2 from the cracking of naphtha.
[00502] [00502] Nanowires provide an alternative to the need for the cracking stage with intense use of energy. In addition, due to the high selectivity of nanowires, downstream separations are drastically simplified, compared to the fractionation that results in a wide range of hydrocarbon products. The reaction is also exothermic so that it can proceed through an autothermal process mechanism. In general, it is estimated that a potential to reduce CO2 emissions by up to 75% compared to conventional methods can be achieved. This amounts to a reduction of one billion tonnes of CO2 over a ten-year period and would save more than 1 M barrels of oil per day.
[00503] [00503] Nanowires also allow the conversion of ethylene into liquid fuels, such as gasoline or diesel, provide ethylene with high reactivity and several publications demonstrate high yield conversion reactions, in an iaboratory environment, from ethylene to gasoline and diesel . On a life cycle basis from fuel cycle analysis, a recent analysis of liquid methane (MTL) using gasoline derived from the F-T process and diese fuels! has shown an emission profile of approximately 20%
[00504] [00504] In addition, a considerable portion of natural gas is found in regions far from markets or gas pipelines. Most of this gas is burned, recirculated back into oil reservoirs, or vented due to its low economic value. The World Bank estimates that burning adds 400 M tonnes of CO2 to the atmosphere each year, as well as contributing to methane emissions. The nanowires of this present revelation also provide economic and environmental incentive! to prevent burning. In addition, the conversion of methane into fuel has several environmental advantages. in relation to fuel derived from oil. Natural gas is the cleanest of all fossil fuels, and does not contain a number of impurities, such as mercury and other heavy metals found in oil. In addition, dopants, including sulfur, are also easily separated from the initial flow of natural gas. The resulting fuels burn much cleaner, without measurable toxic pollutants and provide lower emissions than conventional diesel and gasoline in use today.
[00505] [00505] In view of their wide range of applications, the nanowires of this present disclosure can be used not only to selectively activate the alkanes, but also to activate other classes of inert non-reactive bonds, such as CF, C-Cl or CO bonds . This is important, for example, in the destruction of man-made environmental toxins, such as CFCS, PCBS, dioxins and other pollutants. Therefore, although the invention is described in more detail below in the context of the CCM reaction and other reactions described in this document, catalytic nanowires are in no way limited to this specific reaction.
[00506] [00506] The selective catalytic oxidative coupling of methane in ethylene (ie the OCM reaction) is shown by the following reaction (1): 2CH, + O, 3 CH, CH, + 2 H2O (1)
[00507] [00507] This reaction is exothermic (Reaction Heating -67kcals / mol) and generally occurs at very high temperatures (> 700 ° C). During this reaction, it is believed that methane (CH4) is first oxidatively coupled to ethane (C2H6), and subsequently, ethane (C2H6) is oxidatively dehydrogenated to ethylene (C2H4). Due to the high temperatures used in the reaction, it has been suggested that ethane is produced mainly by the coupling in the gas phase of the methyl radicals generated on the surface (CH3). Reactive metal oxides (oxygen-like ions) are apparently necessary for the activation of CH4 in order to produce the CH3 radicals. The yield of C2H4 and C2H6 is limited by other reactions in the gas phase and to some extent on the surface of the catalyst.
[00508] [00508] With conventional heterogeneous catalysts and reactor systems, reported performance is generally limited to <25% conversion of HC4 to <80% selectivity of C2 combined, with the characteristics of high selectivity in low conversion, or low selectivity in high conversion. In contrast, the nanowires of this present disclosure are highly active and, optionally, can operate at a much lower temperature. In one embodiment, the nanowires disclosed in this document allow an efficient conversion of methane to ethylene in the OCM reaction at lower temperatures than when the material in corresponding volume is used as a catalyst. For example, in one embodiment, the nanowires described in this document allow efficient conversion (i.e., high throughput, conversion, and / or selectivity) of methane to ethylene at temperatures below 900 ° C, below 800 ° C , less than 700 ° C, less than 600 ° C, or less than 500 ° C. In other modalities, the use of staggered oxygen addition, projected heat management, rapid saturation and / or advanced separations can be employed. Accordingly, one embodiment of the present description is a method for preparing ethane and / or ethylene, the method comprising converting methane to ethane and / or ethylene in the presence of a catalytic material, wherein the catalytic material comprises at least one catalytic nanowire, as disclosed herein.
[00509] [00509] Thus, in one embodiment, a highly active, high surface, stable area multifunctional nanowire catalyst is revealed to have active Sites that are isolated and precisely modified by engineering with catalytically active metal centers / sites in the desired proximity (see, for example, figure 1).
[00510] [00510] The exothermic heating of the reaction (free energy) follows the order of the reactions described above and, because of the proximity of the active sites, will mechanically favor the formation of ethylene, while minimizing the complete oxidation reactions that form CO and CO2. Representative nanowire compositions useful for the CMO reaction include, but are not limited to: highly basic oxides selected from the precursor members of the lanthanide oxide series; Group 1 or 2 ions supported on basic oxides, such as Li / MgO, Ba / MgO and Sr / La2O3; and single or mixed transition metal oxides, such as VO, and Re / Ru, which may also contain Group 1 ions.
[00511] [00511] As noted above, the nanowires presently described comprise a better performance than that corresponding to the volume catalysts, for example in one embodiment the catalytic performance of the nanowires in the OCM reaction is better than the catalytic performance of a corresponding volume catalyst. In this regard, several performance criteria can define the "catalytic performance" of catalysts in CMOs (and other reactions). In one embodiment, the catalyst performance is defined by the selectivity of C2 in the OCM reaction, and the C2 selectivity of the nanowires in the OCM reaction is> 5 ° / ,,> 10 ° / o,> 15 ° / o,> 20 ° / ,,> 25 ° / o,> 30 ° /),> 35%,> 40 ° / ,,> 45%,> 5 ° ° / o,> 55%,> 6Õ ° / o,> 65 ° / o, > 70%,> 75% or> 80%.
[00512] [00512] Other important performance parameters used to measure the catalytic performance of the nanowires in the OCM reaction are selected from the percentage conversion of single-pass methane (ie, the percentage of methane converted into a single pass through the catalyst or catallactic bed) , etc.), reaction gas temperature, reaction operating temperature, total reaction pressure, methane partial pressure, gas-hour space velocity (GHSV), O2 source, catalyst stability and ethylene ratio for ethane. In certain embodiments, a better catalytic performance is defined in terms of improving the performance of the nanowires (relative to a corresponding catalyst in volume) with respect to at least one of the preceding performance parameters.
[00514] [00514] The operating temperature of the reaction, in an OCM reaction catalyzed by the described nanowires can generally be maintained at a lower temperature, while maintaining the best performance characteristics, compared to the same reaction catalyzed by a catalyst in corresponding volume under the same reaction conditions. In certain modes at the reaction operating temperature, in an OCM reaction catalyzed by the revealed nanowires is "700 ° C," 675 ° C, "650 ° C, <625 ° C," 600 ° C, <593 ° C, "580 ° C," 570 ° C, <560 ° C, <550 ° C, <540 ° C, "530 ° C," 520 ° C, "510 ° C," 500 ° C, <490 ° C, <480 ° C, <470 ° C.
[00515] [00515] The conversion of single-pass methane into a reaction of
[00516] [00516] In certain embodiments, the total reaction pressure, in a nanowire catalyzed OCM reaction is "1 atm,> 1.1 atm,> 1.2 atm,> 1.3 atm,> 1.4 atm, > 1.5 atm,> 1.6 atm,> 1.7 atm,> 1.8 atm,> 1.9 atm,> 2 atm, "2.1 atm,> 2.1 atm,> 2.2 atm ,> 2.3 atm,> 2.4 atm,> 2.5 atm,> 2.6 atm,> 2.7 atm,> 2.8 atm,> 2.9 atm,> 3.0 atm,> 3.5 atm,> 4.0 atm,> 4.5 atm,> 5.0 atm,> 5.5 atm,> 6.0 atm,> 6.5 atm, "7, Oatm,> 7.5 atm,> 8.0 atm, "8.5 atm,> 9.0 atm,> 1O, Oatm,> 11.0 atm,> 12.0 atm,> 13.0 atm,> 14.0 atm,> 15.0 atm,> 16.0 atm,> 17.0 atm,> 18.0 atm,> 19, Oatmou> 20, Oatm. .
[00517] [00517] In certain other embodiments, the total reaction pressure in a nanowire catalyzed CMO reaction ranges from about 1 atm to about 10 atm, from about 1 atm to about 7 atm, about 1 atm at about 5 atm, about 1 atm at about 3 atm or from about 1 atm at about 2 atm.
[00519] [00519] In some embodiments, GSHV in a nanowire catalyzed OCM reaction is> 20.0OO / h,> 50.0OO / h,> 7500O / h,> 100.OOO/h,> 12000O / h,> 130.0OO / h,> 150.0OO / h,> 200.0OO / h,> 250.0OO / h,> 300.0OO / h,>
[00522] [00522] In some embodiments, the ethylene to ethane ratio in a nanowire catalyzed CMO reaction is better than the ethylene to ethane ratio in a CMO reaction catalyzed by a corresponding volume catalyst under the same conditions. In some embodiments, the ethylene to ethane ratio in a nanowire catalyzed CMO reaction is "0.3," 0.4,> 0.5,> 0.6,> 0.7,> 0.8,> 0.9,> 1,> 1J,> 1.2> 1.3,> 1.4,> 1.5,> 1.6,> 1.7,> 1.8,> 1.9,> 2.0,> 2.1,> 2.2,> 2.3,> 2.4,> 2.5,> 2.6,> 2.7,> 2.8,> 2.9,> 3.0,> 3.5,> 4.0,> 4.5> 5.0,> 5.5,> 6.0,> 6.5,> 7.0,> 7.5,> 8 , 0,> 8.5,> 9.0,> 9.5,> 10.0.
[00523] [00523] As noted above, the OCM reaction employing known volume catalysts suffers from poor yield, selectivity, or conversion. In contrast to a corresponding volume catalyst, applicants have found that certain nanowires, for example, the exemplary nanowires described in this document, have a catalytic activity in the CMO reaction, such that yield, selectivity and / or conversion is better than when the OCM reaction catalyzed by a corresponding volume catalyst. In one embodiment, the development provides a nanowire, with a catalytic activity, such that the conversion of methane to ethylene in the oxidative coupling of the methane reaction is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0 times or 4.0 times the conversion of methane to ethylene compared to the same reaction under the same conditions, but performed with a catalyst prepared from material in volume, with the same chemical composition than the nanowire. In other modalities, the conversion of methane to ethylene in a CMO reaction catalyzed by the nanowire is greater than 10 ° / o, greater than 20 ° / o, greater than 3 ° ° / o, greater than 50%, greater than 75% , or greater than 90 ° / o.
[00524] [00524] In another embodiment, the development provides a nanowire, with a catalytic activity, such that the ethylene yield in the oxidative methane coupling of the reaction is greater than at least 0.1 times, 1.25 times, 1 , 50 times, 2.0 times, 3.0 times or 4.0 times the ethylene yield compared to the same reaction under the same conditions, but performed with a catalyst prepared from material in volume, with the same chemical composition than the nanowire. In some embodiments, the ethylene yield in a CMO reaction catalyzed by the nanowire is greater than 10 ° / o, greater than 20 ° / o, greater than 3 ° / 0, greater than 5 ° / 0, greater than 75%, or greater than 90 ° / j.
[00525] [00525] As noted above, the OCM reaction employing known volume catalysts suffers from poor yield, selectivity, or conversion. In contrast to a corresponding volume catalyst, applicants have found that certain nanowires, for example, the exemplary nanowires described in this document, have a catalytic activity in the CMO reaction such that yield, selectivity and / or conversion are better than when the OCM reaction is catalyzed by a corresponding volume catalyst. In one embodiment, the development provides a nanowire, with a catalytic activity, such that the conversion of methane in the oxidative methane coupling reaction is at least greater than 1.1 times, 1.25 times, 1.50 times , 2.0 times, 3.0 times or 4.0 times methane conversion compared to the same reaction under the same conditions, but carried out with a catalyst prepared from volume material, with the same chemical composition as the nanowire . In other embodiments, the conversion of methane into a CMO reaction catalyzed by the nanowire is greater than 10 ° / o, greater than 20%, greater than 30%, greater than 5 ° ° / o, greater than 75%, or greater than
[00526] [00526] In another embodiment, the development provides a nanowire, with a catalytic activity, such that the C2 yield in the oxidative coupling of the methane reaction is greater than at least 1.1 times, 1.25 times, 1, 50 times, 2.0 times, 3.0 times or 4.0 times the C2 yield compared to the same reaction under the same conditions, but performed with a catalyst prepared from material in volume, with the same chemical composition as the nanowire. In some embodiments, the C2 yield in a CMO reaction catalyzed by the nanowire is greater than 10 ° / o, greater than 20%, greater than 30 ° / j, greater than 50 ° / o, greater than 75 ° / o, or greater than 9 ° / o. In some embodiments, the C2 yield is determined when the catalyst is used as a heterogeneous catalyst in the oxidative coupling of methane, at a temperature of 750 ° C or less, at 700 ° C or less, 650 ° C or less, or even 600 ° C or less. The yield of C2 can also be determined based on a single passage of a gas that comprises methane on the catalyst or can be determined based on multiple passages on the catalyst.
[00527] [00527] In another modality, the development provides a nanowire, with a catalytic activity in the OCM reaction, such that the nanowire has the same catalytic activity (that is, the same selectivity, conversion or yield), but at a lower temperature , compared to a catalyst prepared from bulk material having the same chemical composition as the nanowire. In some embodiments, the catalytic activity of the nanowires in the OCM reaction is the same as the catalytic activity of a catalyst prepared from bulk material, with the same chemical composition as the nanowire, but at a temperature of at least 20 ° C less . In some embodiments, the catalytic activity of the nanowires in the OCM reaction is the same as the catalytic activity of a catalyst prepared from bulk material, with the same chemical composition as the nanowire, but at a temperature of at least 50 ° C less . In some embodiments, the catalytic activity of the nanowires in the OCM reaction is the same as the catalytic activity of a catalyst prepared from material in volume, with the same chemical composition as the nanowire, but at a temperature of at least 100 ° C less . In some embodiments, the catalytic activity of the nanowires in the OCM reaction is the same as the catalytic activity of a catalyst prepared from material in volume, with the same chemical composition as the nanowire, but at a temperature of at least 20 ° C less .
[00528] [00528] In another embodiment, the development provides a nanowire with a catalytic activity, such that the selectivity for CO or CO2 in the oxidative methane coupling reaction is less than at least 0.9 times, 0.8 times, 0 , 5 times, 0.2 times, 0.1 times the selectivity for CO or CO2, compared to the same reaction under the same conditions, but performed with a catalyst prepared from material in volume, with the same chemical composition as the nanowire.
[00529] [00529] In some other embodiments, a method for converting methane to ethylene is provided comprising the use of a catalyst mixture comprising two or more catalysts. For example, the catalyst mixture can be a catalyst mixture having good OCM activity and catalyst showing good ODH activity. This catalyst mixture is described in more detail above.
[00530] [00530] Normally, the OCM reaction is performed on a mixture of oxygen and nitrogen or other inert gas. Such gases are expensive and increase the overall production costs associated with the preparation of ethylene from ethane or methane. However, the present inventors have now discovered that these expensive gases are not necessary and a high throughput, conversion, selectivity, etc., can be obtained when using air as a mixture of gases instead of sources of oxygen and other pre- packaged and purified. So, in one embodiment, the development provides a method for carrying out the OCM reaction in air.
[00531] [00531] In addition to air or O2 gas, the currently disclosed nanowires and associated methods provide use of other oxygen sources in the OCM reaction.
[00532] [00532] As noted above, in the OCM reaction, methane is converted by oxidation to the methyl radicals which are then coupled to form ethane, which is subsequently oxidized to ethylene. In traditional CMO reactions, the oxidizing agent for both the formation of methyl radicals and the oxidation of ethane to ethylene is oxygen. In order to minimize the complete oxidation of methane or ethane to carbon dioxide, that is, to maximize the selectivity of C2, the ratio of methane to oxygen is generally maintained at 4 (that is, the total conversion of methane to methyl radicals) or above. As a result, the OCM reaction is typically limited to oxygen and thus the oxygen concentration in the effluent is zero.
[00533] [00533] Thus, in one embodiment the present disclosure provides a method for increasing the conversion of methane and adding, or in some embodiments, not reducing, the selectivity of C2 in an OCM reaction. The methods described include the addition of a traditional CMO catalyst or another CMO catalyst that uses an oxygen source other than molecular oxygen. In some modalities, the alternative oxygen source is CO2, H2O, SO2, SO3 or combinations thereof. For example, in some modalities, the alternative oxygen source is CO2. In other modalities the alternative oxygen source is H2O.
[00534] [00534] Since C2 selectivity is typically between 5Õ ° / o and 80 ° / o in the OCM reaction, OCM typically produces significant amounts of CO2 as a by-product (CO2 selectivity typically can vary between 20-50 ° / o ). In addition, H2O is produced in abundant quantities, regardless of C2 selectivity. Therefore, both CO2 and H2O would be attractive oxygen sources for OCM in an impoverished O2 environment.
[00535] [00535] Therefore, one embodiment of the present description provides a catalyst (and methods related to its use) that is catalytic in the CMO reaction and that uses CO2, H2O, SO2, SO3 or another alternative oxygen source or combinations of themselves, as a source of oxygen.
[00536] [00536] Examples of CMO catalysts that use CO2 or other oxygen sources instead of O2 include, but are not limited to, catalysts comprising La2O3 / ZnO, CeO2 / ZnO, CaO / ZnO, CaO / CeO2, CaO / Cr2O3, CaO / MnO2, SrO / ZnO, SrO / CeO ,, SrO / Cr, O ,, SrO / MnO ,, SrCO, / MnO2, BaO / ZnO, BaO / CeO ,, BaO / Cr, O ,, BaO / MnO, , CaO / MnO / CeO2, Na2WO4 / Mn / SiO2, Pr2O3, Tb2O3.
[00537] [00537] Some embodiments provide a method for performing OCM, in which a mixture of an OCM catalyst that uses O2 as an oxygen source (referred to in this document as an O2-OCM catalyst), and an OCM catalyst which uses CO2 as an oxygen source (referred to in this document as a CO2-OCM catalyst) is used as the catalytic material, for example, a catalyst bed. Such methods have certain advantages. For example, the CO2-OCM reaction is endothermic and the O2-OCM reaction is exothermic and, therefore, if direct mixing and / or arrangement of the CO2 catalysts - OCM and O2-OCM is used, the methods are particularly useful for control the exotherm of the CMO reaction. In some embodiments, the catalyst bed comprises a mixture of O2-OCM catalyst and CO2-OCM catalysts. The mixture can be in a ratio of 1:99 to 99: 1. The two catalysts work synergistically as the O2-OCM catalyst supplies the CO2-OCM catalyst with the necessary carbon dioxide and the endothermic nature of the C2-OCM reaction serves to control the exotherm of the overall reaction. Alternatively, the CO2 source can be external to the reaction (for example, fed from a CO2 tank, or from another source) and / or the heat required for the CO2-OCM reaction is supplied from an external source (for example, reactor heating).
[00539] [00539] The O2-OCM catalyst and the CO2-OCM catalyst can have the same or different compositions. For example, in some embodiments, the O2-OCM catalyst and the CO2-OCM catalyst have the same composition, but different morphologies (for example, nanowires, folded nanowires, volume etc.). In other embodiments, the O2-OCR catalyst and the CO2-OCM catalyst have different compositions.
[00540] [00540] In addition, CO2-OCM catalysts usually have greater selectivity, but lower yields than an O2-OCM catalyst. Thus, in one embodiment, the methods comprise the use of a mixture of an O2-OCM catalyst and a CO2-OCM catalyst and perform the reaction in an O2-free environment, so that the CO2-OCM reaction is favored and the selectivity is greater. Under suitable conditions, the throughput and selectivity of the OCM reaction can thus be optimized.
[00541] [00541] In some other embodiments, the catalyst bed comprises a mixture of one or more O2-OCM catalysts at low temperature (i.e., a catalyst active at low temperatures, for example, less than 700 ° C) and one or more CO2-OCM catalysts at high temperature (ie, a catalyst active at high temperatures, for example 800 ° C or more). Here, the high temperature required for CO2-OCM can be provided by the heated points produced by the O2-OCM catalyst. In such a scenario, the mixture may be sufficiently coarse so that the access points are not excessively cooled by excessive dilution.
[00543] [00543] In some embodiments, the catalyst bed comprises alternating layers of low temperature O2-OCM catalysts and high temperature CO2-OCM catalysts. Since the CO2-OCM reaction is endothermic, layers of CO2-OCM catalyst can be thin enough to be "heated" by the heated points of the O2-OCM layers. The endothermic nature of the CO2-OCM reaction can be advantageous for the total thermal management of an OCM reactor. In some embodiments, the CO2-OCM catalyst layers act as "internal" cooling for the O2-OCM layers, thus simplifying the requirements for cooling, for example, in a tubular reactor. Therefore, an interesting cycle occurs with the endothermic reaction providing the necessary heat for the endothermic reaction and the endothermic reaction providing the necessary cooling for the exothermic reaction.
[00544] [00544] Accordingly, one embodiment of the present invention is a method for oxidative coupling of methane, wherein the method comprises conversion of methane to ethane and / or ethylene, in the presence of a catalytic material, and wherein the catalytic material comprises a bed of combined layers of O2-OCM catalysts and CO2-OCM catalysts. In other embodiments, the bed comprises a mixture (i.e., not alternating layers) of O2-OCM catalysts and CO2-OCM catalysts.
[00545] [00545] In other modalities, OCM methods include the use of a caged reactor with the exothermic reaction of O2-OCM in the core and the endothermic reaction of CO2-OCM in the mantle. In other modalities, unused CO2 can be recycled and reinjected in the reactor, optionally with recycled CH4. Additional CO2 can also be injected to increase the global methane conversion and help reduce greenhouse gases.
[00546] [00546] In other embodiments, the reactor comprises the alternating phases of O2-OCM catalyst and CO2-OCM catalyst beds. The CO2 required for the CO2-OCM stages is provided by the upstream O2-OCM phase. Additional CO2 can also be injected. The O2 required for the subsequent O2-OCM phases is injected downstream of the CO2-OCM phases. The CO2-OCM phases can provide the necessary cooling for the O2-OCM phases. Alternatively, separate cooling may be provided. Likewise, if necessary, the intake gas of the CO2-OCM phases can be heated further, the CO2-OCM bed can be heated or both.
[00547] [00547] In related modalities, the CO2 that occurs naturally in natural gas is not removed before making CMO, alternatively, CO2 is added to the feed with recycled methane. Instead, CO2-containing natural gas is used as a raw material for CO2-OCM, thus potentially saving a separation step. The amount of naturally occurring CO2 from natural gas depends on the analysis and the methods can be adjusted accordingly, depending on the source of natural gas.
[00548] [00548] The preceding methods can be generalized as a method to control the temperature of very exothermic reactions by coupling them to an endothermic reaction that uses the same raw material (or by-products of the exothermic reaction) to obtain the same product (or a related product). This concept can be reversed, that is, supplying heat to an endothermic reaction through its coupling with an exothermic reaction.
[00549] [00549] For the sake of simplicity, the description above related to the use of the O2-OCM and CO2-OCM catalysts was carried out with reference to the oxidative methane coupling (OCM); however, the same concept is applicable to other catalytic reactions, including, but not limited to, oxidative dehydrogenation (ODH) of alkanes in their corresponding alkenes, selective oxidation of alkanes and alkenes and alkynes, etc. For example, in a related modality a catalyst is provided capable of using an alternative source of oxygen (for example, CO2, H2O, SO2, SO3 or combinations thereof) to catalyze. oxidative dehydrogenation of ethane. Such catalysts, and their uses, are described in more detail below.
[00550] [00550] In addition, the above methods are applicable for creating new catalysts by mixing catalysts that use different reagents for the same catalytic reactions, for example, different oxidants for an oxidation reaction and at least one oxidant is a by-product of one of the catalytic reactions. In addition, the methods can also be generalized to control internal temperature reactors, mixing the catalysts that catalyze reactions that share the same or similar products, but are exothermic and endothermic, respectively. These two concepts can also be coupled together.
[00551] [00551] The worldwide demand for alkenes, mainly ethylene and propylene, is high. The main sources for alkenes include steam cracking,
[00552] [00552] In one embodiment, the disclosed nanowires are useful as catalysts for the oxidative dehydrogenation (ODH) of hydrocarbons (for example, tannins, alkenes and alkynes). For example, in one embodiment, nanowires are useful as catalysts in ODH reactions for the conversion of ethane or propane to ethylene or propylene, respectively. The reaction scheme (9) represents the oxidative dehydrogenation of hydrocarbons: C, Hy + '4 O23CXHy-2 + H2O (9)
[00553] [00553] Representative catalysts useful for the ODH reaction include, but are not limited to, nanowires comprising Zr, V, Mo, Ba, Nd, Ce, Ti, Mg, Nb, La, Sr, Sm, Cr, W, Y or Ca or oxides or combinations thereof. Activation promoters (i.e., dopants) comprising P, K, Ca, Ni, Cr, Nb, Mg, Au, Zn, Mo or their combinations, can also be employed.
[00554] [00554] As mentioned above, improvements in yield, selectivity and / or conversion in the ODH reaction using volume catalysts are necessary. Thus, in one embodiment, the present disclosure provides a nanowire that has a catalytic activity in the ODH reaction, such that the yield, selectivity and / or conversion are better than when the ODH reaction is catalyzed by a volume catalyst corresponding. In one embodiment, the development provides a nanowire, with a catalytic activity, so that the conversion of hydrocarbon to aicene in the ODH reaction is greater than at least 1.1 times, 1.25 times, 1.50 times, 2 , 0 times, 3.0 times or 4.0 times the conversion of alkane to alkene compared to the same reaction under the same conditions, but performed with a catalyst prepared from the material in volume, with the same chemical composition of the nanowire. In other embodiments, the conversion of the hydrocarbon to alkene in an ODH reaction catalyzed by the nanowire is greater than 10%, greater than 2 ° / 0, greater than 30 ° / 0, greater than 5 ° / 0, greater than 75% or greater than 90 ° / o.
[00555] [00555] In another embodiment, the development provides a nanowire, with a catalytic activity such that the yield of the alkene in an ODH reaction is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0 times, or rf · 4.0 times the yield of alkenes compared to the same reaction under the same conditions, but performed with a catalyst prepared from "volume material, with the same chemical composition In some embodiments, the yield of the alkene in an ODH reaction catalyzed by the nanowire is greater than 10%, greater than 20%, greater than 30 ° / o, greater than 5 ° ° / o, greater than 75% or greater at 90 ° / j In another embodiment, the development provides a nanowire, with a catalytic activity in the ODH reaction so that the nanowire has the same catalytic activity, but at a lower temperature, compared to a catalyst prepared from the material in volume, with the same chemical composition as the nanowire. In some modalities the catallactic activity of n anions in the ODH reaction is the same or better than the catalytic activity of a catalyst prepared from materia! by volume, with the same chemical composition as the nanowire, but at a temperature of at least 20 ° C less. In some embodiments, the catalytic activity of the nanowires in the ODH reaction is the same or better than the catalytic activity of a catalyst prepared from bulk material, with the same chemical composition as the nanowire, but at a temperature of at least 50 ° C any less. In some embodiments, the catalytic activity of the nanowires in the ODH reaction is the same or better than the catalytic activity of a catalyst prepared from material in volume, with the same chemical composition as the nanowire, but at a temperature of at least 100 ° C any less. In some embodiments, the catalytic activity of the nanowires in the ODH reaction is the same or better than the catalytic activity of a catalyst prepared from bulk material, with the same chemical composition as the nanowire, but at a temperature of at least 200 ° C any less.
[00556] [00556] In another embodiment, the development provides a nanowire, with a catalytic activity such that the selectivity for alkenes in an ODH reaction is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0 times, or 4.0 times the selectivity for the alkenes compared to the same reaction under the same conditions, but performed with a catalyst prepared from material in volume, with the same chemical composition than the nanowire. In "other modalities, the selectivity for alkenes in an ODH reaction catalyzed by the nanowire is greater than 50 ° / o, greater than 6Õ ° / o, greater than 70%, greater than 8Õ ° / o, greater than 90%, or greater than 95%.
[00557] [00557] In another embodiment, the development provides a nanowire, with a catalytic activity such that the selectivity for CO or CO2, in an ODH reaction is less than at least 0.9 times, 0.8 times, 0 , 5 times, 0.2 times or 0.1 times selectivity for CO or CO2, compared to the same reaction under the same conditions, but performed with a catalyst prepared from material in volume, with the same chemical composition as the nanowire.
[00558] [00558] In one embodiment, the nanowires disclosed in this document allow an efficient conversion of hydrocarbon to aicene in the ODH reaction at lower temperatures than when the corresponding volume material is used as a catalyst. For example, in one embodiment, the nanowires described in this document allow efficient conversion (i.e., high throughput, conversion, and / or selectivity) of hydrocarbon to alkene at temperatures of less than 800 ° C, less than 700 ° C, less than 600 ° C, less than 500 ° C, less than 400 ° C, or less than 300 ° C.
[00559] [00559] The stability of nanowires is defined as the period of time that a catalyst will maintain its catalytic performance, without a significant reduction in performance (for example, a reduction> 2 ° / ,,> 15 ° / 0,> 10 ° / o,> 5 ° / 0, or greater than i ° / o in ODH activity or alkene selectivity, etc.) In some embodiments, nanowires are stable under conditions required for the ODH reaction of> 1 hour,> 5 hours,> 10 hours,> 20 hours,> 50 hours,> 80 hours,> 90 hours,> 100 hours,> 150 hours,> 200 hours,> 250 hours,> 300 hours,> 350 hours,> 400 hours, > 450 hours,> 500 hours,> 550 hours,> 600 hours,> 650 hours,> 700 hours,> 750 hours,> 800 hours,> 850 hours,> 900 hours, 950 hours>,> 1,000 hours,> 2,000 hours, 3,000 hours>,> 4,000 hours,> 5,000 hours,> 6,000 hours,> 7,000 hours,> 8,000 hours,> 9,000 hours,> 10,000 hours,> 11,000 hours,> 12,000 hours,> 13,000 hours,> 14,000 hours,> 15,000 hours,> 16,000 hours,>
[00561] [00561] where x is an integer and Y represents 2x + 2. Compositions useful in this regard include Fe2O3, Cr2O3, MnO2, Ga2O3, Cr / SiO2, Cr / SOrSiO ,, Cr-k / SO, -SiO, , Na, WO4-Mn / SiO ,, Cr-HZSM-5, Cr / Si-MCM-41 (Cr-
[00562] [00562] Catalysts that have ODH activity with alternative oxygen sources (eg CO2, here referred to as a CO2-ODH catalyst) have numerous advantages. For example, in some embodiments, a process for converting methane to ethylene is provided, comprising the use of an O2-OCM catalyst, in the presence of a CO2-ODH catalyst. Catalytic materials comprising at least one O2-OCM catalyst and at least one CO2-ODH catalyst are also provided in some embodiments. This combination of catalysts results in a higher ethylene yield (and / or ethylene to ethane ratio) since the CO2 produced by the OCM reaction is consumed and used to convert ethane into ethylene.
[00563] [00563] In one embodiment, a method for the preparation of ethylene comprises the conversion of methane to ethylene in the presence of two or more catalysts, wherein at least one catalyst is an O2-OCM catalyst and at least one catalyst is a CO2-ODH catalyst. Such methods have certain advantages. For example, the CO2-ODH reaction is endothermic and the O2-OCM reaction is exothermic, so if the mixture and / or arrangement of CO2-ODH and O2-OCM catalysts are used, the methods will be particularly useful for controlling the exotherm of the OCM reaction. In some embodiments, the catalyst bed comprises a mixture of O2-OCM catalyst and CO2-ODH catalysts. The mixture can be in a ratio of 1:99 to 99: 1. The two catalysts work synergistically as the O2-OCR catalyst supplies the CO2-ODH catalyst with the necessary carbon dioxide and the endothermic nature of the C2-OCM reaction serves to control the exotherm of the global reaction !.
[00564] [00564] Since the composition of the gas will tend to become enriched in CO2 as it flows through the catalyst bed (i.e., as the OCM reaction proceeds, more CO2 is produced), some of the embodiments of the present invention provide a OCM method where the catalyst bed comprises a gradient of catalysts that changes from a high concentration of O2-OCM catalysts at the beginning of the bed to a high concentration of ODH catalysts in CO2! the catalyst bed.
[00565] [00565] The O2-OCM catalyst and the CO2-OCM catalyst can have the same or different compositions. For example, in some embodiments, the O2-OCM catalyst and the CO2-OCM catalyst have the same composition, but different morphologies (for example, nanowires, folded nanowires, volume etc.). In other embodiments, the O2-OCR catalyst and the CO2-OCM catalyst have different compositions.
[00566] [00566] In other embodiments, the catalyst effect comprises alternating layers of O2-OCM and CO2-ODH catalysts. The stack of catalyst layers can start with an O2-OCM catalyst layer, so that it can provide the next layer (for example, a CO2-ODH layer) with the necessary CO2. The thickness of the O2-OCM layer can be optimized to be the smallest in which the Q2 conversion is 100 ° / o and, therefore, the CH4 conversion of the layer is maximized. The bed of the catalyst can comprise any number of layers of catalyst, for example, the total number of layers can be optimized to maximize the total CH4 conversion and C2 seivity.
[00567] [00567] In some embodiments, the catalyst bed comprises alternating layers of low temperature O2-OCM catalysts and high temperature CO2-ODH catalysts. Since the CO2-ODH reaction is endothermic, layers of CO2-ODH catalyst can be thin enough to be "heated" by the heating points of the O2-OCM layers.
[00568] [00568] Accordingly, one embodiment of the present invention is a method for oxidative coupling of methane, wherein the method comprises converting methane to ethane and / or ethylene, in the presence of a catalytic material, and wherein the catalytic material comprises a bed of alternating layers of O2-OCM catalysts and CO2-ODH catalysts. In other embodiments, the bed comprises a mixture (i.e., not alternating layers) of O2-OCM catalysts and CO2-ODH catalysts. Such methods increase the ethylene yield and / or the ethylene to ethane ratio compared to other known methods.
[00569] [00569] In other modalities, OCM methods include the use of a caged reactor with the exothermic O2-OCM reaction in the core and the CO2 -ODH endothermic reaction in the blanket. In other modalities, the unused CÔ2 can be recycled and reinjected in the reactor, optionally with the recycled CH4. Additional CO2 can also be injected to increase the global methane conversion and help reduce greenhouse gases.
[00570] [00570] In other embodiments, the reactor comprises the alternating phases of O2-OCM catalyst beds and CO2-ODH catalyst beds. The CO2 required for the CO2-ODH phases is supplied by the step upstream of O2-
[00571] [00571] In related modalities, the CO2 that occurs naturally in natural gas is not removed prior to the CMO, alternatively, the CO2 is added to the feed with recycled methane. Instead, the CO2 that contains natural gas is used as a raw material for CO2-ODH, therefore potentially saving a separation step. The number of natural occurrences of CO2 in natural gas depends on the analysis and the methods can be adjusted accordingly, depending on the source of the natural gas.
[00572] [00572] The reform of methane with carbon dioxide (CDR) is an attractive process for converting CO2 into process streams or sources that occur naturally in valuable chemical, synthesis gas (a mixture of hydrogen and carbon monoxide) . Synthesis gas can then be manufactured in a wide variety of hydrocarbon products using processes such as Fischer-Tropsch synthesis (discussed below) to form liquid fuels, including methanol, ethanol, diesel oil and gasoline. The result is a powerful technique not only to remove CO2 emissions, but also to create a new alternative source of fuels that are not derived from crude oil.The reaction of CDR with methane is exemplified in the reaction scheme (11).
[00575] [00575] In one embodiment, the present disclosure provides nanowires, for example, the exemplary nanowires disclosed in this document, which are useful as catalysts for the reforming of methane with carbon dioxide. For example, in one embodiment, nanowires are useful as catalysts or a CDR reaction for the production of syngas.
[00577] [00577] In another embodiment, the development provides a nanowire, with a catalytic activity such that the CO yield in a CDR reaction is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0 times, or 4.0 times the CO yield compared to the same reaction under the same conditions, but performed with a catalyst prepared from volume material, with the same chemical composition as nanowire. In some embodiments, the CO yield in a nanowire catalyzed CDR reaction is greater than 10 ° / o, greater than 24%, greater than 30%, greater than 50%, greater than 75%, or greater than 9 ° / o.
[00580] [00580] In one embodiment, the nanowires disclosed in this document allow an efficient conversion of CO2 to CO in the CDR reaction at lower temperatures than when the material in corresponding volume is used as a catalyst. For example, in one embodiment, nanowires allow efficient conversion (i.e., high throughput, conversion, and / or selectivity) of CO2 to CO at temperatures of less than 900 ° C, less than 800 ° C, less than
[00581] [00581] Fischer-Tropsch synthesis (FTS) is an important process for converting synthesis gas (i.e. CO and H2) into valuable hydrocarbon fuels, for example, light alkenes, gasoline, diesel, etc. FTS has the potential to reduce current dependence on oil reserves and take advantage of the abundance of coal and natural gas reserves. Current FTS processes suffer from poor performance, selectivity, conversion, catalyst deactivation, low thermal efficiency and other related disadvantages. The production of alkanes through FTS is shown in the reaction scheme (14), where n is an integer.
[00582] [00582] In one embodiment, nanowires are provided and are useful as catalysts in FTS processes. For example, in one embodiment, nanowires are useful as catalysts in an FTS process for the production of alkanes.
[00583] [00583] Improvements are required for yield, selectivity, and / or conversion to FTS processes using volume catalysts. Thus, in one embodiment, the nanowires have a catalytic activity in an FTS process, such that the yield, selectivity and / or conversion are better than when the FTS process is catalyzed by a catalyst in a corresponding volume. In one embodiment, the development provides a nanowire with a catalytic activity such that the conversion of CO to alkane in an FTS process is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0 times or 4.0 times the conversion of CO to alkane compared to the same reaction under the same conditions, but performed with a catalyst prepared from material! by volume, with the same chemical composition as the nanowire. In other modalities, the conversion of CO to African in an FTS process catalyzed by the nanowire is greater than 10 ° / 0, greater than 20%, greater than 3 ° / 0,
[00584] [00584] In another embodiment, the development provides a nanowire, with a catalytic activity in a process such that the SFT nanowire has the same or better catalytic activity, but at a lower temperature, compared to a catalyst prepared from volume by volume, with the same chemical composition as the nanowire.
[00586] [00586] In another embodiment, the development provides a nanowire, with a catalytic activity such that the yield of the alkane in an FTS process is greater than at least 1.1 times, 1.25 times, 1.50 times , 2.0 times, 3.0 times, or 4.0 times the alkane yield compared to the same reaction under the same conditions, but performed with a catalyst prepared from material in volume, with the same chemical composition as the nanowire. In some embodiments, the yield of alkane in a nanowire catalyzed FTS process is greater than 10%, greater than 20 ° / o, greater than 30%, greater than 50 ° / o, greater than 75 ° / o or greater than 9O ° / j.
[00587] [00587] In another embodiment, the development provides a nanowire, with a catalytic activity such that the selectivity of the alkanes in an FTS process is greater than at least 1.1 times, 1.25 times, 1.50 times , 2.0 times, 3.0 times, or 4.0 times the selectivity for alkanes compared to the same reaction under the same conditions, but performed with a catalyst prepared from material in volume, with the same chemical composition as the nanowire. In other modalities, the selectivity for alkanes in an FTS process catalyzed by the nanowire is greater than 10 ° / 0, greater than 20 ° / 0, greater than 30 ° / 0, greater than 5 ° / 0, greater than 75% or greater than 90 ° / o.
[00588] [00588] In one embodiment, the nanowires disclosed in this document allow an efficient conversion of CO in alkanes in a CDR process at lower temperatures than when the material in corresponding volume is used as a catalyst. For example, in one embodiment, nanowires allow efficient conversion (ie, high throughput, conversion, and / or selectivity) of CO to alkanes at temperatures of less than 400 ° C, less than 300 ° C, less than 250 ° C, less than 200 ° C, less than 150 ° C, less than 100 ° C or less than 50 ° C.
[00590] [00590] Catalysts for converting CO to CO2 have been developed, but improvements are needed for known catalysts.
[00591] [00591] In one embodiment, nanowires have a catalytic activity, in a process for converting CO to CO2 so that yield, selectivity and / or conversion are better than when the oxidation of CO to CO2 is catalyzed by a catalyst corresponding volume. In one embodiment, the development provides a nanowire, with a catalytic activity such that the conversion of CO to CO2 is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times , 3.0 times, 4.0 times the conversion of CO to CO2, compared to the same reaction under the same conditions, but carried out with a catalyst prepared from material in volume and with the same chemical composition as the nanowire. In other embodiments, the conversion of CO into CO2 catalyzed by the nanowire is greater than 10 ° / 0, greater than 20 ° / 0, greater than 30 ° / 0, greater than 50 ° / 0, greater than 75% or greater than 90 %.
[00592] [00592] In another embodiment, the development provides a nanowire, with a catalytic activity such that the CO2 yield from CO oxidation is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0 times, 4.0 times the CO2 yield, compared to the same reaction under the same conditions, but performed with a catalyst prepared from material in volume, with the same chemical composition as the nanowire. In some embodiments, the CO2 yield from CO oxidation, catalyzed by the nanowire is greater than 10 ° / o, greater than 2 ° / 0, greater than 30 ° / j, greater than 50 ° / o, greater than 75 % or greater than 90 ° / o.
[00593] [00593] In another embodiment, the development provides a nanowire, with a catalytic activity of a CO oxidation reaction so that the nanowire has the same or better catalytic activity, but at a lower temperature, compared to a catalyst prepared from bulk material, with the same chemical composition as the nanowire. In some embodiments, the catalytic activity of the nanowires in an oxidation of the CO reaction is the same or better than the catalytic activity of a catalyst prepared from material in volume, with the same chemical composition as the nanowire, but at a temperature of at least minus 20 ° C less. In some embodiments, the catalytic activity of the nanowires in an oxidation of the CO reaction is the same or better than the catalytic activity of a catalyst prepared from bulk material, with the same chemical composition as the nanowire, but at a temperature of at least minus 50 ° C less. In some embodiments, the catalytic activity of the nanowires in an oxidation of the CO reaction is the same or better than the catalytic activity of a catalyst prepared from bulk material, with the same chemical composition as the nanowire, but at a hair temperature minus 100 ° C minus. In some embodiments, the catalytic activity of the nanowires in an oxidation of the CO reaction is the same or better than the catalytic activity of a catalyst prepared from bulk material, with the same chemical composition as the nanowire, but at a temperature of at least minus 200 ° C less.
[00594] [00594] In another embodiment, the development provides a nanowire, with a catalytic activity such that the selectivity for CO2 in the oxidation of CO is greater than at least 1.1 times, 1.25 times, 1.50 times , 2.0 times, 3.0 times or 4.0 times selectivity for CO2, compared to the same reaction under the same conditions, but performed with a catalyst prepared from material in volume, with the same chemical composition as the nanowire. In other embodiments, the selectivity for CO2 in the CO oxidation catalyzed by the nanowire is greater than 10 ° / j, greater than 20 ° / o, greater than 30 ° / o, greater than 50%, greater than 75% or greater than 90 ° / o.
[00595] [00595] In one embodiment, the nanowires disclosed in this document allow an efficient conversion of CO to CO2 at lower temperatures than when the material in corresponding volume is used as a catalyst. For example, in one embodiment, nanowires allow efficient conversion (ie, high throughput, conversion, and / or selectivity) of CO to CO2 at temperatures of less than 500 ° C, less than 400 ° C, less than 300 ° C, less than 200 ° C, less than 100 ° C, less than 50 ° C or less than 20 "C.
[00596] [00596] Although several reactions have been described in detail, the disclosed nanowires are useful as catalysts in a variety of other reactions. In general, the nanowires described find utility in any reaction using a heterogeneous catalyst and have a catalytic activity such that the yield, conversion and / or selectivity of the reaction catalyzed by the nanowires are better than the yield, conversion and / or selectivity of the same reaction catalyzed by a corresponding volume catalyst.
[00597] [00597] In another embodiment, the present disclosure provides a nanowire having catalytic activity in a reaction for the catalyzed combustion of hydrocarbons. Such catalytic reactions find utility in catalytic converters for automobiles, for example, by removing unburned hydrocarbons in the exhaust gases by catalytic combustion or soot oxidation captured in the catalyzed particulate filters resulting in the reduction of diesel emissions from the engine. When operating "cold", the exhaust temperature of a diesel engine is quite low, so a low temperature catalyst, such as the disclosed nanowires, is necessary to efficiently eliminate all unburned hydrocarbons. Furthermore, in the case of removing soot from the catalyzed particulate filter, an intimate contact between the soot and the catalyst is necessary; the open-mesh morphology of the catalytic nanowire coating is advantageous to promote this intimate contact between soot and oxidation catalyst.
[00598] [00598] In contrast to a corresponding volume catalyst, applicants have found that certain nanowires, for example, the exemplary nanowires described in this document have a catalytic activity (for example, due to their morphology) in the combustion of hydrocarbons or soot, in such a way so that the yield, selectivity, and / or conversion are better than when the combustion of hydrocarbons is catalyzed by a catalyst in corresponding volume. In a modality, the revision provides a nanowire, with a catalytic activity such that the combustion of hydrocarbons is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0 times or 4.0 times the combustion of hydrocarbons compared to the same reaction under the same conditions, but performed with a catalyst prepared from material in volume, with the same chemical composition as the nanowire. In other embodiments, the total combustion of hydrocarbons catalyzed by the nanowire is greater than 10 ° / j, greater than 20%, greater than 30%, greater than 50%, greater than 75% or greater than 90%.
[00599] [00599] In another embodiment, the development provides a nanowire, with a catalytic activity such that the yield of the burned hydrocarbon products is greater than at least 1.1 times, 1.25 times, 1.50 times , 2.0 times, 3.0 times or 4.0 times the yield of burnt hydrocarbon products, compared to the same reaction under the same conditions, but performed with a catalyst prepared from material in volume, with the same composition chemical than the nanowire. In some embodiments, the yield of hydrocarbon products burned in a reaction catalyzed by the nanowire is greater than 10 ° / 0, greater than 20%, greater than 30%, greater than 50%, greater than 75% or greater than 9 ° ° / ,.
[00601] [00601] In another embodiment, the development provides a nanowire, with a catalytic activity in the combustion of hydrocarbons, so that the nanowire has the same or a better catalytic activity, but at a lower temperature, in comparison with a catalyst prepared from volume material, which has the same chemical composition as the nanowire. In some embodiments, the catalytic activity of nanowires in the combustion of hydrocarbons is the same or better than the catalytic activity of a catalyst prepared from bulk material, with the same chemical composition as the nanowire, but at a temperature of at least 20 ° C minus. In some embodiments, the catalytic activity of the nanowires in hydrocarbon combustion is the same or better than the catalytic activity of a catalyst prepared from bulk material, with the same chemical composition as the nanowire, but at a temperature of at least 50 ° C minus. In some embodiments, the catalytic activity of the nanowires in the combustion of hydrocarbons is the same or better than the catalytic activity of a catalyst prepared from bulk material, with the same chemical composition as the nanowire, but at a temperature of at least 100 ° C minus. In some embodiments, the catalytic activity of the nanowires in the combustion of hydrocarbons is the same or better than the catalytic activity of a catalyst prepared from bulk material, with the same chemical composition as the nanowire, but at a temperature of at least 200 ° C minus.
[00602] [00602] To evaluate the catalytic properties of the nanowires of a given reaction, for example, the reactions mentioned above, several methods can be used to collect and process data, including measurements of the kinetics and quantities of reagents consumed and the products formed. In addition to allowing the assessment of catalytic performance, the data can also help in the design of large-scale reactors, experimentally validate the models and optimize the catalytic process.
[00603] [00603] An exemplary methodology for data collection and processing is shown in figure 10. Three main steps are involved. The first step (block 750) comprises the selection of a reaction and the catalyst. This influences the choice of the reactor and how it is operated, including batch, flow, etc. (block 754).
[00604] [00604] As an example, in a laboratory environment, an Altamira Benchcat 200 can be employed using a 4 mm diameter ID and 0.5 mm capillary diameter quartz tube downstream. Quartz tubes with 2 mm or 6 mm in diameter can also be used. Nanowires are tested in a number of different dilutions and quantities. In some embodiments, the test range is between 10 and 300 mg. In some embodiments, the nanowires are diluted with a non-reactive diluent. This diluent can be quartz (SiO2), or other inorganic materials, which are known to be inert under reaction conditions. The purpose of the diluent is to minimize hot spots and provide an appropriate load inside the reactor. In addition, the catalyst can be mixed with less catalytically active components, as described in more detail above.
[00605] [00605] In a typical procedure, 50 mg is the total nanowire charge, optionally including the diluent. On both sides of the nanowires a small glass wool plug is loaded to hold the nanowires in place. A thermocouple is placed at the entrance side of the nanowire bed inside the glass wool to reach the temperature in the reaction zone. Another thermocouple can be placed at the downstream end of the nanowire bed within the catalyst bed to properly measure exotherms, if any.
[00607] [00607] Once loaded into the reactor, the reactor is inserted into the Altamira instrument and oven and then a temperature and flow program is started.
[00608] [00608] The preliminary analysis of these oxidation catalysis operations is the Gas Chromatographic (GC) analysis of the charge and effluent gases. From these analyzes, the conversion of the feed gases from oxygen and alkane can easily be achieved and estimates of yields and selectivities of products and by-products can be determined.
[00609] [00609] The GC method developed for these experiments employs four columns and two detectors and a complex valve switching system to optimize the analysis. Specifically, a flame ionization detector (FID) is used for the analysis of hydrocarbons only. It is a highly sensitive detector that produces an accurate and reproducible analysis of methane, ethane, ethylene, propane, propylene and all other simple alkanes and alkenes up to five carbon atoms in length and below for ppm levels.
[00610] [00610] There are two columns in series to carry out this analysis, the first is a separating column (alumina) that retains polar materials (including the water by-product and any oxygenates generated) until later confirmation in the cycle. The second column associated with FID is a capillary aiumine column known as a PLOT column, which performs the actual separation of light hydrocarbons. Water and oxygenated compounds are not analyzed in this method.
[00611] [00611] For the analysis of light non-hydrocarbon gases, a thermal conductivity detector (TCD) can be used which also has two columns to perform its analysis. The target molecules for this analysis are CO2, ethylene, ethane, hydrogen, oxygen, nitrogen, methane and CO. The two columns used in this document are a porous polymer column known as Hayes Sep N, which performs some separations for CO2, ethylene and ethane.
[00613] [00613] The final result is a correct analysis of all the components mentioned above from those the gas phase reactions, of fixed content. Analysis of other reactions and gases not specifically described above can be performed in a similar way.
[00614] [00614] As noted above, in one embodiment, the present disclosure relates to nanowires useful as catalysts in reactions for the preparation of a series of valuable hydrocarbon compounds. For example, in one embodiment, nanowires are useful as catalysts for the preparation of ethylene from methane, through the OCM reaction. In another embodiment, nanowires are useful as catalysts for the preparation of ethylene or propylene, through oxidative dehydrogenation of ethane or propane, respectively. Ethylene and propylene are valuable compounds, which can be converted into a variety of consumer products. For example, as shown in figure 11, ethylene can be converted into several different compounds, including low density polyethylene, high density polyethylene, ethylene dichloride, ethylene oxide, ethylbenzene, linear alcohols, vinyl acetate, alkanes, alpha olefins, various hydrocarbon fuels, ethanol and the like. These compounds can then be further processed using methods well known to the person skilled in the art to obtain other valuable substances and consumer products (i.e., the downstream products, shown in figure 11). Propylene can similarly be converted into various compounds and consumer products including polypropylene, propylene oxides, propanol, and the like.
[00615] [00615] Thus, in one embodiment the invention is directed to a method for the preparation of C2 hydrocarbons, through the OCM reaction, the method comprising contacting a catalyst, as described in this document, with a gas containing methane . In some embodiments, C2 hydrocarbons are selected from ethane and ethylene. In other modalities, the review provides a method of preparing any of the products downstream of ethylene observed in figure 11. The method comprises the conversion of ethylene into a product downstream of ethylene, in which ethylene was prepared through a catalytic reaction employing a nanowire, for example, any of the nanowires disclosed in this document. In some embodiments, the product downstream of ethylene is low density polyethylene, high density polyethylene, ethylene dichloride, ethylene oxide, ethylbenzene, ethanol or vinyl acetate from ethylene, in which ethylene was prepared as described above . In other modalities, the product downstream of ethylene is natural gasoline. In still other embodiments, the product downstream from ethylene comprises l-hexene, l-octene, hexane, octane, benzene, toluene, xylene or combinations thereof.
[00618] [00618] In more specific modalities, of any of the above methods, ethylene is produced through a reaction of OCM or ODH or combinations thereof.
[00619] [00619] In a particular embodiment, the disclosure provides a method of preparing a product derived from ethylene and / or ethane, in which the downstream product is a hydrocarbon fuel. For example, the product downstream of ethylene can be a hydrocarbon fuel such as natural gasoline or a C4-C14 hydrocarbon, including alkanes, alkenes and aromatics. Some specific examples include l-butene, l-hexene, l-octene, hexane, octane,
[00620] [00620] As shown in figure 21, the method starts with methane loading (for example, as a component of natural gas) in an OCM reactor.
[00621] [00621] The ethylene is recovered and loaded in an oIigomerization reactor. Optionally, the ethylene stream may contain CÕ2, H2O, N2, ethane, C3 and / or higher hydrocarbons. Oligomerization in higher hydrocarbons (e.g., C4-C14) then proceeds under any number of conditions known to those skilled in the art. For example, oligomerization can be carried out using any number of catalysts known to those skilled in the art. Examples of such catalysts include catalytic zeolites, molecular sieves of crystalline borosilicates, homogeneous metal halide catalysts, Cr catalysts with pyrrole binders or other catalysts. Examples of methods for converting ethylene to higher hydrocarbon products are disclosed in the following references: Catalysis Science & Technology (2011), 1 (1), 69-75; Coordination Chemistry Reviews (2011), 255 (7-8), 861-880; Eur. Pat. Appl. (2011), EP 2287142 A1 20110223; Organometallics (2011), 30 (5), 935-941; Designed Monomers and Polymers (2011), 14 (1), 1-23; Journal of Organometallic Chemistry 689 (2004) 3641-3668; Chemistry - A European Journal (2010), 16 (26), 7670-7676; Acc. Chem. Res. 2005, 38, 784-793; Journal of Organometallic Chemistry, 695 (10-11): 154-1549 May 15, 2010: Catalysis Today Volume 6, lssue 3, January 1990, Pages 329-349; US patent number 5,968,866; US patent number 6,800,702; US patent number
[00622] [00622] In certain modalities, the exemplary CMO and oligomerization modules shown in figure 21 can be adapted to be at the site of natural gas production, for example, a natural gas field. Thus, natural gas can be efficiently converted into more valuable and easily transportable hydrocarbon articles, without the need to transport natural gas to a processing facility.
[00623] [00623] Referring to figure 21, "natural gasoline" refers to a mixture of oligomerized ethylene products. In this regard, natural gasoline comprises hydrocarbons that contain 5 or more carbon atoms. Exemplary components of natural gasoline include linear, branched or cyclic alkanes, alkenes and alkynes, as well as aromatic hydrocarbons. For example, in some embodiments, natural gasoline comprises l-pentene, l-hexene, cyclohexene, l-octene, benzene, toluene, dimethyl-benzene, xylene, naphthalene, or other oligomerized ethylene products or combinations thereof. In some embodiments, natural gasoline may also include C3 and C4 hydrocarbons dissolved in liquid natural gasoline. This mixture finds particular use in any number of industrial applications, for example, natural gasoline is used as a raw material in oil refineries, as a fuel mixture stock by fuel terminal operators, as thinners for heavy oils in oil pipelines and other applications. Other uses for natural gasoline are well known to those skilled in the art.
[00624] [00624] Phage were amplified in DH5 derivative of E. coli (New England Biolabs, NEB5-alpha F 'lq; genotype: F' proA + B + laclq A (| acZ) M15 zzf :: Tn1O (TetR) / fhuA2A (argF -lacZ) U169 phoA glnV44 080A (lacZ) M15 gyrA96 recA1 endA1 thi-l hsdR17) and purified using standard polyethylene glycol and sodium chloride precipitation protocols as described in the following references: Kay, BK; Winter, j .; McCafferty, J. Phage Display of Peptides and Proteins: A Laboratory Manual; Academic Press: San Diego (1996); C.F. Beards, et al., Ed., Phage Display: A Laboratory Manual; Cold Spring Harbor Laboratory Press, Cold Spring Harbor, Ny, USA (2001); and Joseph Sambrook and David W. Russell, Molecular Cloning, 3 'edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY, USA,
[00625] [00625] The phage solutions were further purified by centrifuging at an acceleration of 10,000 g at least once (until no precipitated material was observed), decanting the supernatant and dividing it into 50 ml containers, which were then stored and frozen at - 20 ° C. The frozen phage solutions were thawed only a short time before use.
[00626] [00626] The concentration of the phage solutions was measured using a UV-VlS spectrometer. The concentration of each frozen phage aliquot was measured before use. This method is based on nucleotide absorption spectroscopy in phage DNA and is described in more detail in "Phage Display: A Laboratory Manual" by Barbas, Burton, Scott and Silverman (Cold Spring Harbor Laboratory Press, 2001). The concentration of the phage solutions is expressed in cfu / mL (phage-forming units per milliliter). EXAMPLE 3 Preparation of Mçj (OH) 2 nanowires
[00627] [00627] Figure 12 shows a generic reaction scheme for the preparation of MgO nanowires (with dopant). First, the template solution (for example, phage or non-biological polymer) is prepared and its concentration determined according to the method described above. The template solution is diluted with water to adjust its concentration in the reaction mixture (ie, with all ingredients added) to the desired value, typically 5 and 12 pfu / mL or higher for phage models. The reaction vessel can be anything from a small bottle (for milliliter scale reactions) to large bottles (for liter scale reactions).
[00628] [00628] A magnesium solution and a base solution are added to the phage solution in order to precipitate Mg (OH) 2. The magnesium solution can be any soluble magnesium salt, for example, MgX2 · 6H2O (X = Cl, Br, I), Mg (NO3) 2, MgSO, magnesium acetate, etc., the magnesium concentration range in the reaction mixture is quite narrow, typically 0.01 M. The combination of the concentration model and the magnesium concentration (that is, the relationship between the model molecules and the magnesium ions) is very important to determine both the nanowire formation process window process window and its morphology.
[00629] [00629] The base can be any alkaline metal hydroxide (for example, L1OH, NaOH, KOH), soluble earth alkaline metal hydroxide (for example, Sr (OH) 2, Ba (OH) 2) or any ammonium hydroxide (for example example, NR4OH, R = H, CH3, C2H5, etc.). Some selection criteria for the base include: solubility, adequate (at least several orders of magnitude greater than Mg (OH) 2 for Mg (OH) 2 nanowires), sufficiently high resistance (the pH of the reaction mixture should be at least 11) and an inability to coordinate magnesium (for Mg (OH) 2 nanowires) to form soluble products. L1OH is a preferred choice for the formation of Mg (OH) 2 nanowires because lithium can also be additionally incorporated into Mg (OH) 2 as a dopant, providing a Li / MgO doped catalyst for OCM.
[00630] [00630] Another factor related to the base is the amount of base used or the proportion of OH "/ Mg2" concentration, that is, the ratio between the number of OH equivalents added and the number of moles of Mg added. In order to completely convert Mg ions into the Mg (OH) 2 solution, the required OH / Mg ratio is 2. The OH "/ Mg '" used in the formation of the Mg (OH) 2 nanowires ranges from 0, 5 to 2 and, depending on this ratio, the reaction product morphology changes from fine nanowires to the nanoparticle clusters. The proportion of
[00631] [00631] In view of the narrow magnesium concentration window in which Mg (OH) 2 nanowires can be obtained, the other main synthetic parameters that determine nanowire formation and morphology include, but are not limited to, the phage sequence and its concentration, the proportion of Mg '"/ Vlll protein concentration, the proportion of OH" / Mg' "concentration, model incubation time and Mg2": model incubation time and OH " the sequence of addition of anions and metal ions, pH, the temperature of the solution in the incubation stage and / or the growth stage, the types of precursor metal salt (eg, MgC] 2 or Mg (NO3) 2 ), the types of anion precursor (for example, NaOH or L1OH), the number of additions, the time elapsing between the addition of the metallic salt and anion precursor, including, for example, simultaneously (zero elapsed time) or additions sequential.
[00632] [00632] The Mg salt solution and the base solution were added sequentially, separated by an incubation time (ie, the first incubation time). The addition sequence has an effect on the nanowire morphology. The first incubation time can be at least 1 hour and must be longer, in case the magnesium salt solution is added first. The Mg salt solution and base can be added in a single "shot", or in a continuous slow flow using a syringe pump or in multiple small shots using a liquid dispensing robot. The reaction is then transported in an unsteady manner or with only mild to moderate agitation for a specific time (ie, the second incubation time). The second incubation time is not such a strong factor in the synthesis of Mg (OH) 2 nanowires, but it must be long enough for the nanowires to precipitate out of the reaction solution [for example, several minutes). For practical reasons, the second incubation time can be as long as several hours. The reaction temperature can be from just above the freezing temperature (for example, 4 ° C) to 80 ° C. Temperature affects the morphology of the nanowires.
[00633] [00633] The precipitated Mg (OH) 2 nanowires are isolated by centrifuging the reaction mixture and decanting the supernatant. The precipitated material is then washed at least once with a water solution with pH "10, to avoid further dissolution of Mg (OH) 2 nanowires. Typically, the washing solution used can be a water or hydroxide solution an alkaline metal hydroxide solution (eg L1OH, NaOH, KOH). This mixture is centrifuged and the supernatant decanted. Finally, the product can be dried (see, Example 5) or resuspended in ethanol for TEM analysis.
[00634] [00634] The supernatant decanted from the reaction mixture can be analyzed by UV-VlS spectroscopy to determine the model concentration (see Example 2) and therefore give an estimate of the amount of model incorporated into the Mg (OH) 2 precipitate, (for example, the amount of "mineralized" phage).
[00635] [00635] Figure 12 illustrates a modality for the preparation of Mg (OH) 2 nanowires. In a different embodiment, the order of addition can be reversed, for example, in a 4 mL synthesis on an exemplary scale of Mg (OH) 2 nanowires, 3.94 mL of concentrated phage solution (for example, SEQ ID NO: 3, at a concentration of -5E12 pfu / ml) were mixed in an 8 ml flask with 0.02 ml of 1 M aqueous L1OH solution and allowed to incubate overnight (-15 h).
[00636] [00636] Mg (OH) 2 nanowires prepared according to Example 3 were characterized by TEM, in order to determine their morphology. First, a few microliters (-500) of ethanol were used to suspend the isolated Mg (OH) 2. The nanowires were then deposited on a TEM grid (copper grid with a very thin layer of carbon) placed on filter paper for the capillary transport of any additional liquid. After allowing the ethanol to dry, the TEM grid was loaded in TEM and characterized. TEM was performed at 5KeV in bright field mode in DeLong LVEM5.
[00637] [00637] The nanowires were additionally characterized by XDR (for phase identification) and TGA (for calcination optimization).
[00638] [00638] The nanowires isolated as prepared in Example 3 were dried in an oven at a relatively low temperature (60-120 ° C) before calcination.
[00639] [00639] The dry material was placed in a ceramic boat and calcined in air at 450 ° C in order to convert the Mg (OH) 2 nanowires into MgO nanowires- The calcination recipe can be varied considerably. For example, calcination can be done relatively quickly as in these two examples: - loading in a muffle furnace preheated to 450 ° C, calcination time = 120 minutes
[00640] [00640] Alternatively, the calcination can be carried out in steps that are chosen according to the TGA signals, as in the following example: - load a muffle oven (or tubular oven) at room temperature, rise to 100 ° C with rate of 2 ° C / min., residence of 60 min., rise to 280 ° C with rate of 2 ° C / min., residence of 60 min., rise to 350 ° C with rate of 2 ° C / min. , residence of 60 min. and finally, elevation to 450 ° C with a rate of 2 ° C / min., residence 60 min.
[00641] [00641] Generally, a step recipe is preferable, since it can allow a better, smoother and more complete conversion of Mg (OH) 2 into MgO.
[00642] [00642] Figure 13 shows the X-ray diffraction pattern of Mg nanowires (OH2) and MgO nanowires after calcination. Crystalline structures of two types of nanowires have been confirmed.
[00643] [00643] Doping of the nanowires is obtained using the incipient moisture impregnation method. Before the MgO nanowires were impregnated with the doping solution, maximum wetting (i.e., the nanowires' ability to absorb the doping solution before it became a suspension or liquid before "free" liquid was observed) of the nanowires was determined. This is a very important step for an accurate absorption of the metal doping on the MgO surface. If too much doping agent solution is added and the suspension is formed, a significant amount of unabsorbed doping agent will crystallize during drying and, if sufficient doping solution is not added, significant portions of the MgO surface will be doped.
[00644] [00644] In order to determine the maximum wettability of the MgO nanowires, small portions of water were thrown over the calcined MgO powder until a suspension was formed, that is, until the "free" liquid was observed. Maximum wettability was determined to be the total amount of water added. before the suspension formed. The concentration of the doping solution was then calculated so that the desired amount of doping agent was contained in the doping solution volume corresponding to the maximum wettability of the MgO nanowires. In another way of describing the incipient moisture impregnation method, the volume of the doping solution is adjusted to be equal to the pore volume of the nanowires, which can be determined by BET measurements (Brunauer, Emmett, Tel! Er). The doping solution is then dragged into the pores by capillary action.
[00645] [00645] In one embodiment, the doping metal for MgO-based catalysts for OCM is lithium (see, also, figure 12). Thus, in one embodiment the source of dopant can be any soluble lithium salt, as long as it does not introduce unwanted dopants. Typically, the lithium salts used were LiNO3, L1OH or Li2CO3. LiNO3 and L1OH are preferred because of their greater solubility. In one instance, the lithium content in MgO to OCM catalysts ranges from 0 to 10% by weight (i.e., about 0 to 56%).
[00646] [00646] The calculated amount of doping solution of the desired concentration was doped over the calcined MgO nanowires. The wet powder obtained was dried in an oven at a relatively low temperature (60-120 ° C) and calcined using one of the recipes described above. Note that, during this stage, there is no change of iasis (MgO having already been formed in the previous caicination stage) and, therefore, a recipe stage (see previous paragraph) may not be necessary.
[00647] [00647] The dopant impregnation step can also be performed before calcination, after drying the Mg (OH) 2 nanowires isolated from the reaction mixture. In this case, the catalyst can be calcined immediately after dopant impregnation, that is, no drying and second calcination step would be necessary since its objectives are achieved during the calcination step.
[00648] [00648] Three identical syntheses were made in parallel. In each synthesis 80 ml of concentrated phage solution (SEQ ID NO: 3 in a concentration of z 5E12 pfu / ml) were mixed in a 100 ml glass flask with 0.4 ml of 1 M aqueous L1OH solution and left incubate for 1 hour. 0.8 ml of 1 M aqueous MgCl2 solution was added using a pipette and the mixture was mixed gently by stirring. The reaction mixture was left for 72 hours without shaking by incubating at 60 ° C in an oven. After the incubation time, the mixture was centrifuged. The materia! The precipitate was resuspended in 20 mL of 0.06 M aqueous NH4OH solution (pH = 11), the mixture was centrifuged and the supernatant decanted. The Mg (OH) 2 nanowires obtained were resuspended in ethanol. The ethanol suspensions from the three identical syntheses were combined and a few microliters of the ethane suspension! were used for TEM analysis. The ethanol suspension was centrifuged and the supernatant decanted. The gel-like product was transferred in a ceramic boat and dried for 1 hour at 120 ° C in a vacuum oven.
[00649] [00649] The dry product was calcined in a tube oven using a step recipe (loading in the oven at room temperature, elevation 100 ° C at a rate of 2 ° C / min., Residence time 60 min., Elevation to 280 ° C with rate of 2 ° C min.l, residence time of 60 min., Rise to 350 ° C with rate of 2 ° C / min., Residence time 60 min., Rise to 450 ° C with rate 2 ° C / min, residence time of 60 min and, finally, cooling to room temperature).
[00650] [00650] The calcined product, 10 mg, was impregnated with an aqueous solution of L1OH. First, the maximum wettability was determined by adding water to the calcined product in a ceramic boat until the powder was saturated, but no "free" liquid was observed. The maximum wettability was 12 µL. Since the target doping level was 1 ° / 0 by weight of lithium, the required concentration of aqueous L1OH solution was calculated to be 1.2 M. The calcined product was dried again for 1 h at 120 ° C to remove the water used to determine the wettability of the powder. 12 µL of the 1.2 M L1OH solution was dropped onto the powder of the MgO nanowires. The wet powder was dried for 1 hour at 120 ° C in a vacuum oven and finally calcined in a muffle furnace (charge at room temperature, rise to 460 ° C with rise of 2 ° C / min., Residence time 120 min .).
[00651] [00651] Nanowires prepared using non-biological polymers are .. prepared in an analogous manner.
[00652] [00652] Certain synthetic parameters strongly influence the formation of phage nanowires, including selective binding of metals and / or anions, as well as the surface morphology. Figure 14 shows a number of MgO nanowires synthesized in the presence of a different phage sequence (for example, different pV111), while keeping the other reaction conditions constant. Phages from SEQ ID NOS. 1, 7, 10, 11, 13 and 14 were the respective phages of choice in six reactions performed under identical conditions. Constant reaction conditions can include: Mg2 "concentration rates and functional groups active in the phage; OH" / Mg2 "concentration rates; phage and Mg 'incubation time; phage and OH "incubation time; phage concentration; sequence of addition of anion and metal ions; the temperature of the solution in the incubation step and / or the growth step, etc. As shown, the MgO nanowire morphologies are significantly influenced by phage sequences.
[00653] [00653] Thus, by varying these and other reaction conditions, a diverse class of catalytic nanowires can be produced. In addition, a certain correlation between the reaction conditions and the surface morphologies of the nanowires can be established empirically, thus allowing rational models of catalytic nanowires.
[00654] [00654] 23 mL of a solution of 2.5 and 12 pfu of phage (SEQ ID NO: 3) were mixed in a 40 mL glass flask with 0.046 mL of 0.1 M LaC | 3 aqueous solution and allowed to incubate for 16 hours. After this incubation period, a slow addition of several steps is carried out with 0.15 ml of 0.05 M LaC | 3 - .. solution and 1.84 ml of 0.3 M NH4OH. This addition is carried out in six hours and twenty steps. The reaction mixture was left stirred for an additional 2 h at room temperature.
[00655] [00655] The dried product was then calcined in a muffle furnace with a recipe in stages (loading in the oven at room temperature, raising 200 ° C at a rate of 3 ° C / min., Residence time of 120 min., rise to 400 ° C at a rate of 3 ° C / min., residence time of 120 min., cooling to room temperature). The calcined product was then ground to a fine powder.
[00656] [00656] The calcined product, 5 mg, was impregnated with 0.015 mL of aqueous solution 0.1M Sr (NO3) 2. The powder and solution were mixed on a plate heated to 90 ° C until a paste was formed. The paste was then dried for 1 h at 120 ° C in a vacuum oven and finally calcined in an air muffle furnace (charge in the oven at room temperature, raising 200 ° C at a rate of 3 ° C / min. , residence time 120 min., rise to 400 ° C at a rate of 3 ° C / min., residence time 120 min., rise to 500 ° C with a rate of 3 ° C / min., rise time of 120 min., Cooling to room temperature).
[00657] [00657] As an example, figure 15 shows, schematically, an integrated process 800 for the cultivation of a ZrO2 La2O3 nanowire core / shell structure. A solution phase is prepared, to which a zirconium salt precursor (eg, ZrC | 2) is added to allow nucleation of ZrO2 "in the phage. Subsequently, a hydroxide precursor [eg, L1OH) is added to cause the hydroxide ions to nucleate in the phage. Nanowires 804 are thus formed in which phage 810 is coated with a continuous and crystalline layer 820 of ZrO (OH) 2. To this reaction mixture is added a lanthanum salt precursor ( for example, LAC | 3), under a condition that causes the nucleation of La (OH) 3 on the ZrO (OH) 2 nanowire 804. After calcination, the nanowires of a ZrO2 / La2O3 core / shell structure are formed. Another impregnation step produces ZrO2La2O3 nanowires doped with strontium ions (Sr2 ") 840, in which phage 810 is coated with a layer of ZrO2 830, which in turn is coated with a La2O3 850 shell.
[00658] [00658] ZrO2La2O3 nanowires were thus prepared by mixing 20 ml of phage solution E3 2.5e12 pfu to 0.1 ml of 0.5 M ZrO aqueous solution (NO3) 2.
[00659] [00659] After that, the ethanol solution was mixed with 10 ml of water and 2 ml of 0.05 M ZrO (NO3) 2 with 2 ml of 0.1 M NH4OH were added over a period of 200 minutes, using syringe plungers. The solids are washed with water and resuspended in ethanol for TEM observation.
[00660] [00660] To about 18 mg of suspended ZrO (OH) 2 nanowires, 10 ml of water were added, followed by the addition of 0.5 ml of 0.083 M LaCl3 with 0.5 ml of NH4OH in solution of 0, 3 M, over a period of 50 minutes, using syringe plungers. The solids thus formed were separated by centrifugation to obtain a powder, which was dried in a vacuum oven at 110 ° C for one hour. A small aliquot of dry powder is then suspended in ethanol for MET observation.
[00661] [00661] Similar to Example 9, the La (OH) 3 nanowires were coated with shell ZrO2 shell according to the following process.
[00662] [00662] Further processing can be used on the La (OH) 3 / ZrO2 core / shell nanowires prepared in Example 10, to create hollow shell ZeO2 nanowires. The La (OH) 3 core can be etched using a 1M citric acid solution. Controlled experiments on the calcined and non-calcined La (OH) 3 nanowires show that the nanowires are entirely recorded in about an hour at room temperature. Engraving of La (OH) 3 / ZrO2 core / shell nanowires was performed overnight (about 16 hours).
[00663] [00663] The remaining solid was then separated by centrifugation and MET observation is conducted over the washed solids (washing water). Low-contrast zirconia nanowires were observed after engraving, which indicates that hollow zirconia "fine wires" can be formed using La (OH) 3 nanowire as a model.
[00664] [00664] A 20 mg sample of a L, 2O3 catalyst doped with Sr (5%) based on phage was diluted with 80 mg of quartz sand and placed in a reactor (operation NPS21). The gas flows were kept constant, at 9 sccm of methane, 3 sccm of oxygen and 6 sscm of argon. The temperature upstream (just above the bed) varied from 500 ° C to 800 ° C in increments of 100 ° C and then decreased to 600 ° C in increments of 50 ° C. Analyzes of the ventilation gas were collected at each temperature level. As a point of comparison, 20 mg of mass of 5 ° / 0 catalyst in bulk at 5% Sr on La3O3 were diluted in the same way and operation through the exact flow and temperature protocol.
[00665] [00665] Figure 16 shows the formation of OCM products at 700 ° C, including C2 (ethane and ethylene), as well as other coupling products (propane and propylene).
[00666] [00666] Figures 17A, 17B and 17C show the comparative results of the catalytic performance parameters for a catalytic nanowire (Sr2 "/ La2O3) versus its material in corresponding volume (Sr2" / La2O3 in volume). Conversion rates of methane, selectivity of C2 and yields of C2 are among the important parameters by which the catalytic properties were measured. More specifically, figure 17A shows that methane conversion rates are higher for the catalytic nanowire compared to the volume material, over a wide range of temperatures (e.g., 550-650 ° C). Thus, it has been shown that due to the improvement of both conversion and selectivity simultaneously, the C2 yield can be improved in relation to traditional volume catalysts.
[00667] [00667] Figures 18A-18B demonstrate that nanowires prepared under different synthetic conditions provided different catalytic performances, suggesting that the various synthetic parameters resulted in divergent nanowire morphologies. Figure 18A shows that the nanowires prepared using different phage models (SEQ ID NO: 9 and SEQ ID NO: 3), under identical synthetic conditions, created catalytic nanowires that present different performances in terms of C2 selectivity in an OCM reaction. Figure 18B shows the comparative C2 selectivities of nanowires prepared by an alternative adjustment of the synthetic parameters. In this case, the phage model was the same for both nanowires (SEQ ID NO: 3), but the synthetic conditions were different. Specifically, the nanowires of figure 18A were prepared with shorter incubation and growth times than the nanowires of figure 18B. In addition, the nanowires of figure 18A were calcined in a single step at 400 ° C, instead of high temperature calcinations carried out on the nanowires of figure 18B.
[00668] [00668] These results confirm that the catalytic nanowires behave differently than their material colleagues by volume. In particular, catalytic nanowires allow adjustments to surface morphologies through synthetic design and classification to finally produce high performance catalysts.
[00669] [00669] Nanowires prepared against non-biological polymers are analyzed in a similar way and are expected to have similar catalytic properties.
[00670] [00670] A 10 mg sample of Li doped MgO catalyst based on aug was diluted with 90 mg of quartz sand and placed in a reactor. The gas flows were kept constant in a mixture of 8 sccm alkane, 2 sccm oxygen and 10 sccm argon. The temperature upstream (immediately above the bed) varied from 500 ° C to 750 ° C in increments of 50-100 ° C. The ventilation gas analysis was collected at each temperature level.
[00671] [00671] As a comparative term, 10 mg of MgO catalyst over Li in 1 ° / 0 in volume was diluted in the same way and operated through the exact flow and temperature protocol. The results of this experiment are shown in the figure
[00672] [00672] Nanowires prepared via non-biological polymers are analyzed in an analogous manner and are expected to have similar catalytic properties.
[00673] [00673] Sr-doped La2O3 nanowires were prepared according to the following non-model method indicated.
[00674] [00674] A La (OH) 3 gel was prepared by adding 0.395 g of NH4OH (25%) to 19.2 mL of water, followed by adding 2 mL of a La (NO3) 3 1 M solution. The solution was then mixed vigorously. The solution was first gelled, but the viscosity decreased with continuous stirring. The solution was then left to stand for a period of between 5 and 10 minutes. The solution was then centrifuged at 10,000 g for 5 minutes. The centrifuged gel was recovered and washed with 30 ml of water and the washing process was repeated.
[00675] [00675] To the washed gel, 10.8 ml of water were added to suspend the solid. The suspension was then transferred to a hydrothermal pump (20 ml volume, not stirred). The hydrothermal pump was then loaded in a muffle furnace at 160 ° C and the solution was left to stand under autogenous pressure at 160 ° C for 16 hours.
[00676] [00676] The solids were then isolated by centrifugation at 10,000 g for 5 minutes, and washed with 10 ml of water to produce about 260 mg solids (after drying for 1 hour at 120 ° C in a vacuum oven).
[00677] [00677] A 57 mg aliquot of nanowires was then mixed with 0.174 ml of a 0.1 M solution of Sr (NO3) 2. This mixture was then stirred on a hot plate at 90 ° C until a paste was obtained.
[00678] [00678] The paste was then dried for 1 h at 120 ° C in a vacuum oven and finally calcined in an air muffle oven according to the following procedure: (1) charge in the oven at room temperature; (2) rise to 200 ° C at a rate of 3 ° C / min .; (3) residence time of 120 min .; (3) rise to 400 ° C at a rate of 3 ° C / min .; (4) residence time of 120 min .; (5) rise to 500 ° C at a rate of 3 ° C / min .; and (6) residence time of 120 min. The calcined product was then ground to a fine powder.
[00679] [00679] Figure 20 shows a TEM image of nanowires obtained from this method not directed at the model. As shown in figure 20, nanowires comprise a ratio of the effective length to the actual length of about 1 (i.e., the nanowires comprise a "linear" morphology).
[00680] [00680] La (NO3) 3,6 H2O (10,825 g) is added to 250 ml of distilled water and stirred until all the solids are dissolved. Concentrated ammonium hydroxide (4,885 mL) is added to this mixture and stirred for at least an hour, resulting in a white gel. This mixture is also transferred to five centrifuge tubes and centrifuged for at least 15 minutes. The supernatant is discarded and each microsphere is washed with water, centrifuged, for at least 15 minutes and the supernatant is discarded again.
[00681] [00681] The resulting sediments are combined, suspended in distilled water (125 mL) and heated to 105 ° C for 24 hours. The lanthanum hydroxide is isolated by centrifugation and suspended in ethanol (20 ml). The ethanol supernatant is concentrated and the product is dried at 65 ° C until all the ethanol is removed.
[00682] [00682] The lanthanum hydroxide nanowires prepared above are calcined by heating at 100 ° C for 30 min., 400 ° C for 4 hours and then 550 ° C for 4 hours to obtain the La2O3 nanowires.
[00683] [00683] Concentrated reagent, 25 mL, NH4OH classification are dissolved in 25 mL of distilled water and 1 mL of a 0.001 M aqueous solution of bacteriophage M13 is then added. Mn (NO3) 2, 0.62 g, NaCl, 10.01 g and WO3 2.00 g are then added to the mixture with stirring. The mixture is heated to a temperature of about 95 ° C for 15 minutes. The mixture is then dried overnight at about 10 ° C and calcined at about 400 ° C for 3 hours.
[00684] [00684] Concentrated reagent, 25 mL, NH4OH classification are dissolved in 25 mL of distilled water and 1 mL of a 0.001 M aqueous solution of bacteriophage M13 is then added. 1.01 g NaCl and 2.00 g WO3 are then added to the mixture with stirring. The mixture is heated to a temperature of about 95 ° C for 15 minutes. The mixture is then dried overnight at about 10 ° C and calcined at about 400 ° C for 3 hours. The resulting material is then suspended in 10 ml of distilled water and 0.62 g of Mn (NO3) 2 is added to the mixture with stirring. The mixture is heated to a temperature of about 115 ° C for 15 minutes. The mixture is then dried overnight at about 110 ° C and calcined at about 400 ° C for 3 hours.
[00685] [00685] Nano-wire material Na10MnW5O17 (2.00 g), prepared as described in Example 16 above, is suspended in water, and about 221.20 g of a colloidal dispersion of 40% by weight of SiO2 (silica) while agitated. The mixture is heated to about 100 ° C until near dryness. The mixture is then dried overnight at about 110 ° C and heated under a flow of oxygen gas (i.e., calcined) at about 400 ° C for 3 hours. The calcined product is cooled to room temperature and then crushed to a size of 10-30 mesh.
[00686] [00686] Two identical syntheses were performed in parallel. In each synthesis, 360 ml of a solution of 4 and 12 pfu / ml of phage (SEQ ID NO: 3) were mixed in a 500 ml plastic bottle with 1.6 ml of a 0.1 M aqueous solution of LaC | 3 and allowed to incubate for at least 1 hour. After this incubation period, a slow addition of several steps was performed with 20 ml of 0.1 M LaC | 3 solution and 40 ml of 0.3 M NH4OH. This addition was performed in 24 hours and 100 steps. The reaction mixture was stirred for at least another hour at room temperature. After that time, the suspension was centrifuged to separate the solid phase from the liquid phase. The materia! The precipitate was then resuspended in 25 ml of ethanol. The ethanol suspensions from two identical syntheses were combined and centrifuged to remove unreacted species. The remaining gel-like product was then dried for 15 hours at 65 ° C in an oven and then calcined in an air muffle furnace (charge in the oven at room temperature, elevation to 100 ° C at a rate of 2 ° C / min., Residence time 30 min., Rise to 400 ° C at a rate of 2 ° C / min., Residence time 240 min., Rise to 550 ° C at a rate of 2 ° C / min., residence 240 min., cooling to room temperature).
[00687] [00687] La2O3 nanowires are also prepared in an analogous manner using non-biological models.
[00688] [00688] Two identical syntheses were performed in parallel. In each synthesis, 360 ml of a solution of 4 and 12 pfu / ml. Of phage (SEQ ID NO: 3) were mixed in a 500 ml plastic bottle with 1.6 ml of a 0.1 M LaC aqueous solution | 3 and allowed to incubate for at least 1 hour. After this incubation period, a slow addition of several steps was performed with 20 ml of 0.1 M LaC | 3 solution and 40 ml of 0.3 M NH4OH. This addition was performed in 24 hours and 100 steps. The reaction mixture was stirred for at least another hour at room temperature. After that time, the suspension was centrifuged to separate the solid phase from the liquid phase. The precipitated material was then resuspended in 25 ml of ethanol. The ethanol suspensions from two identical syntheses were combined and centrifuged to remove unreacted species. The remaining gel-like product was then dried for 15 hours at 65 ° C in an oven.
[00689] [00689] The target doping level was 20 ° /, to ° /, of Mg and 5% to Na, to ° /, refers to the atomic percentage), 182 mg of dry product were suspended in
[00690] [00690] Mg / Na / La2O3 nanowires are also prepared in a similar way using non-biological models.
[00691] [00691] La2O3 nanowire catalysts doped with Mg / Na, 50 g, from Example 20, were placed in a tubular reactor (4 mm diameter ID quartz tube, capillary 0.5 mm ID downstream), which were then tested on an Altamira Benchcat 203. Gas flows were kept constant at 46 sccm of methane and 54 sccm of air, which corresponds to a CH4 / O2 ratio of 4 and a space velocity for gas- hour (GHSV) of about
[00692] [00692] Figure 22 shows the start of CMO between 550 ° C and 600 ° C. C2 selectivity, methane conversion and C2 yield at 650 ° C were 57 ° / o, 25 ° / o and 14 ° / o, respectively.
[00693] [00693] In another example, 50 mg of La2O3 catalytic nanowires doped with Mg / N from Example 20, were placed in a tube reactor (4 mm in diameter
[00694] [00694] Figure 23 shows the start of CMO between 550 ° C and 600 ° C. C2 selectivity, methane conversion and C2 yield at 650 ° C were 62%, 20 ° / o and 12%, respectively.
[00695] [00695] Mg / Na / La2O3 nanowires prepared using non-biological models are tested in a similar way and are expected to have similar catalytic activity.
[00696] [00696] Nanowires can be prepared by hydrothermal synthesis from metal hydroxide gels (obtained from metal salt + base). In some embodiments, this method is applicable to lanthanides, for example, La, Nd, Pr, Sm, Eu, and lanthanide containing mixed oxides.
[00697] [00697] Alternatively, nanowires can be prepared by synthesis from metal hydroxide gel (obtained from metal salt + base) under reflux conditions. In some modalities, this method is applicable! to lanthanides, for example, La, Nd, Pr, Sm, Eu, and lanthanides containing mixed oxides.
[00698] [00698] Alternatively, the gel can be aged at room temperature.
[00699] [00699] Nanowires can also be prepared by hydrothermal synthesis aided by polyethylene glycol. For example, nanowires containing Mn can be prepared according to this method, using methods known to those skilled in the art. Alternatively, direct hydrothermal oxide synthesis can be used.
[00700] [00700] Nanostructured catalytic materials can be prepared by a variety of starting materials. In certain embodiments, rare earth oxides are attractive starting materials, since they can be obtained in a high degree of purity and are less expensive than rare earth salt precursors that are typically used in preparative synthesis work. The methods for obtaining rare earth oxide nanowires and their derivatives are described below.
[00701] [00701] Method A: The starting material, lanthanide oxide, can be hydrothermally treated in the presence of ammonium halide to prepare rare earth oxide nanowires. Preparation is a simple, high-yielding container procedure. For example, one gram of lanthanum oxide was placed in 10 mL of distilled water. Ammonium chloride (0.98 g) was added to the water, the mixture was placed in an autoclave and the autoclave was placed in an oven at 160 ° C for 18 h. The autoclave was removed from the oven, cooled, and the product was isolated by filtration. Nanowires in micrometer and submicron dimensions were observed in the TEM images of the product. This method could also be used to prepare mixtures of metal oxides, metal oxyhalides, metal oxinitrates and metal sulfates.
[00702] [00702] Method B: Metal oxide nanowires can be prepared using a solid state reaction of rare earth oxide or bismuth oxide, in the presence of ammonium halide. The solid state reaction is used to prepare bismuth or rare earth oxyhalide. The metal oxyhalide is then placed in water at room temperature and the oxyhalide is slowly converted to the metal oxide with nanowire / needle morphology. This method could also be used to prepare mixed metal oxides. For example: lanthanum oxide, bismuth oxide and ammonium chloride were ground and burned in a ceramic dish to obtain mixed lanthanum and bismuth oxychloride. The metal oxychloride is then placed in water to form the mixed bismuth and lanthanum oxide nanowires.
[00703] [00703] 19.7 ml of a concentrated phage solution (eg, SEQ ID NO: 3, at a concentration of -5E12 pfu / ml) was mixed in a ml bottle with 0.1 ml of aqueous L1OH solution 1 M and allowed to incubate overnight (- 15 h). 0.2 ml of 1 M aqueous MgC | 2 solution was then added using a pipette and the mixture was mixed by gentle stirring. The reaction mixture was incubated without shaking for 72 hours. After the incubation time, the mixture was centrifuged and the supernatant decanted. The precipitated material was resuspended in 5 ml of a 0.001 M aqueous solution of L1OH (pH = 11), the mixture was centrifuged and the supernatant decanted.
[00704] [00704] 19.8 mL of deionized water was added to the Mg (OH) 2 nanowires. The mixture was incubated for 1 h. After the incubation time, 0.2 ml of a 1 M aqueous solution of MnC | 2 was then added with a pipette and the mixture was stirred by gentle stirring. The reaction mixture was incubated for 24 hours without shaking. After the incubation time, the mixture was centrifuged and the
[00705] [00705] The Mg (OH) 2 nanowires coated with MnO (OH) obtained were dried at 65 ° C for 15 h in an oven. Finally, the dry product was calcined in a muffle furnace with a recipe in stages (loading in the oven at room temperature, elevation to 100 ° C at a rate of 2 ° C / min., Residence time 60 min., Elevation to 280 ° C at a rate of 2 ° C / min., Residence time 60 min., Rise to 350 ° C at a rate of 2 ° C / min., Residence time 60 min., Rise to 450 ° C at a rate of 2 ° C / min., Residence time 60 min., Rise to 550 ° C at a rate of 2 ° C / min. Residence time 60 min., Cooling to room temperature) for conversion to MgO core / casing nanowires / Mn2O3.
[00706] [00706] The surface area of the nanowires was determined by BET measurement (Brunauer, Emmett Teller) at 111.5 m 2 / g.
[00707] [00707] 3.96 mL of concentrated phage solution (for example, SEQ ID NO: 3, at a concentration of -5E12 pfu / mL) were mixed in an 8 mL flask with 0.04 mL of 1 M aqueous solution MnC | 2 and incubated for 20 hours. 0.02 ml of 1 M aqueous L1OH solution was then added using a pipette and the mixture was combined by gentle stirring. The reaction mixture was incubated for 72 hours without shaking. After the incubation time, the mixture was centrifuged and the supernatant decanted. The precipitated material was resuspended in 2 ml of a 0.001 M aqueous solution of L1OH (pH = 11), the mixture was centrifuged and the supernatant decanted. The precipitated material was finally resuspended in 2 ml of ethanol, the mixture was centrifuged and the supernatant decanted. The obtained MnO (OH) nanowires were dried at 65 ° C for 15 h in an oven. Finally, the dry product was calcined in a muffle furnace with a recipe in stages (loading in the oven at room temperature, elevation to 100 ° C at a rate of 2 ° C / min., Residence time 60 min., Elevation to 280 ° C at a rate of 2 ° C / min., Residence time 60 min., Rise to 350 ° C at a rate of 2 ° C / min., Residence time 60 min., Rise to 450 ° C at a rate of 2 ° C / min., Residence time 60 min., Rise to 550 ° C at a rate of 2 ° C / min. Residence time 60 min., Cooling to room temperature) for conversion to Mn2O3 nanowires.
[00708] [00708] 1.8 mg of V2O5 were dissolved in 10 ml of a 2.5% by weight aqueous solution of HF. 1 ml of the V2O5 / HF solution was mixed with 1 ml of concentrated phage solution (for example, SEQ ID NO: 3, at a concentration of -5E12 pfu / ml) in a 15 ml plastic centrifuge tube and incubated for 2 h. 1 ml of a saturated solution of boric acid (1 M supernatant of nominally aqueous boric acid solution) was then added with a pipette and the mixture was combined by gentle stirring. The reaction mixture was incubated for 170 hours without shaking. After the incubation time, the mixture was centrifuged and the supernatant decanted. The precipitated material was resuspended in 2 ml of ethanol, the mixture was centrifuged and the supernatant decanted. The V2O5 nanowires obtained were characterized by TEM.
[00709] [00709] 12.5 mL of a 4M MgC | 2 aqueous solution was heated to 70 ° C on a heating plate. 0.1 g of MgO (Aldrich) was then added slowly, over a period of at least 5 minutes, to the solution while being vigorously stirred. The mixture was kept under stirring at 70 ° C for 3 h and then cooled overnight (- 15 h) without stirring.
[00710] [00710] The obtained gel was transferred in a 25 ml hydrothermal pump (Parr pump number 4749). The hydrothermal pump was then charged in an oven at 120 ° C and the solution was left to stand under autogenous pressure at 120 ° C for 3 hours.
[00711] [00711] The product was centrifuged and the supernatant decanted. The precipitated product was suspended in about 50 ml of ethanol and filtered over a 0.45 µm hydrophilic propylene filter using a Büchner funnel. An additional 200 mL of ethanol was used to wash the product.
[00712] [00712] The magnesium hydroxide hydrochloride nanowires obtained were suspended in 12 ml of ethanol and 2.4 ml of deionized water in a 20 ml bottle. 1.6 mL of 5 M NaOH aqueous solution was added and the flask was sealed with its cap. The mixture was then heated to 65 ° C in an oven for h.
[00713] [00713] The product was filtered over a 0.45 µm hydrophilic polypropylene filter using a Büchner funnel. About 250 mL of ethanol was used to wash the product. The Mg (OH) 2 nanowires obtained were dried at 65 ° C for 15 h in an oven. Finally, the dry product was calcined in a muffle furnace with a recipe in stages (loading in the oven at room temperature, elevation at 100 ° C at a rate of 2 ° C / min., Residence time 60 min., Elevation to 280 ° C at a rate of 2 ° C / min., Residence time 60 min., Rise to 350 ° C at a rate of 2 ° C / min., Residence time 60 min., Rise to 450 ° C at a rate of 2 ° C / min., Residence time 60 min., Cooling to room temperature) for conversion to MgO nanowires. EXAMPLE 28
[00714] [00714] 6.8 g of MgC | 2 * 6H2O were dissolved in 5 ml of deionized water in a 20 ml bottle. 0.4 g of MgO (from Aldrich) was then slowly added to the solution while being vigorously stirred. The mixture was kept under stirring at room temperature until it was completely gelled in gel (~ 2 h) and then it was allowed to age for 48 h without stirring.
[00715] [00715] The gel was transferred in a 50 ml centrifuge tube, which was then filled with deionized water and stirred vigorously until a homogeneous suspension was obtained. The suspension was centrifuged and the supernatant decanted. The precipitated product was suspended in about 50 ml of ethanol and filtered over a 0.45 µm hydrophilic polypropylene filter using a Büchner funnel. An additional 350 mL of ethanol was used to wash the product.
[00717] [00717] The product was filtered over a 0.45 µm hydrophilic polypropylene filter using a Büchner funnel. About 400 mL of ethanol was used to wash the product. The Mg (OH) 2 nanowires obtained were dried at 65 ° C for 72 hours in an oven and then dried at 120 ° C for 2 h in a vacuum oven. About 0.697 g of Mg (OH) 2 nanowires were obtained and the surface area of the nanowires was determined by BET measurement (Brunauer, Emmett Teller) at 100.4 m 2 / g.
[00718] [00718] This example describes a method for coating the Mg (OH) 2 nanowires of Example 28 with MnO (OH).
[00719] [00719] Three almost identical syntheses were conducted in parallel. In each synthesis, the Mg (OH) 2 nanowires prepared using the method described in Example 28, but without the drying steps were mixed with 250 ml of deionized water in a 500 ml plastic bottle and stirred for 20 minutes.
[00720] [00720] Mg (OH) 2 / MnO core / shell nanowires were characterized by TEM, before being dried at 65 ° C for 72 hours in an oven and then further dried at 120 ° C for 2 h in an oven vacuum. The yield for the three syntheses was 0.675 g, 0.653 g and 0.688 g, respectively.
[00721] [00721] Mg (OH) 2 / MnO core / shell nanowires can be converted to MgO / Mn2O3 nanowires by calcination in a muffle furnace with a step recipe (charge in the oven at room temperature, elevation 100 ° C with a rate of 2 ° C / min., residence time 60 min., rise to 280 ° C with a rate of 2 ° C / min., residence time 60 min., rise to 350 ° C with a rate of 2 "C / min., residence time 60 min., rise to 450 ° C at a rate of 2 ° C / min., residence time 60 min., rise to 550 ° C at a rate of 2 ° C / min., residence 60 min., cooling to room temperature).
[00722] [00722] Three syntheses were carried out in parallel. In each synthesis, 10 ml of a 2.5 phage solution and 12 pfu / ml (SEQ ID NO: 14) were mixed in a 60 ml glass flask with 25 µL of 0.08 M aqueous solutions of NdC | 3 , EuCl ,, or PrC | 3, respectively and incubation for at least 1 hour. After this incubation period, the slow addition of several steps was performed with 630 µL of 0.08 M LaCl3, EuC | 3 or aqueous solutions of PrCI3, respectively, and 500 µL of 0.3 M NH4OH. This addition was performed in 33 hours and 60 steps. The reaction mixtures were stirred for at least another 10 hours at room temperature. After that time, the suspensions were centrifuged to separate the solid phase from the liquid phase. The precipitated material was then resuspended in 4 ml of ethanol. The ethane suspensions! were centrifuged in order to complete the removal of unreacted species. The remaining gel-like product was then dried for 1 hour at 65 ° C in an oven and then calcined in an air muffle furnace (charge in the oven at room temperature, elevation 100 ° C at a rate of 2 ° C / min., residence time 30 min-, rise to 500 ° C with 2 ° C / min. rate, residence time 240 min., cooling to room temperature). The nanowires obtained from Nd (OH) 3, Eu (OH) 3 and Pr (OH) 3 were characterized by TEM, before being dried.
[00723] [00723] Nd2O3, Eu2O3 and Pr2O3 nanowires are prepared from analogous non-biological models.
[00724] [00724] In synthesis, 15 ml of a phage solution of 5 and 12 pfu / ml (SEQ ID NO: 3) were mixed in a 60 ml glass flask with 15 µL of 0.1 M La aqueous solution ( NOs) 3 and incubation for about 16 hours. After this incubation period, a slow addition of several steps was performed with 550 µL of 0.2 M aqueous solution of Ce (NOs) 3, 950 µL of aqueous solution of 0.2 M La (NO3) 3 and 1,500 µL 0.4 NH3OH. This addition was carried out in 39 hours and 60 steps. The reaction mixtures were stirred for at least another 10 hours at room temperature. After that time, the suspensions were centrifuged to separate the solid phase from the liquid phase. The precipitated material was then resuspended in 4 ml of ethanol. The ethanol suspensions were centrifuged in order to complete the removal of unreacted species. The remaining gel-like product was then dried for 1 hour at 65 ° C in an oven and then calcined in an air muffle furnace (charge in the oven at room temperature, elevation to 100 ° C at a rate of 2 ° C / min., Residence time 30 min., Rise to 500 ° C at a rate of 2 ° C / min., Residence time 120 min., Cooling to room temperature).
[00725] [00725] The mixed oxide Ce2O3 / La2O3 nanowires are prepared from non-biological models in an analogous way.
[00726] [00726] 0.5 mL of 1 M Pr (NO3) 3 aqueous solution and 4.5 mL of 1 M La (NO3) 3 aqueous solution were mixed with 40 mL of deionized water. Once well mixed, 5 mL of a 3M NHOH aqueous solution was quickly injected into the mixture. A precipitate formed immediately. The suspension was kept under stirring for another 10 minutes, then transferred to centrifuge tubes and centrifuged to separate the solid phase from the liquid phase. The precipitated material was then resuspended in 35 ml of deionized water. The solid fraction was separated again by centrifugation and the washing step was repeated again. The remaining gel-like product was then dispersed in deionized water and the volume of the suspension adjusted to 20 ml. The suspension was then transferred to a hydrothermal pump and placed in an oven at 120 ° C for 2 hours. The solids obtained after the hydrothermal treatment were then separated by centrifugation and washed once with 35 ml of deionized water. The washed hydrothermally treated powder was then dried at 120 ° C for 16 hours. The surface area, determined by BET, of the dry powder was about 41 m2 / g. Transmission electron microscopy was used to characterize the morphology of this additional sample. The powder was made up of large particles in aspect ratio, about 30 nm wide by 0.5 to 2 µm long. The powder was calcined in three steps of temperature at 200, 400 and 500 ° C with 3 ° C of elevation and 2 hours of residence time in each step. The surface area of the mixed Pr2O3 La2O3 oxide nanowires was about 36 m2 / g.
[00727] [00727] In this example, Mg (OH) 2 nanowires are used as a support for the development of an Eu (OH) 3 envelope. Mg (OH) 2 nanowires, prepared according to the methods described in Example 28 (wet product, before being dried), were used to prepare a suspension in deionized water with a concentration of 3 g / L of Mg (OH) 2 dry. To the 30 ml of Mg (OH) 2 in suspension, 3 ml of 0.1 M aqueous solution (NO3) 3 and 3 ml of 0.3 M aqueous NH4OH solution were added in a slow addition of several steps. This addition was performed in 48 hours and 360 steps.
[00728] [00728] The rest of the powder was dried at 120 ° C for 3 hours and calcined in three stages at 200, 400 and 500 ° C with 2 hours at each stage and an elevation rate of 3 ° C / min. The surface area, determined by BET, of the MgO / Eu2O3 core / shell nanowires is 209 m '/ g.
[00729] [00729] 0.5 mL of 1 M Y (NO3) 3 aqueous solution and 4.5 mL of 1 M La (NO3) 3 aqueous solution were mixed with 40 mL of deionized water. Once well mixed, 5 mL of a 3M NHOH aqueous solution was quickly injected into the mixture. A precipitate formed immediately. The suspension was kept under stirring for another 10 minutes, then transferred to centrifuge tubes and centrifuged to separate the solid phase from the liquid phase. The precipitated material was then resuspended in 35 ml of deionized water. The solid fraction was separated again by centrifugation and the washing step was repeated again. The remaining gel-like product was then dispersed in deionized water and the voiume of the suspension adjusted to 20 ml. The suspension was then transferred to a hydrothermal pump and placed in an oven at 120 ° C for 2 hours. The solids obtained after the hydrothermal treatment were then separated by centrifugation and washed once with 35 ml of deionized water. The washed hydrothermally treated powder was then dried at 120 ° C for 16 hours. The surface area, determined by BET, of the dry powder was about 20 m2 / g. Transmission electron microscopy was used to characterize the morphology of this additional sample. The powder was made up of large particles in aspect ratio, about 20 to 40 nm wide and 0.5 to 2 µm long. The mixed Y2O3 / La2O3 oxide nanowires were calcined in three temperature steps at 200, 400 and 500 ° C with an increase of 3 ° C / min. and 2 hours of residence time at each stage.
[00730] [00730] 1 g of La2O3 (13.1 mmol) and 0.92 g of NH4C | (18.6 mmol) were placed in a 25 mL stainless steel autoclave with a Tefion coating (Parr Pump No. 4749). 10 ml of deionized water was then added to the dry reagents. The autoclave was sealed and placed in an oven at 160 ° C for 12 h. After 12 hours, the autoclave was allowed to cool. The nanowires were washed several times with 10 ml of water to remove any excess NH4C |
[00731] [00731] 0.5 g of La2O3 (1.5 mmol), 0.52 g of Nd2O3 (1.5 mmol), and 0.325 g of NH4C | (6 mmol) were ground together, using a mortar and pestle. Once the dry reagents were well mixed, the ground powder was placed in a ceramic crucible and the crucible was then transferred to a tube oven. The atmosphere of the tube oven was purged with nitrogen for half an hour. The reagents were then calcined under nitrogen (25 ° C - 450 ° C, rise to 2 ° C / min., Residence time 1 h; 450 ° C-900 ° C; rise to 2 ° C / min., 1 h waiting, cooling to room temperature The product (0.2 g) was placed in 10 ml of deionized water and stirred at room temperature for 24 hours.
[00732] [00732] 0.1 g of ZSM-5 zeolite is loaded into a fixed bed micro-reactor and heated at 400 ° C for 2 h under nitrogen to activate the catalyst. The OCM effluent, containing ethylene and ethane, is reacted on the catalyst at 400 ° C at a flow rate of 50 mL / min. and GSHV 3000-10,000 ml / (g h). The reaction products are separated into liquid and gas components using a cold trap. The gaseous and liquid components are analyzed by gas chromatography.
[00733] [00733] 0.1 g of nickel-doped ZSM-5 zeolite is placed in a fixed bed micro-reactor and heated at 350 ° C for 2 h under nitrogen to activate the catalyst. The OCM effluent containing ethylene and ethane is reacted over the catalyst in the temperature range of 250-400 ° C with GSHV = 1000-10,000 mL / (gh). The reaction products are separated into liquid and gas components using a cold trap. The gaseous and liquid components are analyzed by gas chromatography. Liquid fractions of C4-C1O olefin hydrocarbons, such as butene, hexane and octene represent z 95% of the liquid product ratio, while the C12-C18 hydrocarbon fraction represents the remaining 5 ° / 0 of the product ratio. Some small amounts of odd-numbered olefins are also possible in the product.
[00734] [00734] 0.379 g of Na2WO4 (0.001 mol) was dissolved in 5 ml of deionized water. 0.197 g of MnC! 2 * 6H2O (0.001 ml) was dissolved in 2 ml of deionized water. The two solutions were then mixed and a precipitate was observed immediately. The mixture was placed in a stainless steel autoclave with a Teflon coating (Parr Pump No. 4749). 40 ml of deionized water was added to the reaction mixture and the pH was adjusted to 9.4 with NH4OH. The autoclave was sealed and placed in an oven at 120 ° C. The reaction was reacted for 18 hours and then cooled to room temperature. The product was washed with deionized water and then dried in an oven at 65 ° C.
[00735] [00735] Catalytic nanowires supported with MnWO4 are prepared using the following general protocol. MnWO4 nanowires are prepared using the method described in Example 42. Manganese tungstate nanowires,
[00736] [00736] 50 mg of La2O3 catalytic nanowires, prepared using the method described in Example 19, were placed in a tubular reactor (4 mm diameter ID quartz tube with a 0.5 mm ID capillary downstream) that were then tested in Altamira Benchcat 203. Gas flows were kept constant at 46 sccm of methane and 54 sccm of air, which corresponds to a CH4 / O2 ratio of 4 and an hourly space gas feed speed (GHSV) of about 130.0OO / hour. The reactor temperature varied from 400 ° C to 500 ° C in an increment of 100 ° C and from 500 ° C to 850 ° C in increments of 50 ° C. The exhaust gases were analyzed by gas chromatography (GC) at each temperature level.
[00737] [00737] Figure 24 shows the start of the CMO between 500 ° C and 550 ° C. The C2 selectivity, methane conversion and C2 yield at 650 ° C were 54%, 27% and 14%, respectively.
[00738] [00738] La2O3 nanowires prepared using non-biological models are tested in a similar way and are expected to have similar catalytic properties.
[00739] [00739] La2O3 (3.1 mmol) and NH4NO3 (other different lanthanides and ammonium salts, for example, Cl or acetate and so on, can also be used) (18.6 mmol) were placed in a steel autoclave stainless with a Teflon coating. Water (10 ml) was then added to the dry reagents.
[00740] [00740] La2O3 (1-02 g), NH4NO3 (1 0.64 g) and 20 ml of deionized water were added to a round bottom flask equipped with a stir bar, and a reflux condenser. The suspension was refluxed for 18 h. The product was washed with DI water and dried. The product was then calcined in a muffle furnace, according to the procedure described in Example 42. The formation of the nanowire was confirmed by TEM. Microwave calcination can also be used.
[00741] [00741] In this example, both the microfiltration and ultrafiltration steps were performed using TFF. A batch of filamentous M13 bacteriophages genetically engineered to express AEEEDP at the N-terminus of mature protein pV111 (SEQ ID NO: 3) was amplified by incubation with E. co / i bacteria. The concentration of the amplified solution was quantified by titration to be 7.7E1 1 pfu / mL. 890 ml of the solution was purified using the following parameters.
[00742] [00742] The retentate obtained above was diafiltered with about 2.5 volumes (270 mL) of saline solution buffered with Tris at pH 7.5 (TBS). The TBS filtrate was also collected with a permeate solution containing the phage. The final phage yield in the permeate was 2.3%, as verified by titration (1,007 mL in 1.5E10O pfu / mL). For the ultrafiltration and diafiltration steps, a 100 KD polyethersulfone flat sheet membrane cartridge was used. Before purification, the membrane was cleaned and the normalized water flow was found to be '85% of the factory rating. The clarified phage solution via TFF microfiltration as described above was combined with another batch prepared in a similar manner.
[00743] [00743] The combination resulted in a total of 1,953 mL of the phage solution at a concentration of 4E9 cfu / mL. Flow parameters of approximately 1,640 L / h / m2 and transmembrane pressure of 48.26 kPa were used. The retentate containing the phage product was concentrated 17 times and diafiltered with 10 volumes of deionized water. After sample collection, the system was flushed completely with a volume equivalent to the volume retained (45 mL). The final phage yield in the retentate was -100 ° / o, as verified by titration (113 mL, 6.8E10 O pfu / mL).
[00744] [00744] In this example, instead of microfiltration of TFF, depth filtration was used for the initial stage, in order to clarify the amplification of the phage culture (SEQ ID NO: 3) of the bacterial cells, which developed in a similar way to that described in Example 44, of bacterial cells and cell debris. The second step to filter medium components and particles of bacterial cells of minor contamination, such as proteins, was performed with ultrafiltration and TFF diafiltration. 2,660 ml of the amplification culture with an initial phage concentration of 1.2 E12 pfu / ml was purified using the following parameters. Deep filtration was performed using a passage containing two filters, a fiberglass cartridge with a nominal porosity index of 1.2 µm, followed by a filter with double-pleated polyethersulfone membranes, classified as 0.8 µm and 0 , 45 µm respectively. The filtration was carried out at a constant pressure of 48.26 kPa. The phage yield in the filtrate was 86% (2,500 mL 1.1 E12pfu / mL). For the ultrafiltration and diafiltration steps, a 500 KD polyethersulfone flat sheet membrane cartridge was used. Before purification, the membrane was cleaned and the normalized water flow was verified to be 85% of the initial. 2,007mL of phage purified by the above depth filtration (1,1E12 pfu / mL) were purified. Flow parameters of approximately 2,200 L / h / m2 and transmembrane pressure of 48.23 kPa were used. The solution was concentrated with TFF of 1 hour and 35 min., Until -180 mL remained in the retentate (~ 1x concentration). The phage solution was then diafiltered with 2000 ml of deionized water with recirculation for approximately one hour. The final volume collected was 156 mL at a concentration of 1.4 E13 pfu / mL, which corresponds to 98% of the phage starting material.
[00745] [00745] Nd2O3 nanowires were prepared in a manner analogous to that of Example 14 by substituting La (NO3) 3 with Nd (NO3) 3.
[00746] [00746] A 400 mg aliquot of Nd2O3 nanowires is mixed with 2 g of Dl water and placed in a 5 ml glass bottle containing 2 mm of yttrium-stabilized Zirconia grinding spheres. The flask is placed on a shaker at
[00748] [00748] The core is placed inside a 9.52 mm tube and the catalyst paste is fed on top of the ceramic core and pushed with compressed air through the monolith channel. The excess paste is captured in a 20 mL bottle. The coated core is removed from the 9.5 mm tube and placed in a drying oven at 200 ° C for 1 hour.
[00749] [00749] The coating step is repeated twice more with the remaining paste, followed by drying at 200 ° C and calcination at 500 ° C for 4 hours. The amount of catalyst deposited on the walls of the monolith channel is approximately 50 mg and comprises very good adhesion to the ceramic mesh.
[00750] [00750] Nd2O3 nanowires were prepared in a manner analogous to that of Example 14 by replacing La (NO3) 3 with Nd (NO3) 3.
[00751] [00751] A 400 mg aliquot of Nd2O3 nanowires is mixed with 2 g of Dl water and placed in a 5 ml glass jar of Yttrium-Stabilized Zirconia grinding spheres. The flask is placed on a shaker at 2,000 rpm and shaken for 30 minutes. A thick paste is obtained.
[00752] [00752] A core of 9.52 mm in diameter is cut along a 65 PPl SlC foam (Pore Per Inch) and cut to length, so that the core volume is approximately 1 mL.
[00753] [00753] The core is placed inside a 9.52 mm tube and the catalyst paste is fed on top of the ceramic core and pushed with compressed air through the monolith channel. The excess paste is captured in a 20 mL bottle. The coated core is removed from the 9.5 mm tube and placed in a drying oven at 200 ° C for 1 hour.
[00754] [00754] The coating step is repeated twice more with the remaining paste, followed by drying at 200 ° C and calcination at 500 ° C for 4 hours. The amount of catalyst deposited on the walls of the monolith channel is approximately 50 mg and comprises very good adhesion to the ceramic mesh.
[00755] [00755] Nd2O3 nanowires were prepared in a similar manner to Example 14 by replacing La (NO3) 3 with Nd (NO3) 3.
[00756] [00756] An aliquot of 400 mg of Nd2O3 nanowires is mixed dry with 400 mg of 200-250 mesh SlC particles for 10 minutes or until the mixture appears homogeneous and the yarn groups are no longer visible. The mixture is then placed in a 6.35 mm matrix and pressed in 200 mg batches. The pressed microspheres are then placed in an oven and calcined at 600 ° C for 2 hours. The crushing resistance of the microspheres obtained is comparable to the crushing resistance of a microsphere obtained only from Nd, O, nanowires.
[00757] [00757] Examples of catalytic nanowires comprising La2O3, Nd2O3 La3NdO6 or with one, two, three or four different dopants selected from Eu, Na, Sr, Ho, Tm, Zr, Ca, Mg, Sm, W, La, K , Ba, Zn, and Li, were prepared and tested for their CMO activity according to the general procedures described in the preceding examples. Each of the exemplary catalysts produced a C2 yield greater than 10 ° / 0, a C2 selectivity greater than 5 ° / 0, and a CH4 conversion above 20% when tested as OCM catalysts at 650 ° C or less at pressures ranging from 1 to 10 atm. EXAMPLE 50 Pechini's Synthesis
[00758] [00758] Although any metal salt or combination of metal salts can be combined and processed using the Pechini method to prepare metal oxide catalysts, this example uses Ca, Nd, and Sr salts to prepare a mixed metal oxide CMO catalyst . Aqueous equimolar solutions of strontium nitrate, neodymium nitrate, and calcium nitrate were prepared. Aliquots of each solution were mixed together to prepare a desired formulation of Ca, NdySr, where x, y and z each represent, independently, molar fractions of total metal content, in moles. Representative examples of formulations include, but are not limited to, Ca50Nd30Sr20,
[00759] [00759] Dextran is a water-soluble polymer with a wide range of molecular weights and is a useful source of modeling. Briefly, a metal precursor and dextran are dissolved in water to produce a viscous solution. The solution is dried to obtain an organic metal compound and then calcined (oven or microwave) to remove the dextran model.
[00760] [00760] Agarose is also used to prepare mixed metal oxides for OCM catalysts. Agarose readily forms a gel that can be used as a molding source by impregnating the gel with meta precursors. An agarose gel is impregnated with a metal precursor. Optionally, the wet gel is impregnated with several metal precursors at the same time, or step by step for the eventual preparation of mixed metal oxide materials.
[00761] [00761] In an alternative to the above method, the agarose-metal compound is treated with a base to precipitate metal precursors within the ge! before calcination. Lyophilization is optionally employed to remove water from the agarose-metal compound. Agarose is removed by caicination in the oven or microwave to obtain metal and mixed metal CMO catalysts.
[00762] [00762] Other catalysts are prepared according to the methods mentioned above employing any of the polymers and metal compositions disclosed herein.
[00763] [00763] Sr2 doped La2O3 nanowires are prepared according to the following method.
[00764] [00764] A 57 mg aliquot of La2O3 nanowires prepared as described in this document, is then mixed with 0.174 ml of a 0.1 M solution of Sr (NO3) 2. This mixture is then stirred in a hot plate at 90 ° C until a paste is obtained.
[00765] [00765] The paste is then dried for 1 h at 120 ° C in a vacuum oven and finally calcined in an air muffle oven according to the following procedure: (1) charge in the oven at room temperature; (2) rise to 200 ° C at a rate of 3 ° C / min .; (3) residence time 120 min .; (4) rise to 400 ° C at a rate of 3 ° C / min .; (5) residence time 120 min .; (6) rise to 500 ° C at a rate of 3 ° C / min .; and (7) residence time 120 min.
[00766] [00766] The calcined product is then ground to a fine powder.
[00767] [00767] The various modalities described above can be combined to provide other modalities. All US Patents, United States Patent Application publications, US Patent Applications, Foreign Patents, Foreign Patent Applications and Non-Patent Publications referred to in this specification and / or indicated in the application data sheet, are incorporated herein. as a reference, in its entirety. Aspects of the modalities can be modified, if necessary, to use the concepts of the various Patents, Orders and Publications to provide yet other modalities. These and other changes can be made to the modalities, in the light of the above detailed description. In general, in the claims that follow, the terms used should not be construed as limiting the claims to the specific accomplishments revealed in the specification and in the claims, but should be interpreted in a way. include all possible modalities, together with the full scope of equivalents to which such claims refer. Consequently, the claims are not limited by the present disclosure.

权利要求:
Claims (37)
[1]
1. Catalytic nanowire CHARACTERIZED because it comprises a combination of at least four different doping elements, in which the doping elements are selected from a metallic element, a semi-metallic element and a non-metallic element.
[2]
2. Catalytic nanowire CHARACTERIZED by comprising at least two different doping elements, in which the doping elements are selected from a metallic element, a semi-metallic element and a non-metallic element, and in which at least one of the doping elements is K , Sc, Ti, V, Nb, Ru, Os, Ir, Cd, In, TI, S, Se, Po, Pr, Tb, Dy, Ho, Er, Tm, Lu or an element selected from any of the groups 6, 7, 10, 11, 14, 15 or 17.
[3]
3. Catalytic nanowire CHARACTERIZED for comprising at least one of the following combinations of dopants: Eu / Na, Sr / Na, Na / Zr / Eu / Ca, Mg / Na, Sr / Sm / Ho / Tm, Sr / W, Mg / La / K, Na / K / Mg / Tm, Na / Dy / K, Na / La / Dy, Sr / HF / K, Na / La / Eu, Na / La / Eu / In, Na / La / K, Na / La / Li / Cs, K / La, K / La / S, K / Na, Li / Cs, Li / Cs / La, Li / Cs / La / Tm, Li / Cs / Sr / Tm, Li / Sr / Cs, Li / Sr / Zn / K, Li / Ga / Cs, Li / K / Sr / La, Li / Na, Li / Na / Rb / Ga, Li / Na / Sr, Li / Na / Sr / La, Sr / Zr, Li / Sm / Cs, Ba / Sm / Yb / S, Ba / Tm / K / La, Ba / Tm / Zn / K, Sr / Zr / K, Cs / K / La, Cs / La / Tm / Na, Cs / Li / K / La, Sm / Li / Sr / Cs, Sr / Cs / La, Sr / Tm / Li / Cs, Zn / K, Zr / Cs / K / La, Rb / Ca / In / Ni, Sr / Ho / Tm, La / Nd / S, Li / Rb / Ca, Li / K, Tm / Lu / Ta / P, Rb / Ca / Dy / P, Mg / La / Yb / Zn, Rb / Sr / Lu, Na / Sr / Lu / Nb, Na / Eu / Hf, Dy / Rb / Gd, Sr / Ce, Na / Pt / Bi, Rb / HF, Ca / Cs, Ca / Mg / Na, HF / Bi, Sr / Sn, Sr / W, Sr / Nb, Sr / Ce / K, Zr / W, Y / W, Na / W, Bi / W, Bi / Cs, Bi / Ca, Bi / Sn, Bi / Sb, Ge / Hf, Hf / Sm, Sb / Ag, Sb / Bi, Sb / Au, Sb / Sm, Sb / Sr, Sb / W, Sb / Hf, Sb / Yb, Sb / Sn, Yb / Au, Yb / Ta, Yb / W, Yb / Sr, Yb / Pb, Yb / W, Yb / Ag, Au / Sr, W / Ge, Sr / Tb, Ta / Hf, W / Au, Ca / W, Au / Re, Sm / Li, La / K, Zn / Cs, Na / K / Mg, Zr / Cs, Ca / Ce, Na / Li / Cs, Li / Sr, Cs / Zn, La / Dy / K, Dy / K, La / Mg, Na / Nd / In / K, In / Sr, Sr / Cs, Rb / Ga / Tm / Cs, Ga / Cs, K / La / Zr / Ag, Lu / Fe, Sr / Tb / K, Sr / Tm, La / Dy, Sm / Li / Sr , Mg / K, Sr / Pr, Li / Rb / Ga, Li / Cs / Tm, Zr / K, Li / Cs, Li / K / La, Ce / Zr / La, Ca / Al / La, Sr / Zn /Over there,
Sr / Cs / Zn, Sm / Cs, In / K, Ho / Cs / Li / La, Sr / Pr / K, Cs / La / Na, La / S / Sr, K / La / Zr / Ag, Lu / TI, Pr / Zn, Rb / Sr / La, Na / Sr / Eu / Ca, K / Cs / Sr / La, Na / Sr / Lu, Sr / Eu / Dy, Lu / Nb, La / Dy / Gd, Na / Mg / Tl / P, Na / Pt, Gd / Li / K, Rb / K / Lu, Sr / La / Dy / S, Na / Ce / Co, Na / Ce, Na / Ga / Gd / Al, Ba / Rh / Ta, Ba / Ta, Na / Al / Bi, Sr / HF / Rb, Cs / Eu / S, Sm / Tm / Yb / Fe, Sm / Tm / Yb, Hf / Zr / Ta, Rb / Gd / Li / K, Gd / Ho / Al / P, Na / Ca / Lu, Cu / Sn, Ag / Au, Al / Bi, Al / Mo, Al / Nb, Au / Pt, Ga / Bi, Mg / W, Pb / Au, Sn / Mg, Sr / B, Zn / Bi, Gd / Ho, Zr / Bi, Ho / Sr, Gd / Ho / Sr, Ca / Sr, Ca / Sr / W, Sr / Ho / Tm / Na, Na / Zr / Eu / Tm, Sr / Ho / Tm / Na, Sr / Pb, Sr / W / Li, Ca / Sr / WW or Sr / Hf.
[4]
4. Catalytic nanowire CHARACTERIZED for comprising Ln14-xLn2xO6 and a dopant comprising a metallic element, a semi-metallic element, a non-metallic element or combinations thereof, where Ln1 and Ln2 are each, independently, a lanthanide element, where Ln1 and Ln2 are not the same and x is a number ranging from more than 0 to less than 4.
[5]
5. Catalytic nanowire CHARACTERIZED for comprising a mixed oxide of Y-La, Zr-La, Pr-La, Ce-La or combinations thereof and at least one dopant selected from a metallic element, a semimetallic element and an non-metallic material.
[6]
6. Catalytic nanowire CHARACTERIZED for comprising a mixed oxide of a rare earth element and a Group 13 element, in which the catalytic nanowire further comprises one or more Group 2 elements.
[7]
7. Catalytic nanowire CHARACTERIZED by the fact that the conversion of single-pass methane into an OCM reaction catalyzed by the nanowire is more than 20%.
[8]
8. Catalytic nanowire CHARACTERIZED for having a C2 selectivity greater than 10% in the OCM reaction, when the OCM reaction is carried out with an oxygen source other than air or O2.
[9]
9. Catalytic material in the form of a pressed, extruded or monolithic microsphere, the catalytic material FEATURED for comprising:
a) a plurality of catalytic nanowires comprising a dopant; and b) a diluent or support comprising an alkaline earth metal compound, in which the catalytic material has a C2 yield above 5% when used as a catalytic material in the oxidative coupling of methane at an inlet temperature of 550 ºC and a pressure of entry of about 2 atm into a fixed bed reactor with a gas-hour space velocity (GHSV) of at least about 20,000 / h.
[10]
10. Catalytic material according to claim 9, CHARACTERIZED by the fact that the alkaline earth metal compound is MgO, MgCO3, MgSO4, Mg3 (PO4) 2, MgAl2O4, CaO, CaCO3, CaSO4, Ca3 (PO4) 2 , CaAl2O4, SrO, SrCO3, SrSO4, Sr3 (PO4) 2, SrAl2O4, BaO, BaCO3, BaSO4, Ba3 (PO4) 2, BaAl2O4 or combinations thereof, or in which the alkaline earth metal compound is MgO, CaO, SrO , MgCO3, CaCO3, SrCO3, or combinations thereof.
[11]
11. Catalytic material, according to claim 9, CHARACTERIZED by the fact that the catalytic material is in the form of a pressure-treated pressed microsphere.
[12]
12. Catalytic material according to claim 9, characterized by still comprising a sacrificial binder.
[13]
13. Catalytic material, according to claim 9, CHARACTERIZED by the fact that the catalytic material is in the form of a pressed or extruded microsphere and comprises pores larger than 20 nm in diameter or pores larger than 50 nm in diameter.
[14]
14. Catalytic material according to claim 9, CHARACTERIZED by the fact that the alkaline earth metal compound is an alkaline earth metal oxide, alkaline earth metal carbonate, alkaline earth metal sulfate or alkaline earth metal phosphate.
[15]
15. Catalytic material according to claim 9, CHARACTERIZED by the fact that the plurality of catalytic nanowires has a ratio of effective average length to actual average length less than one and an average aspect ratio greater than ten, as measured by TEM in bright field mode at 5 keV, in which the plurality of catalytic nanowires comprises one or more elements of any of Groups 1 to 7, lanthanides, actinides or combinations thereof.
[16]
16. Catalytic material according to claim 9, CHARACTERIZED by the fact that the plurality of catalytic nanowires substantially comprises straight nanowires.
[17]
17. Catalytic material, according to claim 16, CHARACTERIZED by the fact that the substantially straight nanowires have a ratio of effective length to actual length equal to one.
[18]
18. Catalytic material according to claim 9, CHARACTERIZED by the fact that the plurality of catalytic nanowires comprises at least one nanowire selected from any of Tables 1 to 12.
[19]
19. Catalytic material, according to claim 9, CHARACTERIZED by the fact that the catalytic material still comprises SiC or cordierite or combinations thereof.
[20]
20. Catalytic material according to claim 9, CHARACTERIZED by the fact that the alkaline earth metal compound is MgCO3, MgSO4, Mg3 (PO4) 2, CaO, CaCO3, CaSO4, Ca3 (PO4) 2, CaAl2O4, SrO, SrCO3, SrSO4, Sr3 (PO4) 2, SrAl2O4, BaO, BaCO3, BaSO4, Ba3 (PO4) 2, BaAl2O4 or combinations thereof, or where the alkaline earth metal compound is CaO, SrO, MgCO3, CaCO3, SrCO3 or combinations thereof.
[21]
21. Catalytic material, according to claim 9, CHARACTERIZED by the fact that the catalytic material has a C2 selectivity above
50% when used as a catalytic material in the oxidative methane coupling at an inlet temperature of 550 ºC and an inlet pressure of about 2 atm in a fixed bed reactor with a gas-hour space velocity (GHSV) of at least least about 20,000 / h.
[22]
22. Catalytic material, according to claim 9, CHARACTERIZED by the fact that the catalytic material has a CH4 conversion above 20% when used as a catalytic material in the oxidative methane coupling at an inlet temperature of 550 ºC and an inlet pressure of about 2 atm in a fixed bed reactor with a gas-hour space velocity (GHSV) of at least about 20,000 / h.
[23]
23. Method for the oxidative coupling of methane, the method CHARACTERIZED because it comprises contacting the catalytic material, as defined in claim 9, with methane, in order to convert the methane into ethane, ethylene or combinations thereof.
[24]
24. Method, according to claim 23, CHARACTERIZED by the fact that the oxidative methane coupling is carried out at a gas inlet temperature below 600 ºC or below 550 ºC.
[25]
25. Method, according to claim 23, CHARACTERIZED by the fact that the conversion of methane to ethylene is greater than 10%, or greater than 20%.
[26]
26. Method, according to claim 23, CHARACTERIZED by the fact that the ethylene yield is greater than 10%, or greater than 20%.
[27]
27. Catalytic material in the form of a pressed, pressure-treated microsphere, CHARACTERIZED by the fact that the catalytic material comprises a plurality of catalytic nanowires and substantially no binding material.
[28]
28. Catalytic material FEATURED for comprising a catalytic nanowire, in which the catalytic material is in contact with a reactor.
[29]
29. Catalytic material FEATURED for comprising at least one O2-OCM catalyst and at least one CO2-OCM catalyst.
[30]
30. Catalytic material CHARACTERIZED by comprising at least one O2-OCM catalyst and at least one CO2-ODH catalyst.
[31]
31. Method for preparing a catalytic material, the method CHARACTERIZED by comprising mixing a plurality of catalytic nanowires with a sacrificial binder and removing the sacrificial binder to obtain a catalytic material that comprises substantially no binding material and has a microporosity increased compared to a catalytic material prepared without the sacrificial binder.
[32]
32. Method for purifying a phage solution, the method CHARACTERIZED as comprising: a) a microfiltration step that comprises filtering a phage solution through a membrane comprising pores ranging from 0.1 to 3 µm to obtain a retentate microfiltration and a microfiltration permeate; and b) an ultrafiltration step comprising filtering the microfiltration permeate through a membrane comprising pores ranging from 1 to 1,000 kDa and recovering an ultrafiltration retentate comprising a purified flue solution.
[33]
33. Method for preparing a catalytic nanowire comprising a metal oxide, a metal oxy-hydroxide, a metal oxycarbonate or a metal carbide, the CHARACTERIZED method comprising: a) providing a solution comprising a plurality of molds; b) introducing at least one metal ion and at least one anion to the solution under conditions and for a time sufficient to allow the nucleation and development of a nanowire comprising a plurality of metal salts (MmX-nZp) on the mold; and c) convert the nanowire (MmXnZp) into a metal oxide nanowire comprising
giving a plurality of metal oxides (MxOy), metal oxy-hydroxides (MxO-yOHz), metal oxycarbonates (MxOy (CO3) z), metal carbonates (Mx (CO3) y) or combinations thereof, where: M is, in each occurrence, independently, a metallic element of any of Groups 1 to 7, lanthanides or actinides; X is, in each occurrence, independently, hydroxide, carbonate, bicarbonate, phosphate, hydrogen phosphate, dihydrogen phosphate, sulfate, nitrate or oxalate; Z is O; n, m, x and y are each, independently, a number from 1 to 100; and p is a number from 0 to 100.
[34]
34. Method for preparing catalytic nanowires of metal oxide, metal oxyhydroxide, metal oxycarbonate or metal carbonate in a core / shell structure, the CHARACTERIZED method comprising: (a) providing a solution that includes a plurality of molds; (b) introducing a first metal ion and a first anion to the solution, under conditions and for a time sufficient to allow nucleation and the development of a first nanowire (M1m1X1n1 Zp1) on the mold; and (c) introducing a second metal ion and, optionally, a second anion to the solution, under conditions and for a time sufficient to allow nucleation and the development of a second nanowire (M2m2X2n2 Zp2) on the surface of the first nanowire ( M1m1X1n1 Zp1); (d) convert the first nanowire (M1m1X1n1 Zp1) and the second nanowire (M2m2X2n2 Zp2) in the respective metal oxide nanowires (M1x1Oy1) and (M2x2Oy2), in the respective metal oxyhydroxide nanowires (M1x1Oy1OHz1) and (M2x2Oz1) and (M2x2Hz) metal oxicarbonate nanowires (M1x1Oy1 (CO3) z1) and (M2x2Oy2 (CO3) z2) or in the respective metallic carbonate nanowires (M1x1 (CO3) y1) and (M2x2 (CO3) y2),
where: M1 and M2 are the same or different and selected, independently, from a metallic element; X1 and X2 are the same or different and, independently, hydroxide, carbonate, bicarbonate, phosphate, hydrogen phosphate, dihydrogen phosphate, sulphate, nitrate or oxalate; Z is O; n1, m1n2, m2, x1, y1, z1, x2, y2 and Z2 are each, independently, a number from 1 to 100; and p1 and p2 are, independently, a number from 0 to 100.
[35]
35. Method for preparing a catalytic nanowire, the CHARACTERIZED method as it comprises treating at least one metal compound with an ammonium salt having the formula RN4X, where each R is, independently, H, alkyl, alkenyl, alkynyl or aryl and X is an anion.
[36]
36. Method for oxidative coupling of methane, the method CHARACTERIZED because it comprises converting methane into one or more C2 hydrocarbons in the presence of a catalytic material, where the catalytic material comprises at least one O2-CMO catalyst and at least a CO2-OCM catalyst.
[37]
37. Method for the preparation of ethane, ethylene or combinations of the same, the method CHARACTERIZED for comprising converting methane into ethane, ethylene or combinations thereof, in the presence of a catalytic material, where the catalytic material comprises at least one catalyst O2-OCM and at least a CO2-ODH catalyst.
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法律状态:
2020-11-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2021-01-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2022-01-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US201161564834P| true| 2011-11-29|2011-11-29|

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US201161564836P| true| 2011-11-29|2011-11-29|

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US61/564.836|2011-11-29|

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US61/564.834|2011-11-29|

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US201261651399P| true| 2012-05-24|2012-05-24|

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US61/651.399|2012-05-24|

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PCT/US2012/067124|WO2013082318A2|2011-11-29|2012-11-29|Nanowire catalysts and methods for their use and preparation|

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