CN113529128A - Sulfur-phosphorus co-doped in-situ growth graphene coated nickel-cobalt-iron hydrogen evolution catalyst and preparation method thereof - Google Patents
Sulfur-phosphorus co-doped in-situ growth graphene coated nickel-cobalt-iron hydrogen evolution catalyst and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000001257 hydrogen Substances 0.000 title claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 28
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 25
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 25
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- -1 phosphides Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 241000257465 Echinoidea Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a nickel-cobalt-iron hydrogen evolution catalyst coated by sulfur-phosphorus Co-doped in-situ growth graphene, which consists of Ni, Co, Fe and S, P in the form of phosphorus sulfide and is loaded on carbon paper, wherein the general formula of the catalyst is (Ni)xCoyFez)SvPu@ CP, where x/y is greater than or equal to 0 and less than or equal to 10, x/z is greater than or equal to 0 and less than or equal to 10, v is greater than or equal to 0 and less than or equal to 10, and u is greater than or equal to 0 and less than or equal to 10. In addition, a preparation method of the nickel-cobalt-iron hydrogen evolution catalyst coated by the sulfur-phosphorus co-doped in-situ growth graphene is also disclosed. Inventive integrated (Ni)xCoyFez)SvPuThe @ CP catalyst electrode has the advantages of very outstanding HER activity, higher catalytic activity, higher hydrogen yield and more stable performance, can be widely applied to various hydrogen evolution electrolytic water catalysis, and has the advantages of energy conservation, environmental protection and low cost.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a trimetallic catalyst and a preparation method thereof.
Background
With the growing concern about energy crisis and environmental pollution, the exploration of sustainable energy sources to replace fossil fuels is the goal of the joint efforts of global scientists. Hydrogen is considered the most promising alternative due to its zero carbon emission, and high gravimetric energy density. The use of electrocatalysts to promote Hydrogen Evolution (HER) electrolysis of water has become a promising method of producing hydrogen. In electrolyzed water, noble metals such as Pt are commonly used as electrocatalysts due to their high HER activity and stability over the entire pH range. However, their high cost and scarcity make them unsuitable for large-scale industrial production. Therefore, there has been considerable interest in developing low cost high performance HER catalysts that are free of precious metals.
A variety of abundant rare earth catalysts, including transition metal compounds such as sulfides, phosphides, hydroxides, carbides, etc., are used as catalysts for HER. Among these materials, transition metal sulfides and phosphides have some advantages over other materials, and can facilitate electrocatalytic charge transfer. Such as CoP of nano sea urchin structure, Ni in sheet form3S2And nano NiCoP, all have good HER activity. However, there is still a need to improve their catalytic performance, hydrogen yield, overpotential and stability in order to compete with noble metals. Furthermore, these electrocatalysts only act in acidic or alkaline electrolytes, which limits their application in water electrolysis techniques with different requirements on the pH of the electrolyte.
At present, although transition metal single-metal and double-metal catalysts are reported more, reports about nickel-cobalt-iron hydrogen evolution catalysts coated by sulfur-phosphorus co-doped in-situ growth graphene are not found yet.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a nickel-cobalt-iron hydrogen evolution catalyst coated by sulfur-phosphorus co-doped in-situ growth graphene so as to obtain an electrolyzed water catalytic material with high catalytic activity and stable performance. The invention also aims to provide a preparation method of the nickel-cobalt-iron hydrogen evolution catalyst coated by the sulfur-phosphorus co-doped in-situ growth graphene.
The purpose of the invention is realized by the following technical scheme:
the invention provides a nickel-cobalt-iron hydrogen evolution catalyst coated by sulfur-phosphorus Co-doped in-situ growth graphene, which is prepared from Ni, Co, Fe and S, P in the form of phosphorus sulfideIs formed and loaded on carbon paper and has the general formula of (Ni)xCoyFez)SvPu@ CP, where x/y is greater than or equal to 0 and less than or equal to 10, x/z is greater than or equal to 0 and less than or equal to 10, v is greater than or equal to 0 and less than or equal to 10, and u is greater than or equal to 0 and less than or equal to 10.
The other purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of the nickel-cobalt-iron hydrogen evolution catalyst coated by sulfur-phosphorus co-doped in-situ growth graphene, which comprises the following steps:
(1) mixing and uniformly stirring nickel nitrate hexahydrate, cobalt nitrate hexahydrate, iron (III) nitrate nonahydrate, urea, ammonium acetate and ultrapure water according to the proportion of 1-10 mmol: 1-8 mmol: 1-15 mmol: 1-12 mmol: 0.5-5 mmol: 50-550 ml to form a mixed solution;
(2) firstly, putting carbon paper into the paper with the concentration of 1-3 mol.L-1Carrying out ultrasonic treatment on the acetic acid or hydrochloric acid solution for 30-120 min; then, ultrasonically cleaning the paper by using hydrogen peroxide and deionized water in sequence, and drying the paper in a 70 ℃ drying oven for 0.5-1 h to obtain treated carbon paper;
(3) placing the treated carbon paper in a mixed solution, reacting for 15-35 hours at the temperature of 110-300 ℃ in a hydrothermal mode, taking out the carbon paper, cleaning, and drying for 8-16 hours at the temperature of 50-90 ℃ to obtain a trimetal hydroxide catalyst loaded on the carbon paper;
(4) introducing CS into a trimetal hydroxide catalyst loaded on carbon paper in a tubular furnace under the protection of nitrogen and/or argon2Heating at the temperature of 300-650 ℃ for 1-3 h to obtain a nickel-cobalt-iron trimetal catalyst loaded on carbon paper and subjected to in-situ growth of graphene sulfide;
(5) respectively placing a nickel-cobalt-iron trimetal catalyst and sodium hypophosphite which are loaded on carbon paper and in-situ grown and vulcanized with graphene below and above a tubular furnace, wherein the mass of the sodium hypophosphite is 50-100 times that of the carbon paper; heating at the speed of 1-5 ℃/min, heating at the temperature of 300-650 ℃ for 1-3 h, and cooling at the speed of 1-10 ℃/min to obtain the nickel-cobalt-iron hydrogen evolution catalyst coated by sulfur-phosphorus co-doped in-situ growth graphene.
The invention has the following beneficial effects:
(1) the invention successfully prepares the nickel-cobalt-iron hydrogen evolution catalyst coated by sulfur-phosphorus co-doped in-situ growth graphene by adopting a soaking hydrothermal and calcining method for the first time, and provides a feasible method for preparing a high-performance hydrogen evolution catalytic material. Integrated (Ni)xCoyFez)SvPuThe @ CP catalyst electrode has the advantages of very outstanding HER activity, higher catalytic activity, higher hydrogen yield and more stable performance, can be widely applied to various hydrogen evolution electrolytic water catalysis, and has the advantages of energy conservation, environmental protection and low cost.
(2) Compared with other methods adopted at present, the nickel-cobalt-iron hydrogen evolution catalyst coated by the sulfur-phosphorus co-doped in-situ growth graphene is suitable for large-scale industrial production due to the simple preparation method, low energy consumption and abundant and easily-obtained raw materials.
The present invention will be described in further detail with reference to examples.
Detailed Description
The embodiment of the nickel-cobalt-iron hydrogen evolution catalyst coated by sulfur-phosphorus Co-doped in-situ growth graphene consists of Ni, Co, Fe and S, P in the form of phosphorus sulfide, and is loaded on carbon paper, wherein the general formula of the catalyst is (Ni)xCoyFez)SvPu@ CP, wherein x/y is more than or equal to 0 and less than or equal to 10, x/z is more than or equal to 0 and less than or equal to 10, v is more than or equal to 0 and less than or equal to 10, and u is more than or equal to 0 and less than or equal to 10.
The formulation parameters for each example are shown in table 1.
TABLE 1 examples of the invention (Ni)xCoyFez)SvPuFormula parameters of @ CP catalyst
Examples | x | y | z | v | u |
Example one | 1 | 1 | 1 | 2 | 2 |
Example two | 2 | 1 | 1 | 2 | 2 |
EXAMPLE III | 1 | 1 | 2 | 2 | 3 |
Example four | 1 | 2 | 2 | 3 | 2 |
The embodiment of the invention provides a preparation method of a nickel-cobalt-iron hydrogen evolution catalyst coated by sulfur-phosphorus co-doped in-situ growth graphene, which comprises the following steps:
(1) mixing and uniformly stirring nickel nitrate hexahydrate, cobalt nitrate hexahydrate, iron (III) nitrate nonahydrate, urea, ammonium acetate and ultrapure water according to the proportion of 1-10 mmol: 1-8 mmol: 1-15 mmol: 1-12 mmol: 0.5-5 mmol: 50-550 ml to form a mixed solution; the dosage of the ingredients of each example is shown in table 2;
TABLE 2 ingredient amounts (parts by weight) of the examples of the present invention
(2) Cutting carbon paper into 2cm × 3cm rectangle, adding 1-3 mol/L carbon paper-1Carrying out ultrasonic treatment on the acetic acid or hydrochloric acid solution for 30-120 min; then ultrasonically cleaning for 8min by using hydrogen peroxide and deionized water in sequence, and then drying in an oven at 70 ℃ for 0.5-1 h to obtain treated carbon paper; the process parameters for each example are shown in table 3;
table 3 processing parameters of carbon paper of various embodiments of the present invention
(3) Placing the treated carbon paper in the mixed solution, transferring the mixed solution to a Teflon high-pressure hydrothermal reaction kettle, placing the mixture into a forced air drying oven for hydrothermal treatment, wherein the hydrothermal temperature is 110-300 ℃, and the reaction time is 15-35 h; taking out the carbon paper after reaction, washing the carbon paper for 3 times by using ultrapure water, and drying the carbon paper in a drying oven at the temperature of 50-90 ℃ for 8-16 h to obtain the trimetal hydroxide catalyst loaded on the carbon paper; the process parameters for each example are shown in table 4;
TABLE 4 hydrothermal reaction Process parameters for the examples of the invention
(4) Will be negativeLoading the trimetal hydroxide catalyst on carbon paper, introducing CS in a tubular furnace under the protection of nitrogen and/or argon2Heating at the temperature of 300-650 ℃ for 1-3 h to obtain a nickel-cobalt-iron trimetal catalyst loaded on carbon paper and subjected to in-situ growth of graphene sulfide; the process parameters for each example are shown in Table 5
TABLE 5 examples of the invention access CS2Processing parameters of
(5) Respectively placing a nickel-cobalt-iron trimetal catalyst and sodium hypophosphite which are loaded on carbon paper and subjected to in-situ growth and graphene vulcanization below and above a tubular furnace, wherein the amount of the sodium hypophosphite is 1-10 g; heating at the speed of 1-5 ℃/min, heating at the temperature of 300-650 ℃ for 1-3 h, and cooling at the speed of 1-10 ℃/min to obtain the nickel-cobalt-iron hydrogen evolution catalyst coated by sulfur-phosphorus co-doped in-situ growth graphene. The process parameters for each example are shown in table 6.
TABLE 6 phosphating Process parameters of the examples of the invention
The electrochemical performance of the nickel-cobalt-iron hydrogen evolution catalyst coated by the sulfur-phosphorus co-doped in-situ growth graphene prepared in each embodiment of the invention is shown in table 7.
TABLE 7 electrochemical Properties of catalysts prepared according to the examples of the invention
Claims (2)
1. A nickel cobalt iron hydrogen evolution catalyst coated by sulfur-phosphorus co-doped in-situ growth graphene is characterized in that: consists of Ni, Co, Fe and S, P in the form of phosphorus sulfide and is loaded on carbon paper, and the general formula of the carbon paper is (Ni)xCoyFez)SvPu@ CP, wherein x/y is more than or equal to 0 and less than or equal to 10, x/z is more than or equal to 0 and less than or equal to 10, v is more than or equal to 0 and less than or equal to 10, and u is more than or equal to 0 and less than or equal to 10.
2. The preparation method of the sulfur-phosphorus co-doped in-situ growth graphene coated nickel-cobalt-iron hydrogen evolution catalyst according to claim 1, which is characterized by comprising the following steps:
(1) mixing and uniformly stirring nickel nitrate hexahydrate, cobalt nitrate hexahydrate, iron (III) nitrate nonahydrate, urea, ammonium acetate and ultrapure water according to the proportion of 1-10 mmol: 1-8 mmol: 1-15 mmol: 1-12 mmol: 0.5-5 mmol: 50-550 ml to form a mixed solution;
(2) firstly, putting carbon paper into the paper with the concentration of 1-3 mol.L-1Carrying out ultrasonic treatment on the acetic acid or hydrochloric acid solution for 30-120 min; then, ultrasonically cleaning the paper by using hydrogen peroxide and deionized water in sequence, and drying the paper in a 70 ℃ drying oven for 0.5-1 h to obtain treated carbon paper;
(3) placing the treated carbon paper in a mixed solution, reacting for 15-35 hours at the temperature of 110-300 ℃ in a hydrothermal mode, taking out the carbon paper, cleaning, and drying for 8-16 hours at the temperature of 50-90 ℃ to obtain a trimetal hydroxide catalyst loaded on the carbon paper;
(4) introducing CS into a trimetal hydroxide catalyst loaded on carbon paper in a tubular furnace under the protection of nitrogen and/or argon2Heating at the temperature of 300-650 ℃ for 1-3 h to obtain a nickel-cobalt-iron trimetal catalyst loaded on carbon paper and subjected to in-situ growth of graphene sulfide;
(5) respectively placing a nickel-cobalt-iron trimetal catalyst and sodium hypophosphite which are loaded on carbon paper and in-situ grown and vulcanized with graphene below and above a tubular furnace, wherein the mass of the sodium hypophosphite is 50-100 times that of the carbon paper; heating at the speed of 1-5 ℃/min, heating at the temperature of 300-650 ℃ for 1-3 h, and cooling at the speed of 1-10 ℃/min to obtain the nickel-cobalt-iron hydrogen evolution catalyst coated by sulfur-phosphorus co-doped in-situ growth graphene.
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