CN116555816A - Catalyst for producing hydrogen by water electrolysis, preparation method, electrode plate and production system - Google Patents
Catalyst for producing hydrogen by water electrolysis, preparation method, electrode plate and production system Download PDFInfo
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- CN116555816A CN116555816A CN202310459495.3A CN202310459495A CN116555816A CN 116555816 A CN116555816 A CN 116555816A CN 202310459495 A CN202310459495 A CN 202310459495A CN 116555816 A CN116555816 A CN 116555816A
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- hydrogen
- molybdenum alloy
- water
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 123
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 123
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 118
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910001182 Mo alloy Inorganic materials 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- 238000009713 electroplating Methods 0.000 claims description 17
- 230000001105 regulatory effect Effects 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 150000002751 molybdenum Chemical class 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 5
- 239000011733 molybdenum Substances 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000007747 plating Methods 0.000 description 7
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 6
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005237 degreasing agent Methods 0.000 description 4
- 239000013527 degreasing agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
-
- 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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention belongs to the technical field of materials, and particularly relates to a catalyst for producing hydrogen by water electrolysis, a preparation method, an electrode plate and a production system. The catalyst for producing hydrogen by electrolyzing water comprises nickel-molybdenum alloy and a three-dimensional graphene layer coated outside the nickel-molybdenum alloy. According to the invention, the nickel-molybdenum alloy is coated with the three-dimensional graphene, so that the dissolution of molybdenum is avoided, and the stability of the hydrogen production catalyst by water electrolysis for hydrogen production is effectively improved.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a catalyst for producing hydrogen by water electrolysis, a preparation method, an electrode plate and a production system.
Background
In recent years, energy problems and environmental problems are increasingly prominent, and people's eyes are gradually turned to green clean energy sources such as hydrogen energy. Hydrogen energy is a clean, safe, efficient and sustainable energy source, and is considered as the most potential clean energy source in the 21 st century. The hydrogen energy has the following advantages: the water is not only a raw material of hydrogen energy, but also a combustion product of hydrogen, so that the environment is not polluted, and the material circulation is not negatively influenced; the hydrogen energy is easy to store; the hydrogen energy can be directly used by the fuel cell to generate electricity.
Generally, the hydrogen production method includes a thermochemical method and an electrochemical method, wherein the thermochemical method uses carbohydrates such as natural gas as raw materials, and the raw materials are subjected to high-temperature reaction to obtain a mixed gas containing hydrogen, and then separation and purification are performed. However, by adopting the method for producing hydrogen, the obtained mixed gas contains carbon dioxide isothermal chamber gas. The electrochemical method is a current general hydrogen production method, which takes water as a raw material and obtains hydrogen through electrolysis under the catalysis of a catalyst. Electro-alkaline hydrolysis water hydrogen production is a relatively mature electrolytic water hydrogen production method which is commercially applied, however, the cost of electrolytic water hydrogen production is relatively high. The electrode is an important reaction place for producing hydrogen by water electrolysis, is always a key place for producing hydrogen by water electrolysis, and plays an important role in reducing cost, reducing energy consumption and improving the utilization rate of a catalyst.
Nickel-molybdenum alloy is a good catalytic material for hydrogen evolution reaction, and has excellent catalytic activity, however, molybdenum is possibly oxidized and dissolved out in the hydrogen evolution reaction process because the reduction potential of the molybdenum is lower than that of hydrogen in the hydrogen evolution process, so that the stability of the catalytic activity of the molybdenum is poor.
Disclosure of Invention
In view of the above, the invention aims to provide a catalyst for producing hydrogen by water electrolysis, a preparation method, an electrode plate and a production system.
In some embodiments, the present application provides a catalyst for producing hydrogen by electrolysis of water, which comprises a nickel-molybdenum alloy and a three-dimensional graphene layer coated outside the nickel-molybdenum alloy.
According to the invention, the nickel-molybdenum alloy is coated with the three-dimensional graphene, so that the dissolution of molybdenum is avoided, and the stability of the hydrogen production catalyst by water electrolysis for hydrogen production is effectively improved. Meanwhile, the three-dimensional graphene has a larger specific surface area, more active sites are exposed, and the hydrogen evolution catalytic activity of the water electrolysis hydrogen production catalyst is remarkably improved.
In some embodiments, the nickel-molybdenum alloy is doped with cobalt.
The cobalt is doped in the nickel-molybdenum alloy, so that the hydrogen evolution catalytic activity of the catalyst for producing hydrogen by water electrolysis is improved.
In some embodiments, the three-dimensional graphene layer is doped with nitrogen.
According to the method, the nitrogen is doped in the three-dimensional graphene layer, so that the hydrogen evolution catalytic activity of the catalyst for producing hydrogen by electrolyzing water is improved.
In some embodiments, the present application provides a method of preparing a catalyst for producing hydrogen from electrolyzed water as described above, the method comprising:
s1, preparing nickel-molybdenum alloy;
s2, depositing three-dimensional graphene on the surface of the nickel-molybdenum alloy prepared in the step S1 to form a three-dimensional graphene layer, and obtaining the catalyst for producing hydrogen by water electrolysis.
In some embodiments, in step S1, preparing the nickel-molybdenum alloy comprises:
taking conductive polyurethane as a cathode and taking a pretreated pure nickel sheet as an anode;
preparing molybdenum salt and nickel salt into electroplating solution, regulating the pH value of the electroplating solution to 5.5-9.3, regulating the temperature of the electroplating solution to 30-40 ℃, and performing electrodeposition to obtain the nickel-molybdenum alloy.
In some embodiments, in step S1, the molybdenum salt comprises ammonium molybdate, sodium molybdate, or a mixture of both.
It is understood that ammonium molybdate and cobalt molybdate are included herein as well as their corresponding hydrates.
In some embodiments, in step S1, the nickel salt comprises nickel sulfate.
In some embodiments, the concentration of molybdenum salt in the plating solution of step S1 is 30-45g/L, preferably 30-33g/L.
In some embodiments, the concentration of nickel salt in the plating solution of step S1 is 25-35g/L, preferably 30-33g/L.
It is understood that nickel sulfate includes itself and its corresponding hydrates throughout this application.
In some embodiments, in step S1, the pretreatment includes polishing, degreasing, washing with water, and drying.
In some embodiments, the current density during the electrodeposition of step S1 is 9-15A/dm 2 Preferably 10-15A/dm 2 。
In some embodiments, the electrodeposition time of step S1 is 40-60 minutes, preferably 45-55 minutes.
In some embodiments, in step S2, depositing three-dimensional graphene on the nickel-molybdenum alloy surface produced in step S1 includes:
and (2) placing the nickel-molybdenum alloy prepared in the step (S1) in boiling water, then calcining, placing a calcined product in a sealed cavity, introducing a reducing gas and a gaseous carbon source into the sealed cavity, heating to heat the inner environment of the sealed cavity so as to deposit graphene on the surface of the calcined product, then cooling, turning over the calcined product, and continuing heating to grow graphene on the other side of the calcined product.
In some embodiments, in step S2, the temperature of the calcination is 350-400 ℃, preferably 350-380 ℃; the calcination time is 30-90min, preferably 40-75min.
In some embodiments, in step S2, the reducing gas comprises hydrogen.
In some embodiments, in step S2, the flow rate of the reducing gas is 5-60sccm, preferably 5-20sccm.
In some embodiments, in step S2, the gaseous carbon source comprises at least one of methane, ethylene, acetylene, carbon monoxide, and carbon dioxide.
In some embodiments, in step S2, the gaseous carbon source is provided at a flow rate of 50-100sccm, preferably 60-80sccm.
In some embodiments, in step S2, heating is performed to raise the internal environment of the sealed chamber to 600-1100 ℃, preferably 700-1100 ℃.
In some embodiments, the present application provides an electrolyzed water hydrogen electrode tab comprising a substrate and an active material layer on the substrate, the active material layer comprising an electrolyzed water hydrogen catalyst as described above or an electrolyzed water hydrogen catalyst prepared according to the preparation method described above.
In some embodiments, the present application provides an electrolytic water hydrogen production system comprising an electrolytic water hydrogen production electrode sheet as described above.
Detailed Description
The present invention will be further described with reference to the following specific examples, but it should be noted that the specific material ratios, process conditions, results, etc. described in the embodiments of the present invention are only for illustrating the present invention, and are not intended to limit the scope of the present invention, and all equivalent changes or modifications according to the spirit of the present invention should be included in the scope of the present invention. It should be noted that "wt" in the present invention refers to mass percent unless specifically stated otherwise.
In some embodiments, the present application provides a catalyst for producing hydrogen by electrolysis of water, which comprises a nickel-molybdenum alloy and a three-dimensional graphene layer coated outside the nickel-molybdenum alloy.
In some embodiments, the nickel-molybdenum alloy is doped with cobalt.
In some embodiments, the three-dimensional graphene layer is doped with nitrogen.
In some embodiments, the present application also provides a method of preparing a catalyst for producing hydrogen by electrolysis of water as described above, comprising:
s1, preparing nickel-molybdenum alloy:
taking conductive polyurethane as a cathode and taking a pretreated pure nickel sheet as an anode, wherein the pretreatment comprises polishing, degreasing, washing and drying;
preparing molybdenum salt and nickel salt into electroplating solution with concentration of molybdenum salt of 30-45g/L and nickel salt of 25-35g/L, regulating pH of the electroplating solution to 5.5-9.3, regulating temperature of the electroplating solution to 30-40deg.C, and regulating current density to 9-15A/dm 2 Electrodepositing for 40-60min under the condition to obtain the nickel-molybdenum alloy; molybdenum salts include ammonium molybdate, sodium molybdate, or a mixture of both; the nickel salt comprises nickel sulfate;
s2, placing the nickel-molybdenum alloy prepared in the step S1 in boiling water, calcining for 30-90min at the temperature of 350-400 ℃, placing a calcined product in a sealed cavity, introducing reducing gas and a gaseous carbon source into the sealed cavity, heating to heat the internal environment of the sealed cavity to 600-1100 ℃ so as to deposit graphene on the surface of the calcined product, cooling, turning over the calcined product, and continuously heating to grow graphene on the other surface of the calcined product, thereby obtaining the catalyst for producing hydrogen by electrolyzing water;
the reducing gas comprises hydrogen, and the flow rate of the reducing gas is 5-60sccm;
the gaseous carbon source comprises at least one of methane, ethylene, acetylene, carbon monoxide and carbon dioxide, and the flow rate of the gaseous carbon source is 50-100sccm.
In some embodiments, the present application provides an electrolyzed water hydrogen electrode tab comprising a substrate and an active material layer on the substrate, the active material layer comprising an electrolyzed water hydrogen catalyst as described above or an electrolyzed water hydrogen catalyst prepared according to the preparation method described above.
In some embodiments, the present application provides an electrolyzed water hydrogen electrode tab comprising a substrate and an active material layer disposed on the substrate, the active material layer comprising an electrolyzed water hydrogen catalyst as described above or an electrolyzed water hydrogen catalyst prepared as described above.
In some embodiments, the present application provides an electrolytic water hydrogen production system comprising an electrolytic water hydrogen production electrode sheet as described above.
The present invention will be described in detail with reference to specific exemplary examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, as many insubstantial modifications and variations are within the scope of the invention as would be apparent to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
The embodiment provides a catalyst for producing hydrogen by electrolyzing water, which comprises nickel-molybdenum alloy and a three-dimensional graphene layer coated outside the nickel-molybdenum alloy;
the preparation method of the catalyst for producing hydrogen by electrolyzing water comprises the following steps:
s1, preparing nickel-molybdenum alloy:
polishing a pure nickel sheet to be smooth, then placing the nickel sheet into NL-2011A degreasing agent aqueous solution (the solvent is deionized water) with the temperature of 50 ℃ and the concentration of 12g/L for 45s, rinsing the nickel sheet with deionized water with the temperature of 70 ℃ for 60s, and then drying the nickel sheet in a 60 ℃ oven to obtain a pretreated nickel sheet;
preparing an electroplating solution with the concentration of ammonium molybdate tetrahydrate being 30g/L and the concentration of nickel sulfate heptahydrate being 28g/L by taking conductive polyurethane as a cathode and taking a pretreated nickel sheet as an anode, regulating the pH value of the electroplating solution to 9.0, regulating the temperature of the electroplating solution to 30 ℃ and the current density to be 12A/dm 2 Electrodepositing for 60min under the condition to obtain the nickel-molybdenum alloy;
s2, placing the nickel-molybdenum alloy prepared in the step S1 in boiling water, calcining at 380 ℃ for 40min, placing a calcined product in a sealed cavity, introducing hydrogen and methane into the sealed cavity, wherein the flow of the hydrogen is 20sccm, the flow of the methane is 80sccm, heating to heat the inner environment of the sealed cavity to 1000 ℃ so as to deposit graphene on the surface of the calcined product, stopping heating after 40min, turning over the calcined product after cooling, continuing heating to heat the inner environment of the sealed cavity to 1000 ℃ so as to grow graphene on the other surface of the calcined product, and stopping heating after 15min, wherein the flow of the hydrogen and the methane are kept unchanged in the process, thus obtaining the catalyst for preparing hydrogen by using electrolytic water.
Example 2
The embodiment provides a catalyst for producing hydrogen by electrolyzing water, which comprises nickel-molybdenum alloy and a three-dimensional graphene layer coated outside the nickel-molybdenum alloy;
the preparation method of the catalyst for producing hydrogen by electrolyzing water comprises the following steps:
s1, preparing nickel-molybdenum alloy:
polishing a pure nickel sheet to be smooth, then placing the nickel sheet into NL-2011A degreasing agent aqueous solution (the solvent is deionized water) with the temperature of 50 ℃ and the concentration of 12g/L for 45s, rinsing the nickel sheet with deionized water with the temperature of 70 ℃ for 60s, and then drying the nickel sheet in a 60 ℃ oven to obtain a pretreated nickel sheet;
taking conductive polyurethane as a cathode and taking a nickel sheet after pretreatment as an anode;
preparing ammonium molybdate tetrahydrate and nickel sulfate heptahydrate into a plating solution with the concentration of ammonium molybdate tetrahydrate 40g/L and nickel sulfate heptahydrate 33g/L, regulating the pH value of the plating solution to 9.1, regulating the temperature of the plating solution to 37 ℃ and the current density to 10A/dm 2 Electrodepositing for 45min under the condition to obtain the nickel-molybdenum alloy;
s2, placing the nickel-molybdenum alloy prepared in the step S1 in boiling water, calcining at 360 ℃ for 50min, placing a calcined product in a sealed cavity, introducing hydrogen and ethylene into the sealed cavity, wherein the flow of the hydrogen is 55sccm, the flow of the ethylene is 70sccm, heating to heat the inner environment of the sealed cavity to 810 ℃, depositing graphene on the surface of the calcined product, stopping heating after 40min, turning over the calcined product after cooling, continuing heating to heat the inner environment of the sealed cavity to 810 ℃, growing graphene on the other surface of the calcined product, and stopping heating after 15min, wherein the flow of the hydrogen and the methane are kept unchanged in the process, thus obtaining the catalyst for preparing hydrogen by using the electrolytic water.
Example 3
The embodiment provides a catalyst for producing hydrogen by electrolyzing water, which comprises nickel-molybdenum alloy and a three-dimensional graphene layer coated outside the nickel-molybdenum alloy;
the preparation method of the catalyst for producing hydrogen by electrolyzing water comprises the following steps:
s1, preparing nickel-molybdenum alloy:
polishing a pure nickel sheet to be smooth, then placing the nickel sheet into NL-2011A degreasing agent aqueous solution (the solvent is deionized water) with the temperature of 50 ℃ and the concentration of 12g/L for 45s, rinsing the nickel sheet with deionized water with the temperature of 70 ℃ for 60s, and then drying the nickel sheet in a 60 ℃ oven to obtain a pretreated nickel sheet;
preparing an electroplating solution with the concentration of ammonium molybdate tetrahydrate of 30g/L, the concentration of nickel sulfate heptahydrate of 28g/L and the concentration of cobalt sulfate heptahydrate of 16g/L by taking conductive polyurethane as a cathode and a pretreated nickel sheet as an anode, regulating the pH value of the electroplating solution to 6.1, regulating the temperature of the electroplating solution to 30 ℃ and the current density to 12A/dm 2 Electrodepositing for 60min under the condition to obtain the nickel-molybdenum alloy;
s2, placing the nickel-molybdenum alloy prepared in the step S1 in boiling water, calcining at 380 ℃ for 40min, placing a calcined product in a sealed cavity, introducing hydrogen and methane into the sealed cavity, wherein the flow of the hydrogen is 20sccm, the flow of the methane is 80sccm, heating to heat the inner environment of the sealed cavity to 1000 ℃ so as to deposit graphene on the surface of the calcined product, stopping heating after 40min, turning over the calcined product after cooling, continuing heating to heat the inner environment of the sealed cavity to 1000 ℃ so as to grow graphene on the other surface of the calcined product, and stopping heating after 15min, wherein the flow of the hydrogen and the methane are kept unchanged in the process, thus obtaining the catalyst for preparing hydrogen by using electrolytic water.
Example 4
The embodiment provides a catalyst for producing hydrogen by electrolyzing water, which comprises nickel-molybdenum alloy and a three-dimensional graphene layer coated outside the nickel-molybdenum alloy;
the preparation method of the catalyst for producing hydrogen by electrolyzing water comprises the following steps:
s1, preparing nickel-molybdenum alloy:
polishing a pure nickel sheet to be smooth, then placing the nickel sheet into NL-2011A degreasing agent aqueous solution (the solvent is deionized water) with the temperature of 50 ℃ and the concentration of 12g/L for 45s, rinsing the nickel sheet with deionized water with the temperature of 70 ℃ for 60s, and then drying the nickel sheet in a 60 ℃ oven to obtain a pretreated nickel sheet;
preparing ammonium molybdate tetrahydrate and nickel sulfate heptahydrate by taking conductive polyurethane as a cathode and taking a pretreated nickel sheet as an anodePlating solution with ammonium molybdate tetrahydrate concentration of 30g/L and nickel sulfate heptahydrate concentration of 28g/L, regulating pH of the plating solution to 9.0, regulating temperature of the plating solution to 30deg.C, and regulating current density to 12A/dm 2 Electrodepositing for 60min under the condition to obtain the nickel-molybdenum alloy;
s2, placing the nickel-molybdenum alloy prepared in the step S1 in boiling water, calcining at 380 ℃ for 40min, placing a calcined product in a sealed cavity, introducing hydrogen, methane and ammonia gas into the sealed cavity, wherein the flow of the hydrogen is 20sccm, the flow of the methane is 80sccm, the flow of the ammonia gas is 5sccm, heating to enable the inner environment of the sealed cavity to be heated to 1000 ℃ so as to deposit graphene on the surface of the calcined product, stopping heating after 40min, turning over the calcined product after cooling, continuing heating to enable the inner environment of the sealed cavity to be heated to 1000 ℃, so as to grow graphene on the other surface of the calcined product, stopping heating after 15min, and keeping the flow of the hydrogen and the methane unchanged in the process to obtain the catalyst for preparing hydrogen by electrolyzing water.
Comparative example 1
This comparative example differs from example 1 in that: and S2, namely taking the nickel-molybdenum alloy prepared in the step S1 as a catalyst for producing hydrogen by electrolyzing water.
Testing
Stability and catalytic performance tests were performed on the water electrolysis hydrogen production catalysts of examples 1-4 and comparative example 1:
the stability test steps are as follows:
mixing water and absolute ethyl alcohol according to a volume ratio of 4:1, mixing to obtain a mixed solvent;
adding 4g of electrolytic water hydrogen production catalyst and 8mL of perfluorinated sulfonic acid-based polymer solution (namely Nafion solution) with concentration of 5.0wt% into 1L of mixed solvent, and uniformly stirring to obtain catalyst dispersion liquid;
dropping 5ml of catalyst dispersion liquid on the surface of a glassy carbon electrode (the load capacity is about 0.26 mg/cm) 2 ) Drying, taking a glassy carbon electrode loaded with a catalyst as a working electrode, a carbon rod as a counter electrode, a Saturated Calomel Electrode (SCE) as a reference electrode, taking a KOH solution of 1mol/L as an electrolyte, and carrying out electrolysis for 12h under 150mV overpotential in a three-electrode system by a potentiostatic electrolysis methodThe electrocatalytic hydrogen evolution stability test was performed, and the current density change rate was calculated from the current densities of electrolysis 1h and 11.5h according to the following formula, and the results are shown in table 1:
wherein η is the rate of change of current density; j (J) 0 And J 1 The current densities of electrolysis at 1h and 11.5h are respectively mA/cm 2 。
The catalytic performance test steps are as follows:
mixing water and absolute ethyl alcohol according to a volume ratio of 4:1, mixing to obtain a mixed solvent;
adding 4g of electrolytic water hydrogen production catalyst and 8mL of perfluorinated sulfonic acid-based polymer solution (namely Nafion solution) with concentration of 5.0wt% into 1L of mixed solvent, and uniformly stirring to obtain catalyst dispersion liquid;
dropping 5ml of catalyst dispersion liquid on the surface of a glassy carbon electrode (the load capacity is about 0.26 mg/cm) 2 ) Drying, using a glassy carbon electrode carrying a catalyst as a working electrode, a carbon rod as a counter electrode, a Saturated Calomel Electrode (SCE) as a reference electrode, and a KOH solution of 1mol/L as an electrolyte, and testing the composite catalyst at 100mA/cm by a Linear Scanning Voltammetry (LSV) 2 The hydrogen evolution overpotential at current density and the results are shown in table 1.
Table 1 test results
| Source | Rate of change of current density% | 100mA/cm 2 Hydrogen evolution overpotential at current density, mV |
| Example 1 | 2 | 113 |
| Example 2 | 3 | 121 |
| Example 3 | 2 | 95 |
| Example 4 | 1 | 102 |
| Comparative example 1 | 25 | 189 |
As is clear from Table 1, the current density change rate of the catalysts for water electrolysis hydrogen production of examples 1 to 4 was not more than 3% as compared with comparative example 1. Thus, the catalyst for producing hydrogen by water electrolysis has excellent stability.
As is clear from Table 1, the electrode formed by the catalyst for producing hydrogen by electrolyzing water in comparative example 1 (without three-dimensional graphene coating) was 100mA/cm 2 Hydrogen evolution overpotential at current density is 189mV, and current density change rate is 25%; example 1 (three-dimensional graphene coated) electrode 100mA/cm formed from Water electrolysis Hydrogen production catalyst 2 The hydrogen evolution overpotential at the current density was 113mV, and the current density change rate was 2%. The result shows that the three-dimensional graphene coating is carried out on the nickel-molybdenum alloy, so that the stability of the water electrolysis hydrogen production catalyst for hydrogen evolution reaction is improved, and the hydrogen evolution catalytic activity of the water electrolysis hydrogen production catalyst is improved.
As can be seen from Table 1, the catalyst for producing hydrogen by electrolyzing water in example 1 (cobalt-free nickel-molybdenum alloy)Electrode 100mA/cm 2 The hydrogen evolution overpotential at current density was 113mV, and the electrode formed by the catalyst for producing hydrogen by electrolyzing water in example 3 (cobalt in Ni-Mo alloy) was 100mA/cm 2 The hydrogen evolution overpotential at current density was 95mV. The result shows that the invention improves the hydrogen evolution catalytic activity of the catalyst for preparing hydrogen by electrolyzing water by doping cobalt in the nickel-molybdenum alloy.
As is clear from Table 1, the electrode formed by the catalyst for producing hydrogen by electrolyzing water in example 1 (undoped nitrogen in three-dimensional graphene layer) was 100mA/cm 2 The hydrogen evolution overpotential at current density was 113mV, and the electrode formed by the catalyst for producing hydrogen by electrolyzing water in example 4 (doping nitrogen in three-dimensional graphene layer) was 100mA/cm 2 The hydrogen evolution overpotential at current density was 102mV. The result shows that the hydrogen evolution catalytic activity of the catalyst for preparing hydrogen by electrolyzing water is improved by doping nitrogen in the three-dimensional graphene layer.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. The catalyst for producing hydrogen by electrolyzing water is characterized by comprising nickel-molybdenum alloy and a three-dimensional graphene layer coated outside the nickel-molybdenum alloy.
2. The catalyst for producing hydrogen by water electrolysis according to claim 1, wherein cobalt is doped in the nickel-molybdenum alloy.
3. The catalyst for producing hydrogen by water electrolysis according to claim 1, wherein the three-dimensional graphene layer is doped with nitrogen.
4. A method of preparing a catalyst for producing hydrogen by electrolysis of water as claimed in any one of claims 1 to 3, comprising:
s1, preparing nickel-molybdenum alloy;
s2, depositing three-dimensional graphene on the surface of the nickel-molybdenum alloy prepared in the step S1 to form a three-dimensional graphene layer, and obtaining the catalyst for producing hydrogen by water electrolysis.
5. The method of claim 4, wherein in step S1, preparing the nickel-molybdenum alloy comprises:
preparing electroplating solution from molybdenum salt and nickel salt by taking conductive polyurethane as a cathode and taking a pretreated pure nickel sheet as an anode, regulating the pH value of the electroplating solution to 5.5-9.3, regulating the temperature of the electroplating solution to 30-40 ℃, and performing electrodeposition to obtain the nickel-molybdenum alloy.
6. The method according to claim 5, wherein in step S1, the pretreatment comprises polishing, degreasing, washing with water and drying;
and/or, in step S1, the molybdenum salt comprises ammonium molybdate, sodium molybdate, or a mixture of both;
and/or, in the electroplating solution in the step S1, the concentration of molybdenum salt is 30-45g/L;
and/or, in step S1, the nickel salt comprises nickel sulfate;
and/or, in the electroplating solution in the step S1, the concentration of nickel salt is 25-35g/L;
and/or, in the electrodeposition process of step S1, the current density is 9-15A/dm 2 ；
And/or, the electrodeposition time in the step S1 is 40-60min.
7. The method of claim 4, wherein in step S2, depositing three-dimensional graphene on the nickel-molybdenum alloy surface produced in step S1 comprises:
and (2) placing the nickel-molybdenum alloy prepared in the step (S1) in boiling water, then calcining, placing a calcined product in a sealed cavity, introducing a reducing gas and a gaseous carbon source into the sealed cavity, heating to heat the internal environment of the sealed cavity so as to deposit graphene on the surface of the calcined product, then cooling, turning over the calcined product, and continuing heating to grow graphene on the other surface of the calcined product.
8. The method according to claim 7, wherein in the step S2, the calcination temperature is 350-400 ℃ and the calcination time is 30-90min;
and/or, in step S2, the reducing gas includes hydrogen;
and/or, in the step S2, the flow rate of the reducing gas is 5-60sccm;
and/or, in step S2, the gaseous carbon source comprises at least one of methane, ethylene, acetylene, carbon monoxide and carbon dioxide;
and/or, in the step S2, the flow rate of the gaseous carbon source is 50-100sccm;
and/or, in step S2, heating to raise the internal environment of the sealed chamber to 600-1100 ℃.
9. A water electrolysis hydrogen production electrode sheet, characterized in that the water electrolysis hydrogen production electrode sheet comprises a base material and an active material layer positioned on the base material, wherein the active material layer comprises the water electrolysis hydrogen production catalyst according to any one of claims 1 to 3 or the water electrolysis hydrogen production catalyst prepared according to the preparation method of any one of claims 4 to 8.
10. A water electrolysis hydrogen production system, comprising the water electrolysis hydrogen production electrode sheet of claim 9.
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