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    • 专利摘要:
    The present invention relates to an electrode comprising an electroconductive support of which at least part of the surface is covered by a deposit of a metal selected from the group consisting of copper, iron, nickel, zinc, cobalt, manganese titanium and a mixture thereof, the surface of said deposit being in oxidized, sulphured, selenated and / or tellurized form and the deposition having a specific surface area greater than 1 m 2 / g; a method of preparing such an electrode; an electrochemical device comprising such an electrode; and a method of oxidizing water to oxygen with such an electrode.
    公开号:FR3050740A1
    申请号:FR1653753
    申请日:2016-04-27
    公开日:2017-11-03
    发明作者:Marc Fontecave；Victor Mougel；Ngoc Huan Tran
    申请人:Centre National de la Recherche Scientifique CNRS；Universite Pierre et Marie Curie Paris 6；Paris Sciences et Lettres Quartier Latin；
    IPC主号:
    专利说明:

    The subject of the present invention is a metal / metal chalcogenide electrode (in particular metal oxide or sulphide metal) with a high specific surface area and its preparation method, as well as an electrochemical device containing it and its use, in particular in electrolysis processes. and more particularly oxidation of water to dioxygen. The oxidation of water to dioxygen (also known as Oxygen Evolution Reaction, OER) is a key reaction in the use of water as a source of electrons, particularly in the context of electrochemical and photoelectrochemical devices used to the reduction of compounds such as carbon dioxide or water itself. This reaction can be schematized as follows: 2H2O ^ 02 + 4H "+ 4e"
    An effective water oxidation system requires the use of catalytic systems having good stability and selectivity but above all allowing catalysis of the reaction at a high current density and with a low overvoltage. Such a catalytic system is particularly difficult to obtain because the reaction involves the loss of four protons and four electrons. Effective electron and proton transfer is therefore necessary.
    Since the 1970s, a large number of catalytic systems have been proposed. Most early systems consisted of molecular complexes or metallic oxides of iridium or ruthenium. However, the scarcity and cost of these noble metals limit their use, especially on an industrial scale. Recently, major research efforts have been devoted to replacing these metals with more abundant and less expensive metals to allow a wider application of these electrochemical and photoelectrochemical systems.
    Examples of catalysts based on Co, Ni, Fe or Mn have been proposed, whether in heterogeneous or molecular catalytic systems (Nocera 2012). While these systems have resulted in good catalytic activities, particularly with cobalt-based materials, they still suffer from relatively low current densities and high overvoltages (eg, 0.1 mA / cm 3 to 320 mV). overvoltage has been observed for a cobalt phosphate catalyst, see Kanan et al., 2008). Recently, heterogeneous electrodes based on cupric oxide (CuO) or cuprous oxide-based electrodes (CU2O) have been developed for the oxidation of water to dioxygen (Liu et al., 2016 (a) and ( b)). The results obtained were comparable to those obtained with cobalt-based systems but using a much cheaper material, copper being 5 times cheaper than cobalt. However, these electrodes still suffer from overvoltage too high for the production of oxygen.
    There is therefore still a real need to develop new catalytic systems capable of catalyzing the oxidation reaction of water with a high current density and a low overvoltage.
    The present invention therefore has as its first object an electrode comprising an electrically conductive support of which at least a part of the surface is covered by a deposit of a metal selected from the group consisting of copper, iron, nickel, zinc , cobalt, manganese, titanium and a mixture thereof, the surface of said deposit being in an oxidized, sulphurized and / or tellurized form and the deposition having a high specific surface area, and more particularly a specific surface area greater or equal to 1 m 2 / g.
    Such an electrode can be used to catalyze the oxidation reaction of water with high current density and low overvoltage (typically 10 mA / cm 2 at less than 350 mV overvoltage). Such an electrode thus surprisingly gives much better results than those obtained in the prior art with, for example, an electrode consisting of a deposit of cobalt phosphate on a conductive electrode (1 mA / cm 2 at 410 mV overvoltage - Kanan et al., 2008) or using a copper / copper oxide electrode (1 mA / cm ^ at 485 mV - Du et al., 2015)
    By "electrode" is meant in the sense of the present invention an electronic conductor capable of capturing or releasing electrons. The electrode that releases electrons is called the anode. The electrode that captures electrons is called a cathode.
    By "electrically conductive support" is meant in the sense of the present invention a support capable of conducting electricity.
    Such a support will be constituted, at least in part and preferably completely, by an electrically conductive material which may be a composite material consisting of several distinct electroconductive materials. The electrically conductive material may be chosen in particular from a metal such as copper, steel, aluminum, zinc; a metal oxide such as fluorine-doped titanium oxide (ΠΌ-Fluorine-doped Tin Oxide in English) or indium-doped tin oxide (ITO - Indium Tin Oxide in English); a metal sulfide such as cadmium sulphide or zinc sulphide; carbon in particular in the form of carbon felt, graphite, vitreous carbon, boron-doped diamond; a semiconductor such as silicon; and a mixture thereof.
    This support may take any form suitable for use as an electrode, the person skilled in the art being able to determine the shape and dimensions of such a support according to the intended use.
    The surface of such a support is at least partially covered by the metal deposit. Advantageously, at least 5%, in particular at least 20%, in particular at least 50%, preferably at least 80%, of the surface of the support is covered by the metal deposition. According to a particular embodiment, the entire surface of the support is covered by the metal deposit.
    By "deposition of a metal", also called "metal deposition" is meant in the sense of the present invention a deposition of a metal (which may be in the form of a mixture of metals) to the oxidation degree 0. The metal deposit thus forms a metal layer on the surface of the support.
    The metal is advantageously deposited on the support by electrodeposition.
    The metal deposition advantageously has a thickness of between 10 .mu.m and 2 mm, in particular between 50 .mu.m and 0.5 mm, preferably between 70 .mu.m and 300 .mu.m.
    Such a thickness can be measured in particular by measuring a sample cut by scanning electron microscopy (SEM).
    The metal deposit has a high specific surface area.
    The metal deposit more particularly has a specific surface greater than or equal to 1 m 2 / g, in particular greater than or equal to 2 m 2 / g, in particular greater than or equal to 3 m 2 / g, for example greater than or equal to 5 m ^ / g or even greater than or equal to 10 m ^ / g. The specific surface may be between 1 m 2 / g and 500 m 2 / g, for example between 1 m 2 / g and 200 m 2 / g, especially between 2 m 2 / g and 100 m 2 / g, preferably between 3 m 2 / g and 50 m 2 / g, for example between 5 m 2 / g and 50 m 2 / g or between 10 m 2 / g and 50 m 2 / g. The specific surface value is indicated per gram of metal deposition. Such a specific surface is advantageously determined by the BET method (Brunauer, Emmett and Teller). This BET method will advantageously be applied to a metal deposition sample obtained by mechanical abrasion using a PVC (polyvinyl chloride) blade having a thickness of 1 mm of said metal deposit present on the electrical support. driver.
    The specific surface area can also be expressed in cm.sup.2 / cm.sup.2 cm.sup.2. In this case, the specific surface area value is indicated per cm.sup.2 of electrode and can advantageously be greater than or equal to 5.times.10.sup.-cm.sup.2 cm.sup.2 cm.sup.2 cm.sup.3 cm.sup.3 cm.sup.3 cm.sup.3 cm.sup.3 cm.sup.3 cm.sup.3 cm.sup.3 cm.sup.3 cm.sup.3 cm.sup.3 cm.sup.3 cm.sup.3. or equal to 10 cm ^ / cm ^ geometrical, in particular greater than or equal to 15 cm ^ / cm ^ geometrical · The specific surface may be between 5 and 500 cm ^ / cm ^ geometrical, for example between 10 and 200 cm ^ / cm ^ geometrique, especially between 15 and 100 cm ^ / cm ^ geometreque "preferably between 15 and 50 cm ^ / cm ^ geometrical · Such a specific surface is advantageously determined by electrochemical measurement (via the Randles- Sevcik), more particularly according to the conditions described hereinafter in the general considerations of the experimental part.
    The metal deposit will also advantageously have a porous structure.
    The metal deposit will advantageously have a porosity with an average pore size of between 10 μm and 500 μm, especially between 20 μm and 200 μm, and preferably between 30 μm and 70 μm. The average pore size can be determined by means of scanning electron microscopy or tunnel effect microscopy, more particularly according to the conditions described hereinafter in the general considerations of the experimental part.
    The metal deposited on the support is selected from copper, iron, nickel, zinc, cobalt, manganese, titanium and a mixture thereof, especially selected from copper, iron, nickel, zinc and a mixture of these. The metal may be more particularly copper. Other metals (than the aforementioned main metal) may be present in this metal deposition layer, such as gold, silver, lead, ruthenium, iridium or a mixture thereof. Advantageously, these other metals will not represent more than 80%, especially not more than 50% by weight, preferably not more than 30% by weight of the metal deposition layer.
    The surface of this metal deposit (i.e. the outer surface of the metal deposit not in contact with the electrically conductive support) is in an oxidized, sulphurized, selenated and / or tellurized form, that is, that is, the metal on the surface of this metal deposit is in an oxidized, sulphured, selenated and / or tellurized form.
    For the purposes of the present invention, the term "oxidized, sulphured, selenated and / or tellurium form" of a metal M is understood to mean the chemical forms MxOy, MxSy, MxSey, MxTey, and mixtures thereof where x and y represent integers depending on the degree of oxidation of the metal M. For example, in the case of copper, the oxidized forms can be CuO and CuaO, the sulfurized forms can be CuS and CU2S, the selected forms can be CuSe and Cu2Se and the telluric forms can be CuTe and Cu2Te
    According to a particular embodiment of the invention, the surface of the metal deposit is in an oxidized, sulphured, selenated or tellurium form.
    According to another particular embodiment of the invention, the surface of the metal deposit is in an oxidized and / or sulphurized form, in particular oxidized or sulphured.
    This oxidized, sulphurized, selenated and / or surface-layered metallic deposit represents the catalytic system that makes it possible, in particular, to oxidize the water to dioxygen in an electrolysis process.
    The second subject of the present invention is a process for preparing an electrode according to the present invention comprising the following successive steps: (i) electroplating of a metal chosen from the group consisting of copper, iron, nickel and zinc , cobalt, manganese, titanium and a mixture thereof on at least a portion of the surface of an electrically conductive support to form a deposit of said metal on said at least a portion of the surface of the electro-magnetic support -conductor, and (ii) oxidation, sulfuration, selenation and / or tellurization of the surface of said metal deposit.
    The electrically conductive support will be as defined above. Thus, such a support will be constituted, at least in part and preferably completely, by an electrically conductive material which may be a composite material consisting of several separate electroconductive materials. The electrically conductive material may be chosen in particular from a metal such as copper, steel, aluminum, zinc; a metal oxide such as fluorine-doped titanium oxide (FTO) or indium-doped tin oxide (ITO) (Indium Tin Oxide); a metal sulfide such as cadmium sulphide or zinc sulphide; carbon in particular in the form of carbon felt, graphite, vitreous carbon, boron-doped diamond; a semiconductor such as silicon; and a mixture thereof.
    This support may take any form suitable for use as an electrode, the person skilled in the art being able to determine the shape and dimensions of such a support according to the intended use. The surface of such a support is at least partially covered by the metal deposit. Advantageously, at least 5%, in particular at least 20%, in particular at least 50%, preferably at least 80%, of the surface of the support is covered by the metal deposition. According to a particular embodiment, the entire surface of the support is covered by the metal deposit.
    This electroconductive support will advantageously be cleaned before performing electroplating according to techniques well known to those skilled in the art.
    The metal deposited on the support is advantageously chosen from copper, iron, nickel, zinc, cobalt, manganese, titanium and a mixture thereof, especially from copper, iron, nickel, zinc and a mixture thereof. The metal may be more particularly copper.
    Step (i): The electroplating may advantageously be carried out according to the following steps: (a) at least partially immersing the electroconductive support in an acidic aqueous solution containing ions of the metal to be deposited, and (b) applying a current between the electrically conductive support and a second electrode.
    Step (a):
    The acidic aqueous solution containing ions of the metal to be deposited will be more particularly an acidic aqueous solution containing a salt of the metal to be deposited (also called metal salt), optionally introduced in a hydrated form. This metal salt, optionally in a hydrated form, may be any water-soluble salt of said metal. It may be, for example: for copper: CuSO 4, CuCl 3, Cu (ClO 4) 2, for iron: FeSO 4, Fe 2 (SO 4) 3, FeCl 3, FeCl 3, Fe (ClO 4) 3, for nickel: NiSO 4 , NiC2, Ni (O104) 2, for zinc: ZnSO4, ZnCl2, Zn (ClO4) 2, for cobalt: CO4SO4, CoCl2, Co (ClO4) 2, for manganese: MnCl4, MnSO4, Mn ( ClO4) 2, for titanium: TiCl2, (2) (804) 3, or a mixture thereof.
    It may be in particular CUSO4.
    The metal salt will be present in the solution advantageously at a concentration of between 0.1 mM and 10 M, in particular between 1 mM and 1 M.
    It could also be envisaged to use metal complexes formed between the metal ion to be deposited and one or more organic ligands such as, for example, porphyrins, amino acids or amines, to introduce the metal ions into the aqueous solution. The acid introduced into the aqueous solution may be any acid, whether organic or inorganic. It may be, for example, sulfuric acid, hydrochloric acid, hydrobromic acid, formic acid or acetic acid, especially sulfuric acid. Preferably, it will not be nitric acid. This acid may be present in the acidic aqueous solution advantageously at a concentration between 0.1 mM and 10 M, in particular between 10 mM and 3 M.
    The acidic aqueous solution is advantageously prepared using deionized water to better control the ionic composition of the solution.
    The electroconductive support will be totally or partially immersed in the acidic aqueous solution containing the ions of the metal to be deposited according to whether a deposit over the entire surface or only a part of the surface of the support is desired.
    In order to obtain a deposit on only a portion of the surface of the support, it may also be envisaged to apply a mask consisting of an insulating material on the parts of the support which must not be covered by the metal deposit. In this case, the complete support, on which the mask has been applied, may be immersed in the acidic aqueous solution containing the ions of the metal to be deposited. This mask will be removed from the support after deposition of the metal.
    Step (b):
    In this step, the electrically conductive support will act as a cathode, while the second electrode will play the role of anode.
    The second electrode will advantageously be immersed in the acidic aqueous solution containing the ions of the metal to be deposited but may also be immersed in another electrolyte solution electrically connected to the first. The use of a single electrolyte solution, namely the acidic aqueous solution containing the ions of the metal to be deposited, remains preferred.
    The nature of the second electrode is not critical. It is just necessary for the realization of electroplating by an electrolysis process. It may be for example a platinum or titanium electrode.
    The current applied between the electrically conductive support and the second electrode may be alternating or continuous. It will advantageously be continuous and will preferably have a high current density of between 0.1 mA / cm 2 and 5 A / cm 2, in particular between 0.1 mA / cm 2 and 1 mA / cm 2. Alternatively, a voltage to generate an equivalent current density can be applied between the electrodes.
    During the application of the current, two reduction reactions will take place at the cathode: on the one hand the reduction of metal ions to metal of oxidation degree 0 according to the following reaction with M representing the metal and x representing its degree of oxidation. initial oxidation:
    + xe 'M on the other hand the reduction of protons to dihydrogen according to the following reaction: 2H "+ 2e' Hz
    Similarly, an oxidation reaction will take place at the anode during the application of the current. The nature of this oxidation reaction is not crucial. It may be for example the oxidation of water. The electroplating thus allows the deposition on the surface of the electroconductive support of a thin metal layer with a high specific surface, the growth of the metal on the surface of the electrically conductive support being dendritic. In addition, the formation of dihydrogen bubbles on the surface of the electrically conductive support, thanks to the proton reduction reaction, also makes it possible to confer a porous structure on this metal deposition layer, thus making it possible to further increase this specific surface area. The choice of the current density will make it possible in particular to optimize the size and the number of bubbles formed so as to obtain the structure and the specific surface area required for the metal deposition.
    The current will also be applied for a time sufficient to obtain the desired amount of deposit, in particular to obtain a thickness of said metal deposition layer of between 10 μm and 2 mm, in particular between 50 μm and 0.5 mm, preferably between 70 pm and 300 pm. For example, the current may be applied for a period of between 1 and 3600 s, for example between 15 and 1200 s, in particular between 30 and 300 s.
    The duration of application and the current density can be adapted according to the chosen reaction conditions such as the nature and the concentration of the metal ions, the concentration of acid, etc. to obtain the desired metal deposition, especially with the desired specific surface and thickness. The electroplating will be advantageously carried out by a galvanostatic method, that is to say by applying a constant current throughout the duration of the deposit.
    Once the current is applied, the electrically conductive support of which at least a portion of the surface is covered by a metal deposit may be removed from the solution in which it was immersed. It must be cleaned, especially with water (eg distilled water), before being dried, especially under vacuum, or under an inert gas stream (argon, nitrogen, helium, etc.).
    Step (ii):
    Once the metal is deposited on at least a portion of the surface of the electrically conductive support, the outer surface of the metal deposit will be oxidized, sulphured, selenated and / or tellurium. The oxidation step will advantageously be carried out in an atmosphere containing oxygen (eg air) or in the presence of H 2 O, preferably in an atmosphere containing oxygen (eg air). The sulphurisation step will advantageously be carried out in the presence of elemental sulfur or of H 2 S, preferably in the presence of elemental sulfur. The selenation step will advantageously be carried out in the presence of elemental selenium or of H2Se, preferably in the presence of elemental selenium. The telluration step will advantageously be carried out in the presence of elemental tellurium or H2Te, preferably in the presence of elemental tellurium.
    This oxidation, sulphurization, selenation and / or telluration step will advantageously be carried out at an elevated temperature, especially at a temperature of between 30 and 700 ° C., in particular between 50 and 500 ° C., in particular between 100 and 400 ° C. vs.
    An annealing step may be performed following the oxidation step, sulphidation, selenation and / or tellurization. This annealing step will advantageously be carried out at a temperature of between 50 ° C. and 1000 ° C., in particular between 100 ° C. and 400 ° C. This annealing step will advantageously be carried out under an inert gas atmosphere (Ar, N 2, He , ...) or under vacuum. This annealing step will advantageously be carried out for a sufficiently long period, in particular for a time of between 10 minutes and 48 hours, in particular between 1 and 3 hours.
    Surprisingly, a high specific surface area is maintained after this oxidation, sulphurization, selenation and / or tellurization and optionally annealing step.
    The present invention thus also relates to an electrode obtainable by the aforementioned method. Such an electrode corresponds to an electrode according to the present invention, having in particular the characteristics mentioned above.
    The third subject of the present invention is an electrochemical device comprising an electrode according to the present invention.
    For the purposes of the present invention, the term "electrochemical device" is intended to mean a device for converting electrical energy into chemical energy (for example an electrolysis device) or conversely for converting chemical energy into electrical energy (e.g. a fuel cell). The electrochemical device according to the present invention will therefore be more particularly an electrolysis device or a fuel cell.
    Such an electrochemical device will comprise a second electrode which may optionally also be an electrode according to the present invention. One of the electrodes will act as anode where oxidation will occur, the other electrode will act as a cathode where a reduction will occur.
    Such a device will therefore use a substance to be oxidized (eg H2 in a fuel cell or H2O in an electrolysis device) and a substance to be reduced (eg O2 in a fuel cell or H2O or CO2 in a fuel cell). an electrolysis device). In an electrolysis device, the oxidation-reduction reaction will be forced, that is to say caused by the applied electric current. In the fuel cell, the oxidation-reduction reaction will be spontaneous, allowing the generation of electrical energy.
    Such devices will include other elements well known to those skilled in the field of electrochemistry such as one or more other electrodes (in particular a potential reference electrode), a source of energy, a membrane, a bottom salt, a device for the flow of reagents, a device for collecting the gases formed, etc. Those skilled in the art, however, perfectly know how to make and implement such an electrochemical device.
    The electrochemical device according to the present invention will advantageously be an electrolysis device. Advantageously, this device will use the electrode according to the present invention as anode, in particular for oxidizing water to oxygen according to the following reaction: 2H2O O2 + 4H "+ 4e '
    An example of a water electrolysis device is shown in Figure 6.
    The fourth subject of the present invention is also a process for the oxidation of water with oxygen, comprising the application of an electric current between an anode and a cathode, the anode being an electrode according to the invention immersed in water. or in a fluid containing water.
    By "immersed" in a fluid is meant in the sense of the invention that the electrode is immersed in the fluid at least partially. In the case of the electrode according to the invention, the part of the electrode covered by the metal deposition, whose surface is oxidized, sulphured, selenated and / or tellurium, must be at least partially immersed in the fluid.
    In such a process, the anode, corresponding to an electrode according to the present invention, will be immersed preferably in water, and more particularly in water having a basic pH (between 7 and 14, preferably between 10 and 14), obtained for example by adding sodium hydroxide.
    The cathode may also be immersed in the same fluid or may be immersed in another fluid. CO2 may be added to this fluid by bubbling or pressurizing the medium. In the case where the anode and cathode are not immersed in the same fluid, these two fluids can be separated for example by an ion exchange membrane (eg protons), osmotic or dialysis to allow the passage of charges or solvent molecules from one fluid to another.
    The cathode may be any electrode conventionally used in the art as a cathode and which is well known to those skilled in the art. Such a cathode may be for example platinum, cobalt, copper ...
    When applying a current between the anode and the cathode, the water will be oxidized to dioxygen at the anode according to the following reaction: 2H2O ^ 02 + 4H "+ 4e 'thus allowing the production of oxygenates at the level of the anode.
    The current applied between the two electrodes will have in particular a potential difference of between 1.2 V and 10 V, in particular between 1.4 V and 4 V. The use of an electrode according to the invention makes it possible to carry out this oxidation reaction of water to dioxygen with an overvoltage of less than 350 mV for a current density of 10 mA or even lower than 550 mV for a current density of 100 mA. In the case of a copper / copper oxide electrode according to the invention, this reaction can be performed with an overvoltage of 340 mV for a current density of 10 mA or 530 mV for a current density of 100 mA. The electrode according to the invention thus makes it possible to efficiently perform the oxidation reaction of water with oxygen, while having an inexpensive catalytic system.
    An example of a method according to the invention is illustrated in FIG.
    The present invention is illustrated by the figures and non-limiting examples below.
    FIGURES
    FIGS. 1A to 1D show SEM scanning electron microscopy images of the Cu / CUxOy electrodes obtained in Example 1 (FIGS. 1A and 1C) and Cu / CUxSy obtained in Example 2 (FIGS. 1B and 1D).
    Figure 2 shows the X-ray diffractogram of the Cu / CUxOy electrode obtained in Example 1.
    FIGS. 3A and 3B respectively represent the linear scanning voltammetry (A) and the Tafel plot (B) of the Cu / CUxOy electrode obtained in Example 1 in aqueous 1.0M NaOH solution.
    FIGS. 4A and 4B show the wide spectrum (A) and the high-resolution spectrum centered on the sulfur (B) obtained by X-ray photoelectron spectrometry of the Cu / CuxSy electrode obtained in Example 2.
    Figures 5A and 5B show the linear scanning voltammetry (A) and the Tafel plot (B) of the Cu / CUxSy electrode obtained in Example 2, respectively, in a 1.0M aqueous solution of NaOH.
    Figure 6 illustrates a method / device for electrolysis of water in which water is oxidized to oxygen at the anode which is an electrode according to the present invention.
    EXAMPLES
    General considerations:
    The electrocatalytic measurements and the electrolysis experiments are carried out in a three-electrode cell with two compartments, allowing separation of the products in the gas phase to the anode and cathode compartments using an SP300 Bio-Logic potentiostat. An Ag / AgCl reference electrode is placed in the same compartment as the working electrode. A platinum counter-electrode is placed in a separate compartment connected by a porosity sintered glass filled with the electrolytic solution. The potentials are referenced with respect to the reversible hydrogen electrode (ERH) using the equation below:
    Eerh = EAg / Agci + 0.197 + 0.059 * pH
    The result of linear scanning voltammetry is not compensated for the ohmic drop. The faradic efficiency was obtained by comparing the theoretical amount of oxygen produced on the basis of the feedstock consumed with the amount of oxygen determined by gas chromatography. Scanning electron microscopy (SEM) images were acquired using a Hitachi S-4800 scanning electron microscope. The X-ray powder diffraction patterns of the patterns were recorded using an analytical X'Pert Pro P diffractometer equipped with a Cu-Ka radiation source (λΚαΙ = 1.540598Å, λΚα2 = 1.544426 nm) or a Co-Ka radiation source (λΚαΙ = 1.78897 Å, λΚα2 = 1.79285 Å) with an X'Celerator detector. Gas chromatography was performed on a GC-2014 Shimadzu chromatograph equipped with a Quadrex Molsieve 5A pad column, a thermal conductivity detector and using He as a carrier gas (30 ml / min). For preparation of the electrode, the surface of the Cu plate (3cm x 1cm) was cleaned using sandpaper (p 1200) followed by immersion in a 5.0M HCl solution for 30 s . The plate is then rinsed with ethanol before being dried in air. The Randles-Sevcik equation (1) is used to calculate Ad, ff, the electroactive surface of the electrode: 7p = 2.69 x 10 (1)
    The current ip is the peak current corresponding to the reduction of the redox couple (Fe ^ * / Fe ^ *), determined by cyclic voltammetry of K3 [Fe (CN) 6], n is the number of electrons exchanged, D is the diffusion coefficient of the analyte (7.5 χ 10 cm -1 for K3 [Fe (CN) 6]), C (mol · cm) is the molar concentration of the analyte and v is the scanning speed (Vs ^). The electroactive surface of the electrodes is measured using a 1 cm geometric surface electrode immersed in a solution containing 5 mM K3 [Fe (CN) 6] and 0.1 M phosphate buffer pH 7.0. The application of equation (1) then allows the determination of the electroactive surface value Adiff, and therefore of the specific surface area determined by electrochemistry, by dividing this value by the geometrical surface of the electrode according to the relation: Specific surface area determined by electrochemistry = Ad, ff / Agea (in cm ^ / cm ^ geometrical) · The samples used for BET measurements were obtained by mechanical abrasion using a PVC (polyvinyl chloride) blade. 1 mm thick of the metal deposit present on the support.
    Example 1 Preparation of a copper / copper oxide electrode according to the invention 1 cm 2 of a freshly cleaned copper plate is immersed in 20 ml of a 0.2 M solution of CUSO 4, 1.5 M H 2 SO 4 and a current of 0.5 A is applied using a galvanostatic method for a period of 80 s. The electrode is then removed from the solution and cleaned with large amounts of distilled water and dried under vacuum (10 mbar). The electrode is then transferred to an oven under a static air atmosphere (1 bar). The temperature is raised to 310 ° C at a rate of 10 ° C per minute, and the temperature is kept constant for 1 hour. After this step, the electrode is cooled to room temperature and stored in air. This electrode is named Cu / CUxOy electrode thereafter. FIGS. 1A and 1C show SEM images obtained from this electrode and illustrate the porous nanostructures and the large specific surface area of the material. The X-ray powder diffractogram of this electrode is shown in Figure 2 and reveals the presence of Cu, CU2O and CuO. The linear scanning voltammetry between 1.2V and 2.0V VS ERH (Hydrogen Reversible Electrode) in an aqueous solution of 1.0M NaOH with a scanning rate of 10mV / s is presented in Figure 3A. A current density of 10mA.cm 3 was obtained at 340mV overvoltage for the production of oxygen. The Tafel plot of the electrode is shown in Figure 3B. The catalytic activity increases linearly from 1.56V to 1.66V vs ERH. The slope of the Tafel line was determined in this region equal to 38mV.dec '. The electrochemically determined specific surface area is 19.6 cm 2 / cm 2 geometric. The specific surface area determined by BET is 3.4 m 2 / g.
    Example 2 Preparation of a copper / copper sulphide electrode according to the invention
    1 cm 2 of a freshly cleaned copper plate is immersed in 20 ml of a 0.2 M solution of CUSO 4, 1.5 M H 2 SO 4 and a stream of 0.5 A is applied using a galvanostatic method for one hour. duration of 80 s. The electrode is then removed from the solution and cleaned with large amounts of distilled water and dried under vacuum (10 mbar). The electrode is then transferred to a glass reactor containing 15 mg of elemental sulfur powder in a separate compartment but connected to the rest of the reactor where the electrode is located. The vacuum (0.01 mbar) is made in the reactor (including the compartment containing the elemental sulfur) which is kept under static vacuum and introduced into an oven. The temperature of the assembly is raised to 150 ° C at a rate of 15 ° C per minute, and the temperature is maintained at 150 ° C for 2 minutes. After this step, the reactor is removed from the oven and allowed to cool to room temperature while evacuating the reactor (dynamic vacuum). After cooling to room temperature, the compartment containing the elemental sulfur is disconnected from the reactor containing the electrode and the reactor containing the electrode is reintroduced into the oven while evacuating (dynamic vacuum - 0.01 mbar). The oven temperature is raised to 150 ° C at a rate of 15 ° C per minute, and the temperature is maintained at 150 ° C for 1 hour. After this annealing step, the electrode is cooled to room temperature under dynamic vacuum and used quickly after its preparation.
    This electrode is named Cu / CUxSy electrode thereafter. Figures 1B and 1D show SEM images obtained from this electrode and illustrate the porous nanostructures and the large specific surface area of the material. The spectrum obtained by X-ray photoelectron spectrometry of this electrode is shown in Figure 4, and reveals the presence of copper and copper sulfide. The linear scanning voltammetry between 1.2V and 2.0V vs. ERH in a 1.0M aqueous NaOH solution with a scan rate of 10mV / sec is shown in Figure 5A. A current density of 10mA.cm 3 was obtained at 340mV overvoltage for the production of oxygen. The Tafel plot of the electrode is shown in Figure 5B. The catalytic activity increases linearly from 1.56V to 1.66V vs ERH. The slope of the Tafel line was determined in this region equal to 40 mV.dec V The electrochemically determined specific surface area is 23.0 cm ^ / cm ^ geometrical · The specific surface area determined by BET is 3.8 m ^ / g.
    EXAMPLE 3 Measurement of the Catalytic Activity for the Oxidation of the Water of the Cu / CUxOy Electrode The electrolysis of the water is carried out with an applied fixed surge of 400 mV using the Cu / CUxOy electrode as Working electrode in aqueous solution of 1.0 M NaOH The generation of a large amount of oxygen gas is observed at the electrode. The oxygen produced is quantified by gas chromatography. After 10 minutes of electrolysis, the faradic efficiency for the evolution of O 2 is estimated at 89% (2.2 C consumed, 5.14 μmol O 2 generated, 0.5 cm 2 dipping electrode in the solution).
    EXAMPLE 4 Measurement of the Catalytic Activity for the Oxidation of the Water of the Cu / CUxSy Electrode The electrolysis of the water is carried out with an applied fixed overvoltage of 400 mV using the Cu / CUxSy electrode as Working electrode in aqueous solution of 1.0 M NaOH The generation of a large amount of oxygen gas is observed at the electrode. The oxygen produced is quantified by gas chromatography. After 10 minutes of electrolysis, the faradic efficiency for the evolution of O 2 is estimated at 92% (2.0 C consumed, 4.83 pmol O 2 generated, 0.5 cm 2 dipping electrode in the solution).
    EXAMPLE 5 Durability of the Cu / CuxOy Electrode Under Catalytic Conditions The electrolysis of the water is carried out with an applied fixed surge of 600 mV using the Cu / CUxOy electrode as the working electrode in an aqueous solution of NaOH. , 1 M. During the entire duration of the experiment (4 h), a large quantity of oxygen gas is constantly generated. No sign of deactivation is observed, a stable current density of 20 mA / cm 2 being observed throughout the duration of the experiment.
    BILIOGRAPHIC REFERENCES
    From the stall. Angew. Chem. 2015, 2073 Kanan et al. Science 2008, 1072
    Liu et al. (a) J. Phys. Chem. C 2016, 831; (b) Electrochem. Acta 2016, 381 Nocera Acc. Chem. Res. 2012, 76
    权利要求:
    Claims (16)
    [1" id="c-fr-0001]
    An electrode comprising an electrically conductive support of which at least a part of the surface is covered by a deposit of a metal selected from the group consisting of copper, iron, nickel, zinc, cobalt, manganese, titanium and a mixture thereof, the surface of said deposit being in oxidized, sulphured, selenated and / or tellurized form and the deposition having a specific surface area greater than or equal to 1 m 2 / g.
    [2" id="c-fr-0002]
    2. Electrode according to claim 1, characterized in that the electroconductive support is constituted, at least in part, by an electrically conductive material selected from a metal such as copper, steel, aluminum, zinc; a metal oxide such as fluorine doped titanium oxide (FTO) or indium doped tin oxide (ITO); a metal sulfide such as cadmium sulphide or zinc sulphide; carbon in particular in the form of carbon felt, graphite, vitreous carbon, boron-doped diamond; a semiconductor such as silicon; and a mixture thereof.
    [3" id="c-fr-0003]
    3. Electrode according to any one of claims 1 and 2, characterized in that the metal deposition has a thickness between 10 pm and 2 mm, in particular between 50 pm and 0.5 mm, preferably between 70 pm and 300 pm.
    [4" id="c-fr-0004]
    4. Electrode according to any one of claims 1 to 3, characterized in that the metal deposition has a specific surface area of between 1 m 2 / g and 500 m 2 / g, for example between 1 m 2 / g and 200 m ^ / g, especially between 2 m ^ / g and 100 m ^ / g, preferably between 3 m ^ / g and 50 m ^ / g.
    [5" id="c-fr-0005]
    5. Electrode according to any one of claims 1 to 4, characterized in that the metal deposition has a porous structure with an average pore size of between 10 μm and 500 μm, in particular between 20 μm and 200 μm, preferably between 30 pm and 70 pm.
    [6" id="c-fr-0006]
    6. Electrode according to any one of claims 1 to 5, characterized in that the metal is selected from copper, iron, nickel, zinc and a mixture thereof and is preferably copper.
    [7" id="c-fr-0007]
    7. Electrode according to any one of claims 1 to 6, characterized in that the surface of the metal deposition is in an oxidized form and / or sulphured, especially in an oxidized or sulphured form.
    [8" id="c-fr-0008]
    8. A method of preparing an electrode according to any one of claims 1 to 7 comprising the following successive steps: (i) electroplating a metal selected from the group consisting of copper, iron, nickel, zinc , cobalt, manganese, titanium and a mixture thereof on at least a portion of the surface of an electrically conductive support to form a deposit of said metal on said at least a portion of the surface of the electro-magnetic support -conductor, and (ii) oxidation, sulfuration, selenation and / or tellurization of the surface of the metal deposit.
    [9" id="c-fr-0009]
    9. Process according to claim 8, characterized in that step (i) is carried out according to the following successive steps: (a) at least partially immersing the electroconductive support in an acidic aqueous solution containing ions of the metal to be deposited and (b) applying a current between the electroconductive medium and a second electrode.
    [10" id="c-fr-0010]
    10. Process according to Claim 9, characterized in that the acidic aqueous solution containing ions of the metal to be deposited is an aqueous acid solution containing a water-soluble salt of the metal to be deposited, in particular chosen from CUSO4, CUCI2, Cu (ClO4) 2, FeSO4, Fe2 (SO4) 3, FeCb, FeCl2, Fe (ClO4) 3, NiSO4, NiCb, Ni (ClO4) 2, ZnSO4, ZnCl2, Zn (ClO4) 2, CoSO4, CoCl2, Co (ClO4) 2, MnCl2, MnSO4, Mn (ClO4) 2, TiCh, Ti2 (SO4) 3 and a mixture thereof.
    [11" id="c-fr-0011]
    11. Method according to any one of claims 9 and 10, characterized in that the current of step (b) has a current density between 0.1 mA / cm ^ and 5 A / cm ^, including between 0.1 mA / cm 2 and 1 mA / cm 2.
    [12" id="c-fr-0012]
    12. Method according to any one of claims 8 to 11, characterized in that step (ii) comprises: a step of oxidation, sulfuration, selenation and / or telluration carried out at a temperature between 30 and 700 ° C , in particular between 50 and 500 ° C., in particular between 100 and 400 ° C., in which the oxidation step is carried out in an atmosphere containing dioxygen or in the presence of H2O, the sulphurization step is carried out in presence of elemental sulfur or of H2S, the selenation step is carried out in the presence of elemental selenium or of H2Se, and the tellurization step is carried out in the presence of elemental tellurium or of H2Te, and optionally an annealing step carried out at a temperature of temperature between 50 ° C and 1000 ° C, in particular between 100 ° C and 400 ° C, preferably for a time between 10 min and 48 h, in particular between 1 and 3 h.
    [13" id="c-fr-0013]
    13. Electrode obtainable by a method according to any one of claims 8 to 12.
    [14" id="c-fr-0014]
    An electrochemical device comprising an electrode according to any one of claims 1 to 7 and 13.
    [15" id="c-fr-0015]
    15. An electrochemical device according to claim 14, characterized in that it is an electrolysis device or a fuel cell.
    [16" id="c-fr-0016]
    16. Oxygen water oxidation process comprising the application of an electric current between an anode and a cathode, the anode being an electrode according to any one of claims 1 to 7 and 13 immersed in the water or in a fluid containing water, preferably at basic pH.
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    同族专利:
    公开号 | 公开日
    CN109415825A|2019-03-01|
    US20190119822A1|2019-04-25|
    EP3449042A1|2019-03-06|
    KR20190031197A|2019-03-25|
    CA3022198A1|2017-11-02|
    WO2017186454A1|2017-11-02|
    FR3050740B1|2021-01-29|
    AU2017258442A1|2018-12-06|
    CN109415825B|2021-04-13|
    JP2019518869A|2019-07-04|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1653753A|FR3050740B1|2016-04-27|2016-04-27|METAL / METAL CHALCOGENIDE ELECTRODE WITH HIGH SPECIFIC SURFACE|FR1653753A| FR3050740B1|2016-04-27|2016-04-27|METAL / METAL CHALCOGENIDE ELECTRODE WITH HIGH SPECIFIC SURFACE|
    AU2017258442A| AU2017258442A1|2016-04-27|2017-03-31|Metal / metal chalcogenide electrode with high specific surface area|
    PCT/EP2017/057756| WO2017186454A1|2016-04-27|2017-03-31|Metal / metal chalcogenide electrode with high specific surface area|
    CA3022198A| CA3022198A1|2016-04-27|2017-03-31|Metal / metal chalcogenide electrode with high specific surface area|
    US16/096,740| US20190119822A1|2016-04-27|2017-03-31|Metal / Metal Chalcogenide Electrode With High Specific Surface Area|
    EP17714480.5A| EP3449042A1|2016-04-27|2017-03-31|Metal / metal chalcogenide electrode with high specific surface area|
    CN201780030120.8A| CN109415825B|2016-04-27|2017-03-31|Metal/metal chalcogenide electrodes with high specific surface area|
    KR1020187033459A| KR20190031197A|2016-04-27|2017-03-31|Metal / metal chalcogenide electrode having a high specific surface area|
    JP2018556434A| JP2019518869A|2016-04-27|2017-03-31|Metal / metal chalcogenide electrode with high specific surface area|
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