CN111545221B - Homologous metal gradient material and preparation method and application thereof - Google Patents
Homologous metal gradient material and preparation method and application thereof Download PDFInfo
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- CN111545221B CN111545221B CN202010323919.XA CN202010323919A CN111545221B CN 111545221 B CN111545221 B CN 111545221B CN 202010323919 A CN202010323919 A CN 202010323919A CN 111545221 B CN111545221 B CN 111545221B
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- 239000000463 material Substances 0.000 title claims abstract description 126
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 111
- 239000002184 metal Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 39
- 150000003624 transition metals Chemical class 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 23
- 239000007769 metal material Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 229910052798 chalcogen Inorganic materials 0.000 claims abstract description 14
- 150000001787 chalcogens Chemical class 0.000 claims abstract description 14
- 230000007704 transition Effects 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 239000012495 reaction gas Substances 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000002484 cyclic voltammetry Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 18
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000010955 niobium Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 238000001212 derivatisation Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 23
- 239000011148 porous material Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 10
- 238000004806 packaging method and process Methods 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- PHDAFAYBFCDDPY-UHFFFAOYSA-N tantalum(5+);pentasulfide Chemical compound [S-2].[S-2].[S-2].[S-2].[S-2].[Ta+5].[Ta+5] PHDAFAYBFCDDPY-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000861 blow drying Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- NUXLSBINLJQBHM-UHFFFAOYSA-N niobium(5+);pentasulfide Chemical compound [S-2].[S-2].[S-2].[S-2].[S-2].[Nb+5].[Nb+5] NUXLSBINLJQBHM-UHFFFAOYSA-N 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- JAAVTMIIEARTKI-UHFFFAOYSA-N [S--].[S--].[Ta+4] Chemical compound [S--].[S--].[Ta+4] JAAVTMIIEARTKI-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- FAWYJKSBSAKOFP-UHFFFAOYSA-N tantalum(iv) sulfide Chemical compound S=[Ta]=S FAWYJKSBSAKOFP-UHFFFAOYSA-N 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- -1 transition metal chalcogenide Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/61—
-
- B01J35/657—
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
Abstract
The invention discloses a homologous metal gradient material and a preparation method and application thereof, wherein the preparation method of the homologous metal gradient material comprises the following steps: (1) Taking a transition metal material to perform chemical oxidation treatment to form a transition metal-metal oxide material; (2) And adding a chalcogen source into the transition metal-metal oxide material, and introducing inert gas and reaction gas to react to obtain the homologous metal gradient material, wherein the reaction gas can reduce metal oxides in the transition metal-metal oxide material. The invention takes the transition metal material as the base material, utilizes the in-situ derivatization of the homologous metal to prepare the homologous metal gradient material, has good stability, has better electrocatalytic hydrogen evolution performance than other transition metal-based catalysts, and has wide application prospect in water electrolysis hydrogen production, supercapacitors and ion batteries.
Description
Technical Field
The invention relates to the field of transition metal materials, in particular to a homologous metal gradient material, a preparation method and application thereof.
Background
As fossil energy is increasingly exhausted, and with environmental degradation, more and more research is beginning to focus on green pollution-free energy to advance the sustainable development of society. Among various energy sources, hydrogen energy is clean, pollution-free, high in energy density and renewable, and is one of the energy carriers with the most practical application potential in the future. Unlike traditional fossil energy, there is no large amount of hydrogen available directly in nature, so large-scale and low-cost preparation of hydrogen is the primary problem to be solved in the current development of hydrogen energy. At present, the commonly used hydrogen preparation methods mainly comprise three methods of high-temperature pyrolysis of natural gas, a water gas method, a photolysis water method and an electrolysis water method. The natural gas and the water gas are subjected to pyrolysis to prepare hydrogen under the high-temperature condition, the process has high energy consumption, and carbon dioxide gas with greenhouse effect is inevitably generated in the hydrogen preparation process. If the reaction is incomplete, carbon monoxide gas is generated, and the carbon monoxide has poisoning effect on a noble metal catalyst in the high-temperature pyrolysis energy conversion device, so that the activity and stability of the catalyst are seriously affected. Compared with the method, the method for preparing the hydrogen by electrolyzing the water has mild preparation conditions, does not need to operate at high temperature, does not need to purify and separate the hydrogen, and has very high purity. Compared with other hydrogen production methods, the electrolyzed water has the best economic benefit and is a core technology for large-scale hydrogen production in the future.
The electrolytic water hydrogen production reaction consists of two half reactions, namely anodic Oxygen Evolution (OER) and cathodic Hydrogen Evolution (HER). The reactions of the cathode and anode differ among the different electrolytes, and thus the catalytic activity exhibited by the catalyst also varies. The higher the overpotential required for the half-reaction during electrolysis of water, the greater the loss of electrical energy required for the reaction. Therefore, it is necessary to provide a catalyst capable of reducing the reaction overpotential in the process to improve the water electrolysis efficiency. Currently, noble metal platinum (Pt) based catalysts have the best catalytic activity for cathodic hydrogen evolution reactions. The initial potential of the reaction of the platinum catalyst is close to 0V, and the platinum catalyst is the most ideal hydrogen evolution catalytic material. However, noble metal platinum resources are scarce and expensive, and are not suitable for being used as catalytic materials for large-scale hydrogen production reaction. Therefore, the method for simply developing and realizing the large-scale preparation of the catalyst applicable to the hydrogen production by water electrolysis has great significance in the field.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides the homologous metal gradient material, and the preparation method and application thereof, wherein the preparation method is easy for large-scale production, the required raw materials and the process cost are low, and the prepared homologous metal gradient material has good catalytic activity and can achieve the purpose of improving the overall electrocatalytic hydrogen production performance.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, a method for preparing a homogenous metallic gradient material is provided, comprising the steps of:
(1) Taking a transition metal material to perform chemical oxidation treatment to form a transition metal-metal oxide material;
(2) And adding a chalcogen source into the transition metal-metal oxide material, and introducing inert gas and reaction gas to react to obtain the homologous metal gradient material, wherein the reaction gas can reduce metal oxides in the transition metal-metal oxide material.
The role of the chalcogen sources described above is to participate in the reaction to form transition metal dichalcogenides (TMD's). The transition metal dichalcogenide formed in the homologous metal gradient material is prepared based on in-situ derivatization of the transition metal material used, and the transition metal in the transition metal dichalcogenide is derived from the transition metal material used.
The metal oxide material generated by the chemical oxidation treatment of the transition metal material is combined with the reaction gas and the chalcogen source in the step (2) to form transition metal dichalcogenide, and the transition metal dichalcogenide can be controlled to be partially or completely converted into the transition metal dichalcogenide in the process, and the chalcogen source gradually penetrates from the surface contacted with the metal oxide to the inside for reaction, so that the chalcogen element after the reaction is distributed in the final material in a gradient manner, and the homologous metal gradient material is formed. The transition metal dichalcogenide has better electrocatalytic hydrogen evolution effect, so that the final material obtained by controlling the total conversion of the metal oxide into the transition metal dichalcogenide has more excellent electrocatalytic hydrogen evolution performance, and the final material obtained by controlling the partial conversion of the metal oxide into the transition metal dichalcogenide has more excellent performance in lithium ion batteries and supercapacitors because the metal oxide is more prone to lithium ion or charge adsorption.
Non-limiting examples of transition metal materials used may be tantalum (Ta), niobium (Nb), vanadium (V), molybdenum (Mo), tungsten (W), nickel (Ni), iron (Fe), cobalt (Co).
According to some embodiments of the invention, the method further comprises the step of pore-forming on the transition metal material, the transition metal-metal oxide material or the homo-metal gradient material. The homologous metal gradient material which is not subjected to the pore-forming step has a catalytic effect, and the purpose of pore-forming is to accelerate proton transmission and gas diffusion in the hydrogen evolution reaction because the hydrogen evolution speed is high under the high current density, so that the catalytic effect of the material under the high current density is improved. The pore-forming may be performed in any step of the material preparation process, for example, the transition metal material used may be first pore-formed to form a porous transition metal material before the chemical oxidation treatment, or the pore-forming may be performed in a subsequent step. According to some embodiments of the invention, the pore size is 10-50 microns.
According to some embodiments of the invention, the pore-forming is performed by physical laser pore-forming or electrochemical selective etching pore-forming.
According to some embodiments of the invention, the reactant gas is hydrogen or hydrogen sulfide. The reaction gas can also select other gases with reducing property, and the reaction gas has the function of reducing the metal oxide and combining with a reaction precursor chalcogen source to prepare the transition group metal dichalcogenide.
According to some embodiments of the invention, the reactant gas is introduced at a gas flow rate of 60-300sccm.
According to some embodiments of the invention, the chemical oxidation treatment is performed in step (1) by heating at a temperature of 60-600 ℃.
According to some embodiments of the invention, the time of the chemical oxidation treatment in step (1) is 2 to 120 minutes.
According to some embodiments of the invention, the method further comprises a process of treating with electrochemical cyclic voltammetry using the homogenous metal gradient material as a cathode. The electrochemical cyclic voltammetry is adopted to play a role in stripping, so that the electrochemical active area of the prepared homologous metal gradient material is increased, and more catalytic active sites are exposed.
Further in accordance with some embodiments of the invention, the electrochemical cyclic voltammetry is performed for a number of electrochemical cycles in the range of 1000 to 30000.
According to some embodiments of the invention, the chalcogen source in step (2) comprises at least one of a sulfur source, a selenium source, and a tellurium source.
According to some embodiments of the invention, the sulfur source comprises any one of sulfur powder, sodium sulfide, carbon disulfide, and mercaptans.
According to some embodiments of the invention, the transition metal-metal oxide material is reacted with a chalcogen source, a reactant gas in step (2) by chemical vapor deposition. In the step (2), the metal oxide material in the transition metal-metal oxide material and the chalcogen source are subjected to a sulfuration reaction to form the transition metal dichalcogenide, so that the catalyst has excellent catalytic activity, and chalcogen elements in the transition metal dichalcogenide are distributed in the homologous metal gradient material in a gradient manner.
According to some embodiments of the invention, the temperature of the reaction in step (2) is 200-1000 ℃.
According to some embodiments of the invention, the time of the reaction in step (2) is 30 to 300 minutes.
In a second aspect of the present invention, there is provided a homogeneous metal gradient material, prepared according to the above-described method for preparing a homogeneous metal gradient material.
In a third aspect, the invention provides the application of the homologous metal gradient material in water electrolysis hydrogen production, lithium ion batteries and supercapacitors. The homogeneous metal gradient material belongs to a metallic material, has good conductivity, high specific surface area and rich pore canal structure, is favorable for lithium ion intercalation and charge adsorption, and can be applied to different energy storage and conversion devices.
The embodiment of the invention has the beneficial effects that:
in the prior art, the transition metal chalcogenide can be prepared in small batches in a laboratory only by a traditional chemical vapor deposition method or a hydrothermal method, so that the industrial requirement facing the large-scale application cannot be met, the amount of the obtained product is small by adopting a traditional chemical vapor deposition method for preparing the metal chalcogenide, and the product generally needs to be transferred and reused. The embodiment of the invention provides a preparation method of a homologous metal gradient material, which takes a transition metal material as a substrate material, utilizes homologous metal in-situ derivatization to obtain a transition metal dichalcogenide, and the transition metal dichalcogenide is stably connected with the substrate material through chemical bonds, so that the formed homologous metal gradient material can be used as an electrolytic water electrode without being transferred to other substrates, in addition, the substrate transition metal in the homologous metal gradient material has an electron injection effect on the transition metal dichalcogenide, and the hydrogen adsorption energy of the transition metal dichalcogenide can be further optimized, thereby improving the overall catalytic activity of the material, and the homologous metal gradient material is formed by regulating and controlling the valence state of the transition metal or the content of chalcogen element in the transition metal dichalcogenide in the preparation process. The method provided by the embodiment of the invention can realize large-scale preparation, the obtained homologous metal gradient material has good stability, the electrocatalytic hydrogen evolution performance is superior to that of other transition metal-based catalysts, and the method has wide application prospects in hydrogen production by water electrolysis, supercapacitors and lithium ion batteries.
Drawings
FIG. 1 is a schematic diagram of the preparation of homogeneous metal gradient material in example 1;
FIG. 2 is an optical microscope image of the porous metal tantalum foil of example 1;
FIG. 3 is a pore size distribution diagram of a porous metal tantalum foil in example 1;
FIG. 4 is an optical photograph of a homogenous metal (Ta) gradient material not subjected to electrochemical cyclic voltammetry treatment in example 1;
FIG. 5 is a scanning electron microscope image of a homogenous metal (Ta) gradient material without electrochemical cyclic voltammetry treatment in example 1;
FIG. 6 is a scanning electron microscope image of a homogenous metal (Ta) gradient material treated by electrochemical cyclic voltammetry in example 1;
FIG. 7 is a high power transmission electron microscopy image of an electrochemically cyclic voltammetry treated graded material of homologous metal (Ta) in example 1;
FIG. 8 is a linear sweep voltammogram of an electrochemically cyclic voltammetry treated graded material of homologous metal (Ta) in example 1;
FIG. 9 is a graph of hydrogen production performance from electrolyzed water of an electrochemically cyclic voltammetry treated graded material of homologous metal (Ta) in example 1;
FIG. 10 is a graph of time-current stability of an electrochemically cyclic voltammetry treated graded material of homologous metal (Ta) as a catalyst in example 1;
FIG. 11 is a pore size distribution diagram of a porous metal tantalum foil in example 2;
FIG. 12 is a linear sweep voltammogram of an electrochemically cyclic voltammetry treated graded material of homologous metal (Ta) in example 2;
FIG. 13 is a linear sweep voltammogram of an electrochemically cyclic voltammetry treated graded material of homologous metal (Ta) in example 3;
FIG. 14 is a scanning electron microscope image of an electrochemically cyclic voltammetry-treated homologous metal (Nb) gradient material in example 4;
FIG. 15 is a linear sweep voltammogram of an electrochemically cyclic voltammetry-treated graded material of homologous metal (Nb) in example 4.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
Referring to fig. 1, fig. 1 is a schematic diagram of the preparation of a homogeneous metal gradient material according to this embodiment, and this embodiment provides a homogeneous metal gradient material prepared according to the following steps:
(1) The metal tantalum foil (Ta foil, 2 cm multiplied by 2 cm) is taken and flattened by a tablet press, then the porous metal tantalum foil is formed by pore-forming by a laser technology, and pore-forming is carried out in a region of 1 cm multiplied by 1 cm of the Ta foil, and the pore diameter is 10 micrometers. Then sequentially ultrasonically cleaning by using ethanol and water, blow-drying by using a nitrogen gun, and packaging for later use under the inert atmosphere condition.
(2) And (3) placing the porous metal tantalum foil in a high-temperature heating furnace for chemical oxidation treatment, heating the furnace to 500 ℃, keeping the temperature at the heating rate of 10 ℃/min, keeping the temperature at 500 ℃ for 15 minutes, stopping heating, naturally cooling the furnace to room temperature, obtaining a porous tantalum-tantalum oxide sample, and packaging under the inert atmosphere condition for later use.
(3) Placing a porous tantalum-tantalum oxide sample in a chemical vapor deposition system, heating the temperature in a furnace to 900 ℃, heating the sulfur powder to 130 ℃ at the speed of 50 ℃/min, introducing argon in the heating process, keeping the temperature at 90sccm and 900 ℃ for 2 hours, stopping heating, and introducing argon and hydrogen in the constant temperature process, wherein the flow rates are 90sccm and 10sccm respectively. After the reaction is finished, argon and hydrogen are introduced, the flow rates are respectively 100sccm and 5sccm, simultaneously, a sulfur powder heater is removed, the cooling rate is controlled to be 2 ℃/min, and the furnace is naturally cooled to room temperature, thus obtaining tantalum-tantalum sulfide (Ta-TaS) 2 ) And (3) packaging the sample (namely the homologous metal (Ta) gradient material) under the inert atmosphere condition for later use.
(4) Putting the tantalum-tantalum sulfide sample (i.e. the homologous metal (Ta) gradient material) prepared in the step (3) into an electrode clamp to serve as a cathode, a graphite rod as an anode, an Ag/AgCl electrode as a reference electrode, and electrolyte of 0.5M H 2 SO 4 . The electrochemical cyclic voltammetry technology is adopted for treatment, the scanning speed is set to be 20 mV/min, and the scanning times are 15000 times. And after the treatment is finished, taking out the homologous metal (Ta) gradient material treated by the electrochemical cyclic voltammetry, cleaning with a large amount of deionized water, blow-drying by a nitrogen gun, and packaging under the inert atmosphere condition for later use.
Taking the porous metal tantalum foil obtained in the step (1) for appearance and structure characterization, wherein fig. 2 is an optical microscope image of the porous metal tantalum foil, fig. 3 is a pore size distribution diagram of the porous metal tantalum foil, and the pore size of the porous metal tantalum foil is about 10 mu m, and the pore size difference value is within +/-2 mu m.
Fig. 4 is an optical picture of the tantalum-tantalum sulfide sample (i.e., the homogeneous metal (Ta) gradient material) obtained in step (3), and the homogeneous metal (Ta) gradient material is characterized by using a scanning electron microscope, and as a result, as shown in fig. 5, the homogeneous metal (Ta) gradient material is a layered material.
Fig. 6 is a scanning electron microscope image of a homogeneous metal (Ta) gradient material obtained by electrochemical cyclic voltammetry treatment in step (4), showing that the tantalum-tantalum sulfide sample in step (3) can be subjected to electrochemical cyclic voltammetry treatment to peel off the layered structure, and the obtained material is a porous layered material. Further using a high resolution transmission electron microscope for characterization, fig. 7 is a high resolution transmission electron microscope image of the homologous metal (Ta) gradient material treated by the electrochemical cyclic voltammetry in step (4), and the image shows that the surface of the obtained homologous metal (Ta) gradient material is a high quality tantalum disulfide crystal.
The electrochemically cyclic voltammetry-treated homologous metal (Ta) gradient material (Ta-TaS) prepared in step (4) of this example 2 ) As working electrode, electrochemical tests were performed directly, all on a three-electrode system of electrochemical workstation (VMP 3). The graphite rod is used as a counter electrode, ag/AgCl is used as a reference electrode, the electrolyte is a dilute sulfuric acid solution with the concentration of 0.5mol/L, and all potentials are calibrated to a Reversible Hydrogen Electrode (RHE). The test was performed by using a linear sweep voltammetry at a sweep rate of 5mV/s and a platinum plate (Pt) as a reference under the same conditions as those described above, and the test results are shown in FIG. 8, when the current density was 2000mA cm -2 When the embodiment of the invention is used, the homologous metal (Ta) gradient material tantalum-tantalum sulfide (Ta-TaS) 2 ) Only 399mV was required for the overpotential of (C), while 710mV was required for the noble metal platinum under the same conditions. Homologous Metal (Ta) gradient Material (Ta-TaS) treated by electrochemical cyclic voltammetry according to this example 2 ) And a platinum (Pt) electrode, the hydrogen production performance by water electrolysis is shown as figure 9, the homologous metal (Ta) gradient material (Ta-TaS) 2 ) At 1000mA cm -2 Only 1.98V is needed for the current density, far superior to other transition metal based catalysts, the homologous metal (Ta) gradient material (Ta-TaS 2 ) The Ta metal substrate in the method has an electron injection effect on metal disulfide, so that the hydrogen adsorption energy of the metal disulfide can be further optimized, and the overall catalytic activity of the material is improved. FIG. 10 shows the gradient material of homologous metal (Ta) (Ta-TaS after electrochemical cyclic voltammetry treatment according to the present example 2 ) As a time-current stability curve for an electrolyzed water catalyst, its stability after a period of 50 hours of operationStill kept good, which shows that the TaS in the homologous metal (Ta) gradient material provided by the embodiment of the invention 2 The bonding ability with the substrate Ta is strong. The experiment shows that the homologous metal (Ta) gradient material (Ta-TaS) 2 ) Exhibits excellent electrocatalytic hydrogen evolution performance at high current density at 2000mA cm -2 The overpotential at the current density of (3) is only about 399mV, and the water electrolysis device is at 1000mA cm -2 The electric potential of only 1.98V is needed under the current density, which is far superior to other transition metal-based catalysts, and stable electrocatalytic hydrogen evolution reaction can be realized under a lower external electric field.
Taking the Ta-TaS prepared in step (3) of this example 2 Samples, i.e., homogeneous metal (Ta) gradient materials not subjected to electrochemical cyclic voltammetry (0 cycles), were tested by linear sweep voltammetry in the same manner as the measurement conditions described above for FIG. 8 at 2000mA cm -2 The required overpotential under the current density of (3) is about 818mV, which is higher than the value after 15000 times of circulation, which shows that the homologous metal (Ta) gradient material which is not treated by the electrochemical cyclic voltammetry has certain catalytic hydrogen evolution performance, but the electrochemical cyclic voltammetry can strip the material, so that the electrochemical active area of the material is increased, more catalytic active sites are exposed, and the catalytic activity of the material is further improved.
Comparative effects example 1
Comparative example 1: the comparative example provides a glassy carbon-metal disulfide material, which adopts nonmetallic glassy carbon as a base material, grows metal tantalum disulfide on the base material, mixes sulfur powder and tantalum pentachloride according to the mass ratio of 2.5:1, and is placed in a quartz boat after grinding; sequentially placing a quartz boat filled with glassy carbon and a quartz boat filled with a mixture of a sulfur source and a tantalum source in a tube furnace with two temperature areas according to the direction from an air inlet to an air outlet, introducing nitrogen and/or a mixed gas of argon and hydrogen, setting the temperature of the temperature area of the mixture of the sulfur source and the tantalum source to be 230 ℃, setting the temperature of the temperature area of the glassy carbon to be 750 ℃, heating to a preset temperature at the speed of 50 ℃/min, and growing for 60min; and after the growth is finished, the mixed gas is closed, and the glassy carbon-metal disulfide material is obtained after cooling in a nitrogen and/or argon atmosphere.
The glassy carbon-metal disulfide material of comparative example 1 was tested by linear sweep voltammetry under the same conditions as in example 1, and the test results showed that the glassy carbon-metal disulfide material of comparative example 1 required an overpotential of 177mV at 10mA cm-2, as compared with the homologous metal (Ta) gradient material of the examples of the present invention (Ta-TaS 2 ) 110mV higher, thus requiring more charge to drive the reaction. And because the bonding force between the glass carbon and the metal disulfide is weak, the stability requirement under the heavy current cannot be met, so that the glass carbon-metal disulfide cannot realize the efficient and stable hydrogen evolution reaction under the heavy current density.
Example 2
This example provides a homogeneous metal (Ta) gradient material (Ta-TaS) 2 ) Other conditions and steps are the same as in example 1, except that step (1) is: and (3) taking a metal tantalum foil (2 multiplied by 2 cm), flattening by a tablet press, carrying out pore forming by a laser technology to form a porous metal tantalum foil, and carrying out pore forming in a region of 1 cm multiplied by 1 cm of the Ta foil, wherein the pore diameter is 50 micrometers. Sequentially ultrasonically cleaning ethanol and water, blow-drying by a nitrogen gun, and packaging under the inert atmosphere condition for later use.
FIG. 11 is a graph showing pore size distribution of the porous metal tantalum foil obtained in the step (1) of the present example, wherein the pore size of the porous metal tantalum foil sample is about 50 μm, and the pore size difference is within.+ -. 4. Mu.m.
FIG. 12 shows the electrochemical cyclic voltammetry-treated graded material (Ta-TaS) 2 ) Is measured when the current density is 2000mA cm -2 When the pore size is about 50 μm, tantalum-tantalum sulfide (Ta-TaS 2 ) About 475mV was required for the overpotential of (a) and the pore size was smaller in unit area than in example 1, so that the pore passage was also less in phase strain, and the finally produced homogeneous metal (Ta) gradient material (Ta-TaS 2 ) The electrochemically active area is relatively reduced.
Example 3
The present embodiment provides a transcendental electrochemical deviceHomologous Metal (Ta) gradient Material after chemical cyclic voltammetry treatment (Ta-TaS 2 ) Other conditions and steps are the same as in example 1, except that step (4) is: placing the tantalum-tantalum sulfide sample prepared in the step (3) into an electrode clamp to serve as a cathode, taking a graphite rod as an anode, taking an Ag/AgCl electrode as a reference electrode, and taking electrolyte of 0.5M H 2 SO 4 . The electrochemical cyclic voltammetry technology is adopted for treatment, the scanning speed is set to be 20 mV/min, and the scanning times are 5000 times. And after the treatment is finished, taking out the homologous metal (Ta) gradient material treated by the electrochemical cyclic voltammetry, cleaning with a large amount of deionized water, blow-drying by a nitrogen gun, and packaging under the inert atmosphere condition for later use.
FIG. 13 shows the electrochemical cyclic voltammetry-treated graded material (Ta-TaS) 2 ) Is measured when the current density is 2000mA cm -2 At the time of scanning, tantalum-tantalum sulfide (Ta-TaS) 2 ) About 685mV higher than in example 1. This is because the electrochemical cycling process is a two-dimensional tantalum sulfide ion intercalation stripping process, and the more cycles, the more samples are stripped, and thus the larger the electrochemical active area, so when the number of scans is 5000, the material exposes less electrocatalytically active area than in example 1.
Example 4
The embodiment provides a homologous metal gradient material, which is prepared according to the following steps:
(1) The metal niobium foil (Nb foil, 2 cm. Times.2 cm) was flattened using a sheeter, then the porous metal niobium foil was apertured using laser technology, and the apertures were 10 microns in the 1 cm. Times.1 cm area of the Ta foil. Sequentially ultrasonically cleaning ethanol and water, blow-drying by a nitrogen gun, and packaging under the inert atmosphere condition for later use.
(2) Placing porous metal niobium foil into a high-temperature heating furnace, heating the furnace to 430 ℃ at a heating rate of 10 ℃/min, keeping the temperature at 430 ℃ for 15 minutes, stopping heating, naturally cooling the furnace to room temperature, taking out a porous niobium-niobium oxide sample, and packaging under an inert atmosphere condition for later use.
(3) Taking a porous niobium-niobium oxide sample to be placedIn a chemical vapor deposition system, the temperature in a furnace is increased to 850 ℃, the heating rate is 50 ℃/min, meanwhile, sulfur powder is heated to 130 ℃, argon is introduced in the heating process, the heating is stopped after the temperature is kept at 850 ℃ for 2 hours, and the argon and the hydrogen are introduced in the constant temperature process, wherein the flow is 90sccm and 10sccm respectively. After the reaction, argon and hydrogen were introduced at a flow rate of 100sccm and 5sccm, respectively. Meanwhile, removing the sulfur powder heater, controlling the cooling rate to be 2 ℃/min, and naturally cooling the furnace to room temperature to obtain niobium-niobium sulfide (Nb-NbS) 2 ) And (3) packaging the sample (namely the homologous metal (Nb) gradient material) under the inert atmosphere condition for later use.
(4) Niobium-niobium sulfide (Nb-NbS) 2 ) The sample is placed in an electrode clamp to be used as a cathode, a graphite rod is used as an anode, an Ag/AgCl electrode is used as a reference electrode, and electrolyte is 0.5M H 2 SO 4 . The electrochemical cyclic voltammetry technology is adopted for treatment, the scanning speed is set to be 20 mV/min, and the scanning times are 12000 times. And after the treatment is finished, taking out the homologous metal (Nb) gradient material treated by the electrochemical cyclic voltammetry, cleaning with a large amount of deionized water, blow-drying by a nitrogen gun, and packaging under the inert atmosphere condition for later use.
FIG. 14 is a scanning electron microscope image of a homogeneous metal (Nb) gradient material treated by electrochemical cyclic voltammetry in this example, showing the porous structure of the material. The homologous metal (Nb) gradient material treated by the electrochemical cyclic voltammetry in this example was directly tested as a working electrode, and all electrochemical tests were performed on a three-electrode system of an electrochemical workstation (VMP 3). The graphite rod is used as a counter electrode, ag/AgCl is used as a reference electrode, the electrolyte is a dilute sulfuric acid solution with the concentration of 0.5mol/L, and all potentials are calibrated to a Reversible Hydrogen Electrode (RHE). The test was performed using a linear sweep voltammetry at a sweep rate of 5mV/s. Meanwhile, the platinum sheet is used as a comparison for testing, the testing conditions are the same as the conditions, the testing result is shown in FIG. 15, when the current density is 2000mA cm -2 When the embodiment of the invention is used, the homologous metal (Nb) gradient material niobium-niobium sulfide (Nb-NbS) 2 ) Only 435mV is needed for the overpotential of the noble metal platinum, while 710mV is needed for the noble metal platinum under the same conditions, indicating that the homologous metal (Nb) gradient material of the embodiment of the invention has more excellent propertiesElectrocatalytic properties.
Claims (9)
1. The preparation method of the integrated homologous metal gradient material is characterized by comprising the following steps of:
(1) Taking a transition metal material for chemical oxidation treatment to form an integrated transition metal-metal oxide material;
(2) Adding a chalcogen source into the integrated transition metal-metal oxide material, introducing inert gas and reaction gas, and reacting to obtain a homologous metal gradient material, wherein the reaction gas can reduce metal oxide in the transition metal-metal oxide material to form a component gradient;
the method also comprises a process of treating by electrochemical cyclic voltammetry by taking the integrated homologous metal gradient material as a cathode;
the transition metal material comprises at least one of tantalum, niobium, vanadium, molybdenum, tungsten, nickel, iron or cobalt;
in the electrochemical cyclic voltammetry: electrolyte of 0.5. 0.5M H 2 SO 4 。
2. The method of claim 1, further comprising the step of pore-forming on the transition metal material, the integrated transition metal-metal oxide material, or the homogenous metal gradient material.
3. The method for producing a homogeneous metal gradient material according to claim 1, wherein the reaction gas is hydrogen or hydrogen sulfide.
4. The method for preparing a homogeneous metal gradient material according to claim 1, wherein the chemical oxidation treatment is performed by heating in the step (1) at a temperature of 60-600 ℃.
5. The method of producing a homologous metal gradient material of any of claims 1 to 4, wherein the chalcogen source in step (2) comprises at least one of a sulfur source, a selenium source, and a tellurium source.
6. The method of claim 5, wherein the sulfur source comprises any one of sulfur powder, sodium sulfide, carbon disulfide, and mercaptan.
7. The method for producing an integrated homogeneous metal gradient material according to any one of claims 1 to 4, wherein the temperature of the reaction in step (2) is 200 to 1000 ℃.
8. An integrated homogenous metallic gradient material, characterized in that it is produced by a method for producing a homogenous metallic gradient material according to any one of claims 1 to 7.
9. The use of the integrated homogenous metal gradient material of claim 8 in hydrogen production by electrolysis of water, lithium ion batteries, and supercapacitors.
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