EP3887572A1 - Procede de preparation d'un materiau catalytique d'electrode pour des reactions de reduction electrochimique prepare par electroreduction - Google Patents
Procede de preparation d'un materiau catalytique d'electrode pour des reactions de reduction electrochimique prepare par electroreductionInfo
- Publication number
- EP3887572A1 EP3887572A1 EP19806186.3A EP19806186A EP3887572A1 EP 3887572 A1 EP3887572 A1 EP 3887572A1 EP 19806186 A EP19806186 A EP 19806186A EP 3887572 A1 EP3887572 A1 EP 3887572A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- precursor
- metal
- mixture
- atoms
- catalytic material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 43
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- 239000002184 metal Substances 0.000 claims abstract description 99
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- 238000005470 impregnation Methods 0.000 claims abstract description 38
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- 238000001354 calcination Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 100
- 239000000203 mixture Substances 0.000 claims description 63
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 39
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- 150000002576 ketones Chemical class 0.000 description 1
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- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
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- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000001907 polarising light microscopy Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940070891 pyridium Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
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- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
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- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/98—Raney-type electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Definitions
- the present invention relates to the field of electrochemistry, and more particularly to electrodes suitable for being used for electrochemical reduction reactions, in particular for the electrolysis of water in a liquid electrolytic medium in order to produce hydrogen.
- the present invention relates to a process for preparing a catalytic material for an electrode comprising an active phase comprising at least one group VI metal obtained from a solution comprising at least one group VI element in electroreduced form.
- the hydrogen evolution reaction occurs at the cathode and the oxygen evolution reaction (OER) occurs at the anode.
- the overall reaction is:
- Catalysts are required for both reactions. Different metals have been studied as catalysts for the reaction to produce dihydrogen at the cathode. Today, platinum is the most used metal because it has an overvoltage (voltage required to dissociate the water molecule) negligible compared to other metals. However, the rarity and the cost (> 25 k € / kg) of this noble metal are obstacles to the economic development of the hydrogen sector in the long term. This is the reason why, for a number of years now, researchers have been turning to new catalysts, without platinum, but based on inexpensive metals which are abundant in nature.
- Water electrolysis is an electrolytic process which breaks down water into O 2 and H 2 gas with the help of an electric current.
- the electrolytic cell consists of two electrodes - usually made of inert metal (in the potential and pH zone considered) like platinum - immersed in an electrolyte (here water itself) and connected to the opposite poles of the source of direct current.
- the electric current dissociates the water molecule (H 2 0) into hydroxide ions (HO) and hydrogen H + : in the electrolytic cell, the hydrogen ions accept electrons at the cathode in a redox reaction by forming gaseous dihydrogen (H 2 ), depending on the reduction reaction:
- the materials based on MoS 2 have a lamellar structure and can be promoted by Ni or Co in order to increase their electrocatalytic activity.
- the active phases can be used in mass form when the conduction of electrons from the cathode is sufficient or else in the supported state, then bringing into play a support of a different nature.
- the support must have specific properties: - large specific surface to promote the dispersion of the active phase;
- Carbon is the most commonly used support in this application.
- the challenge lies in the preparation of this sulfurized phase on the conductive material.
- a catalyst having a high catalytic potential is characterized by an associated active phase perfectly dispersed on the surface of the support and having a high active phase content. It should also be noted that, ideally, the catalyst must have accessibility to the active sites with respect to the reactants, here water, while developing a high active surface, which can lead to specific constraints in terms of structure and texture, specific to the support constituting said catalysts.
- the usual methods leading to the formation of the active phase of catalytic materials for the electrolysis of water consist of a deposit of precursor (s) comprising at least one metal from group VIB, and optionally at least one metal from group VIII, on a support by the technique known as "dry impregnation” or by the technique known as “excess impregnation”, followed by at least one possible heat treatment to remove the water and by a final stage of generating sulphurization of the active phase, as mentioned above.
- an electrochemical group VIB metal makes it possible to obtain catalytic performances, in particular in terms of activity, at least as good, or even better than the electrode catalytic materials prepared according to the prior art, while being free from the introduction of any additional reducing and potentially deleterious chemical agent to catalytic activity.
- a first object according to the invention relates to a process for the preparation of a catalytic material for an electrode for electrochemical reduction reactions, said material comprising at least one active phase based on a metal from group VIB and an electro- conductor, which method comprises at least the following steps:
- step b) a step of impregnating said support with said solution obtained in step a) to obtain a precursor of catalytic material; c) a step of drying said precursor obtained in step b) at a temperature below 250 ° C., without subsequent calcination;
- step d) a step of sulfurization of the precursor of catalytic material obtained in step c) at a temperature between 100 ° C and 600 ° C.
- step a) is carried out in an electrolyser comprising at least two electrochemical compartments separated by a membrane or a porous separator and respectively containing one the anode and the other the cathode.
- the current density applied in step a) is between 5 and 500 mA / cm 2 .
- said precursor comprising at least one metal from group VI is chosen from polyoxometallates corresponding to the formula (H h X x M m O y ) q in which X is an element chosen from phosphorus (P), silicon ( Si), boron (B), nickel (Ni) and cobalt (Co), M is one or more metal (s) chosen from molybdenum (Mo), tungsten (W), nickel ( Ni), cobalt (Co) and iron (Fe), O being oxygen, h being an integer between 0 and 12, x being an integer between 0 and 4, m being an integer equal to 5.6 , 7, 8, 9, 10, 11, 12 and 18, y being an integer between 17 and 72 and q being an integer between 1 and 20, it being understood that M is not a nickel atom or an atom cobalt alone.
- X is an element chosen from phosphorus (P), silicon ( Si), boron (B), nickel (Ni) and cobalt (Co)
- M is one or more metal (s) chosen
- the m atoms M are either only molybdenum (Mo) atoms, or only tungsten (W) atoms, or a mixture of molybdenum (Mo) and tungsten atoms ( W), either a mixture of molybdenum (Mo) and cobalt (Co) atoms, or a mixture of molybdenum (Mo) and nickel (Ni) atoms, or a mixture of tungsten (W) atoms and nickel (Ni).
- the m atoms M are either a mixture of nickel (Ni), molybdenum (Mo) and tungsten (W) atoms, or a mixture of cobalt (Co) atoms , molybdenum (Mo) and tungsten (W).
- At least one precursor of the active phase is introduced comprising at least one metal from group VIII, said precursor being brought into contact with the electrically conductive support by impregnation either:
- step b1) before the impregnation step b) of said support with the solution obtained in step a), in a so-called pre-impregnation step b1) using a solution comprising at least one phase precursor active ingredient comprising at least one group VIII metal; ii) during the impregnation step b), in co-impregnation with said solution comprising at least one precursor of the active phase comprising at least one partially reduced group VIB metal obtained in step a);
- step c) after step c) of sulfurization, in a step called post-impregnation b3) using a solution comprising at least one precursor of the active phase comprising at least one metal from group VIII.
- said group VIII metal is chosen from nickel, cobalt and iron.
- the sulfurization temperature is between 350 ° C. and 550 ° C.
- the sulfurization temperature is between 100 ° C and 250 ° C or between 400 ° C and 600 ° vs.
- said electrically conductive support comprises at least one material chosen from carbonaceous structures of the carbon black type, graphite, carbon nanotubes or graphene.
- said electrically conductive support comprises at least one material chosen from gold, copper, silver, titanium, silicon.
- At least one ionic conductive polymeric binder is dissolved in a solvent or a mixture of solvent;
- step 2) adding to the solution obtained in step 1) at least one catalytic material prepared according to the invention, in powder form, to obtain a mixture;
- steps 1) and 2) being carried out in an indifferent order, or simultaneously;
- step 2) the mixture obtained in step 2) is deposited on a metallic or metallic type support or collector.
- Another object according to the invention relates to an electrolysis device comprising an anode, a cathode, an electrolyte, said device being characterized in that one in the month of the anode or of the cathode is an electrode according to the invention .
- Another object according to the invention relates to the use of the electrolysis device in electrochemical reactions, and more particularly as according to the invention as:
- group VIII according to the CAS classification corresponds to the metals in columns 8, 9 and 10 according to the new IUPAC classification.
- BET surface is understood to mean the specific surface determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 established on the basis of the BRUNAUER - EMMET - TELLER method described in the periodical "The journal of the American Chemical Society", 60 , 309 (1938).
- catalytic precursor comprising at least one metal from group VI B in partially reduced form means a precursor of which at least one metal atom from group VI B has a valence of less than 6.
- the preparation process according to the invention makes it possible to carry out the prior reduction of a solution containing at least one precursor of the active phase of the catalytic material comprising at least one metal of group VI B by an electrochemical route allowing performance to be obtained. less as good in terms of activity, or even improved, as the materials prepared according to the prior art, while dispensing with the introduction of any additional reducing chemical agent (potentially toxic such as hydrazine) and / or potentially deleterious to catalytic activity.
- any additional reducing chemical agent potentially toxic such as hydrazine
- the present invention relates to a process for the preparation of electrode catalytic material for carrying out an electrochemical reduction reaction, and in particular for the production of hydrogen by electrolysis of water, said catalytic material comprising at least one metal from group VIB, and optionally from group VIII, from a solution comprising at least one precursor of the active phase comprising at least one metal from group VIB electro-reduced, which has undergone electrolysis via an electrochemical circuit, making it possible to generate part of the atoms of the group VIB at a lower valence than their normal VIB valence, as it is in molybdates, tungstates, polymolybdates and polytungstates.
- the process for preparing a catalytic material for an electrode for electrochemical reduction reactions comprises at least the following steps:
- step b) a step of impregnating said support with said solution obtained in step a) to obtain a precursor of catalytic material
- step b) a step of drying said precursor obtained in step b) at a temperature below 250 ° C, without subsequent calcination;
- step c) a step of sulfiding the precursor of catalytic material obtained in step c) at a temperature between 100 and 600 ° C.
- the term “calcination” means any heat treatment carried out at a temperature greater than or equal to 250 ° C., in an atmosphere comprising O 2 .
- Step a) of the preparation process according to the invention makes it possible to reduce at least part of the metals of group VIB to a valence of less than +6.
- Precursors comprising at least one metal from group VIB
- the precursors of the active phase comprising at least one metal from group VIB can be chosen from all the precursors of elements from group VIB known to those skilled in the art. They can be chosen from polyoxometallates (POM) or salts of precursors of elements of group VIB, such as molybdates, thiomolybdates, tungstates or even thiotungstates. They can be chosen from organic or inorganic precursors, such as M0CI5 or WCI 4 or WCI 6 or the alkoxides of Mo or W, for example Mo (OEt) 5 or W (OEt) 5 .
- POM polyoxometallates
- salts of precursors of elements of group VIB such as molybdates, thiomolybdates, tungstates or even thiotungstates.
- organic or inorganic precursors such as M0CI5 or WCI 4 or WCI 6 or the alkoxides of Mo or W, for example Mo (OEt) 5 or W (OEt
- polyoxometallates is understood to be the compounds corresponding to the formula (H h X x M m O y ) q in which H is hydrogen, X is an element chosen from phosphorus (P), silicon (Si), boron (B), nickel (Ni) and cobalt (Co), said element being taken alone, M is one or more element (s) chosen from molybdenum (Mo), tungsten (W), nickel (Ni), cobalt (Co) and iron (Fe), O being oxygen, h being an integer between 0 and 12, x being an integer between 0 and 4, m being an integer equal to 5, 6, 7, 8, 9, 10, 1 1, 12 and 18, y being an integer between 17 and 72 and q being an integer between 1 and 20.
- H hydrogen
- X is an element chosen from phosphorus (P), silicon (Si), boron (B), nickel (Ni) and cobalt (Co), said element being taken alone
- M is one or more element (s) chosen from molybdenum (
- the element M cannot be a nickel atom or a cobalt atom alone.
- the polyoxometallates defined according to the invention include two families of compounds, isopolyanions and heteropolyanions. These two families of compounds are defined in the article Heteropoly and Isopoly Oxometallates, Pope, Ed Springer-Verlag, 1983.
- the m atoms M of said isopolyanions are either only molybdenum atoms, or only tungsten atoms, or a mixture of molydene and tungsten atoms, or a mixture of molybdenum and cobalt atoms, or a mixture of molybdenum and nickel atoms, either a mixture of tungsten and cobalt atoms, or a mixture of tungsten and nickel atoms.
- the m atoms M of said isopolyanions can also be either a mixture of nickel, molybdenum and tungsten atoms or a mixture of cobalt, molybdenum and tungsten atoms.
- m is equal to 7.
- W tungsten
- Isopolyanons Mo 7 0 2 4 6 and H 2 W 12 0 o 6 are advantageously used as active phase precursors in the context of the invention.
- Heteropolyanions generally have a structure in which the element X is the "central" atom and the element M is a metallic atom practically systematically in octahedral coordination with X different from M.
- the m atoms M are either only molybdenum atoms, or only tungsten atoms, or a mixture of molybdenum and cobalt atoms, or a mixture of molybdenum and nickel, or a mixture of atoms tungsten and molybdenum, either a mixture of tungsten and cobalt atoms, or a mixture of tungsten and nickel atoms.
- the m atoms M are either solely molybdenum atoms, or a mixture of molybdenum and cobalt atoms, or a mixture of molybdenum and nickel.
- the m atoms M cannot be only nickel atoms, nor only cobalt atoms.
- the element X is at least one phosphorus atom or one Si atom.
- Heteropolyanions are negatively charged polyoxometallate species. To compensate for these negative charges, it is necessary to introduce counterions and more particularly cations. These cations can advantageously be H + protons, or any other cation of NH 4 + type or metal cations and in particular metal cations of Group VIII metals.
- the molecular structure comprising the heteropolyanion and at least one proton constitutes a heteropolyacid.
- the heteropolyacids which can be used as active phase precursors in the present invention can be, for example, phosphomolybdic acid (3H + , PMo 12 O 40 3 ) or alternatively phosphotungstic acid (3H + , PW 12 O 40 3 ) ⁇
- the polyoxometallates used according to the invention are the compounds corresponding to the formula (H h X x M m O y ) q in which H is hydrogen, X is an element chosen from phosphorus (P), silicon (Si), boron (B), nickel (Ni) and cobalt (Co), said element being taken alone, M is one or more element (s) chosen from molybdenum (Mo), tungsten (W), nickel (Ni), cobalt (Co) and iron (Fe), O being oxygen, h being an integer between 0 and 6, x being an integer which can be equal to 0, 1 or 2, m being an integer equal to 5, 6, 7, 9, 10, 1 1 and 12, y being an integer between 17 and 48 and q being an integer between 3 and 12.
- the polyoxometallates used according to the invention are the compounds corresponding to the formula (H h X x M m O y ) q in which h being an integer equal to 0, 1, 4 or 6, x being a integer equal to 0, 1 or 2, m being an integer equal to 5, 6, 10 or 12, y being an integer equal to 23, 24, 38, or 40 and q being an integer equal to 3, 4, 6 and 7, H, X, M and O having the above meaning.
- the preferred polyoxometallates used according to the invention are advantageously chosen from the polyoxometallates of formula PMoi 2 0 4 o 3 , HPCoMon0 4 o 6 , HPNiMonO 40 6 , P2M05O23 6 , CO 2 MOI O 0 38 H 4 6 , COMO 6 0 24 H 6 4 taken alone or as a mixture.
- Preferred polyoxometallates which can advantageously be used in the process according to the invention are the so-called Anderson heteropolyanions of general formula XM 6 0 24 q for which the ratio m / x is equal to 6 and in which the elements X and M and the charge q have the abovementioned meaning.
- the elements X is therefore an element chosen from phosphorus (P), silicon (Si), boron (B), nickel (Ni) and cobalt (Co), said element being taken alone, M is one or several element (s) chosen from molybdenum (Mo), tungsten (W), nickel (Ni) and cobalt (Co), and q is an integer between 1 and 20 and preferably between 3 and 12.
- the Anderson heteropolyanion contains within its structure cobalt and molybdenum, a mixture of the two monomeric forms of formula CoMo 6 0 24 H 6 3 and dimeric of formula Co 2 Mo 1 o0 38 H 4 6 of said heteropolyanion, the two forms being in equilibrium, can advantageously be used.
- said Anderson heteropolyanion is preferably dimeric with the formula Co 2 Mo 1 o0 38 H 4 6 .
- the Anderson heteropolyanion contains within its structure nickel and molybdenum, a mixture of the two monomeric forms of formula NiMo 6 0 24 H 6 4 and dimeric of formula Ni 2 Moio0 38 H 4 8 of said heteropolyanion , the two forms being in balance, can advantageously be used.
- said Anderson heteropolyanion is preferably monomeric with the formula NiMo 6 0 24 H 6 4 .
- Anderson heteropolyanion salts can also be advantageously used as active phase precursors according to the invention.
- Said Anderson heteropolyanion salts are advantageously chosen from the cobalt or nickel salts of the monomeric ion 6-molybdocobaltate respectively of formula CoMo 6 0 24 H 6 3 , 3/2 Co 2+ or COMO 6 0 24 H 6 3 , 3/2 Ni 2+ having an atomic ratio of said promoter (Co and / or Ni) / Mo of 0.41, the cobalt or nickel salts of the dimeric decamolybdocobaltate ion of formula C0 2 M0 10 O 38 H 4 6 , 3 Co 2+ or C0 2 M0 10 O 38 H 4 6 , 3 Ni 2+ having an atomic ratio of said promoter (Co and / or Ni) / Mo of 0.5, the cobalt or nickel salts of the 6- molybdonickellate ion of formula NiMo 6 0 24 H 6 4 , 2 Co 2+ or NiMo 6
- the highly preferred Anderson heteropolyanion salts used in the invention are chosen from the dimeric heteropolyanion salts containing cobalt and molybdenum within their structure of formula C0 2 M0 10 O 38 H 4 6 , 3 Co 2 + and C0 2 M0 10 O 38 H 4 6 , 3 Ni 2+ .
- a salt Even more preferred Anderson heteropolyanions is the dimeric Anderson heteropolyanion salt of formula C0 2 M0 10 O 38 H 4 6 , 3 Co 2+
- Keggin heteropolyanions of general formula XM 12 0 4 o q for which the m / x ratio is equal to 12 and the so-called incomplete Keggin heteropolyanions of general formula XMn0 39 q for which the ratio m / x is equal to 1 1 and in which the elements X and M and the charge q have the abovementioned meaning.
- X is therefore an element chosen from phosphorus (P), silicon (Si), boron (B), nickel (Ni) and cobalt (Co), said element being taken alone, M is one or more element ( s) chosen from molybdenum (Mo), tungsten (W), nickel (Ni) and cobalt (Co), and q being an integer between 1 and 20 and preferably between 3 and 12.
- Keggin species are advantageously obtained for variable pH ranges according to the methods of production described in the publication by A. Griboval, P. Blanchard, E. Payen, M. Fournier, J. L. Dubois, Chem. Lett., 1997, 12, 1259.
- Keggin heteropolyanion is the heteropolyanion of formula PM0 12 O 40 3 or PW 12 O 40 3 or SiMoi 2 O 40 4 or SiW 12 O 40 4 .
- Keggin heteropolyanion can also be advantageously used in the invention in its heteropolyacid form of formula PMOI 2 O 40 3 , 3H + or PW 12 O 40 3 , 3H + or SiMoi 2 O 40 4 , 4H + or SiW 12 O 40 4 , 4H + .
- Salts of heteropolyanions of the Keggin or Keggin lacunary type can also be advantageously used according to the invention.
- Preferred salts of heteropolyanions or heteropolyacids of the Keggin and Keggin type are advantageously chosen from cobalt or nickel salts of phosphomolybdic, silicomolybdic, phosphotungstic or silicitungstic acids.
- Said salts of heteropolyanions or heteropolyacids of the Keggin or Keggin lacunary type are described in US Pat. No. 2,547,380.
- a Keggin type heteropolyanion salt is nickel phosphotungstate of formula 3 / 2Ni 2+ , PW 12 O 40 3 having an atomic ratio of the metal of group VIB to the metal of group VIII, that is to say Ni / W of 0.125.
- Another preferred polyoxometallate which can advantageously be used as a precursor used in the process according to the invention is the Strandberg heteropolyanion of formula H h P 2 Mo 5 0 23 ⁇ 6 h) , h being equal to 0, 1 or 2 and for which the ratio m / x is equal to 5/2.
- the preparation of said Strandberg heteropolyanions and in particular of said heteropolyanion of formula H h P 2 Mo 5 0 23 (6 h) is described in the article by WC. Cheng, NP Luthra, J. Catal., 1988, 109, 163.
- polyoxometallates and their associated salts are available.
- all these polyoxometallates and their associated salts can be advantageously used during the electrolysis implemented in the process according to the invention.
- the above list is not exhaustive, however, and other combinations can be envisaged.
- Precursors comprising at least one group VIII metal:
- the preferred group VIII elements are non-noble elements: they are chosen from Ni, Co and Fe. Preferably, the group VIII elements are Co and Ni.
- the group VIII metal can be introduced in the form of salts, chelating compounds, alkoxides or glycoxides.
- the sources of group VIII elements which can advantageously be used in the form of salts, are well known to those skilled in the art. They are chosen from nitrates, sulfates, hydroxides, phosphates, carbonates, halides chosen from chlorides, bromides and fluorides.
- Said precursor comprising at least one metal from group VIII is partially soluble in the aqueous phase or in the organic phase.
- the solvents used are generally water, an alkane, an alcohol, an ether, a ketone, a chlorine compound or an aromatic compound. Acidified water, toluene, benzene, dichloromethane, tetrahydrofuran, cyclohexane, n-hexane, ethanol, methanol and acetone are preferred.
- the group VIII metal is preferably introduced in the form of acetylacetonate or acetate when an organic solvent is used, in the form of nitrate when the solvent is water and in the form of hydroxides or carbonates or hydroxycarbonates when the solvent is water at an acidic pH, ie less than 7, advantageously less than 2.
- any organic compound or any other doping element can be introduced at any stage mentioned above or in an additional stage.
- said organic compound is advantageously deposited by impregnation, before the impregnation of the metal precursors, in co-impregnation with the metal precursors or in post-impregnation after impregnation of the metal precursors.
- Said organic compound can be chosen from all the organic compounds known to those skilled in the art, and is selected in particular from chelating agents, non-chelating agents, reducing agents, non-reducing agents.
- Said doping element can be chosen from precursors of B, P or Si.
- the electrolysis method according to the invention consists in preparing a solution comprising at least one precursor of the catalytic material comprising at least one metal from group VI B in partially reduced form by the application of a cathode current aimed at maximizing in this solution , the quantity of metal of degree VIB reduced to a lower valence.
- a compartmentalized electrolysis system is used. It consists of two separate electrochemical compartments separated by a membrane or a separator.
- a filter press system known to those skilled in the art can be used.
- an ion exchange membrane is preferred, to guarantee better selectivity in the transport of ions and reduce the phenomena of migration of species.
- Perfluorosulfonée a membrane (such as Nafion membranes sold under the name ® or Aquivion ®) is preferably used.
- the principle is to maximize the quantity of precursor comprising at least one reduced group VIB metal.
- the reduction potential is controlled, in particular by means of a reference electrode, the evolution of the current is followed until it becomes weak, a sign that the major part of the precursor (s) comprising at least one metal from group VIB are converted.
- the potential is limited to a certain value so as not to generate a significant secondary reaction, such as degradation of the solvent.
- reference is made to the potential of the cathode if a reference electrode is used, or in the absence of a reference, to the value of the overall electrolysis voltage.
- the range of reduction potential is defined beforehand.
- This reduction potential is deduced from the voltammetry curves under conditions similar to those of electrolysis, namely, same electrode material, same pH and concentration of catalyst precursor comprising at least one metal from group VI B.
- the potential cathode target for electrolysis is necessarily greater (in absolute value) than the potential of the first reduction wave observed in cyclic voltammetry, depending on the nature of the catalyst precursors comprising at least one group VI B metal, their concentration, the solvent, the nature of the electrode material.
- the potential is then chosen between the reduction potential of the catalyst precursor comprising at least one metal from group VI B and the reduction potential of the solvent, so that, when the electrolysis is carried out in potentiostatic mode, the residual current once the species is reduced is low ( ⁇ 1/5 of the initial reduction current of the catalyst precursors comprising at least one metal from group VIB, preferably ⁇ 1/10 of this current).
- This makes it possible to ensure that the secondary reactions (electrolysis of the solvent for example) are minimal and therefore that the reduction yield of the catalyst precursors comprising at least one metal from group VIB is high.
- the concentration of degree VI metal in the catholyte is between 0.1 M and 8 M of metal, and preferably between 0.8 M and 5 M of metal.
- the solvent used to dissolve the catalyst precursors comprising at least one metal from group VIB is selected from water, alcohols, preferably ethanol, polar solvents of alkyl carbonate type (such as dimethyl carbonate, diethyl carbonate, propylene carbonate), DMF, DMSO, taken alone or in mixtures.
- the material constituting the cathode is chosen from metals (Pt, W, Ni, Au, or any other platinum metal, such as titanium, stainless steel), or certain carbons such as vitreous carbon, or certain graphites with low porosity. (for example graphites coated with a pyrolitic carbon deposit such as the Fabmate-BG® grade from the company Poco-Graphite®).
- a platinized metal is, for example, a good cost / performance compromise.
- the anodic reaction can vary, but we make sure of the nature of the cationic species which migrate through the membrane and of the consequences that this migration could have on the speciation or the solubility of the catalyst precursors comprising at least one metal of group VIB. or also on the final activity of the catalyst. Typically for polyoxometallates stable in an acid medium, an anodic reaction will be preferred, leading to the release of protons, the latter migrate through the membrane and join the catholyte to balance the electroneutrality.
- An anodic reaction useful for the invention is the oxidation of water.
- the anolyte is preferably an aqueous solution of sulfuric acid.
- the range of current density useful for the invention is between 5 and 500 mA / cm 2 and preferably between 10 and 200 mA / cm 2 .
- the solvent used in step a) is aqueous or organic.
- the precursor comprising at least one metal from group VIB is a polyoxometallate
- it generally consists of an alcohol.
- the precursor of the catalytic material comprising at least one metal from group VIB is a polyoxometallate
- water and ethanol are then preferably used.
- Step b) is a step of impregnating said support with said solution obtained in step a).
- the impregnations are well known to those skilled in the art.
- the impregnation method according to the invention is chosen from dry impregnation or excess impregnation.
- said step b) is carried out by dry impregnation, which consists in bringing the electrically conductive support of the catalytic material into contact with a solution containing at least one precursor of the active phase comprising at least one metal from group VIB , obtained at the end of step a) of the preparation process, and whose volume of the solution is between 0.25 and 1.5 times the volume of the support to be impregnated.
- the method for preparing the catalytic material comprises an additional step of introducing at least one precursor of the active phase comprising at least one metal from group VIII.
- the impregnation of said precursor comprising at least one group VIII metal with the electrically conductive support is carried out either:
- the precursor of the active phase comprising at least one group VIII metal is introduced into the solution comprising at least one precursor of the active phase of at least one metal of group VI B either before step a) electrolysis either after step a) of electrolysis (but before step b) of impregnation);
- an optional second maturing step and a second drying step c2) at a temperature below 250 ° C, preferably below 180 ° C, can be carried out under the same conditions as the conditions described in stages of maturation of the precursor of the active phase comprising at least one metal from group VIB and in the drying stage c) described below;
- step d) after step d) of sulfurization, in a step called post-impregnation b3) using a solution comprising at least one precursor of the active phase comprising at least one metal from group VIII.
- a new maturation step a new drying step c3) at a temperature below 250 ° C., preferably below 180 ° C. and advantageously a new sulfurization step d3).
- the drying of the precursor obtained in step b) is intended to remove the impregnating solvent.
- the atmosphere is preferably free of O 2 in order to avoid reoxidizing the reduced precursors previously impregnated.
- the temperature must not exceed 250 ° C, preferably 180 ° C, in order to keep intact said precursors deposited on the surface of the support. More preferably, the temperature will not exceed 120 ° C.
- the drying is carried out under vacuum at a temperature not exceeding 60 ° C. This step can be carried out alternately by passing an inert gas flow.
- the drying time is between 30 min and 16h. Preferably, the drying time does not exceed 4 hours.
- the sulfurization carried out during step d) is intended to at least partially sulfurize the metal of group VI and optionally at least partially the metal of group VIII.
- Step d) of sulfurization can advantageously be carried out using a H 2 S / H 2 or H 2 S / N 2 gas mixture containing at least 5% by volume of H 2 S in the mixture or under flow pure H 2 S at a temperature between 100 and 600 ° C, under a total pressure equal to or greater than 0.1 MPa for at least 2 hours.
- the sulfurization temperature is between 350 ° C. and 550 ° C.
- the sulfurization temperature is between 100 ° C and 250 ° C or between 400 ° C and 600 ° C.
- the activity of the catalytic material of the electrode capable of being used for electrochemical reduction reactions, and in particular for the production of hydrogen by electrolysis of water, is ensured by an element of group VIB and by at least one element of group VIII.
- the active function is chosen from the group formed by the combinations of the elements nickel-molybdenum or cobalt-molybdenum or nickel-cobalt-molybdenum or nickel-tungsten or nickel-molybdenum-tungsten.
- the molybdenum content (Mo) is generally between 4 and 60% by weight of Mo element relative to the weight of the final catalytic material, and preferably between 7 and 50% weight relative to the weight of the final catalytic material, obtained after the last preparation step, ie after the sulfurization.
- the tungsten content (W) is generally between 7 and 70% by weight of element W relative to the weight of the final catalytic material, and preferably between 12 and 60% by weight relative to the weight of the final catalytic material, obtained after the last stage of preparation, ie sulfurization.
- the surface density which corresponds to the quantity of molybdenum atoms Mo deposited per surface unit of support, will advantageously be between 0.5 and 20 atoms of [Mo + W] per square nanometer of support and preferably between 1 and 15 atoms of [Mo + W] per square nanometer of support.
- the group VIII promoter elements are advantageously present in the catalytic material at a content of between 0.1 and 15% by weight of group VIII element, preferably between 0.5 and 10% by weight relative to the weight of the final catalytic material obtained. after the last stage of preparation, ie sulfurization. Support
- the support for the catalytic material is a support comprising at least one electrically conductive material.
- the support for the catalytic material comprises at least one material chosen from carbonaceous structures of the carbon black type, graphite, carbon nanotubes or graphene.
- the support for the catalytic material comprises at least one material chosen from gold, copper, silver, titanium, silicon.
- a porous and non-electrically conductive material can be made electrically conductive by depositing on the surface thereof an electrically conductive material; let us quote for example a refractory oxide, such as an alumina, within which graphitic carbon is deposited.
- the support for the catalytic material advantageously has a BET specific surface area (SS) greater than 75 m 2 / g, preferably greater than 100 m 2 / g, very preferably greater than 130 m 2 / g.
- the catalytic material capable of being obtained by the preparation process according to the invention can be used as an electrode catalytic material capable of being used for electrochemical reactions, and in particular for the electrolysis of water in the medium liquid electrolytic.
- the electrode comprises a catalytic material obtained by the preparation process according to the invention and a binder.
- the binder is preferably a polymeric binder chosen for its capacity to be deposited in the form of a layer of variable thickness and for its capacity for ionic conduction in an aqueous medium and for diffusion of dissolved gases.
- the layer of variable thickness advantageously between 1 and 500 ⁇ m, in particular of the order of 10 to 100 ⁇ m, may in particular be a gel or a film.
- the ionic conductive polymer binder is:
- - polymers stable in an aqueous medium which can be perfluorinated, partially fluorinated or non-fluorinated and having cationic groups allowing the conduction of hydroxide anions, said cationic groups being of quaternary ammonium, guanidinium, imidazolium, phosphonium, pyridium or sulfide type;
- * is a conductor of cationic groups allowing the conduction of protons and is chosen from the group comprising in particular:
- polymers stable in an aqueous medium and having cationic groups allowing the conduction of anions mention may in particular be made of polymer chains of perfluorinated type such as for example polytetrafluoroethylene (PTFE), of partially fluorinated type, such as for example polyvinylidene fluoride (PVDF) or non-fluorinated type such as polyethylene, which will be grafted with anionic conductive molecular groups.
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- non-fluorinated type such as polyethylene
- Mention may in particular be made of Nafion®, phosphonated sulfonated polybenzimidazole (PBI), sulfonated or phosphonated polyetheretherketone (PEEK).
- any mixture comprising at least two polymers, at least one of which is chosen from the groups of polymers mentioned above, provided that the final mixture is ionic conductor in an aqueous medium.
- a mixture comprising a polymer stable in an alkaline medium and having cationic groups allowing the conduction of hydroxide anions with a polyethylene which is not grafted with anionic conductive molecular groups, provided that this final mixture is anionic conductor in medium alkaline.
- polybenzimidazole is used in the present invention as a binder. It is intrinsically not a good ionic conductor, but in an alkaline or acidic medium, it turns out to be an excellent polyelectrolyte with respectively very good anionic or cationic conduction properties.
- PBI is a polymer generally used, in grafted form, in the manufacture of proton-conducting membranes for fuel cells, in membrane-electrode assemblies and in PEM-type electrolysers, as an alternative to Nafion®. In these applications, the PBI is generally functionalized / grafted, for example by sulfonation, in order to make it proton conductive.
- the role of PBI in this type of system is therefore different from that that it has in the manufacture of electrodes according to the present invention where it only serves as a binder and has no direct role in the electrochemical reaction.
- chitosan also usable as an anionic or cationic conductive polymer, is a polysaccharide having ionic conduction properties in basic medium which are similar to those of PBI (G. Couture, A. Alaaeddine, F. Boschet, B. Ameduri, Progress in Polymer Science 36 (2011) 1521-1557).
- the electrode according to the invention is formulated by a process which further comprises a step of removing the solvent at the same time or after step 3).
- the removal of the solvent can be carried out by any technique known to a person skilled in the art, in particular by evaporation or phase inversion.
- the solvent is an organic or inorganic solvent whose evaporation temperature is lower than the decomposition temperature of the polymeric binder used.
- examples that may be mentioned are dimethylsulfoxide (DMSO) or acetic acid.
- the electrode is suitable for being used for the electrolysis of water in an alkaline liquid electrolyte medium and the polymeric binder is then an anionic conductor in an alkaline liquid electrolyte medium, in particular conductor d 'hydroxides.
- alkaline liquid electrolyte medium means a medium whose pH is greater than 7, advantageously greater than 10.
- the binder is advantageously conductive of hydroxides in an alkaline medium. It is chemically stable in electrolysis baths and has the capacity to diffuse and / or transport the OH ions involved in the electrochemical reaction to the surface of the particles, seats of the redox reactions for the production of H 2 and O 2 gases. . Thus, a surface which is not in direct contact with the electrolyte is nevertheless involved in the electrolysis reaction, a key point in the efficiency of the system.
- the chosen binder and the shaping of the electrode do not impede the diffusion of the gases formed and limit their adsorption, thus allowing their evacuation.
- the electrode is suitable for being used for the electrolysis of water in an acidic liquid electrolyte medium and the polymeric binder is a cationic conductor in an acidic liquid electrolyte medium, in particular conductor of protons.
- the term “acid medium” is intended to mean a medium whose pH is less than 7, advantageously less than 2.
- the mass ratio of polymer binder / catalytic material is between 5/95 and 95/5, preferably between 10/90 and 90/10, and more preferably between 10/90 and 40/60.
- the electrode can be prepared according to techniques well known to those skilled in the art. More particularly, the electrode is formulated by a preparation process comprising the following steps:
- At least one ionic conductive polymeric binder is dissolved in a solvent or a mixture of solvent;
- step 2) adding to the solution obtained in step 1) at least one catalytic material prepared according to the invention, in powder form, to obtain a mixture;
- steps 1) and 2) being carried out in an indifferent order, or simultaneously;
- step 2) the mixture obtained in step 2) is deposited on a metallic or metallic conductive support or collector.
- catalytic material powder means a powder consisting of particles of micron, sub-micron or nanometric size.
- the powders can be prepared by techniques known to those skilled in the art.
- the expression “support or collector of metallic type” means any conductive material having the same conduction properties as metals, for example graphite or certain conductive polymers such as polyaniline and polythiophene.
- This support can see any shape allowing the deposition of the mixture obtained (between the binder and the catalytic material) by a method chosen from the group notably comprising soaking, printing, induction, pressing, coating , spinning (or “spin-coating” according to English terminology), filtration, vacuum deposition, spray deposition, casting, extrusion or rolling.
- Said support or said collector may be solid or perforated.
- a grid perforated support
- a plate or a sheet of stainless steel 304L or 316L for example
- solid supports solid supports
- the mixture can be prepared by any technique known to a person skilled in the art, in particular by mixing the binder and the at least one catalytic material in powder form in a suitable solvent or a mixture of solvents suitable for 'obtaining a mixture with rheological properties allowing the deposition of electrode materials in the form of a film of controlled thickness on an electronic conductive substrate.
- the use of the catalytic material in powder form allows a maximization of the surface developed by the electrodes and an enhancement of the associated performances.
- Those skilled in the art will be able to make the choices of the different formulation parameters in the light of their general knowledge and the physico-chemical characteristics of said mixtures.
- Another object according to the invention relates to an electrolysis device comprising an anode, a cathode, an electrolyte, in which at least one of the anode or the cathode is an electrode according to the invention.
- the electrolysis device can be used as a water electrolysis device for the production of a gaseous mixture of hydrogen and oxygen and / or the production of hydrogen alone comprising an anode, a cathode and an electrolyte, said device being characterized in that at least one of the cathode or the anode is an electrode according to the invention, preferably the cathode.
- the electrolysis device consists of two electrodes (an anode and a cathode, electronic conductors) connected to a direct current generator, and separated by an electrolyte (ionically conductive medium).
- the anode is the seat of water oxidation.
- the cathode is the seat of proton reduction and hydrogen formation.
- the electrolyte can be:
- a polymeric proton exchange membrane which ensures the transfer of protons from the anode to the cathode and allows the separation of the anode and cathode compartments, which avoids reoxidizing the reduced species at the cathode and vice versa; - either an ion-conducting ceramic membrane 0 2 .
- SOEC solid oxide electrolysis
- 'Solid Oxide Electrolyser Cell according to English terminology.
- the minimum water supply for an electrolysis device is 0.8 l / Nm 3 of hydrogen. In practice, the real value is close to 1 l / Nm 3 .
- the water introduced must be as pure as possible because the impurities remain in the equipment and accumulate over the electrolysis, ultimately disrupting the electrolytic reactions by:
- the reaction has a standard potential of -1.23 V, which means that it ideally requires a potential difference between the anode and the cathode of 1.23 V.
- a standard cell generally operates under a potential difference of 1 , 5 V and at room temperature. Some systems may operate at higher temperatures. Indeed, it has been shown that high temperature electrolysis (HTE) is more efficient than electrolysis of water at room temperature, on the one hand, because part of the energy necessary for the reaction can be provided by heat (cheaper than electricity) and, on the other hand, because the activation of the reaction is more effective at high temperature. HTE systems generally operate between 100 ° C and 850 ° C.
- the electrolysis device can be used as a nitrogen electrolysis device for the production of ammonia, comprising an anode, a cathode and an electrolyte, said device being characterized in that at least one of the cathode or anode is an electrode according to the invention, preferably the cathode.
- the electrolysis device consists of two electrodes (an anode and a cathode, electronic conductors) connected to a direct current generator, and separated by an electrolyte (ionic conductive medium).
- the anode is the seat of water oxidation.
- the cathode is the seat of nitrogen reduction and the formation of ammonia. Nitrogen is continuously injected into the cathode compartment.
- the nitrogen reduction reaction is:
- the electrolyte can be:
- an aqueous solution Na 2 S0 4 or HCL, preferably saturated with nitrogen;
- a polymeric proton exchange membrane which ensures the transfer of protons from the anode to the cathode and allows the separation of the anode and cathode compartments, which avoids reoxidizing at the anode the reduced species at the cathode and vice versa.
- the electrolysis device can be used as a carbon dioxide electrolysis device for the production of formic acid, comprising an anode, a cathode and an electrolyte, said device being characterized in that at least one of the cathode or anode is an electrode according to the invention.
- An example of anode and electrolyte which can be used in such a device is described in detail in the document FR3007427.
- the electrolysis device can be used as a fuel cell device for the production of electricity from hydrogen and oxygen comprising an anode, a cathode and an electrolyte (liquid or solid), said device being characterized in that at least one of the cathode or the anode is an electrode according to the invention.
- the fuel cell device consists of two electrodes (an anode and a cathode, electronic conductors) connected to a load C to deliver the electric current produced, and separated by an electrolyte (ionic conductive medium).
- the anode is the seat of hydrogen oxidation.
- the cathode is the seat of oxygen reduction.
- the electrolyte can be:
- either a proton-exchange polymer membrane which ensures the transfer of protons from the anode to the cathode and allows the separation of the anode and cathode compartments, which avoids reoxidizing at the anode the reduced species at the cathode and vice versa;
- Example 1 Preparation of an electro-reduced solution based on M in solution
- the working electrode is a titanium plate coated with platinum.
- the counter electrode is a metal alloy based on iron-chromium-nickel.
- the Ag / AgCI type reference electrode is placed in a salt bridge filled with KCI (3M) and agar-agar, itself placed in a glass piece located between the pump and the inlet of the electrolyser. cathode side.
- the pumps provide a flow rate between 10 and 20 ml / min.
- the blue color of the electroreduced solution appears very quickly.
- the speed of reduction of the HPA solution decreases over time, the current density gradually decreases from -30 mA / cm 2 to -2.4 mA / cm 2 in 1 hour of electrolysis by regularly varying the potential imposed from 400 mV to 300 mV vs Ag / AgCI.
- the amount of final charge then rises to 1500 ° C. after only 1 hour of electrolysis.
- the catalytic material C1 (conforming) is prepared by dry impregnation of 10 g of commercial carbon type support (ketjenblack) with 10 ml of electroreduced solution obtained in Example 1.
- the preparation of the catalyst continues with a maturation step where the impregnated solid is kept under argon for 18 hours before undergoing a final drying step under an inert atmosphere and at reduced pressure (by drawing under vacuum) at 60 ° C. 'oil).
- the precatalyst is sulfurized under pure H2S at a temperature of 400 ° C. for 2 hours under 0.1 MPa of pressure.
- the characterization of the catalytic activity of catalytic materials is carried out in a cell with 3 electrodes.
- This cell is composed of a working electrode, a platinum counter electrode and an Ag / AgCI reference electrode.
- the electrolyte is an aqueous solution of sulfuric acid (H 2 S0 4 ) at 0.5 mol / L. This medium is deoxygenated by bubbling with nitrogen and the measurements are made under an inert atmosphere (deaeration with nitrogen).
- the working electrode consists of a 5 mm diameter disc of vitreous carbon set in a Teflon tip (rotating disc electrode). Glassy carbon has the advantage of having no catalytic activity and of being a very good electrical conductor.
- a catalytic ink is formulated. This ink consists of a binder in the form of a solution of 10 ⁇ L of Nafion® 15% by mass, of a solvent (1 ml of 2-propanol) and of 5 mg of catalyst (C1, C2). The role of the binder is to ensure the cohesion of the particles of the supported catalyst and the adhesion to vitreous carbon.
- This ink is then placed in an ultrasonic bath for 30 to 60 minutes in order to homogenize the mixture. 12 ⁇ L of the prepared ink is deposited on the working electrode (described above). The ink is then deposited on the working electrode and then dried in order to evaporate the solvent.
- - linear voltammetry it consists in applying a potential signal to the working electrode which varies over time, ie from 0 to - 0.5 V vs RHE at a speed of 2 mV / s, and measuring the current faradaic response, that is to say the current due to the oxidation-reduction reaction taking place at the working electrode.
- This method is ideal for determining the catalytic power of a material for a given reaction. It allows, among other things, to determine the overvoltage necessary for the reduction of protons to H 2 .
- chronopotentiometry it consists of applying a current or a current density for a determined time and measuring the resulting potential. This study makes it possible to determine the catalytic activity at constant current but also the stability of the system over time. It is carried out with a current density of - 10 mA / cm 2 and for a given time.
- the catalytic performances are collated in Table 1, below. They are expressed in overvoltage at a current density of -10 mA / cm 2 .
- the catalytic material C1 has performances relatively close to that of platinum vis-à-vis according to the prior art. This result demonstrates the indisputable interest of this material for the development of the hydrogen sector by electrolysis of water.
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FR1872181A FR3089134B1 (fr) | 2018-11-30 | 2018-11-30 | Procédé de préparation d’un matériau catalytique d’électrode pour des réactions de réduction électrochimique préparé par électroréduction. |
PCT/EP2019/081705 WO2020109062A1 (fr) | 2018-11-30 | 2019-11-19 | Procede de preparation d'un materiau catalytique d'electrode pour des reactions de reduction electrochimique prepare par electroreduction |
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FR3133544B1 (fr) | 2022-03-18 | 2024-03-08 | Ifp Energies Now | Matériau catalytique à base d’un élément du groupe VIB et d’un élément du groupe IVB pour la production d’hydrogène par électrolyse de l’eau |
CN114908375A (zh) * | 2022-05-25 | 2022-08-16 | 中国科学技术大学 | 电催化co2还原中具有稳定活性位点的铜催化剂及其制备方法与应用 |
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US2547380A (en) | 1945-10-01 | 1951-04-03 | Union Oil Co | Catalyst for hydrocarbon conversion |
JP5732470B2 (ja) * | 2009-12-16 | 2015-06-10 | イエフペ エネルジ ヌヴェルIfp Energies Nouvelles | 第viii族および第vib族金属を含み、酢酸およびc1−c4ジアルキルスクシナートを有する、水素化処理において使用可能な触媒および調製 |
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FR2984763B1 (fr) * | 2011-12-22 | 2013-12-20 | IFP Energies Nouvelles | Procede de preparation d'un catalyseur utilisable en hydroconversion comprenant au moins une zeolithe nu-86 |
FR3004968B1 (fr) * | 2013-04-30 | 2016-02-05 | IFP Energies Nouvelles | Procede de preparation d'un catalyseur a base de tungstene utilisable en hydrotraitement ou en hydrocraquage |
FR3004967B1 (fr) * | 2013-04-30 | 2016-12-30 | Ifp Energies Now | Procede de preparation d'un catalyseur a base de molybdene utilisable en hydrotraitement ou en hydrocraquage |
FR3007427B1 (fr) | 2013-06-20 | 2016-07-01 | Ifp Energies Now | Couche active a base de particules metalliques sur support conducteur poreux, methode de fabrication et utilisation en tant que cathode pour l'electroreduction de dioxyde de carbone. |
CN106917105B (zh) * | 2017-01-13 | 2019-05-31 | 太原理工大学 | 一种水分解用自支撑过渡金属硫化物泡沫电极的制备方法 |
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KR101894964B1 (ko) * | 2017-08-08 | 2018-09-05 | 한국과학기술원 | 그래핀 액정섬유-전이금속계 촉매 섬유복합체 및 이의 제조방법 |
FR3075664A1 (fr) * | 2017-12-22 | 2019-06-28 | IFP Energies Nouvelles | Catalyseur d'hydrotraitement et/ou d'hydrocraquage prepare par electroreduction |
CN108855146B (zh) * | 2018-06-27 | 2020-05-05 | 北京师范大学 | NiFeMoS复合体及其制备方法 |
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