CN113430533A - Nickel-cobalt-iron trimetal catalyst for in-situ growth of graphene through phosphorization and sulfuration and preparation method thereof - Google Patents
Nickel-cobalt-iron trimetal catalyst for in-situ growth of graphene through phosphorization and sulfuration 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 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 22
- 238000005987 sulfurization reaction Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 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 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/056—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of textile or non-woven fabric
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical Kinetics & Catalysis (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a nickel-cobalt-iron trimetal catalyst for in-situ growth of graphene, which is prepared by firstly phosphorizing and then vulcanizing, consists of Ni, Co, Fe and P, S in the form of phosphorus sulfide, is loaded on carbon paper, and has a general formula of (Ni)xCoyFez)PvSu@ 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, the preparation method of the nickel-cobalt-iron trimetal catalyst with the in-situ growth of the graphene after phosphorization and sulfuration is also disclosed. The transition metal phosphorus and sulfur co-doping and in-situ grown graphene coating of the invention are integratedxCoyFez)PvSu@ CP catalyst, effectiveThe overpotential of the electrolyzed water is reduced, the oxygen evolution capacity of the electrolyzed water is improved, the outstanding oxygen evolution catalytic activity is presented, the durability is improved, the efficiency is higher when the electrolyzed water is used for oxygen evolution, and the electrolyzed water has great potential when being used in an electrolytic cell in the future; meanwhile, the method has wide prospect in the application of the future new energy field, and particularly has great value for the industry when being used for hydrogen fuel cell driven electric automobiles.
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
The increasing energy demand, depletion of fossil energy and associated negative environmental impacts have led to a constant push for the human being to study various clean and sustainable energy conversion, storage technologies in order to make them cheaper and more environmentally friendly. Solar energy is one of the most abundant natural resources, and various methods for utilizing solar energy have been explored. One of the most typical methods is to fabricate solar cells (i.e., solid-state photovoltaic devices and dye-sensitized solar cells) to convert solar energy into electrical energy. However, there is a problem in that energy cannot be stored. Furthermore, solar energy is often discontinuous and variable due to regional or seasonal factors, and it is therefore necessary to efficiently store the collected solar energy.
The photocatalytic and electrolytic water production of hydrogen fuel and oxygen is one of the most potential and attractive strategies for the conversion of solar/electrical energy into chemical energy, and can overcome the intermittent weakness of solar energy and realize the storage of energy. In addition, hydrogen is a sustainable, carbon-neutral, abundant energy carrier because of its high energy density, non-polluting combustion and no carbon emissions. Electrolyzed water can be divided into two half-reactions, Oxygen Evolution (OER) and Hydrogen Evolution (HER). Among them, the hydrogen evolution reaction is simple and can occur at a low overpotential on many metals. In contrast, oxygen evolution is inherently more complex and has slow oxygen release kinetics. Because it involves a four electron transfer process, it requires the removal of four protons from a water molecule to produce one oxygen molecule, with a large overpotential, which affects the overall water electrolysis efficiency, which also hinders the industrial large-scale production of hydrogen.
Therefore, there is an urgent need to develop an effective and stable oxygen evolution electrocatalyst to promote the reaction, thereby improving the energy conversion efficiency. At present, although transition metal single-metal, double-metal and tri-metal catalysts are reported more, no report on a nickel-cobalt-iron tri-metal catalyst obtained by in-situ growth of graphene through phosphorization and then sulfurization is found.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a nickel-cobalt-iron trimetal catalyst for in-situ growth of graphene, wherein the nickel-cobalt-iron trimetal catalyst is subjected to phosphorization and then vulcanization 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 trimetal catalyst for in-situ growth of graphene, wherein the nickel-cobalt-iron trimetal catalyst is subjected to phosphorization and then sulfuration.
The purpose of the invention is realized by the following technical scheme:
the invention provides a nickel-cobalt-iron trimetal catalyst for in-situ growth of graphene, which is prepared by firstly phosphorizing and then vulcanizing, consists of Ni, Co, Fe and P, S in the form of phosphorus sulfide, is loaded on carbon paper, and has a general formula of (Ni)xCoyFez)PvSu@ 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 a nickel-cobalt-iron trimetal catalyst for in-situ growth of graphene, which comprises the following steps:
(1) 1-15 parts of nickel source, 2-20 parts of cobalt source, 3-30 parts of iron source, 4-50 parts of urea and 50-500 parts of deionized water are mixed and stirred uniformly to form a mixed solution;
(2) firstly, putting the carbon paper into the paper with the concentration of 0.3-6 mol.L-1Carrying out ultrasonic treatment on the nitric acid solution for 20-70 min; then, ultrasonically cleaning for 4-15 min by using ethanol, acetone and deionized water in sequence, and drying 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 to obtain a trimetal hydroxide catalyst loaded on the carbon paper;
(4) reacting a trimetal hydroxide catalyst loaded on carbon paper in a tubular furnace under the protection of nitrogen or argon by taking sodium hypophosphite as a phosphorus source at the temperature rise speed of 3-20 ℃/min at the temperature of 260-600 ℃ to obtain a phosphatized nickel-cobalt-iron trimetal catalyst loaded on the carbon paper;
(5) by CS2Putting the phosphorized nickel-cobalt-iron trimetal catalyst loaded on carbon paper into a tubular furnace as a source of sulfur and graphene, heating at the speed of 1-15 ℃/min, reacting at the temperature of 500-1100 ℃, and cooling to obtain the in-situ growth graphene nickel-cobalt-iron trimetal catalyst which is firstly phosphorized and then vulcanized.
Further, the nickel source, the cobalt source and the iron source are one or a combination of sulfate, nitrate and acetate.
The invention has the following beneficial effects:
(1) the invention successfully prepares the nickel-cobalt-iron trimetal catalyst for the in-situ growth of the graphene for electrolyzing water and oxygen evolution, which is firstly phosphorized and then sulfurized by adopting a hydrothermal and solid-phase sintering method for the first time, and provides a feasible method for preparing a high-performance catalytic material. Integrated (Ni)xCoyFez)PvSuThe @ CP catalyst electrode exhibits a very outstanding oxygen evolution catalytic activity with higher efficiency for the electrolysis of water for oxygen evolution.
(2) Compared with other methods adopted at present, the transition metal phosphorus and sulfur co-doped and in-situ grown graphene-coated catalyst disclosed by the invention effectively reduces the overpotential of electrolyzed water, improves the oxygen evolution capacity of the electrolyzed water, improves the durability of the electrolyzed water, and has great potential for use in future electrolytic cells. Meanwhile, the method has wide prospect in the application of the future new energy field, and particularly has great value for the industry when being used for hydrogen fuel cell driven electric automobiles.
The present invention will be described in further detail with reference to examples.
Detailed Description
The embodiment of the nickel-cobalt-iron trimetal catalyst for in-situ growth of graphene, which is subjected to phosphorization and then sulfurization, consists of Ni, Co, Fe and P, S in the form of phosphorus sulfide and is loadedOn carbon paper, the general formula is (Ni)xCoyFez)PvSu@ 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 formulation parameters for each example are shown in table 1.
TABLE 1 examples of the invention (Ni)xCoyFez)PvSuFormula parameters of @ CP catalyst
| Examples | x | y | z | v | u |
| Example one | 2 | 3 | 3 | 2 | 2 |
| Example two | 5 | 4 | 4 | 2 | 3 |
| EXAMPLE III | 8 | 2 | 4 | 3 | 2 |
| Example four | 10 | 5 | 30 | 3 | 3 |
The embodiment of the invention provides a preparation method of a nickel-cobalt-iron trimetal catalyst for in-situ growth of graphene, which comprises the following steps:
(1) 1-15 parts of nickel source, 2-20 parts of cobalt source, 3-30 parts of iron source, 4-50 parts of urea and 50-500 parts of deionized water are mixed and stirred uniformly 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 4cm × 8cm rectangles, and adding 0.3-6 mol.L-1Carrying out ultrasonic treatment on the nitric acid solution for 20-70 min; then, ultrasonically cleaning for 4-15 min by using ethanol, acetone and deionized water in sequence, and drying in a vacuum oven at 60 ℃ for 3h 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 a mixed solution, transferring the mixed solution to a hydrothermal reaction kettle, reacting for 15-35 hours at the temperature of 110-300 ℃ in a hydrothermal mode, taking out the carbon paper, washing for 2 times by using ethanol, and placing the carbon paper in an oven for drying to obtain a 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) Reacting a trimetal hydroxide catalyst loaded on carbon paper for 2 hours at 260-600 ℃ in a tubular furnace under the protection of nitrogen or argon by using sodium hypophosphite as a phosphorus source at the temperature rise speed of 3-20 ℃/min to obtain a phosphatized nickel-cobalt-iron trimetal catalyst loaded on the carbon paper;
(5) by CS2Putting the phosphorized nickel-cobalt-iron trimetal catalyst loaded on carbon paper into a tubular furnace as a source of sulfur and graphene, heating at the speed of 1-15 ℃/min, reacting for 2h at the temperature of 500-1100 ℃, and cooling to obtain the nickel-cobalt-iron trimetal catalyst with in-situ grown graphene subjected to phosphorization and then vulcanization. The process parameters for each example are shown in table 5.
TABLE 5 preparation Process parameters of nickel-cobalt-iron trimetallic catalyst for in-situ growth of graphene, phosphorization of the catalyst and then sulfurization of the catalyst according to various embodiments of the present invention
The electrochemical properties of the nickel-cobalt-iron trimetallic catalyst prepared by the in-situ growth of graphene, which is subjected to phosphorization and then sulfurization, are shown in table 6.
TABLE 6 electrochemical Properties of catalysts prepared according to the examples of the invention
Claims (3)
1. The nickel-cobalt-iron trimetal catalyst for in-situ growth of graphene, which is subjected to phosphorization and then sulfuration, is characterized in that: consists of Ni, Co, Fe and P, S in the form of phosphorus sulfide and is loaded on carbon paper, and the general formula of the carbon paper is (Ni)xCoyFez)PvSu@ 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.
2. The method for preparing the nickel-cobalt-iron trimetal catalyst for in-situ growth of graphene, phosphorization of the graphene and vulcanization of the graphene as recited in claim 1 is characterized by comprising the following steps:
(1) 1-15 parts of nickel source, 2-20 parts of cobalt source, 3-30 parts of iron source, 4-50 parts of urea and 50-500 parts of deionized water are mixed and stirred uniformly to form a mixed solution;
(2) firstly, putting the carbon paper into the paper with the concentration of 0.3-6 mol.L-1Carrying out ultrasonic treatment on the nitric acid solution for 20-70 min; then, ultrasonically cleaning for 4-15 min by using ethanol, acetone and deionized water in sequence, and drying 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 to obtain a trimetal hydroxide catalyst loaded on the carbon paper;
(4) reacting a trimetal hydroxide catalyst loaded on carbon paper in a tubular furnace under the protection of nitrogen or argon by taking sodium hypophosphite as a phosphorus source at the temperature rise speed of 3-20 ℃/min at the temperature of 260-600 ℃ to obtain a phosphatized nickel-cobalt-iron trimetal catalyst loaded on the carbon paper;
(5) by CS2Putting the phosphorized nickel-cobalt-iron trimetal catalyst loaded on carbon paper into a tubular furnace as a source of sulfur and graphene, heating at the speed of 1-15 ℃/min, reacting at the temperature of 500-1100 ℃, and cooling to obtain the in-situ growth graphene nickel-cobalt-iron trimetal catalyst which is firstly phosphorized and then vulcanized.
3. The method for preparing the nickel-cobalt-iron trimetal catalyst for in-situ growth of graphene, which is subjected to phosphorization and then sulfuration according to claim 2, is characterized in that: the nickel source, the cobalt source and the iron source are one or a combination of sulfate, nitrate and acetate.
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