CN110512228B - Preparation method of nickel phosphide/nickel foam electrochemical functional hydrogen evolution material - Google Patents
Preparation method of nickel phosphide/nickel foam electrochemical functional hydrogen evolution material Download PDFInfo
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- CN110512228B CN110512228B CN201910871606.5A CN201910871606A CN110512228B CN 110512228 B CN110512228 B CN 110512228B CN 201910871606 A CN201910871606 A CN 201910871606A CN 110512228 B CN110512228 B CN 110512228B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 562
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 278
- 239000006260 foam Substances 0.000 title claims abstract description 208
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000001257 hydrogen Substances 0.000 title claims abstract description 61
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 61
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000007747 plating Methods 0.000 claims abstract description 89
- 239000000126 substance Substances 0.000 claims abstract description 61
- 239000002243 precursor Substances 0.000 claims abstract description 54
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- 239000011574 phosphorus Substances 0.000 claims abstract description 20
- 238000011068 loading method Methods 0.000 claims abstract description 13
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 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 56
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 56
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- 239000008367 deionised water Substances 0.000 claims description 43
- 229910021641 deionized water Inorganic materials 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 37
- 239000011248 coating agent Substances 0.000 claims description 36
- 238000000576 coating method Methods 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 35
- 238000009210 therapy by ultrasound Methods 0.000 claims description 35
- 238000004140 cleaning Methods 0.000 claims description 33
- 238000001291 vacuum drying Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 229910052593 corundum Inorganic materials 0.000 claims description 21
- 239000010431 corundum Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 229910052573 porcelain Inorganic materials 0.000 claims description 21
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 20
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 20
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 20
- 229960004011 methenamine Drugs 0.000 claims description 20
- 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 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 17
- 239000001632 sodium acetate Substances 0.000 claims description 17
- 235000017281 sodium acetate Nutrition 0.000 claims description 17
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 14
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 14
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 14
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 12
- 239000001119 stannous chloride Substances 0.000 claims description 12
- 235000011150 stannous chloride Nutrition 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 9
- 239000003755 preservative agent Substances 0.000 description 9
- 230000002335 preservative effect Effects 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 5
- 238000010494 dissociation reaction Methods 0.000 description 5
- 230000005593 dissociations Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 238000004832 voltammetry Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229910001096 P alloy Inorganic materials 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010530 solution phase reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- 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
- C25B11/031—Porous electrodes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a nickel phosphide/nickel foam electrochemical functional hydrogen evolution material, which relates to the technical field of hydrogen energy application and comprises the steps of pretreating a nickel foam current collector, preparing a chemical nickel and phosphorus plating solution, loading a chemical nickel and phosphorus plating layer on the surface of a nickel foam sheet, and preparing a nickel hydroxide/nickel foam precursor containing the nickel and phosphorus plating layer and a nickel phosphide/nickel foam self-supporting electrode. The nickel phosphide/nickel foam self-supporting electrode prepared by the method has the advantages of excellent electrochemical catalytic hydrogen evolution performance, efficient and stable property, wide application range, wide sources of required materials, convenient preparation process, wide requirements on pH value conditions, green and pollution-free preparation process, simple and easy technical implementation process, low cost and easy industrial popularization.
Description
Technical Field
The invention relates to the technical field of hydrogen energy application, in particular to a preparation method of a nickel phosphide/nickel foam electrochemical functional hydrogen evolution material.
Background
The development of efficient renewable clean energy is an important measure for solving the problems of environment and energy at present, in an efficient renewable energy system, a potential key energy storage means is to convert electric energy into chemical energy stored in a fuel form, and the most important and simple step in the process is to decompose water to produce hydrogen. Compared with the hydrogen production method relying on primary energy in industry, the hydrogen production by water electrolysis is concerned by the characteristics of simple device, high hydrogen production purity, high energy conversion rate and the like; the efficiency of decomposing water to produce hydrogen depends on catalysts of two half reactions of cathode hydrogen evolution reaction and anode oxygen uptake, so the performance of the catalyst for electrochemical cathode hydrogen evolution reaction is a key for restricting the efficiency of decomposing water to produce hydrogen. At present, the industrial water decomposition mainly depends on the traditional platinum-based catalyst, but considering the defect that the precious metals such as platinum and the like cannot meet the requirements of engineering application because of small storage amount and high price in the earth crust, the method is very urgent to develop non-precious metal catalysts which have wide sources, convenient use, high-efficiency and stable catalytic hydrogen evolution performance, low price and easy availability. In addition, in the hydrogen production process, different electrolysis devices such as proton exchange membrane fuel cells, microbial fuel cells and the like have different requirements on the pH of the electrolysis cell, so that the non-noble metal-based electrochemical cathode hydrogen evolution catalytic material has the characteristics of high efficiency, stability, low price, easiness in obtaining and the like of hydrogen evolution catalysis, and also needs to have a wide pH application range, which is the core of green hydrogen production measures.
Among non-noble metal-based cathode catalytic materials, nickel-phosphorus alloys and transition metal phosphides represented by nickel phosphide have attracted much attention as hydrogen evolution materials because of their low cost and availability. Researchers at home and abroad carry out a plurality of researches in the field, and the research on researching the preparation way of the nickel phosphide and evaluating the hydrogen evolution performance of the water and electricity dissociation is the key research point in the field. At present, the solution phase reaction such as hydrothermal synthesis for preparing nickel phosphide mainly uses white phosphorus or tri-n-octylphosphine as a phosphorus source, but the reaction temperature range is limited to a certain extent, and the toxicity of intermediate products in the reaction process is high. Therefore, the researchers improved the above process, and patent CN109650360A discloses a method for continuously preparing nickel phosphide nanoparticles by using a microchannel reactor, which comprises mixing an organic nickel precursor and an organic phosphorus source, diluting with a high boiling point multi-carbon organic substance as a diluent, subjecting the obtained suspension to ultrasonic treatment, directly injecting into the microchannel reactor for reaction, and precipitating, separating, washing and vacuum drying the obtained product to obtain nickel phosphide nanoparticles. Although the prepared nickel phosphide nano-particles have the characteristics of extremely small size, uniform size, good dispersibility and the like, the nickel phosphide nano-particles need to use various toxic chemical substances such as triphenylphosphine, 1-octadecene and the like, and have great harm to human bodies. Patent CN109267095A mentions a preparation method of a novel nickel phosphide catalytic material, which comprises the steps of firstly synthesizing a metal organic framework precursor containing nitrogen and phosphorus atoms by a micro-droplet method, then sintering and thermally treating the precursor at the high temperature of 900-1100 ℃, and then preparing a nickel phosphide catalytic hydrogen evolution material. Based on the technical defects of the existing nickel phosphide preparation, the preparation technology of the nickel phosphide, which has the advantages of wide material source, convenient preparation process, no pollution, easy industrial popularization, high and stable hydrogen evolution performance and wide pH application range, is sought, and is an important measure for promoting the hydrogen production by cathode water and electricity dissociation.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a nickel phosphide/nickel foam electrochemical functional hydrogen evolution material, and the prepared product has excellent electrochemical catalytic hydrogen evolution performance, efficient and stable properties, wide application range, wide sources of required materials, convenient and fast preparation process, wide requirements on pH value conditions, green and pollution-free preparation process, simple and easy technical implementation process, low cost and easy industrial popularization.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a nickel phosphide/nickel foam electrochemical functional hydrogen evolution material comprises the following steps:
(1) pretreatment of a foamed nickel current collector: cutting the foamed nickel into a specified size, and performing pretreatment; immersing the foam nickel sheet obtained by the pretreatment in a stannous chloride solution, fully reacting, cleaning, immersing in a palladium chloride solution, fully reacting, cleaning and drying;
(2) preparing chemical nickel and phosphorus plating solution: adding nickel sulfate, citric acid, succinic acid, sodium acetate and ammonium bifluoride into a container containing distilled water in sequence according to a certain proportion, and heating and stirring to completely dissolve the nickel sulfate, the citric acid, the succinic acid, the sodium acetate and the ammonium bifluoride; adding sodium hypophosphite into the solution, heating and stirring to dissolve the sodium hypophosphite, dropwise adding ammonia water into the solution after the solution is cooled to room temperature to adjust the pH value of the solution to 4.6-5.0, and stirring uniformly to obtain the chemical nickel and phosphorus plating solution;
(3) loading a chemical nickel and phosphorus plating layer on the surface of a foam nickel sheet: heating the chemical nickel-phosphorus plating solution to a certain temperature, immersing the foam nickel sheet treated in the step (1) in the chemical nickel-phosphorus plating solution, keeping the temperature of the plating solution, controlling the plating time, taking out the foam nickel sheet after full plating, cleaning and drying;
(4) preparing nickel hydroxide/foam nickel precursor containing nickel-phosphorus plating layer: weighing hexamethylenetetramine and nickel nitrate hexahydrate according to a certain proportion, placing the hexamethylenetetramine and the nickel nitrate hexahydrate in a beaker filled with deionized water, stirring to dissolve the hexamethylenetetramine and the nickel nitrate hexahydrate, pouring the solution into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into a reaction kettle, heating, carrying out hydrothermal reaction to obtain nickel hydroxide/nickel foam precursor containing a nickel-phosphorus coating, and cleaning and drying the nickel hydroxide/nickel foam precursor;
(5) preparation of nickel phosphide/foamed nickel self-supporting electrode: respectively placing nickel hydroxide/nickel foam precursor containing nickel-phosphorus coating and sodium hypophosphite powder into two corundum porcelain boats, placing the two corundum porcelain boats into a tubular furnace hearth with nitrogen atmosphere, heating the hearth, preserving heat for a period of time, and then carrying out a phosphating reaction to obtain a nickel phosphide/nickel foam electrochemical functional hydrogen evolution material, in particular to a nickel phosphide/nickel foam self-supporting electrode.
The technical scheme of the invention is further improved as follows: the pretreatment step in the step (1) comprises the steps of placing the cut foam nickel sheet into a beaker filled with acetone, placing the beaker into an ultrasonic cleaner for ultrasonic treatment, taking the treated foam nickel sheet out of the beaker, cleaning the foam nickel sheet for 5 times by using deionized water, placing the beaker into a beaker filled with hydrochloric acid for etching, placing the beaker into an ultrasonic cleaner for ultrasonic treatment, taking the foam nickel sheet out of the beaker, cleaning the foam nickel sheet for 5 times by using the deionized water, placing the foam nickel sheet into a beaker filled with absolute ethyl alcohol for ultrasonic treatment, taking the foam nickel sheet treated by the absolute ethyl alcohol out of the beaker, cleaning the foam nickel sheet for 5 times by using the deionized water, and placing the foam nickel sheet into a vacuum drying oven for drying.
The technical scheme of the invention is further improved as follows: immersing the foamed nickel sheet in a solution of stannous chloride with the concentration of 10g/L in the solution, performing ultrasonic treatment at room temperature by using an ultrasonic cleaner, taking the foamed nickel sheet out of the stannous chloride solution, and cleaning the foamed nickel sheet for 5 times by using deionized water; immersing the foamed nickel sheet into 0.2g/L palladium chloride solution, performing ultrasonic treatment at room temperature by using an ultrasonic cleaner, taking the foamed nickel sheet out of the palladium chloride solution, and cleaning the foamed nickel sheet for 5 times by using deionized water; and finally, placing the cleaned foam nickel sheet in a vacuum drying oven for drying.
The technical scheme of the invention is further improved as follows: the mass ratio of nickel sulfate, sodium hypophosphite, citric acid, succinic acid, sodium acetate and ammonium bifluoride in the step (2) is 25-30: 15-30: 10-15: 3-5: 3-5: 3 to 5.
The technical scheme of the invention is further improved as follows: firstly, adding nickel sulfate, citric acid, succinic acid, sodium acetate and ammonium bifluoride into a beaker filled with distilled water, placing the beaker on a magnetic stirrer, rotating a stirring control knob, turning on a heating control switch, controlling the temperature of the solution to be 40-50 ℃, and stirring the solution to completely dissolve all added reagents; and adding sodium hypophosphite into the solution, stirring to dissolve the sodium hypophosphite, and after the sodium hypophosphite is completely dissolved, closing a heating control switch of the magnetic stirrer to naturally cool the solution to room temperature.
The technical scheme of the invention is further improved as follows: placing the beaker containing the chemical nickel-phosphorus plating solution in a constant-temperature magnetic stirring water bath containing deionized water, heating the temperature of the chemical nickel-phosphorus plating solution to 80-85 ℃, immersing the foam nickel sheet in the chemical nickel-phosphorus plating solution, keeping the temperature of the plating solution at 80-85 ℃, and controlling the plating time to be 40-60 min; after complete reaction, the foam nickel sheet is taken out of the chemical nickel-phosphorus plating solution, washed for 5 times by deionized water and then placed in a vacuum drying oven for drying.
The technical scheme of the invention is further improved as follows: in the step (4), the mole ratio of hexamethylene tetramine to nickel nitrate hexahydrate is 1: 1.
the technical scheme of the invention is further improved as follows: : in the step (3), the ratio of the loading amount of the nickel-phosphorus coating on the surface of the foam nickel sheet to the molar ratio of the sodium hypophosphite is 1: and 5, the loading amount is the mass difference of the foamed nickel sheet before and after chemical plating.
The technical scheme of the invention is further improved as follows: and (5) placing the corundum porcelain boat containing the sodium hypophosphite on one side close to the nitrogen inlet of the tubular furnace, heating the hearth to 300 ℃, and preserving heat for 2 hours.
The technical scheme of the invention is further improved as follows: after the two corundum porcelain boats are placed in the center of the hearth of the tubular furnace in the step (5), opening a switch knob of a nitrogen cylinder to enable nitrogen to slowly enter the tubular furnace, wherein the introduction amount of the nitrogen is 10-30 mL/min; and simultaneously, starting a heating switch of the tubular furnace, raising the temperature of the hearth from room temperature to 300 ℃ at the heating rate of 1-5 ℃/min, and keeping the temperature to carry out the phosphorization reaction of the nickel hydroxide/the foam nickel precursor containing the nickel-phosphorus coating for 2 hours.
Due to the adoption of the technical scheme, the invention has the technical progress that:
the nickel phosphide/nickel foam self-supporting electrode prepared by the method has excellent electrochemical catalytic hydrogen evolution performance, high and stable properties, wide application range, high-efficiency catalytic hydrogen production efficiency in acidic and alkaline media, and wide application prospect in the fields of electrochemical catalytic hydrogen production, hydrodesulfurization, selective hydrogenation and other hydrogen-involved reactions. The invention has the advantages of wide sources of materials required by the process, cheap and easily obtained raw materials, convenient preparation process, wide requirements on pH value conditions, green and pollution-free preparation process, simple technical implementation process and easy operation, and is beneficial to large-scale industrial production and application.
The corundum porcelain boat containing the sodium hypophosphite is placed on one side close to a nitrogen gas inlet of the tubular furnace, so that the phosphine gas decomposed by the sodium hypophosphite can be ensured to be fully contacted with the nickel hydroxide/nickel foam precursor containing the nickel-phosphorus coating to be phosphorized, and the reaction efficiency is improved.
The nickel phosphide hydrogen evolution catalyst is firmly loaded on the foam nickel support without the help of the adhesive action of a binder, and has good chemical stability.
Drawings
FIG. 1 is a scanning electron microscope image of untreated nickel foam;
FIG. 2 is an enlarged view of a portion of FIG. 1;
FIG. 3 is a scanning electron microscope image of a nickel foam sheet bearing electroless nickel-phosphorous plating on its surface;
FIG. 4 is an enlarged view of a portion of FIG. 3;
FIG. 5 is an X-ray diffraction pattern of a nickel phosphide/nickel foam self-supporting electrode and nickel foam;
FIG. 6 is a linear sweep voltammetry curve for a nickel phosphide/nickel foam self-supporting electrode, nickel foam, commercial glassy carbon electrode in acidic media;
FIG. 7 is a linear sweep voltammetry curve for a nickel phosphide/nickel foam self-supporting electrode, nickel foam, commercial glassy carbon electrode in alkaline medium.
Detailed Description
The technical scheme and the working principle of the invention are further explained in detail by combining the schematic diagram and the specific embodiment. The drawings of the present invention only show a part of the technical solutions related to the claims of the present invention, but not all of them, and the embodiments of the present invention are only described by a part of the best embodiments, not all of the technical solutions to achieve the objects of the present invention, and the embodiments are not to be regarded as the scope of the claims of the present invention. The present invention will be described in further detail with reference to the following examples:
example 1
(1) Pretreatment of a foamed nickel current collector:
cutting and pretreating foam nickel:
firstly, cutting commercially available foam nickel into small pieces with the length and the width of 2cm, then placing the cut foam nickel pieces into a beaker filled with 50mL of acetone, sealing the mouth of a container by using a preservative film, then placing the beaker into an ultrasonic cleaner for ultrasonic treatment, wherein the power of the ultrasonic cleaner is 90W, and the ultrasonic treatment time is 30min, so that the foam nickel pieces are degreased at room temperature; and then taking out the foam nickel sheet subjected to oil removal treatment by acetone under ultrasound from the beaker, cleaning the foam nickel sheet for 5 times by using deionized water, then placing the foam nickel sheet subjected to the acetone treatment and cleaned in the beaker filled with 50mL of hydrochloric acid with the concentration of 2mol/L for etching, sealing the container opening by using a preservative film, then placing the beaker in an ultrasonic cleaner for ultrasonic treatment, wherein the power of the ultrasonic cleaner is 90W, and the ultrasonic treatment time is 30 min. And taking the foamed nickel sheet subjected to ultrasonic etching treatment by hydrochloric acid out of the beaker, washing the foamed nickel sheet for 5 times by using deionized water, and finally placing the foamed nickel sheet subjected to hydrochloric acid treatment and washed clean in the beaker filled with 50mL of absolute ethyl alcohol to remove other impurities. Sealing the container mouth with a preservative film, placing the beaker in an ultrasonic cleaner for ultrasonic treatment, wherein the power of the ultrasonic cleaner is 90W, and the ultrasonic treatment time is 30 min. And then taking the foam nickel sheet treated by the absolute ethyl alcohol out of the beaker, washing the foam nickel sheet for 5 times by using deionized water, and drying the foam nickel sheet in a vacuum drying oven at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa.
Activation treatment of the foam nickel sheet:
immersing the pretreated nickel foam sheet into a stannous chloride solution with the concentration of 10g/L prepared in advance, carrying out ultrasonic treatment for 10-20 min at room temperature, wherein the power of an ultrasonic cleaner is 90W, then taking the nickel foam sheet out of the stannous chloride solution, and cleaning the nickel foam sheet for 5 times by using deionized water.
Sensitizing the foam nickel sheet:
immersing the activated foam nickel sheet into a pre-prepared 0.2g/L palladium chloride solution, performing ultrasonic treatment for 20-30 min at room temperature, wherein the power of an ultrasonic cleaner is 90W, taking out the foam nickel sheet from the palladium chloride solution, and cleaning the foam nickel sheet for 5 times by using deionized water; and finally, drying the cleaned foam nickel sheet in a vacuum drying oven at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa.
(2) Preparing chemical nickel and phosphorus plating solution:
chemical raw materials used are as follows:
the nickel sulfate, sodium hypophosphite, citric acid, succinic acid, sodium acetate and ammonium bifluoride are used in the following mass proportion relationship: sodium hypophosphite: citric acid: succinic acid: sodium acetate: ammonium bifluoride 25: 15: 10: 3: 3: 3;
preparing the chemical nickel-phosphorus plating solution:
firstly, sequentially adding nickel sulfate, citric acid, succinic acid, sodium acetate and ammonium bifluoride into a beaker filled with 1L of distilled water, placing the beaker on a magnetic stirrer, starting a rotary stirring control knob and a heating control switch, controlling the temperature of a solution to be 40-50 ℃, and stirring the solution to completely dissolve all added reagents;
after the reagents are completely dissolved, adding sodium hypophosphite into the solution, stirring to dissolve the sodium hypophosphite, and after the sodium hypophosphite is completely dissolved, closing a heating control switch of a magnetic stirrer to naturally cool the solution from 40-50 ℃ to room temperature;
dropwise adding an ammonia water solution with the mass percentage concentration of 25% into the solution by using a dropper to adjust the pH value of the solution to 4.6, simultaneously placing a pH meter probe into the solution to monitor the change of the pH value, and slowly stirring the solution for 10-20 min by using a magnetic stirrer after the pH value is adjusted to prepare the chemical nickel-phosphorus plating solution.
(3) Loading a chemical nickel and phosphorus plating layer on the surface of a foam nickel sheet:
placing a beaker containing chemical nickel and phosphorus plating solution in a constant-temperature magnetic stirring water bath containing deionized water, and heating to ensure that the temperature of the plating solution is 80 ℃;
immersing the activated and sensitized foam nickel sheet in the step (1) into chemical nickel-phosphorus plating solution after the temperature of the chemical nickel-phosphorus plating solution rises to 80 ℃, and chemically plating and depositing a nickel-phosphorus plating layer on the surface of the foam nickel sheet, wherein the temperature of the plating solution is kept at 80 ℃ in the plating process, and the plating time is 40 min;
thirdly, after the chemical plating is finished, taking out the foamed nickel sheet from the chemical nickel-phosphorus plating solution, cleaning the foamed nickel sheet for 5 times by using deionized water, and then placing the foamed nickel sheet in a vacuum drying oven to be dried at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa;
and fourthly, calculating the load capacity of the nickel-phosphorus coating on the surface of the foam nickel sheet, wherein the mass difference of the foam nickel sheet before and after chemical plating is the load capacity of the nickel-phosphorus coating.
(4) Preparing nickel hydroxide/foam nickel precursor containing nickel-phosphorus plating layer:
preparing materials:
the nickel hydroxide/nickel foam precursor containing nickel-phosphorus coating is prepared from analytically pure hexamethylenetetramine and nickel nitrate hexahydrate, wherein the molar ratio of the raw materials is hexamethylenetetramine: nickel nitrate hexahydrate = 2: 1;
preparing nickel hydroxide/nickel-phosphorus-plating-layer-containing foam nickel precursor:
accurately weighing 1.402g of hexamethylenetetramine and 1.454g of nickel nitrate hexahydrate, placing the hexamethylenetetramine and the nickel nitrate hexahydrate in a beaker filled with 20mL of deionized water, and then placing the beaker on a magnetic stirrer to be stirred to be uniformly dissolved, wherein the stirring time is 6 hours, and the stirring temperature is room temperature; pouring the solution into a polytetrafluoroethylene lining with the volume of 25mL after stirring, then putting the polytetrafluoroethylene lining into a reaction kettle, screwing the polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a hearth with the temperature of 100 ℃ for hydrothermal reaction for 10 hours, after the furnace is cooled to room temperature, taking out the prepared precursor, respectively cleaning the precursor with deionized water and ethanol for three times, finally drying the precursor in a vacuum drying box at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying box is-0.1 MPa, and thus obtaining the nickel hydroxide/nickel-phosphorus-plated-layer-containing foam nickel precursor.
(5) Preparing a nickel phosphide/foamed nickel self-supporting electrode:
preparing materials:
the materials used for preparing the nickel phosphide/nickel foam self-supporting electrode comprise analytically pure sodium hypophosphite and nickel hydroxide/nickel foam precursor containing a nickel-phosphorus coating, and the mass ratio of the sodium hypophosphite to the nickel hydroxide/nickel foam precursor containing the nickel-phosphorus coating is measured by the ratio of the negative load of the sodium hypophosphite to the negative load of the nickel-phosphorus coating on a nickel foam sheet; the molar ratio of the loading amount of the nickel-phosphorus coating on the surface of the foamed nickel sheet to the sodium hypophosphite is 1: 5;
preparing the nickel phosphide/foamed nickel self-supporting electrode:
a. firstly, respectively placing nickel hydroxide/nickel-phosphorus-plated foam nickel precursor and sodium hypophosphite powder into two corundum porcelain boats, and then placing the two corundum porcelain boats into the center of a hearth of a tubular furnace, wherein the corundum porcelain boat containing sodium hypophosphite is placed at one side close to a nitrogen gas inlet of the tubular furnace, so as to ensure that phosphine gas decomposed by the sodium hypophosphite can be fully contacted with the nickel hydroxide/nickel-phosphorus-plated foam nickel precursor to be phosphorized;
b. after the two corundum porcelain boats are placed in the center of the hearth of the tubular furnace, a switch knob of a nitrogen cylinder is turned on, so that nitrogen slowly enters the tubular furnace, and the introduction amount of the nitrogen is 10 mL/min; simultaneously, a heating switch of the tube furnace is opened, so that the temperature of the hearth is increased from room temperature to 300 ℃ at the heating rate of 1 ℃/min, and the nickel hydroxide/foam nickel precursor containing the nickel-phosphorus coating is subjected to a phosphating reaction for 2 hours at the temperature of 300 ℃;
c. and after the phosphorization reaction is finished, closing the power supply of the tubular furnace, naturally cooling the hearth to room temperature, and taking out the nickel hydroxide/nickel foam precursor containing the nickel-phosphorus coating after the phosphorization treatment after the hearth of the tubular furnace is cooled to room temperature to obtain the nickel phosphide/nickel foam self-supporting electrode for hydrogen dissociation and hydrogen evolution of water and electricity.
(6) Electrochemical cathodic hydrogen evolution performance test of nickel phosphide/nickel foam self-supporting electrode:
a standard three-electrode system is adopted, a foamed nickel electrode, a commercial platinum carbon electrode and a prepared nickel phosphide/foamed nickel self-supporting electrode are used as working electrodes, a saturated Ag/AgCl electrode is used as a reference electrode, a carbon rod is used as a counter electrode, a Shanghai Chenghua CHI660E electrochemical workstation is utilized, a linear scanning voltammetry method is adopted, hydrogen evolution performance evaluation is respectively carried out in 0.5mol/L sulfuric acid and 1.0mol/L potassium hydroxide solution, relative to the potential of a reversible hydrogen electrode, the test range is 0-0.7V, and the scanning rate is 2 mV/s.
Fig. 1 and 2 are scanning electron microscope images of untreated nickel foam, and the surface of the nickel foam sheet is clean and has not been treated. As can be seen from the figure, the foam nickel sheets are in a net structure inside and are mutually interwoven, the surfaces of the foam nickel sheets are smooth and have no protrusions and metal grains.
Fig. 3 and 4 are scanning electron microscope images of a nickel foam sheet with a chemical nickel-phosphorus plating layer supported on the surface, and scanning electron microscope images of nickel phosphide synthesized by a low-temperature two-step method after chemical nickel-phosphorus plating on the surface of the nickel foam sheet, wherein it can be seen that flower-shaped nickel phosphide with the radius of about 4 μm uniformly grows on a nickel foam framework, the surface of the flower-shaped nickel phosphide is rough, and the flower-shaped nickel phosphide has a plurality of pore structures and can provide a larger active specific surface area.
Fig. 5 is an X-ray diffraction pattern of the nickel phosphide/nickel foam self-supporting electrode and the nickel foam, wherein the horizontal X-axis represents an angle (°), and the longitudinal y-axis represents intensity (a.u.), wherein three strong peaks appearing around 2 θ =44.8 °, 52.2 ° and 76.8 ° are (111) (200) (220) crystal planes of nickel, respectively, and the rest peaks except the three strong peaks of the generated flower-like nickel phosphide/nickel foam are matched with a diffraction peak standard card of nickel phosphide and have good crystallinity.
FIG. 6 is a linear sweep voltammetry curve for a nickel phosphide/nickel foam self-supporting electrode, nickel foam, commercial glassy carbon electrode in acidic media, polarization curve in a 0.5mol/L sulfuric acid solution at pH =0, horizontal x-axis represents potential in mV; the longitudinal y-axis represents the current density in mA/cm2. The scanning rate was 2mV/s, using a commercial platinum-carbon electrode, and a current density of-10 mA/cm2The corresponding voltage is-78 mV, which is superior to most phosphide catalytic materials that have been disclosed so far.
FIG. 7 is a linear sweep voltammetry curve for a nickel phosphide/nickel foam self-supporting electrode, nickel foam, commercial glassy carbon electrode in alkaline medium, polarization curve in a 1.0mol/L potassium hydroxide solution pH =14, horizontal x-axis represents potential in mV; the longitudinal y-axis represents the current density in mA/cm2. The scanning rate was 2mV/s, using a commercial platinum-carbon electrode, and a current density of-10 mA/cm2The corresponding voltage is-91 mV, with a significant gain effect compared to most phosphide catalytic materials that have been disclosed so far.
Example 2
(1) Pretreatment of a foamed nickel current collector:
cutting and pretreating foam nickel:
firstly, cutting commercially available foam nickel into small pieces with the length and the width of 2cm, then placing the cut foam nickel pieces into a beaker filled with 50mL of acetone, sealing the mouth of a container by using a preservative film, then placing the beaker into an ultrasonic cleaner for ultrasonic treatment, wherein the power of the ultrasonic cleaner is 90W, and the ultrasonic treatment time is 30min, so that the foam nickel pieces are degreased at room temperature; and then taking out the foam nickel sheet subjected to oil removal treatment by acetone under ultrasound from the beaker, cleaning the foam nickel sheet for 5 times by using deionized water, then placing the foam nickel sheet subjected to the acetone treatment and cleaned in the beaker filled with 50mL of hydrochloric acid with the concentration of 2mol/L for etching, sealing the container opening by using a preservative film, then placing the beaker in an ultrasonic cleaner for ultrasonic treatment, wherein the power of the ultrasonic cleaner is 90W, and the ultrasonic treatment time is 30 min. And taking the foamed nickel sheet subjected to ultrasonic etching treatment by hydrochloric acid out of the beaker, washing the foamed nickel sheet for 5 times by using deionized water, and finally placing the foamed nickel sheet subjected to hydrochloric acid treatment and washed clean in the beaker filled with 50mL of absolute ethyl alcohol to remove other impurities. Sealing the container mouth with a preservative film, placing the beaker in an ultrasonic cleaner for ultrasonic treatment, wherein the power of the ultrasonic cleaner is 90W, and the ultrasonic treatment time is 30 min. And then taking the foam nickel sheet treated by the absolute ethyl alcohol out of the beaker, washing the foam nickel sheet for 5 times by using deionized water, and drying the foam nickel sheet in a vacuum drying oven at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa.
Activation treatment of the foam nickel sheet:
immersing the pretreated nickel foam sheet into a stannous chloride solution with the concentration of 10g/L prepared in advance, carrying out ultrasonic treatment for 10-20 min at room temperature, wherein the power of an ultrasonic cleaner is 90W, then taking the nickel foam sheet out of the stannous chloride solution, and cleaning the nickel foam sheet for 5 times by using deionized water.
Sensitizing the foam nickel sheet:
immersing the activated foam nickel sheet into a pre-prepared 0.2g/L palladium chloride solution, performing ultrasonic treatment for 20-30 min at room temperature, wherein the power of an ultrasonic cleaner is 90W, taking out the foam nickel sheet from the palladium chloride solution, and cleaning the foam nickel sheet for 5 times by using deionized water; and finally, drying the cleaned foam nickel sheet in a vacuum drying oven at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa.
(2) Preparing chemical nickel and phosphorus plating solution:
chemical raw materials used are as follows:
the nickel sulfate, sodium hypophosphite, citric acid, succinic acid, sodium acetate and ammonium bifluoride are used in the following mass proportion relationship: sodium hypophosphite: citric acid: succinic acid: sodium acetate: ammonium acid fluoride ═ 28: 23: 13: 4: 4: 4;
preparing the chemical nickel-phosphorus plating solution:
firstly, sequentially adding nickel sulfate, citric acid, succinic acid, sodium acetate and ammonium bifluoride into a beaker filled with 1L of distilled water, placing the beaker on a magnetic stirrer, starting a rotary stirring control knob and a heating control switch, controlling the temperature of a solution to be 40-50 ℃, and stirring the solution to completely dissolve all added reagents;
after the reagents are completely dissolved, adding sodium hypophosphite into the solution, stirring to dissolve the sodium hypophosphite, and after the sodium hypophosphite is completely dissolved, closing a heating control switch of a magnetic stirrer to naturally cool the solution from 40-50 ℃ to room temperature;
dropwise adding an ammonia water solution with the mass percentage concentration of 25% into the solution by using a dropper to adjust the pH value of the solution to 4.8, simultaneously placing a pH meter probe into the solution to monitor the change of the pH value, and slowly stirring the solution for 10-20 min by using a magnetic stirrer after the pH value is adjusted to prepare the chemical nickel-phosphorus plating solution.
(3) Loading a chemical nickel and phosphorus plating layer on the surface of a foam nickel sheet:
placing a beaker containing chemical nickel and phosphorus plating solution in a constant-temperature magnetic stirring water bath containing deionized water, and heating to ensure that the temperature of the plating solution is 83 ℃;
immersing the activated and sensitized foam nickel sheet in the step (1) into chemical nickel-phosphorus plating solution after the temperature of the chemical nickel-phosphorus plating solution rises to 83 ℃, and chemically plating and depositing a nickel-phosphorus plating layer on the surface of the foam nickel sheet, wherein the temperature of the plating solution is kept at 83 ℃ in the plating process, and the plating time is 50 min;
thirdly, after the chemical plating is finished, taking out the foamed nickel sheet from the chemical nickel-phosphorus plating solution, cleaning the foamed nickel sheet for 5 times by using deionized water, and then placing the foamed nickel sheet in a vacuum drying oven to be dried at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa;
and fourthly, calculating the load capacity of the nickel-phosphorus coating on the surface of the foam nickel sheet, wherein the mass difference of the foam nickel sheet before and after chemical plating is the load capacity of the nickel-phosphorus coating.
(4) Preparing nickel hydroxide/foam nickel precursor containing nickel-phosphorus plating layer:
preparing materials:
the nickel hydroxide/nickel foam precursor containing nickel-phosphorus coating is prepared from analytically pure hexamethylenetetramine and nickel nitrate hexahydrate, wherein the molar ratio of the raw materials is hexamethylenetetramine: nickel nitrate hexahydrate = 2: 1;
preparing nickel hydroxide/nickel-phosphorus-plating-layer-containing foam nickel precursor:
accurately weighing 1.402g of hexamethylenetetramine and 1.454g of nickel nitrate hexahydrate, placing the hexamethylenetetramine and the nickel nitrate hexahydrate in a beaker filled with 20mL of deionized water, and then placing the beaker on a magnetic stirrer to be stirred to be uniformly dissolved, wherein the stirring time is 6 hours, and the stirring temperature is room temperature; pouring the solution into a polytetrafluoroethylene lining with the volume of 25mL after stirring, then putting the polytetrafluoroethylene lining into a reaction kettle, screwing the polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a hearth with the temperature of 100 ℃ for hydrothermal reaction for 10 hours, after the furnace is cooled to room temperature, taking out the prepared precursor, respectively cleaning the precursor with deionized water and ethanol for three times, finally drying the precursor in a vacuum drying box at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying box is-0.1 MPa, and thus obtaining the nickel hydroxide/nickel-phosphorus-plated-layer-containing foam nickel precursor.
(5) Preparing a nickel phosphide/foamed nickel self-supporting electrode:
preparing materials:
the materials used for preparing the nickel phosphide/nickel foam self-supporting electrode comprise analytically pure sodium hypophosphite and nickel hydroxide/nickel foam precursor containing a nickel-phosphorus coating, and the mass ratio of the sodium hypophosphite to the nickel hydroxide/nickel foam precursor containing the nickel-phosphorus coating is measured by the ratio of the negative load of the sodium hypophosphite to the negative load of the nickel-phosphorus coating on a nickel foam sheet; the molar ratio of the loading amount of the nickel-phosphorus coating on the surface of the foamed nickel sheet to the sodium hypophosphite is 1: 5;
preparing the nickel phosphide/foamed nickel self-supporting electrode:
a. firstly, respectively placing nickel hydroxide/nickel-phosphorus-plated foam nickel precursor and sodium hypophosphite powder into two corundum porcelain boats, and then placing the two corundum porcelain boats into the center of a hearth of a tubular furnace, wherein the corundum porcelain boat containing sodium hypophosphite is placed at one side close to a nitrogen gas inlet of the tubular furnace, so as to ensure that phosphine gas decomposed by the sodium hypophosphite can be fully contacted with the nickel hydroxide/nickel-phosphorus-plated foam nickel precursor to be phosphorized;
b. after the two corundum porcelain boats are placed in the center of the hearth of the tubular furnace, a switch knob of a nitrogen cylinder is turned on, so that nitrogen slowly enters the tubular furnace, and the introduction amount of the nitrogen is 20 mL/min; simultaneously, a heating switch of the tube furnace is opened, so that the temperature of the hearth is increased from room temperature to 300 ℃ at the heating rate of 3 ℃/min, and the nickel hydroxide/foam nickel precursor containing the nickel-phosphorus coating is subjected to a phosphating reaction for 2 hours at the temperature of 300 ℃;
c. and after the phosphorization reaction is finished, closing the power supply of the tubular furnace, naturally cooling the hearth to room temperature, and taking out the nickel hydroxide/nickel foam precursor containing the nickel-phosphorus coating after the phosphorization treatment after the hearth of the tubular furnace is cooled to room temperature to obtain the nickel phosphide/nickel foam self-supporting electrode for hydrogen dissociation and hydrogen evolution of water and electricity.
(6) Electrochemical cathodic hydrogen evolution performance test of nickel phosphide/nickel foam self-supporting electrode:
a standard three-electrode system is adopted, a foamed nickel electrode, a commercial platinum carbon electrode and a prepared nickel phosphide/foamed nickel self-supporting electrode are used as working electrodes, a saturated Ag/AgCl electrode is used as a reference electrode, a carbon rod is used as a counter electrode, a Shanghai Chenghua CHI660E electrochemical workstation is utilized, a linear scanning voltammetry method is adopted, hydrogen evolution performance evaluation is respectively carried out in 0.5mol/L sulfuric acid and 1.0mol/L potassium hydroxide solution, relative to the potential of a reversible hydrogen electrode, the test range is 0-0.7V, and the scanning rate is 2 mV/s.
The hydrogen evolution performance of the catalyst is not obviously different from that of the sample prepared in the example 1, so the details are not given.
Example 3
(1) Pretreatment of a foamed nickel current collector:
cutting and pretreating foam nickel:
firstly, cutting commercially available foam nickel into small pieces with the length and the width of 2cm, then placing the cut foam nickel pieces into a beaker filled with 50mL of acetone, sealing the mouth of a container by using a preservative film, then placing the beaker into an ultrasonic cleaner for ultrasonic treatment, wherein the power of the ultrasonic cleaner is 90W, and the ultrasonic treatment time is 30min, so that the foam nickel pieces are degreased at room temperature; and then taking out the foam nickel sheet subjected to oil removal treatment by acetone under ultrasound from the beaker, cleaning the foam nickel sheet for 5 times by using deionized water, then placing the foam nickel sheet subjected to the acetone treatment and cleaned in the beaker filled with 50mL of hydrochloric acid with the concentration of 2mol/L for etching, sealing the container opening by using a preservative film, then placing the beaker in an ultrasonic cleaner for ultrasonic treatment, wherein the power of the ultrasonic cleaner is 90W, and the ultrasonic treatment time is 30 min. And taking the foamed nickel sheet subjected to ultrasonic etching treatment by hydrochloric acid out of the beaker, washing the foamed nickel sheet for 5 times by using deionized water, and finally placing the foamed nickel sheet subjected to hydrochloric acid treatment and washed clean in the beaker filled with 50mL of absolute ethyl alcohol to remove other impurities. Sealing the container mouth with a preservative film, placing the beaker in an ultrasonic cleaner for ultrasonic treatment, wherein the power of the ultrasonic cleaner is 90W, and the ultrasonic treatment time is 30 min. And then taking the foam nickel sheet treated by the absolute ethyl alcohol out of the beaker, washing the foam nickel sheet for 5 times by using deionized water, and drying the foam nickel sheet in a vacuum drying oven at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa.
Activation treatment of the foam nickel sheet:
immersing the pretreated nickel foam sheet into a stannous chloride solution with the concentration of 10g/L prepared in advance, carrying out ultrasonic treatment for 10-20 min at room temperature, wherein the power of an ultrasonic cleaner is 90W, then taking the nickel foam sheet out of the stannous chloride solution, and cleaning the nickel foam sheet for 5 times by using deionized water.
Sensitizing the foam nickel sheet:
immersing the activated foam nickel sheet into a pre-prepared 0.2g/L palladium chloride solution, performing ultrasonic treatment for 20-30 min at room temperature, wherein the power of an ultrasonic cleaner is 90W, taking out the foam nickel sheet from the palladium chloride solution, and cleaning the foam nickel sheet for 5 times by using deionized water; and finally, drying the cleaned foam nickel sheet in a vacuum drying oven at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa.
(2) Preparing chemical nickel and phosphorus plating solution:
chemical raw materials used are as follows:
the nickel sulfate, sodium hypophosphite, citric acid, succinic acid, sodium acetate and ammonium bifluoride are used in the following mass proportion relationship: sodium hypophosphite: citric acid: succinic acid: sodium acetate: ammonium bifluoride 30: 30: 15: 5: 5: 5;
preparing the chemical nickel-phosphorus plating solution:
firstly, sequentially adding nickel sulfate, citric acid, succinic acid, sodium acetate and ammonium bifluoride into a beaker filled with 1L of distilled water, placing the beaker on a magnetic stirrer, starting a rotary stirring control knob and a heating control switch, controlling the temperature of a solution to be 40-50 ℃, and stirring the solution to completely dissolve all added reagents;
after the reagents are completely dissolved, adding sodium hypophosphite into the solution, stirring to dissolve the sodium hypophosphite, and after the sodium hypophosphite is completely dissolved, closing a heating control switch of a magnetic stirrer to naturally cool the solution from 40-50 ℃ to room temperature;
dropwise adding an ammonia water solution with the mass percentage concentration of 25% into the solution by using a dropper to adjust the pH value of the solution to 5.0, simultaneously placing a pH meter probe into the solution to monitor the change of the pH value, and slowly stirring the solution for 10-20 min by using a magnetic stirrer after the pH value is adjusted to prepare the chemical nickel-phosphorus plating solution.
(3) Loading a chemical nickel and phosphorus plating layer on the surface of a foam nickel sheet:
placing a beaker containing chemical nickel and phosphorus plating solution in a constant-temperature magnetic stirring water bath containing deionized water, and heating to ensure that the temperature of the plating solution is 85 ℃;
immersing the activated and sensitized foam nickel sheet in the step (1) into chemical nickel-phosphorus plating solution after the temperature of the chemical nickel-phosphorus plating solution rises to 85 ℃, and chemically plating and depositing a nickel-phosphorus plating layer on the surface of the foam nickel sheet, wherein the temperature of the plating solution is kept at 85 ℃ in the plating process, and the plating time is 60 min;
thirdly, after the chemical plating is finished, taking out the foamed nickel sheet from the chemical nickel-phosphorus plating solution, cleaning the foamed nickel sheet for 5 times by using deionized water, and then placing the foamed nickel sheet in a vacuum drying oven to be dried at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa;
and fourthly, calculating the load capacity of the nickel-phosphorus coating on the surface of the foam nickel sheet, wherein the mass difference of the foam nickel sheet before and after chemical plating is the load capacity of the nickel-phosphorus coating.
(4) Preparing nickel hydroxide/foam nickel precursor containing nickel-phosphorus plating layer:
preparing materials:
the nickel hydroxide/nickel foam precursor containing nickel-phosphorus coating is prepared from analytically pure hexamethylenetetramine and nickel nitrate hexahydrate, wherein the molar ratio of the raw materials is hexamethylenetetramine: nickel nitrate hexahydrate = 2: 1;
preparing nickel hydroxide/nickel-phosphorus-plating-layer-containing foam nickel precursor:
accurately weighing 1.402g of hexamethylenetetramine and 1.454g of nickel nitrate hexahydrate, placing the hexamethylenetetramine and the nickel nitrate hexahydrate in a beaker filled with 20mL of deionized water, and then placing the beaker on a magnetic stirrer to be stirred to be uniformly dissolved, wherein the stirring time is 6 hours, and the stirring temperature is room temperature; pouring the solution into a polytetrafluoroethylene lining with the volume of 25mL after stirring, then putting the polytetrafluoroethylene lining into a reaction kettle, screwing the polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a hearth with the temperature of 100 ℃ for hydrothermal reaction for 10 hours, after the furnace is cooled to room temperature, taking out the prepared precursor, respectively cleaning the precursor with deionized water and ethanol for three times, finally drying the precursor in a vacuum drying box at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying box is-0.1 MPa, and thus obtaining the nickel hydroxide/nickel-phosphorus-plated-layer-containing foam nickel precursor.
(5) Preparing a nickel phosphide/foamed nickel self-supporting electrode:
preparing materials:
the materials used for preparing the nickel phosphide/nickel foam self-supporting electrode comprise analytically pure sodium hypophosphite and nickel hydroxide/nickel foam precursor containing a nickel-phosphorus coating, and the mass ratio of the sodium hypophosphite to the nickel hydroxide/nickel foam precursor containing the nickel-phosphorus coating is measured by the ratio of the negative load of the sodium hypophosphite to the negative load of the nickel-phosphorus coating on a nickel foam sheet; the molar ratio of the loading amount of the nickel-phosphorus coating on the surface of the foamed nickel sheet to the sodium hypophosphite is 1: 5;
preparing the nickel phosphide/foamed nickel self-supporting electrode:
a. firstly, respectively placing nickel hydroxide/nickel-phosphorus-plated foam nickel precursor and sodium hypophosphite powder into two corundum porcelain boats, and then placing the two corundum porcelain boats into the center of a hearth of a tubular furnace, wherein the corundum porcelain boat containing sodium hypophosphite is placed at one side close to a nitrogen gas inlet of the tubular furnace, so as to ensure that phosphine gas decomposed by the sodium hypophosphite can be fully contacted with the nickel hydroxide/nickel-phosphorus-plated foam nickel precursor to be phosphorized;
b. after the two corundum porcelain boats are placed in the center of the hearth of the tubular furnace, a switch knob of a nitrogen cylinder is turned on, so that nitrogen slowly enters the tubular furnace, and the introduction amount of the nitrogen is 30 mL/min; simultaneously, a heating switch of the tube furnace is opened, so that the temperature of the hearth is increased from room temperature to 300 ℃ at the heating rate of 5 ℃/min, and the nickel hydroxide/foam nickel precursor containing the nickel-phosphorus coating is subjected to a phosphating reaction for 2 hours at the temperature of 300 ℃;
c. and after the phosphorization reaction is finished, closing the power supply of the tubular furnace, naturally cooling the hearth to room temperature, and taking out the nickel hydroxide/nickel foam precursor containing the nickel-phosphorus coating after the phosphorization treatment after the hearth of the tubular furnace is cooled to room temperature to obtain the nickel phosphide/nickel foam self-supporting electrode for hydrogen dissociation and hydrogen evolution of water and electricity.
(6) Electrochemical cathodic hydrogen evolution performance test of nickel phosphide/nickel foam self-supporting electrode: :
a standard three-electrode system is adopted, a foamed nickel electrode, a commercial platinum carbon electrode and a prepared nickel phosphide/foamed nickel self-supporting electrode are used as working electrodes, a saturated Ag/AgCl electrode is used as a reference electrode, a carbon rod is used as a counter electrode, a Shanghai Chenghua CHI660E electrochemical workstation is utilized, a linear scanning voltammetry method is adopted, hydrogen evolution performance evaluation is respectively carried out in 0.5mol/L sulfuric acid and 1.0mol/L potassium hydroxide solution, relative to the potential of a reversible hydrogen electrode, the test range is 0-0.7V, and the scanning rate is 2 mV/s.
The hydrogen evolution performance of the catalyst is not obviously different from that of the sample prepared in the example 1, so the details are not given.
Claims (10)
1. A preparation method of a nickel phosphide/nickel foam electrochemical functional hydrogen evolution material is characterized by comprising the following steps: the method comprises the following steps:
(1) pretreatment of a foamed nickel current collector: cutting the foamed nickel into a specified size, and performing pretreatment; immersing the foam nickel sheet obtained by the pretreatment in a stannous chloride solution, fully reacting, cleaning, immersing in a palladium chloride solution, fully reacting, cleaning and drying;
(2) preparing chemical nickel and phosphorus plating solution: adding nickel sulfate, citric acid, succinic acid, sodium acetate and ammonium bifluoride into a container containing distilled water in sequence according to a certain proportion, and heating and stirring to completely dissolve the nickel sulfate, the citric acid, the succinic acid, the sodium acetate and the ammonium bifluoride; adding sodium hypophosphite into the solution, heating and stirring to dissolve the sodium hypophosphite, dropwise adding ammonia water into the solution after the solution is cooled to room temperature to adjust the pH value of the solution to 4.6-5.0, and stirring uniformly to obtain the chemical nickel and phosphorus plating solution;
(3) loading a chemical nickel and phosphorus plating layer on the surface of a foam nickel sheet: heating the chemical nickel-phosphorus plating solution to a certain temperature, immersing the foam nickel sheet treated in the step (1) in the chemical nickel-phosphorus plating solution, keeping the temperature of the plating solution, controlling the plating time, taking out the foam nickel sheet after full plating, cleaning and drying;
(4) preparing nickel hydroxide/foam nickel precursor containing nickel-phosphorus plating layer: weighing hexamethylenetetramine and nickel nitrate hexahydrate according to a certain proportion, placing the hexamethylenetetramine and the nickel nitrate hexahydrate in a beaker filled with deionized water, stirring to dissolve the hexamethylenetetramine and the nickel nitrate hexahydrate, pouring the solution into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into a reaction kettle, heating, carrying out hydrothermal reaction to obtain nickel hydroxide/nickel foam precursor containing a nickel-phosphorus coating, and cleaning and drying the nickel hydroxide/nickel foam precursor;
(5) preparation of nickel phosphide/foamed nickel self-supporting electrode: respectively placing nickel hydroxide/nickel foam precursor containing nickel-phosphorus coating and sodium hypophosphite powder into two corundum porcelain boats, placing the two corundum porcelain boats into a tubular furnace hearth with nitrogen atmosphere, heating the hearth, preserving heat for a period of time, and then carrying out a phosphating reaction to obtain a nickel phosphide/nickel foam electrochemical functional hydrogen evolution material, in particular to a nickel phosphide/nickel foam self-supporting electrode.
2. The method for preparing the nickel phosphide/nickel foam electrochemical functional hydrogen evolution material according to claim 1, wherein the method comprises the following steps: the pretreatment step in the step (1) comprises the steps of placing the cut foam nickel sheet into a beaker filled with acetone, placing the beaker into an ultrasonic cleaner for ultrasonic treatment, taking the treated foam nickel sheet out of the beaker, cleaning the foam nickel sheet for 5 times by using deionized water, placing the beaker into a beaker filled with hydrochloric acid for etching, placing the beaker into an ultrasonic cleaner for ultrasonic treatment, taking the foam nickel sheet out of the beaker, cleaning the foam nickel sheet for 5 times by using the deionized water, placing the foam nickel sheet into a beaker filled with absolute ethyl alcohol for ultrasonic treatment, taking the foam nickel sheet treated by the absolute ethyl alcohol out of the beaker, cleaning the foam nickel sheet for 5 times by using the deionized water, and placing the foam nickel sheet into a vacuum drying oven for drying.
3. The method for preparing the nickel phosphide/nickel foam electrochemical functional hydrogen evolution material according to claim 1, wherein the method comprises the following steps: immersing the foamed nickel sheet in a solution of stannous chloride with the concentration of 10g/L in the solution, performing ultrasonic treatment at room temperature by using an ultrasonic cleaner, taking the foamed nickel sheet out of the stannous chloride solution, and cleaning the foamed nickel sheet for 5 times by using deionized water; immersing the foamed nickel sheet into 0.2g/L palladium chloride solution, performing ultrasonic treatment at room temperature by using an ultrasonic cleaner, taking the foamed nickel sheet out of the palladium chloride solution, and cleaning the foamed nickel sheet for 5 times by using deionized water; and finally, placing the cleaned foam nickel sheet in a vacuum drying oven for drying.
4. The method for preparing the nickel phosphide/nickel foam electrochemical functional hydrogen evolution material according to claim 1, wherein the method comprises the following steps: the mass ratio of nickel sulfate, sodium hypophosphite, citric acid, succinic acid, sodium acetate and ammonium bifluoride in the step (2) is 25-30: 15-30: 10-15: 3-5: 3-5: 3 to 5.
5. The method for preparing the nickel phosphide/nickel foam electrochemical functional hydrogen evolution material according to claim 1, wherein the method comprises the following steps: firstly, adding nickel sulfate, citric acid, succinic acid, sodium acetate and ammonium bifluoride into a beaker filled with distilled water, placing the beaker on a magnetic stirrer, starting a rotary stirring control knob and a heating control switch, controlling the temperature of the solution to be 40-50 ℃, and stirring the solution to completely dissolve all added reagents; and adding sodium hypophosphite into the solution, stirring to dissolve the sodium hypophosphite, and after the sodium hypophosphite is completely dissolved, closing a heating control switch of the magnetic stirrer to naturally cool the solution to room temperature.
6. The method for preparing the nickel phosphide/nickel foam electrochemical functional hydrogen evolution material according to claim 1, wherein the method comprises the following steps: placing the beaker containing the chemical nickel-phosphorus plating solution in a constant-temperature magnetic stirring water bath containing deionized water, heating the temperature of the chemical nickel-phosphorus plating solution to 80-85 ℃, immersing the foam nickel sheet in the chemical nickel-phosphorus plating solution, keeping the temperature of the plating solution at 80-85 ℃, and controlling the plating time to be 40-60 min; after complete reaction, the foam nickel sheet is taken out of the chemical nickel-phosphorus plating solution, washed for 5 times by deionized water and then placed in a vacuum drying oven for drying.
7. The method for preparing the nickel phosphide/nickel foam electrochemical functional hydrogen evolution material according to claim 1, wherein the method comprises the following steps: in the step (4), the mole ratio of hexamethylene tetramine to nickel nitrate hexahydrate is 1: 1.
8. the method for preparing the nickel phosphide/nickel foam electrochemical functional hydrogen evolution material according to claim 1, wherein the method comprises the following steps: in the step (3), the ratio of the loading amount of the nickel-phosphorus coating on the surface of the foam nickel sheet to the molar ratio of the sodium hypophosphite is 1: and 5, the loading amount is the mass difference of the foamed nickel sheet before and after chemical plating.
9. The method for preparing the nickel phosphide/nickel foam electrochemical functional hydrogen evolution material according to claim 1, wherein the method comprises the following steps: and (5) placing the corundum porcelain boat containing the sodium hypophosphite on one side close to the nitrogen inlet of the tubular furnace, heating the hearth to 300 ℃, and preserving heat for 2 hours.
10. The method for preparing the nickel phosphide/nickel foam electrochemical functional hydrogen evolution material according to claim 1, wherein the method comprises the following steps: after the two corundum porcelain boats are placed in the center of the hearth of the tubular furnace in the step (5), opening a switch knob of a nitrogen cylinder to enable nitrogen to slowly enter the tubular furnace, wherein the introduction amount of the nitrogen is 10-30 mL/min; and simultaneously, starting a heating switch of the tubular furnace, raising the temperature of the hearth from room temperature to 300 ℃ at the heating rate of 1-5 ℃/min, and keeping the temperature to carry out the phosphorization reaction of the nickel hydroxide/the foam nickel precursor containing the nickel-phosphorus coating for 2 hours.
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| CN112206793B (en) * | 2020-09-28 | 2023-05-19 | 沈阳理工大学 | Method for preparing non-noble metal phosphide catalyst |
| CN113186564B (en) * | 2021-04-30 | 2022-05-03 | 济宁学院 | Preparation method and application of nickel phosphide-ruthenium phosphide/nickel foam three-dimensional self-supporting electrode material |
| CN113481529B (en) * | 2021-07-07 | 2022-07-05 | 华中师范大学 | Iron and cobalt modified nickel phosphide nanosheet array and preparation method thereof |
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