CN116062722A - Catalyst and preparation method and application thereof - Google Patents
Catalyst and preparation method and application thereof Download PDFInfo
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- CN116062722A CN116062722A CN202310183223.5A CN202310183223A CN116062722A CN 116062722 A CN116062722 A CN 116062722A CN 202310183223 A CN202310183223 A CN 202310183223A CN 116062722 A CN116062722 A CN 116062722A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 96
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 48
- 239000006260 foam Substances 0.000 claims abstract description 43
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 35
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 150000002815 nickel Chemical class 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001868 cobalt Chemical class 0.000 claims abstract description 14
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 11
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 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 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 6
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 6
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- -1 preferably NiCl Chemical compound 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
- C01B25/088—Other phosphides containing plural metal
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
-
- 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
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- 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
- 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
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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 & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of electrocatalytic hydrogen evolution, in particular to a catalyst and a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: soluble nickel salt, soluble cobalt salt, co (NH) 2 ) 2 Mixing ammonium fluoride, water and foam nickel, and performing hydrothermal reaction to obtain a precursor; carrying out gas-phase phosphating treatment on the precursor to obtain cobalt nickel phosphide loaded on a foam nickel substrate; with a three-electrode system, the nickel foam is loaded with the catalystAnd (3) performing cyclic voltammetry treatment in an acidic electrolyte by taking cobalt nickel phosphide on the substrate as a working electrode, a platinum sheet as a counter electrode and a platinum source and a mercurous sulfate electrode as a reference electrode to obtain the catalyst. The catalyst prepared by the preparation method has better catalytic performance and low cost.
Description
Technical Field
The invention relates to the technical field of electrocatalytic hydrogen evolution, in particular to a catalyst and a preparation method and application thereof.
Background
Hydrogen energy is considered as the ultimate energy source for solving energy and environmental problems. The use of renewable energy sources to electrolyze water to prepare hydrogen is considered as a feasible mode, but the current electrolytic tank for preparing hydrogen by using the electrolyzed water generally adopts noble metal platinum as a catalyst, the platinum is large in dosage, the catalyst is easy to deactivate, the cost of preparing hydrogen by using the electrolyzed water is high, and large-scale application is difficult, so that a hydrogen preparation electrolytic tank with lower cost is required to be developed, and the development of a hydrogen evolution catalyst with low cost and high performance is important.
The most effective electrocatalyst is a noble metal-based catalyst such as platinum, palladium, iridium or ruthenium, the platinum loading of the traditional platinum-carbon catalyst is about 20-50%, the catalyst cost is high due to the fact that a large amount of noble metal is used, and the consumption of the noble metal is reduced as much as possible on the premise of not sacrificing the catalyst performance, so that the catalyst cost is effectively reduced.
Disclosure of Invention
The invention aims to provide a catalyst, a preparation method and application thereof, wherein the catalyst prepared by the preparation method has better catalytic performance and is low in cost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a catalyst, which comprises the following steps:
soluble nickel salt, soluble cobalt salt, co (NH) 2 ) 2 Mixing ammonium fluoride, water and foam nickel, and performing hydrothermal reaction to obtain a precursor;
carrying out gas-phase phosphating treatment on the precursor to obtain cobalt nickel phosphide loaded on a foam nickel substrate;
and adopting a three-electrode system, taking the cobalt nickel phosphide loaded on the foam nickel substrate as a working electrode, taking a platinum sheet as a counter electrode and a platinum source, taking a mercurous sulfate electrode as a reference electrode, and carrying out cyclic voltammetry treatment in an acidic electrolyte to obtain the catalyst.
Preferably, the soluble nickel salt comprises nickel chloride and/or nickel nitrate;
the soluble cobalt salt comprises cobalt chloride and/or cobalt nitrate.
Preferably, the molar ratio of the soluble nickel salt to the soluble cobalt salt is (0.1 to 0.5): (3-4).
Preferably, the soluble nickel salt, co (NH) 2 ) 2 And the molar ratio of the ammonium fluoride is (0.1-0.5): (6-8): (3-4).
Preferably, the temperature of the hydrothermal reaction is 100-130 ℃ and the time is 30-40 h.
Preferably, the phosphating agent adopted by the gas-phase phosphating treatment comprises sodium hypophosphite and/or potassium hypophosphite;
the mole ratio of the soluble nickel salt to the phosphating agent is (0.1-0.5): (2-3).
Preferably, the temperature of the gas-phase phosphating treatment is 400-500 ℃ and the time is 3-4 h.
Preferably, the acidic electrolyte is a perchloric acid solution with the concentration of 1-1.2 mol/L;
the high overpotential of the cyclic voltammetry treatment is 0-30 mV, the low overpotential is 150-300 mV, and the voltage scanning rate is 5-10 mV/s.
The invention also provides a catalyst prepared by the preparation method of the technical scheme, which comprises a foam nickel substrate and cobalt nickel phosphide and platinum loaded on the foam nickel substrate.
The invention also provides application of the catalyst in electrocatalytic hydrogen evolution reaction.
The invention provides a preparation method of a catalyst, which comprises the following steps: soluble nickel salt, soluble cobalt salt, co (NH) 2 ) 2 Mixing ammonium fluoride, water and foam nickel, and performing hydrothermal reaction to obtain a precursor; carrying out gas-phase phosphating treatment on the precursor to obtain cobalt nickel phosphide loaded on a foam nickel substrate; with a three-electrode system, supported on the foamAnd (3) performing cyclic voltammetry treatment in an acidic electrolyte by taking cobalt nickel phosphide on a nickel substrate as a working electrode, a platinum sheet as a counter electrode and a platinum source and a mercurous sulfate electrode as a reference electrode to obtain the catalyst. The invention synthesizes transition metal phosphide (cobalt nickel phosphide) by adopting a hydrothermal method, deposits trace platinum on the surface of the transition metal phosphide by adopting an electrochemical deposition method, plays a role in catalysis together with the transition metal phosphide, effectively reduces the cost on the premise of ensuring the performance of the catalyst, and is beneficial to the commercial application of large-scale electrocatalytic hydrogen production.
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
the cobalt nickel phosphide has the characteristic of good catalytic hydrogen evolution performance, and can play a role in catalyzing with platinum while playing a role in catalyzing the catalyst carrier, so that the catalytic performance is improved;
the noble metal catalyst used in large scale at present is mostly synthesized by adopting a chemical method, the noble metal dosage is high, and the invention adopts an electrochemical mode to deposit trace platinum on the surface of the cobalt nickel phosphide carrier, so that compared with the chemical synthesis mode, the dosage of platinum is greatly reduced, the utilization efficiency of platinum atoms is improved, and the cost of the catalyst is greatly reduced;
in the process of electrochemically depositing Pt (the process of applying pulse voltage), the Pt source adopted is not Pt salt adopted in the conventional electroplating, but a platinum sheet is utilized, the Pt is ionized by the pulse voltage, and the Pt is transferred to the surface of the catalyst through the electrolyte and deposited again, so that the utilization rate of Pt is improved.
Drawings
FIG. 1 is a graph showing the catalytic performance of nickel foam, nickel cobalt phosphide (CoNi-P) and catalyst (Pt-CoNi-P) supported on a nickel foam substrate as described in example 1;
FIG. 2 is a graph showing the catalytic performance of cobalt nickel phosphide (CoNiP) and catalyst (Pt-CoNiP) supported on a foamed nickel substrate as described in example 2;
FIG. 3 is the catalytic performance of the catalyst described in example 1 (Pt-CoNi-P) and a commercial platinum carbon catalyst (Pt/C-20%);
FIG. 4 is a graph showing the stability of the catalyst described in example 1;
FIG. 5 is an SEM image of a catalyst according to example 1;
FIG. 6 is a graph showing the Pt element distribution on the surface of the catalyst described in example 1.
Detailed Description
The invention provides a preparation method of a catalyst, which comprises the following steps:
soluble nickel salt, soluble cobalt salt, co (NH) 2 ) 2 Mixing ammonium fluoride, water and foam nickel, and performing hydrothermal reaction to obtain a precursor;
carrying out gas-phase phosphating treatment on the precursor to obtain cobalt nickel phosphide loaded on a foam nickel substrate;
and adopting a three-electrode system, taking the cobalt nickel phosphide loaded on the foam nickel substrate as a working electrode, taking a platinum sheet as a counter electrode and a platinum source, taking a mercurous sulfate electrode as a reference electrode, and carrying out cyclic voltammetry treatment in an acidic electrolyte to obtain the catalyst.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
The invention combines soluble nickel salt, soluble cobalt salt, co (NH) 2 ) 2 Mixing ammonium fluoride, water and foam nickel, and performing hydrothermal reaction to obtain a precursor.
In the present invention, the soluble nickel salt preferably comprises nickel chloride, preferably NiCl, and/or nickel nitrate 2 ·6H 2 O; when the soluble nickel salt is nickel chloride and nickel nitrate, the invention does not have any special limitation on the proportion of the nickel chloride and the nickel nitrate, and the soluble nickel salt and the nickel nitrate are mixed according to any proportion.
In the present invention, the soluble cobalt salt preferably comprises cobalt chloride and/or cobalt nitrate, the cobalt chloride preferably being CoCl 2 ·6H 2 O; when the soluble cobalt salt is cobalt chloride or cobalt nitrate, the inventionThe proportion of the cobalt chloride and the cobalt nitrate is not particularly limited, and the cobalt chloride and the cobalt nitrate are mixed according to any proportion.
In the present invention, the nickel foam is preferably subjected to pretreatment, which preferably includes sequentially cutting and washing the nickel foam. In the present invention, the surface density of the nickel foam is preferably 350g/m 2 The specific surface area is preferably 0.08cm 2 The pore density per gram is preferably 110ppi, the porosity is preferably 98% and the nickel-containing mass percentage is preferably 99.9%. The cutting process is not particularly limited, and may be performed by a process known to those skilled in the art. In the invention, the washing is preferably carried out by adopting acetone, 3mol/L hydrochloric acid solution and absolute ethyl alcohol to wash for 15min respectively. In the present invention, the purpose of the cleaning is to remove organic matter and oxide layers that may remain during the processing of the nickel foam surface.
In the present invention, the molar ratio of the soluble nickel salt to the soluble cobalt salt is preferably (0.1 to 0.5): (3 to 4), more preferably (0.2 to 0.4): (3.2 to 3.8), most preferably (0.25 to 0.35): (3.3-3.6).
In the present invention, the soluble nickel salt, co (NH) 2 ) 2 And the molar ratio of ammonium fluoride is preferably (0.1 to 0.5): (6-8): (3 to 4), more preferably (0.2 to 0.4): (6.5-7.5): (3.2 to 3.8), most preferably (0.25 to 0.35): (6.8-7.2): (3.3-3.6).
In the present invention, the ratio of the soluble nickel salt to water is preferably (0.1 to 0.5) mmol:80mL, more preferably (0.2 to 0.4) mmol:80mL, most preferably (0.25-0.35) mmol:80mL.
In the present invention, the mixing is preferably to mix a soluble nickel salt, a soluble cobalt salt, co (NH) 2 ) 2 After mixing ammonium fluoride and water, nickel foam was added. The mode of the mixing is not particularly limited in the present invention, and the mixing may be performed by a process well known to those skilled in the art and may be ensured to be uniform. In the present invention, the mixing is preferably performed in a teflon lined stainless steel autoclave.
In the present invention, the temperature of the hydrothermal reaction is preferably 100 to 130 ℃, more preferably 110 to 120 ℃, and most preferably 113 to 116 ℃; the time is preferably 30 to 40 hours, more preferably 32 to 38 hours, and most preferably 34 to 36 hours.
In the present invention, the precursor preferably includes nickel foam and nickel cobalt hydroxide supported in the nickel foam.
After the precursor is obtained, the precursor is subjected to gas-phase phosphating treatment to obtain cobalt nickel phosphide loaded on a foam nickel substrate.
In the present invention, the phosphating agent used for the gas-phase phosphating treatment preferably includes sodium hypophosphite and/or potassium hypophosphite; the sodium hypophosphite is preferably NaH 2 PO 2 ·H 2 O; when the phosphating agent is sodium hypophosphite and potassium hypophosphite, the ratio of the sodium hypophosphite to the potassium hypophosphite is not limited in any particular way, and the sodium hypophosphite and the potassium hypophosphite are mixed according to any ratio.
In the present invention, the molar ratio of the soluble nickel salt to the phosphating agent is preferably (0.1 to 0.5): (2 to 3), more preferably (0.2 to 0.4): (2.2 to 2.8), most preferably (0.25 to 0.35): (2.4-2.6).
In the present invention, the temperature of the gas-phase phosphating treatment is preferably 400 to 500 ℃, more preferably 420 to 480 ℃, and most preferably 440 to 460 ℃; the time is preferably 3 to 4 hours, more preferably 3.2 to 3.8 hours, and most preferably 3.4 to 3.6 hours. In the present invention, the vapor phase phosphating treatment is preferably performed in an argon atmosphere. In the present invention, the gas-phase phosphating treatment is preferably to phosphorylate the precursor using phosphine gas generated by pyrolysis.
In the present invention, the gas-phase phosphating is preferably carried out by placing the precursor downstream of the tube furnace and the phosphating agent upstream of the tube furnace.
After cobalt nickel phosphide loaded on a foam nickel substrate is obtained, a three-electrode system is adopted, cobalt nickel phosphide loaded on the foam nickel substrate is used as a working electrode, a platinum sheet is used as a counter electrode and a platinum source, a mercurous sulfate electrode is used as a reference electrode, cyclic voltammetry treatment is carried out in an acidic electrolyte, and pulse voltage is applied to obtain the catalyst.
In the present invention, the acidic electrolyte is preferably a perchloric acid solution having a concentration of 1 to 1.2 mol/L.
In the present invention, the cyclic voltammetry treatment preferably applies a pulsed voltage; the cyclic voltammetric treatment preferably has a high overpotential of 0 to 30mV, a low overpotential of 150 to 300mV, and a voltage sweep rate of 5 to 10mV/s.
In the invention, the cyclic voltammetry treatment is used for transferring trace platinum on the platinum sheet electrode to the cobalt-nickel phosphide carrier through the electrolyte.
The invention also provides a catalyst prepared by the preparation method of the technical scheme, which comprises a foam nickel substrate and cobalt nickel phosphide and platinum loaded on the foam nickel substrate.
The invention also provides application of the catalyst in electrocatalytic hydrogen evolution reaction. The method of the present invention is not particularly limited, and may be carried out by methods known to those skilled in the art.
The catalysts, methods of preparation and use thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the invention.
Example 1
0.1mmolNiCl 2 ·6H 2 O、4mmolCoCl 2 ·6H 2 O、7mmolCo(NH 2 ) 2 、3mmol NH 4 F, adding 80mL of water into a Teflon-lined stainless steel autoclave, uniformly mixing, adding washed foam nickel, sealing, transferring into a baking oven, reacting for 35 hours at 120 ℃, and washing with water and ethanol in sequence to obtain a precursor;
2mmolNaH 2 PO 2 ·H 2 O is arranged at the upstream of a tube furnace, the precursor is arranged at the downstream of the tube furnace, and is treated for 4 hours at 400 ℃ in argon atmosphere, so that cobalt nickel phosphide loaded on a foam nickel substrate is obtained;
adopting a standard three-electrode system, taking the cobalt nickel phosphide loaded on the foam nickel substrate as a working electrode, taking a high-purity platinum sheet as a counter electrode and a platinum source, taking a mercurous sulfate electrode as a reference electrode, adopting an acidic electrolyte (perchloric acid solution with the concentration of 1.0 mol/L), performing cyclic voltammetry treatment for 24 hours (the condition of the cyclic voltammetry treatment is that the high overpotential is 0-30 mV, the low overpotential is 150-300 mV, and the voltage scanning rate is 5-10 mV/s), and transferring trace platinum on the platinum sheet electrode to the cobalt nickel phosphide carrier through the electrolyte to obtain the catalyst;
the catalyst is subjected to SEM test, the test result is shown in fig. 5-6, wherein fig. 5 is an SEM image of the catalyst, fig. 6 is a Pt element distribution diagram of the surface of the catalyst, and as can be seen from fig. 5, cobalt nickel phosphide in the catalyst uniformly grows on the foam nickel substrate, and the microscopic morphology is in a fine needle shape, so that the morphology is favorable for full contact between reactants and the catalyst, the specific surface area of the catalyst is improved, and the catalytic performance of the catalyst is improved; as can be seen from fig. 6, the trace amount of platinum in the catalyst is supported on the surface of the substrate, and is mostly present as a single atom or cluster of atoms.
Example 2
Will be 0.5mmolNi (NO) 3 ) 2 、3mmolCoCl 2 ·6H 2 O、3mmolCo(NO 3 ) 2 、6mmol CO(NH 2 ) 2 、3mmolNH 4 F, adding 80mL of water into a Teflon-lined stainless steel autoclave, uniformly mixing, adding washed foam nickel, sealing, transferring into a baking oven, reacting at 130 ℃ for 30 hours, and washing with water and ethanol in sequence to obtain a precursor;
2mmolNaH 2 PO 2 ·H 2 O and 2mmolKH 2 PO 2 Placing the precursor at the upstream of a tube furnace, placing the precursor at the downstream of the tube furnace, and treating the precursor for 3 hours at 450 ℃ in an argon atmosphere to obtain cobalt nickel phosphide loaded on a foam nickel substrate;
and (3) adopting a standard three-electrode system, taking the cobalt nickel phosphide loaded on the foam nickel substrate as a working electrode, taking a high-purity platinum sheet as a counter electrode and a platinum source, taking a mercurous sulfate electrode as a reference electrode, adopting an acidic electrolyte (perchloric acid solution with the concentration of 1.2 mol/L), carrying out cyclic voltammetry treatment for 24 hours (the condition of the cyclic voltammetry treatment is that the high overpotential is 0-30 mV, the low overpotential is 150-300 mV and the voltage scanning rate is 5-10 mV/s), and transferring trace platinum on the platinum sheet electrode to the cobalt nickel phosphide carrier through the electrolyte to obtain the catalyst.
Test case
The catalytic performance test of the foamed nickel described in example 1, cobalt nickel phosphide (CoNi-P) and catalyst (Pt-CoNi-P) supported on a foamed nickel substrate was carried out by using a three-electrode standard system, and the polarization curve measurement was carried out by using a 1MKOH solution as the electrolyte; as shown in FIG. 1, it is clear from FIG. 1 that the performance of the grown cobalt nickel phosphide is much better than that of the foam nickel, 1000 mA.cm -2 The overpotential is reduced from 560mV to 255mV under the current density, and after a trace of Pt is continuously deposited, the performance is further improved by 1000mA cm -2 The overpotential is reduced from 255mV to 130mV under the current density, and Pt is utilized to the greatest extent possible;
the cobalt nickel phosphide (CoNiP) and the catalyst (Pt-CoNiP) supported on the foam nickel substrate described in example 2 were subjected to a catalytic performance test, wherein a three-electrode standard system was adopted, and a 1MKOH solution was adopted as an electrolyte for polarization curve measurement; the test results are shown in fig. 2, and as can be seen from fig. 2, the catalytic performance of the cobalt nickel phosphide supported on the foam nickel substrate is better, the catalytic performance of the catalyst is further improved on the basis of the above, and Pt is utilized to the greatest extent possible;
the catalyst described in example 1 (Pt-CoNi-P) and a commercial platinum carbon catalyst (Pt/C-20%) were subjected to a catalytic performance test, wherein a three-electrode standard system was adopted, and a 1MKOH solution was adopted as an electrolyte for polarization curve measurement; as shown in fig. 3, it can be seen from fig. 3 that the catalytic activity of the catalyst of example 1 is far higher than that of the commercial platinum-carbon catalyst, and the catalytic effect is better than that of the commercial platinum-carbon catalyst (Pt/C-20%) with only a small amount of Pt, so that the cost of the catalyst is greatly reduced;
the catalyst described in example 1 was subjected to stability testing using a three-electrode standard system, and the electrolyte was 1m koh solution for polarization curve measurement; the test results are shown in fig. 4, and as can be seen from fig. 4, the catalyst showed a visible decay in catalytic performance after 24 hours of continuous operation.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for preparing a catalyst, comprising the steps of:
soluble nickel salt, soluble cobalt salt, co (NH) 2 ) 2 Mixing ammonium fluoride, water and foam nickel, and performing hydrothermal reaction to obtain a precursor;
carrying out gas-phase phosphating treatment on the precursor to obtain cobalt nickel phosphide loaded on a foam nickel substrate;
and adopting a three-electrode system, taking the cobalt nickel phosphide loaded on the foam nickel substrate as a working electrode, taking a platinum sheet as a counter electrode and a platinum source, taking a mercurous sulfate electrode as a reference electrode, and carrying out cyclic voltammetry treatment in an acidic electrolyte to obtain the catalyst.
2. The method of claim 1, wherein the soluble nickel salt comprises nickel chloride and/or nickel nitrate;
the soluble cobalt salt comprises cobalt chloride and/or cobalt nitrate.
3. The preparation method according to claim 1 or 2, wherein the molar ratio of the soluble nickel salt and the soluble cobalt salt is (0.1 to 0.5): (3-4).
4. A method according to claim 3, wherein the soluble nickel salt, co (NH 2 ) 2 And the molar ratio of the ammonium fluoride is (0.1-0.5): (6-8): (3-4).
5. The method according to claim 1, 2 or 4, wherein the hydrothermal reaction is carried out at a temperature of 100 to 130℃for a period of 30 to 40 hours.
6. The method according to claim 1, wherein the phosphating agent used for the vapor phase phosphating treatment comprises sodium hypophosphite and/or potassium hypophosphite;
the mole ratio of the soluble nickel salt to the phosphating agent is (0.1-0.5): (2-3).
7. The process according to claim 1 or 6, wherein the vapor phase phosphating is carried out at a temperature of 400 to 500℃for a period of 3 to 4 hours.
8. The method according to claim 1, wherein the acidic electrolyte is a perchloric acid solution having a concentration of 1 to 1.2 mol/L;
the high overpotential of the cyclic voltammetry treatment is 0-30 mV, the low overpotential is 150-300 mV, and the voltage scanning rate is 5-10 mV/s.
9. The catalyst prepared by the preparation method according to any one of claims 1 to 8, which is characterized by comprising a foam nickel substrate and cobalt nickel phosphide and platinum supported on the foam nickel substrate.
10. Use of the catalyst of claim 9 in electrocatalytic hydrogen evolution reactions.
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