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    • 专利摘要:
    The invention relates to a composition containing a first semiconductor SC1, particles comprising one or more element (s) M in the metallic state chosen from an element of groups IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA and VA of the periodic table of elements, and a second semiconductor SC2 comprising indium oxide, said first semiconductor SC1 being in direct contact with said particles comprising one or more element (s) M in the metallic state, said particles being in direct contact with said second semiconductor SC2 comprising indium oxide so that the second semiconductor SC2 covers at least 50% of the surface of the particles comprising one or more several element (s) M in the metallic state. The invention also relates to its preparation process as well as its application in photocatalysis.
    公开号:FR3026966A1
    申请号:FR1459849
    申请日:2014-10-14
    公开日:2016-04-15
    发明作者:Eric Puzenat；Christophe Geantet
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] The field of the invention is that of composite materials and their application in photocatalysis. By composite material is meant a solid consisting of at least two compounds of different chemical natures.
    [0002] In the following, the groups of chemical elements are given according to the classification CAS (CRC Handbook of Chemistry and Physics, publisher CRC press, editor-in-chief D. R. Lide, 81 st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
    [0003] PRIOR ART Examples of composite materials containing semiconductors, in particular composite materials composed of core-layer particles on the surface of a semiconductor substrate, exist in the literature. This type of solid has particularly been developed in photocatalytic applications. C. Li et al (J. Hydrogen Energy, 37, pp. 6431-6437, 2012) have unveiled the synthesis of TiO 2 nanotube-based solids on which are deposited in a photo-assisted manner oxidized metallic copper particles in their entirety. area. H. Lin et al. (Cat., 21: 91-95, 2012) propose a composite prepared by coprecipitation composed of AgBr / Ag / Agl, AgBr and Agl both being semiconductors. C. Wang et al. (Chem Eng J., 237, p.29-37, 2014) prepared by successive impregnations a material having contacts between WO3 and Pt on the one hand and Pt and TiO2 on the other hand. Finally, H. Tada (Nature Materials, 5, pp. 782-786, 2006) proposes a solid based on hemispherical particles having a layer of CdS around an Au core, which particles are deposited on the semiconductor surface. TiO2 conductor. The object of the invention is to provide a composition containing a first semiconductor SC1, particles comprising one or more element (s) M in the metallic state chosen from a group element IVB, VB, VIB, VIIB , VIIIB, IB, IIB, IIIA, IVA and VA of the periodic table of elements, and a second semiconductor SC2 comprising indium oxide, said first semiconductor SC1 being in direct contact with said particles comprising a or more than one element M in the metallic state, said particles being in direct contact with said second semiconductor SC2 comprising indium oxide so that the second semiconductor SC2 covers at least 50 % of the surface of the particles comprising one or more element (s) M in the metallic state. The use of indium oxide constituting the semiconductor SC2 makes it possible, surprisingly, to obtain a photocatalyst having improved photocatalytic performance compared to photocatalysts known from the state of the art. According to a preferred variant, the first semiconductor SC1 is furthermore in direct contact with the second semiconductor SC2. According to a preferred variant, said first semiconductor SC1 forms a support, said support contains at its surface core-layer type particles, said layer being formed by said semiconductor SC2 comprising indium oxide, said core being formed by said particles having one or more element (s) M in the metallic state. According to one variant, the indium oxide is predominantly composed of In203. According to one variant, the element M in the metallic state is chosen from platinum, palladium, gold, nickel, cobalt, ruthenium, silver, copper, rhenium or rhodium.
    [0004] According to one variant, the content of indium oxide, expressed as In element, is between 0.01 and 50% by weight relative to the total weight of the composition. According to one variant, the content of element (s) M in the metallic state is between 0.001 and 20% by weight relative to the total weight of the composition. According to a variant, said particles comprising one or more element (s) M in the metallic state are in the form of particles of sizes between 0.5 nm and 1000 nm. According to one variant, the composition is in the form of a nanometric powder. According to one variant, the semiconductor SC1 is selected from TiO2, Bi2S3, Bi2O3, Fe2O3, ZnO, WO3, CuO, ZnFe2O4, MoS2, and In (OH) 3. According to one variant, the layer has a thickness of 1 nm to 1000 nm. The invention also relates to its preparation process comprising the following steps: a) a suspension containing a first semiconductor SC1 is prepared under stirring in a liquid mixture composed of water and / or one or more organic compounds, and at least one metal precursor selected from an element of Groups IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA and VA of the Periodic Table of Elements, and the suspension is irradiated by an irradiation source such that at least a part of the emission spectrum of said source is composed of photons of energies greater than the forbidden band width of the semiconductor SC1; b) the said irradiation source is introduced under agitation and under irradiation; indium precursor to the degree of oxidation +3 soluble in the suspension obtained in step a), c) is then introduced with stirring and irradiation of said irradiation source a basic agent so as to p rovocate the precipitation of indium oxide, d) then the composition is separated from the suspension of step c), e) the composition obtained in step d) is dried, f) optionally, the dried composition obtained in step e) to a heat treatment. According to one variant, the metal precursor is chosen from a precursor of platinum, palladium, gold, nickel, cobalt, ruthenium, silver, copper, rhenium or rhodium. According to a variant, in step c) the pH is between 5 and 13 after the introduction of the basic agent.
    [0005] The invention also relates to the use of the composition according to the invention or prepared according to the preparation method as a photocatalyst. DETAILED DESCRIPTION OF THE INVENTION Composition according to the invention The invention relates to a composition containing a first semiconductor SC1, particles comprising one or more element (s) M in the metallic state chosen from an element of groups IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA and VA of the periodic table of the elements, and a second semiconductor SC2 comprising indium oxide, said first semiconductor SC1 being in accordance with FIG. direct contact with said particles having one or more element (s) M in the metallic state, said particles being in direct contact with said second semiconductor SC2 comprising indium oxide so that the second semiconductor SC2 covers at least 50% of the surface of the particles comprising one or more element (s) M in the metallic state. Preferably, the composition consists of a first semiconductor SC1, particles comprising one or more element (s) M in the metallic state chosen from an element of groups IVB, VB, VIB, VIIB, VIIIB, IB, IIB IIIA, IVA and VA of the periodic table of elements, and a second semiconductor SC2 comprising indium oxide. According to an important aspect of the invention, the first semiconductor SC1 is in direct contact with particles comprising one or more element (s) M in the metallic state, said particles being in direct contact with a second semiconductor SC2 comprising indium oxide. Preferably, the first semiconductor SC1 is also in direct contact with the second semiconductor SC2. According to a preferred variant of the invention, said first semiconductor SC1 forms a support, said support contains on its surface core-layer type particles, said layer being formed by said semiconductor SC2 comprising indium, said core being formed by said particles having one or more element (s) M in the metallic state. The use of indium oxide constituting the layer of the core-layer-type particles at the surface of a semiconductor substrate SC1 according to the invention makes it possible, surprisingly, to obtain a photocatalyst having photocatalytic performance improved by compared to known photocatalysts of the state of the art not containing the supported core-layer architecture. The second semiconductor SC2 covers at least 50% of the surface of the particles having one or more element (s) M in the metallic state a surface, preferably greater than 60% and very preferably greater than 75% . The layer has a thickness of 1 nm to 1000 nm, preferably 1 nm to 500 nm, and particularly preferably 2 to 50 nm.
    [0006] The composition contains a first semiconductor SC1. SC1 semiconductors used according to the invention comprise at least one inorganic, organic or organic-inorganic composite semiconductor. The band gap width of the inorganic, organic or organic-inorganic semiconductor is generally between 0.1 and 5.5 eV. According to a first variant, the semiconductor SC1 comprises at least one inorganic solid. The inorganic semiconductor may comprise one or more of the elements selected from Group IVA elements, such as silicon, germanium, silicon carbide or silicon-germanium. It can also be composed of elements of groups IIIA and VA, such as GaP, GaN, InP and InGaAs, or elements of groups IIB and VIA, such as CdS, ZnO and ZnS, or elements of groups IB and VIIA, such as CuCl and AgBr, or elements of groups IVA and VIA, such as PbS, PbO, SnS and PbSnTe, or elements of groups VA and VIA, such as Bi2Te3 and Bi203, or elements of groups IIB and VA, such as Cd3P2, Zn3P2 and Zn3As2, or elements of groups IB and VIA, such as CuO, Cu2O and Ag2S, or elements of groups VIII and VIA, such as CoO, PdO, Fe2O3 and NiO, or elements of groups VIB and VIA, such as MoS2 and WO3, or elements of groups VB and VIA, such as V205 and Nb2O5, or elements of groups IVB and VIA, such as TiO2 and HfS2, or elements of groups IIIA and VIA, such as In203, In253 or In (OH) 3, or elements of groups VIA and lanthanides, such as Ce203, Pr203, Sm253, Tb2S3 and La2S3, or elements VIA groups and actin ides, such as UO2 and UO3. Preferably, the semiconductor is selected from TiO2, Bi2S3, Bi203, CdO, Ce203, CeO2, CoO, Cu2O, Fe2O3, FeTiO3, In (OH) 3, NiO , PbO, ZnO, WO3, CuO, ZnFe2O4, MoS2, Ag2S, CdS, Ce2S3, Cu2S, CuInS2, In2S3, ZnFe2O3, ZnS and ZrS2 and 'In (OH) 3. Very preferably, the semiconductor is selected from TiO2, Si2S3, Bi2O3, Fe2O3, ZnO, WO3, CuO, ZnFe2O4, MoS2, and In (OH) 3. According to another variant, the semiconductor SC1 comprises at least one organic semiconductor. Among the organic semiconductors, mention may be made of tetracene, anthracene, polythiophene, polystyrene sulphonate, phosphyrenes and fullerenes.
    [0007] In another variant, the semiconductor SC1 comprises at least one organic-inorganic semiconductor. Among the organic-inorganic semiconductors, mention may be made of crystalline solids of MOF type (for Metal Organic Frameworks according to the English terminology). The MOFs consist of inorganic subunits (transition metals, lanthanides, etc.) and are interconnected by organic ligands (carboxylates, phosphonates, imidazolates, etc.), thus defining crystallized hybrid networks, sometimes porous. The semiconductor SC1 may optionally be doped with one or more ions chosen from metal ions, such as, for example, ions of V, Ni, Cr, Mo, Fe, Sn, Mn, Co, Re, Nb, Sb, La, Ce, Ta, Ti, non-metallic ions, such as for example C, N, S, F, P, or a mixture of metal and non-metallic ions. According to another variant, the semiconductor SC1 may be surface-sensitized with any organic molecules capable of absorbing photons. The semiconductor SC1 may be in different forms (nanoscale powder, nanoobjects with or without cavities, etc.) or shaped (films, monolith, beads of micrometric or millimetric size, etc.). The composition contains a second SC2 semiconductor. The semiconductor SC2 comprises indium oxide. Preferably, the indium element is at the +3 oxidation state. Very preferably, the indium oxide is predominantly composed of In 2 O 3. The term "predominantly composed of In203" an In203 content greater than 50% by weight, preferably greater than 60% by weight and particularly preferably greater than 70% of the total weight of the semiconductor SC2. Optionally, the semiconductor SC2 may further contain indium hydroxides. The semiconductor SC2 preferably contains no other element of the group of metals than indium. The indium oxide content, expressed as In element, is between 0.01 and 50% by weight, preferably between 0.5 and 20% by weight relative to the total weight of the composition.
    [0008] The composition comprises particles comprising one or more metal element (s) M chosen from an element of groups IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA and VA of the periodic table of elements.
    [0009] These particles comprising one or more element (s) M are in direct contact with said semiconductor SC1 and SC2 respectively. Said particles can be composed of a single element in the metallic state or of several elements in the metallic state that can form an alloy.
    [0010] The term "element in the metallic state" means an element belonging to the family of metals, said element being at the zero oxidation state (and therefore in the form of metal). Preferably, the element or elements M in the metallic state are chosen from a metal element of groups VIIB, VIIIB, IB and IIB of the periodic table of elements, and particularly preferably from platinum, palladium gold, nickel, cobalt, ruthenium, silver, copper, rhenium or rhodium. Said particles comprising one or more element (s) M in the metallic state are preferably in the form of particles of sizes between 0.5 nm and 1000 nm, very preferably between 0.5 nm and 100 nm.
    [0011] The content of element (s) M in the metallic state is between 0.001 and 20% by weight, preferably between 0.01 and 10% by weight relative to the total weight of the composition. The composition according to the invention may be in different forms (nanometric powder, nanoobjects with or without cavities, etc.) or shaped (films, monolith, beads of micrometric or millimetric size, etc.). The composition according to the invention is advantageously in the form of a nanometric powder.
    [0012] Preparation of the solid The composition according to the invention may be prepared according to any method known to those skilled in the art. According to one embodiment, the composition is obtained by photodeposition of the metal element (s) M forming the metal particles (and thus the core in a supported core-layer architecture), then by condensation induced by precipitation under irradiation of a precursor of indium of +3 oxidation state (forming the layer in a supported core-layer architecture) on a semiconductor SC1 (forming the support in a supported core-layer architecture) containing the metal particles on its surface.
    [0013] It should be noted that a preparation by the dry impregnation technique (generally seeking a high dispersion of the metal on the support) of a copper precursor does not make it possible to obtain a composition according to the invention in which the second semiconductor SC2 comprising copper oxide covers at least 50% of the surface of the particles comprising one or more element (s) M in the metallic state. More particularly, the process for preparing the composition according to the invention comprises the following steps: a) a suspension containing a first semiconductor SC1 is prepared with stirring in a liquid mixture composed of water and / or one or a plurality of organic compounds and at least one metal precursor selected from an element of Groups IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA and VA of the Periodic Table of Elements, and the suspension is irradiated by a source of irradiation such that at least a portion of the emission spectrum 15 of said source is composed of photons of energies greater than the bandgap width of the semiconductor SC1, b) is introduced with stirring and under irradiation of said source irradiation an indium precursor to the degree of oxidation +3 soluble in the suspension obtained in step a), c) is then introduced with stirring and irradiation of said irradiation source a basic agent in order to cause the precipitation of the indium oxide, d) then the composition is separated from the suspension of step c), e) the composition obtained in step d), f) is dried. the dried composition obtained in step e) is subjected to a heat treatment. Thus, in step a), a suspension containing a SC1 semiconductor, preferably in the form of nanopowder, is prepared with stirring in a liquid mixture composed of water and / or one or more organic compounds and at least one metal precursor selected from an element of Groups IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA and VA of the Periodic Table of Elements, and the suspension is irradiated by an irradiation source such that at least a portion of the emission spectrum of said source is composed of photons of energies greater than the forbidden bandgap of semiconductor SC1. The percentage of organic compounds contained in the suspension varies from 0 to 100% by volume. The organic compounds are generally primary or secondary alcohols, preferably the organic compounds are methanol, ethanol or isopropanol, alone or as a mixture. The metal precursor is introduced into the mixture in the form of a soluble powder or in solution, preferably in aqueous solution. The metal precursor is generally based on acetate, acetylacetonate, chloride, nitrate or sulfate. Preferably, the metal precursor is based on chloride or nitrate. The metal precursor is chosen from an element of groups IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA and VA of the periodic table of elements, preferably from groups VIIB, VIIIB, IB and IIB of the periodic classification of the elements. Very preferably, the precursor is a precursor of platinum, palladium, gold, nickel, cobalt, ruthenium, silver, copper, rhenium or rhodium. The amounts of the metal precursor introduced into the suspension are chosen such that the content of element (s) M in the metallic state is between 0.001 and 20% by weight, preferably between 0.01 and 10%. by weight relative to the total weight of the composition. The semiconductor SC1 introduced in step a) is one of the semiconductors described above. The mixing is preferably carried out at room temperature with stirring, preferably mechanically or by bubbling. The mixture is irradiated by a source such that at least a portion of the emission spectrum is composed of photons of energies greater than the forbidden band width of the semiconductor employed. Preferably the source emits at least a wavelength range greater than 280 nm, very preferably 315 nm to 800 nm, which includes the UV spectrum and / or the visible spectrum. The source of radiation may be any source of artificial or natural electromagnetic radiation, such as natural sunlight, a type of lamp Hg, a lamp type Xe, a lamp type LED.
    [0014] The duration of this step is preferably between 1 minute and 20 hours under irradiation, preferably between 1 minute and 5 hours. During step a), the M5 + metal ions of the precursor are reduced in the form of metal particles M ° at the surface of the seri-conductor SC1 under the action of the electrons generated by the absorption of photons by said semiconductor. When the composition is in the form of a supported core-layer architecture, these metal particles will form the core of the composition according to the invention.
    [0015] In step b), an indium precursor with a degree of oxidation +3 soluble in the suspension obtained in step a) is introduced with stirring and under irradiation of the said irradiation source. The indium precursor is generally based on chloride, iodide, bromide, fluoride, acetate, acetylacetonate, nitrate, sulfate, hydroxide. Preferably, the precursor is indium nitrate or indium chloride. The indium precursor may be solubilized before being introduced into water or a liquid mixture composed of water and one or more organic compounds such as primary or secondary alcohols, and preferably, methanol, ethyl alcohol and the like. ethanol or isopropanol, alone or in admixture.
    [0016] Optionally, and in order to ascertain the solubility of the indium precursor, an acidic agent may be added to the mixture to modulate the pH of the solution. The acidic agent is preferably selected from inorganic acids such as nitric, sulfuric, phosphoric, hydrochloric or hydrobromic acid or organic acids such as carboxylic or sulphonic acids. The pH of the solution is less than 7, preferably less than 5. The amounts of the indium precursor introduced into the suspension are chosen such that the indium oxide content, expressed as In element, is between 0.01 and 50% by weight, preferably between 0.5 and 20% by weight relative to the total weight of the composition.
    [0017] The stirring and irradiation conditions are those described for step a). The agitation and irradiation conditions are preferably identical to those of step a). The duration of this step is preferably between 1 minute and 20 hours, preferably between 1 minute and 5 hours.
    [0018] In step c), a basic agent is introduced under agitation and under irradiation of the said irradiation source so as to cause the precipitation of indium oxide, in particular of In203. Preferably, the pH is modified by the addition of a basic agent in such a way that it is in a range between 5 and 13 after addition of the agent. The basic agent is preferably selected from alkali or alkaline earth hydroxides, organic bases such as amines or ammonia. The agitation and irradiation conditions of step c) are those described for step a). The agitation and irradiation conditions are preferably identical to those of step a). The duration of this step is preferably between 1 minute and 20 hours, preferably between 1 minute and 5 hours. During step c), the metal ions In3 + precipitate in the form of an In203 metal oxide layer at the surface of the metal particles M deposited in step a), under the action of the introduced basic agent. The M / semiconductor SC1 interface promotes the localization of the photogenerated electrons by the absorption of photon in said semiconductor SC1 at the surface of the metal particles M and thus induces a negative surface charge of said metal particles M, from which the preferential location of the In203 oxide layer on the metal particles due to the electrostatic attraction between In3 + and M (5-). In step d), the composition is separated from the suspension of step c). The separation can be carried out by filtration or by centrifugation. Preferably it is carried out by centrifugation. Generally, this centrifugation takes place for 10 to 60 minutes from 2000 to 10,000 rpm. Preferably, one to three washes with water are then carried out. In step e), the composition obtained in step d) is dried. Drying is carried out at 30 ° C to 200 ° C, usually for 1 to 48 hours, preferably under air. Optionally, this drying can be carried out under an inert atmosphere. Drying may optionally be carried out in an oven or rotary evaporator. The drying step may optionally be carried out under partial vacuum.
    [0019] According to one embodiment, between steps a) and b) a separation step can be carried out, preferably by centrifugation, an optional washing step, and a drying step under the conditions described above.
    [0020] Optionally, the dried composition obtained in step e) is subjected to a heat treatment (step f). The heat treatment is carried out under air flow, nitrogen, hydrogen or partial vacuum, generally at a temperature between 50 ° C and 500 ° C, preferably for a period between 1 and 16 hours.
    [0021] The invention also relates to the use of the composition according to the invention as a photocatalyst, and in particular as a photocatalyst for the degradation of organic compounds, such as, for example, formic acid. The photocatalytic process for the degradation of organic compounds, such as, for example, the photocatalytic degradation of formic acid, is carried out by bringing into contact a stream containing an organic compound with said composition according to the invention. Then the composition is irradiated with at least one irradiation source producing at least one wavelength suitable for activating said composition so as to degrade the organic compound, for example formic acid with hydrogen and with CO2. The composition can be used in a photocatalytic process in a liquid or gaseous medium. The implementation of the photocatalytic process can be done in fixed bed crossed, in fixed bed licking or in suspension (also called "slurry" according to the English terminology). It can also be done in totally glass reactors or with non-absorbing optical windows to allow the radiation to reach the surface of the solid. The type of reactor technology for the implementation of the solid is generally adapted to a suspension. This type of technology is also called "slurry" according to the English terminology. The type of reactor technology may further be of the solar panel type with licking or through bed on a porous or non-porous support. The photocatalyst can also be deposited directly on optical fibers.
    [0022] Any irradiation source emitting at least one wavelength suitable for activating said composition, that is to say absorbable by the composition, may be used according to the invention. The irradiation of the source is therefore such that at least a portion of the emission spectrum of said source is composed of photons with energies greater than the bandgap width of the composition according to the invention. Preferably, the source emits at least a wavelength range greater than 280 nm, very preferably 315 nm to 800 nm, which includes the UV spectrum and / or the visible spectrum. The radiation source may be any source of artificial or natural electromagnetic radiation, such as natural sunlight, a Hg type lamp, a Xe type lamp, an LED type lamp. The use of the composition is conditioned by the provision of photons adapted to the photocatalytic system for the reaction envisaged and is therefore not limited to a specific pressure or temperature range apart from those for ensuring the stability of the photocatalytic system. or product (s). The temperature range employed for use of the composition is generally from -10 ° C to + 200 ° C, preferably from 0 to 150 ° C, and most preferably from 0 to 50 ° C. The pressure range used for the use of the composition is generally from 0.01 MPa to 70 MPa (0.1 to 700 bar), more preferably from 0.1 MPa to 2 MPa (1 to 20 bar).
    [0023] The invention is illustrated by the following examples which in no way present a limiting character. EXAMPLES Example 1: Solid A according to the invention In203 / Pt / TiO2 0.0712 g of H2PtC16.6H2O (37.5% by weight of metal) is added to 500 ml of distilled water. 50 ml of this solution are taken and inserted into a double jacketed glass reactor. 3 ml of methanol then 250 mg of TiO2 (P25, DegussaTM) are then added with stirring to form a suspension. The mixture is then left under stirring and under UV radiation for two hours. The lamp used to provide UV radiation is a 125W Mercury vapor HPKTM lamp. The mixture is then centrifuged for 10 minutes at 3000 rpm to recover the solid. Two washes with water are then carried out, each of the washes being followed by centrifugation. The recovered powder is finally placed in an oven at 70 ° C. for 24 hours. The solid A 'Pt / TiO 2 is then obtained. The content of Pt element is measured by atomic emission spectrometry plasma source (or inductively coupled plasma atomic emission spectroscopy "ICP-AES" in the English terminology) at 0.93% by mass. A solution of In (NO3) 3 is prepared by dissolving 0.05 g of In (NO3) 3, xH2O (Sigma-AldrichTM, 99.9%) in 50 ml of H2O.
    [0024] In the reactor were introduced: 0.10 g of solid A ', 25 ml of distilled water and finally 25 ml of isopropanol. The system is purged in the dark under a stream of argon (100 ml / min) for 2 hours. The reactor is thermostated at 25 ° C. throughout the synthesis. The argon flow is then slowed down to 30 ml / min and the irradiation of the reaction mixture starts. The lamp used to provide the UV radiation is a 125 W mercury vapor HPKTM lamp. Then, 5 ml of the indium nitrate solution is added to the mixture. The mixture is left for 1 hour with stirring and irradiation. 1 ml of a 30% solution of NH3 is then added. The mixture is again left for 1 hour with stirring and irradiation.
    [0025] The mixture is then centrifuged for 10 minutes at 3000 rpm to recover the solid. Two washings with water are then carried out, each washing being followed by centrifugation. The recovered powder is finally placed in an oven at 70 ° C. for 24 hours. The solid is then obtained In203 / Pt / TiO2. The content of element In is measured by ICP-AES at 1.9% by weight. By measurement XPS (X-Ray Photoelectron Spectrometry according to the English terminology), a platinum particle coverage greater than 79% is measured. Transmission electron microscopy measured an average layer thickness of 5 nm indium oxide around the metal particles.
    [0026] EXAMPLE 2: B solid according to the invention In 2 O 3 / Pt / TiO 2 0.0710 g of H 2 PtCl 6 H 2 O (37.5% by weight of metal) is inserted into 500 ml of distilled water. 50 ml of this solution are taken and inserted into a double glass jacket reactor. 3 ml of methanol then 250 mg of TiO2 (P25, DegussaTM) are then added with stirring to form a suspension. The mixture is then left stirring and under UV radiation for two hours. The lamp used to provide the UV radiation is a 125W HPKTM 5 mercury vapor lamp. The mixture is then centrifuged for 10 minutes at 3000 rpm to recover the solid. Two washings with water are then carried out, each washing being followed by centrifugation. The recovered powder is finally placed in an oven at 70 ° C. for 24 hours.
    [0027] The solid B 'Pt / TiO 2 is then obtained. The content of Pt element is measured by ICP-AES at 0.92% by mass. A solution of In (NO3) 3 is prepared by dissolving 0.05 g of In (NO3) 3, xH2O (Sigma-AldrichTM, 99.9%) in 50 ml of H2O.
    [0028] In the reactor were introduced: 0.10 g of solid B ', 25 ml of distilled water and finally 25 ml of isopropanol. The system is purged in the dark under a stream of argon (100 ml / min) for 2 hours. The reactor is thermostated at 25 ° C. throughout the synthesis. The argon flow is then slowed down to 30 ml / min and the irradiation of the reaction mixture starts. The lamp used to provide the UV radiation is a 125 W mercury vapor HPKTM lamp. Then, 10 ml of the indium nitrate solution is added to the mixture. The mixture is left for 1 hour with stirring and irradiation. 1 ml of a 30% solution of NH3 is then added. The mixture is again left for 1 hour with stirring and irradiation.
    [0029] The mixture is then centrifuged for 10 minutes at 3000 rpm to recover the solid. Two washings with water are then carried out, each washing being followed by centrifugation. The recovered powder is finally placed in an oven at 70 ° C. for 24 hours. The solid B In 2 O 3 / Pt / TiO 2 is then obtained. The content of element In is measured by ICP-AES at 3.7% by mass. By XPS measurement, a recovery of platinum particles greater than 89% is measured. Transmission electron microscopy measured an average layer thickness of 10 nm indium oxide around the metal particles.
    [0030] EXAMPLE 3: C solid according to the invention In 2 O 3 / Pt / ZnO 0.0710 g of H 2 PtCl 6 6H 2 O (37.5% by weight of metal) is inserted into 500 ml of distilled water. 50 ml of this solution are taken and inserted into a double jacketed glass reactor. 3 ml of methanol then 250 mg of ZnO (Lotus SynthesisTM, surface area 50 m 2 / g) are then added with stirring to form a suspension. The mixture is then left stirring and under UV radiation for two hours. The lamp used to provide UV radiation is a 125W Mercury vapor HPKTM lamp.
    [0031] The mixture is then centrifuged for 10 minutes at 3000 rpm to recover the solid. Two washings with water are then carried out, each washing being followed by centrifugation. The recovered powder is finally placed in an oven at 70 ° C. for 24 hours. The solid C 'Pt / ZnO is then obtained. The Pt element content is measured by ICP-AES at 0.80 wt%. A solution of In (NO3) 3 is prepared by dissolving 0.05 g of In (NO3) 3, xH2O (Sigma-AldrichTM, 99.9%) in 50 ml of H2O. In the reactor were introduced: 0.10 g of the solid C ', 25 ml of distilled water and finally 25 ml of isopropanol. The system is purged in the dark under a stream of argon (100 ml / min) for 2 hours. The reactor is thermostated at 25 ° C. throughout the synthesis. The argon flow is then slowed down to 30 ml / min and the irradiation of the reaction mixture starts. The lamp used to provide the UV radiation is a 125 HPH mercury vapor lamp. Then 10 ml of the indium nitrate solution is added to the mixture. The mixture is left for 1 hour with stirring and irradiation. 1 ml of a 30% solution of NH3 is then added. The mixture is again left for 1 hour with stirring and irradiation. The mixture is then centrifuged for 10 minutes at 3000 rpm to recover the solid. Two washings with water are then carried out, each washing being followed by centrifugation. The recovered powder is finally placed in an oven at 70 ° C. for 24 hours. The solid C In203 / Pt / ZnO is then obtained. The content of element In is measured by ICP-AES at 3.9% by weight. By XPS measurement, platinum particle coverage greater than 92% was measured. By transmission electron microscopy, an average layer thickness of 12 nm indium oxide is measured around the metal particles.
    [0032] Example 4: D solid according to the invention In 2 O 3 / Au / TiO 2 0.0470 g of HAuCl 4, xH 2 O (52% by weight of metal, AldrichTM) is inserted into 500 ml of distilled water. 50 ml of this solution are taken and inserted into a double jacketed glass reactor. 3 mL of methanol then 250 mg of TiO2 (P25, DegussaTM) are then added with stirring to form a suspension.
    [0033] The mixture is then left under stirring and under UV radiation for two hours. The lamp used to provide UV radiation is a 125W Mercury vapor HPKTM lamp. The mixture is then centrifuged for 10 minutes at 3000 rpm to recover the solid. Two washings with water are then carried out, each of the washes being followed by centrifugation. The recovered powder is finally placed in an oven at 70 ° C. for 24 hours. An Au / TiO 2 solid is then obtained. The Au element content is measured by ICP-AES at 0.95% by mass.
    [0034] A solution of In (NO3) 3 is prepared by dissolving 0.05 g of In (NO3) 3, xH2O (Sigma-AldrichTM, 99.9%) in 50 ml of H2O. In the reactor were introduced: 0.10 g of solid D ', 25 ml of distilled water and finally 25 ml of isopropanol. The system is purged in the dark under a stream of argon (100 ml / min) for 2 hours. The reactor is thermostated at 25 ° C throughout the synthesis. The argon flow is then slowed down to 30 ml / min and the irradiation of the reaction mixture starts. The lamp used to provide the UV radiation is a 125 W mercury vapor HPKTM lamp. Then, 10 ml of the indium nitrate solution is added to the mixture. The mixture is left for 1 hour with stirring and irradiation.
    [0035] Then 1 ml of a 30% solution of NH3 is added. The mixture is again left for 1 hour with stirring and irradiation. The mixture is then centrifuged for 10 minutes at 3000 rpm to recover the solid. Two washings with water are then carried out, each of the washes being followed by centrifugation. The recovered powder is finally placed in an oven at 70 ° C. for 24 hours. The solid D In 2 O 3 / Au / TiO 2 is then obtained. The content of element In is measured by ICP-AES at 3.8% by weight. By XPS measurement, a gold particle coverage greater than 86% was measured. Transmission electron microscopy measured an average layer thickness of cerium oxide of 11 nm around the metal particles. Example 5: Solid E not in accordance with the invention In 2 O 3 / Pt / TiO 2 0.0710 g of H 2 PtCl 6 6H 2 O (37.5% by weight of metal, AldrichTM) is inserted in 500 ml of distilled water. 50 ml of this solution are taken and inserted into a double jacketed glass reactor. 3 ml of methanol then 250 mg of TiO2 (P25, DegussaTM) are then added with stirring to form a suspension. The mixture is then left under stirring and under UV radiation for two hours. The lamp used to provide the UV radiation is a mercury vapor HPKTM lamp of 125 W. The mixture is then centrifuged for 10 minutes at 3000 rpm to recover the solid. Two washings with water are then carried out, each washing being followed by centrifugation. The recovered powder is finally placed in an oven at 70 ° C. for 24 hours. A solid E 'Pt / TiO 2 is then obtained. The content of Pt element is measured by ICP-AES at 0.94% by mass. A solution of In (NO3) 3 is prepared by dissolving 0.05 g of In (NO3) 3, xH2O (Sigma-AldrichTM, 99.9%) in 50 ml of H2O. In the reactor were introduced: 0.10 g of the solid E ', 25 ml of distilled water and finally 25 ml of isopropanol. The system is purged in the dark under a stream of argon (100 ml / min) for 2 hours. The reactor is thermostated at 25 ° C. throughout the synthesis.
    [0036] The argon flow is then slowed down to 30 ml / min. Then 10 ml of the indium nitrate solution is added to the mixture. The mixture is left stirring for 1 hour and without irradiation. 1 ml of a 30% solution of NH3 is then added. The mixture is again left for 1 hour with stirring and without irradiation.
    [0037] The mixture is then centrifuged for 10 minutes at 3000 rpm to recover the solid. Two washings with water are then carried out, each washing being followed by centrifugation. The recovered powder is finally placed in an oven at 70 ° C. for 24 hours.
    [0038] The solid In203 / Pt / TiO 2 is then obtained. The element content In is measured by ICP-AES at 3.6% by weight. By XPS measurement, platinum particle coverage is measured on the order of 16%. By transmission electron microscopy, an indium oxide layer is sometimes distinguished around the metal particles without being able to measure an average thickness due to inhomogeneity of the distribution. Example 6: Solid F (not according to the invention) TiO2 Solid F is commercial titanium dioxide TiO2 P25, DegussaTM Example 7: Evaluation of photocatalytically degraded solids of formic acid Solids A, B, C, D , E and F are subjected to a photocatalytic test for the production of dihydrogen by formic acid degradation in a pyrex semi-open stirred reactor equipped with a quartz optical window and a jacket to regulate the test temperature. 100 mg of solids are suspended in 60 ml of a 0.5 mol / l aqueous formic acid solution. The tests are carried out at 25 ° C. under atmospheric pressure with an argon flow rate of 5 ml / min to entrain the hydrogen gas product which is analyzed by gas chromatography. The UV-Visible irradiation source is provided by an Xe-Hg lamp (AsahiTM, MAX302TM). The irradiation power is always maintained at 100%. The duration of the test is 20 hours. Photocatalytic activities are expressed in moles of dihydrogen produced per hour and per gram of photocatalyst. The results are reported in Table 1. The activity values show that the solids according to the invention systematically have the best photocatalytic performance.
    [0039] Photocatalyst SC2 / M / SC1 initial activity (ilmol / h / g) Solid A (compliant) In203 / Pt / TiO2 1141 Solid B (compliant) In203 / Pt / TiO2 1345 Solid C (compliant) In203 / Pt / ZnO 905 Solid D (compliant) In203 / Au / TiO2 1023 Solid E (non-compliant) In203 / Pt / TiO2 172 Solid F (non-compliant) TiO2 12 Table 1: Initial activity solids performance for dihydrogen production by degradation formic acid
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONS1. Composition containing a first semiconductor SC1, particles comprising one or more element (s) M in the metallic state chosen from an element of groups IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA and VA of the periodic table of elements, and a second semiconductor SC2 comprising indium oxide, said first semiconductor SC1 being in direct contact with said particles comprising one or more element (s) M in the metallic state said particles being in direct contact with said second semiconductor SC2 comprising indium oxide such that the second semiconductor SC2 covers at least 50% of the surface of the particles comprising one or more element (s) M in the metallic state.
    [0002]
    2) The composition of claim 1, wherein the first semiconductor SC1 is in direct contact with the second semiconductor SC2.
    [0003]
    3) Composition according to one of claims 1 or 2, wherein said first semiconductor SC1 forms a support, said support contains on its surface core-layer type particles, said layer being formed by said SC2 semiconductor comprising indium oxide, said core being formed by said particles having one or more element (s) M in the metallic state.
    [0004]
    4) Composition according to one of claims 1 to 3, wherein the indium oxide is predominantly composed of In203.
    [0005]
    5) Composition according to one of claims 1 to 4, wherein the element M in the metallic state is selected from platinum, palladium, gold, nickel, cobalt, ruthenium, silver, copper, rhenium or rhodium.
    [0006]
    6) Composition according to one of claims 1 to 5, wherein the indium oxide content, expressed as In element, is between 0.01 and 50% by weight relative to the total weight of the composition.
    [0007]
    7) Composition according to one of claims 1 to 6, wherein the content of element (s) M in the metallic state is between 0.001 and 20% by weight relative to the total weight of the composition.
    [0008]
    8) Composition according to one of claims 1 to 7, wherein said particles comprising one or more element (s) M in the metallic state are in the form of particle size between 0.5 nm and 1000 nm. 3026966 22
    [0009]
    9) Composition according to one of claims 1 to 8, which is in the form of nanoscale powder.
    [0010]
    10) Composition according to one of claims 1 to 9, wherein the semiconductor SC1 is selected from TiO2, Bi2S3, Bi203, Fe2O3, ZnO, WO0, CuO, ZnFe2O4, MoS2, and the in (OH) 3.
    [0011]
    11) Composition according to one of claims 3 to 10, wherein the layer has a thickness of 1 nm to 1000 nm.
    [0012]
    12) Process for the preparation of the composition according to claims 1 to 11 comprising the following steps: a) a suspension containing a first SC1 semiconductor in a liquid mixture composed of water and / or a plurality of organic compounds and at least one metal precursor selected from an element of Groups IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA and VA of the Periodic Table of Elements, and the suspension is irradiated by a source. irradiation such that at least a portion of the emission spectrum of said source is composed of photons of energies greater than the forbidden band width of the semiconductor SC1, b) is introduced with stirring and under irradiation of said source irradiation an indium precursor to the degree of oxidation +3 soluble in the suspension obtained in step a), c) is then introduced with stirring and irradiation of said irradiation source a basic agent of precipitation of the indium oxide, d) then the composition is separated from the suspension of step c), e) the composition obtained in step d) is dried, f) optionally, subjecting the dried composition obtained in step e) to a heat treatment.
    [0013]
    13) A process according to claim 12, wherein the metal precursor is selected from platinum, palladium, gold, nickel, cobalt, ruthenium, silver, copper, rhenium or of rhodium.
    [0014]
    14) Preparation process according to one of claims 12 or 13, wherein in step c) the pH is between 5 and 13 after the introduction of the basic agent. 3026966 23
    [0015]
    15) Use of the composition according to claims 1 to 11 or prepared according to the process according to claims 12 to 14 as a photocatalyst.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20060210636A1|2002-12-09|2006-09-21|Ralph Nonninger|Nanoscale core/shell particles and the production thereof|
    US7193671B2|2003-09-02|2007-03-20|Sony Corporation|Reflective liquid crystal display device having obliquely evaporated alignment film on vertically evaporated film, method of manufacturing the same, and vertically aligned liquid crystal display unit|
    KR100691276B1|2005-08-25|2007-03-12|삼성전기주식회사|Nanowire light emitting device and method of fabricating the same|WO2020049081A1|2018-09-06|2020-03-12|Total S.A.|Noble metal promoted supported indium oxide catalyst for the hydrogenation of co2 to methanol and process using said catalyst|
    CN109806888B|2019-02-23|2021-03-30|华南理工大学|1T-MoS2Modified ZnCoS solid solution hollow dodecahedron nanocomposite and preparation method and application thereof|
    CN110152741B|2019-05-28|2020-11-10|浙江天蓝环保技术股份有限公司|Efficient composite visible-light-driven photocatalyst with core-shell structure and preparation method and application thereof|
    CN110227466B|2019-06-20|2020-12-08|浙江大学|Titanium dioxide photocatalyst modified by nickel ions and preparation method and application thereof|
    CN110252342B|2019-07-26|2021-12-07|西南大学|Zinc sulfide-indium sulfide heterojunction material and preparation method and application thereof|
    CN110937653A|2019-12-18|2020-03-31|扬州大学|Method for treating hexavalent chromium-containing wastewater through indium oxide-indium sulfide-titanium dioxide composite photocatalytic reduction|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1459849|2014-10-14|
    FR1459849A|FR3026966B1|2014-10-14|2014-10-14|PHOTOCATALYTIC COMPOSITION COMPRISING METALLIC PARTICLES AND TWO SEMICONDUCTORS, INCLUDING ONE INDIUM OXIDE|FR1459849A| FR3026966B1|2014-10-14|2014-10-14|PHOTOCATALYTIC COMPOSITION COMPRISING METALLIC PARTICLES AND TWO SEMICONDUCTORS, INCLUDING ONE INDIUM OXIDE|
    JP2017520973A| JP6726664B2|2014-10-14|2015-10-06|Photocatalyst composition including metal particles and two kinds of semiconductors, and the two kinds of semiconductors include indium oxide|
    US15/518,931| US10695753B2|2014-10-14|2015-10-06|Photocatalytic composition that comprises metal particles and two semiconductors including one made of indium oxide|
    EP15775205.6A| EP3206789B1|2014-10-14|2015-10-06|Photocatalytic composition comprising metallic particles and two semiconductors, one of which is composed of indium oxide|
    ES15775205T| ES2722132T3|2014-10-14|2015-10-06|Photocatalytic composition comprising metal particles and two semiconductors, one of which is composed of indium oxide|
    PCT/EP2015/072997| WO2016058863A1|2014-10-14|2015-10-06|Photocatalytic composition comprising metallic particles and two semiconductors, one of which is composed of indium oxide|
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