CN113638005A - Preparation method and application of efficient and bifunctional heterostructure full-electrolysis water-electricity catalyst - Google Patents
Preparation method and application of efficient and bifunctional heterostructure full-electrolysis water-electricity catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 16
- 238000007747 plating Methods 0.000 claims abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 229910052751 metal Chemical class 0.000 claims description 22
- 239000002184 metal Chemical class 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 239000006262 metallic foam Substances 0.000 claims description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000002135 nanosheet Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000006172 buffering agent Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000002474 experimental method Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000011056 performance test Methods 0.000 claims description 3
- -1 salt cation Chemical class 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 2
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 2
- 150000001450 anions Chemical class 0.000 claims 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims 2
- 229910052802 copper Inorganic materials 0.000 claims 2
- 239000010949 copper Substances 0.000 claims 2
- 229910052742 iron Inorganic materials 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- 239000001632 sodium acetate Substances 0.000 claims 2
- 235000017281 sodium acetate Nutrition 0.000 claims 2
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims 1
- 229910000085 borane Inorganic materials 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- 235000010338 boric acid Nutrition 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 235000015424 sodium Nutrition 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000012279 sodium borohydride Substances 0.000 claims 1
- 229910000033 sodium borohydride Inorganic materials 0.000 claims 1
- 239000001509 sodium citrate Substances 0.000 claims 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims 1
- 235000011083 sodium citrates Nutrition 0.000 claims 1
- 239000001540 sodium lactate Substances 0.000 claims 1
- 229940005581 sodium lactate Drugs 0.000 claims 1
- 235000011088 sodium lactate Nutrition 0.000 claims 1
- PRWXGRGLHYDWPS-UHFFFAOYSA-L sodium malonate Chemical compound [Na+].[Na+].[O-]C(=O)CC([O-])=O PRWXGRGLHYDWPS-UHFFFAOYSA-L 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 claims 1
- 239000010935 stainless steel Substances 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 125000005842 heteroatom Chemical group 0.000 abstract description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 abstract 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 239000010411 electrocatalyst Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 101150036540 Copb1 gene Proteins 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical group [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical group [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
-
- 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 provides a preparation method of a high-efficiency and bifunctional heterostructure full-electrolysis water-electricity catalyst, which comprises the following steps: thiourea is used as a sulfur source, nickel nitrate and copper nitrate are used as raw materials, and a heteroatom-doped honeycomb nickel sulfide substrate is prepared by a hydrothermal method; and immersing the nickel sulfide base body into chemical plating solution to react to prepare the high-efficiency and bifunctional heterostructure catalytic electrode. In the heterostructure electrocatalyst, nickel sulfide is doped with heteroatoms, so that the morphology and the electronic structure of the catalyst are regulated, the specific surface area can be increased, and active sites can be exposed. The composite catalyst has a current density of 50mA cm‑2The overpotential for hydrogen evolution is only 69mV, and the overpotential for oxygen evolution is 340mV, and can stably evolve hydrogen and oxygen for a long time. The catalytic electrode prepared by the invention can be used as an electrolytic water hydrogen evolution electrode andthe oxygen evolution electrode is used, and has the characteristics of low overpotential and high chemical stability in an alkaline electrolysis environment.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, energy and catalysis, and relates to a preparation method and application of a high-efficiency and bifunctional heterostructure full-electrolysis water-electricity catalyst.
Background
The hydrogen production by water electrolysis is a clean and efficient hydrogen production technology, the preparation conditions are mild, the requirement on equipment is low, the purity of the prepared hydrogen can reach 99.99 percent, and the method has practical economic benefits and social benefits. Compared with other hydrogen production methods, the hydrogen production by electrolyzing water utilizes clean water as a reaction raw material, and the preparation method is green and environment-friendly, so that the method is known as a method for continuously producing hydrogen. Therefore, the water electrolysis hydrogen production technology will become the core technology of the future hydrogen production industry.
In alkaline electrolyte, the stability and catalytic activity of pure transition metal are poor, so that the development of high-performance water electrolysis catalyst is urgently needed. The transition metal sulfide has the electronic structure and catalytic property of noble metal, and has wide application in the field of catalysis. The sulfide prepared by doping the heteroatom can realize the regulation and control of the micro-morphology and the electronic structure, increase the specific surface area and expose the catalytic active site; the chemical plating method deposits the metal alloy by autocatalysis, can further expose more active sites, and increases the stability of the catalyst in alkaline electrolyte.
Differences in fermi levels of the metal and semiconductor in the heterojunction will result in spontaneous flow of electrons at the heterojunction interface, resulting in the formation of relatively stable, locally hydrophilic and nucleophilic domains. The method is beneficial to improving the dispersibility, structural stability and conductivity of the catalyst, thereby realizing the design and construction of a new-structure and high-performance nano catalyst. Therefore, the hetero-atom doped nickel-based sulfide and the metal alloy heterostructure deposited by the chemical plating method are constructed, the current density of the electrolyzed water in the alkaline electrolyte is effectively improved, and the stability of the electrolyzed water is improved.
The invention aims to provide a preparation method and application of a high-efficiency and bifunctional heterostructure full-electrolysis water-electricity catalyst. In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
step (1): the metal foam substrate pretreatment process comprises the following steps: the metal foam substrate is ultrasonically cleaned in an acidic solution, an organic solvent and deionized water for several times to remove oxides and impurities on the surface thereof.
Step (2): preparing nickel-based sulfide by a hydrothermal method: weighing and mixing urea, nickel nitrate and metal salt according to the proportion by taking metal foam nickel as a carrier, dissolving the urea, the nickel nitrate and the metal salt in a methanol solution, preparing the honeycomb nickel-based hydroxide composite nanosheet by adopting a hydrothermal reaction, and carrying out the hydrothermal reaction on the reacted substance in a thiourea solution to finally obtain the honeycomb nickel-based sulfide nanosheet.
And (3): preparing a plating solution: the metal salt, the reducing agent, the complexing agent, the buffering agent and the deionized water in different proportions are weighed and mixed according to a certain proportion to obtain the prepared plating solution.
And (4): chemical plating experiment: immersing the honeycomb nickel-based sulfide nanosheet substrate into the chemical plating solution prepared in the step (3), carrying out chemical plating reaction at a certain temperature for a certain time, taking out the catalyst after the reaction is finished, repeatedly washing the catalyst for a plurality of times by using absolute ethyl alcohol and deionized water, and drying the catalyst at a certain temperature to obtain the catalyst with the heterostructure.
The catalytic electrode prepared by the method can be used as an electrolytic water hydrogen evolution electrode and an oxygen evolution electrode at the same time. In the alkaline electrolyte, the electrolyte has the characteristics of low overpotential, high current density and long service life. The preparation method of the catalytic electrode is simple, the reaction condition is mild, no special equipment requirement is required, the cost is low, and the prepared heterojunction electrocatalysis has excellent regular morphology performance.
Drawings
FIG. 1 is CuNi3S2The performance test result of water electrolysis hydrogen evolution of the CoPB catalytic electrode.
FIG. 2 is CuNi3S2The electrolytic water oxygen evolution performance test result of the CoPB catalyst electrode.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1
Step (1): the metal foam substrate pretreatment process comprises the following steps: cutting commercial foam nickel into a 1 x 2 cm-shaped metal foam substrate, ultrasonically cleaning the metal foam substrate in a 1M hydrochloric acid solution for 30min, respectively ultrasonically cleaning the metal foam substrate with ethanol for 10-15 min after washing, ultrasonically cleaning the metal foam substrate with acetone for 10-15 min, then ultrasonically cleaning the metal foam substrate with deionized water for 2-3 times for 10-15 min each time, and drying the metal foam substrate in an oven at 50-60 ℃.
Step (2): preparing nickel-based sulfide by a hydrothermal method: weighing urea, nickel nitrate and metal salt by taking metal foam nickel as a carrier, weighing and mixing the urea, the nickel nitrate and the metal salt according to the using amount in proportion, dissolving the mixture in a methanol solution, preparing the honeycomb nickel-based hydroxide composite nanosheet through a first step of hydrothermal reaction, and then reacting the reacted substances in a thiourea solution in a second step to finally obtain the honeycomb nickel-based sulfide nanosheet.
In the step (2), the concentration of urea is 0.05g/mL, and the concentration of nickel nitrate is 0.025 g/mL; the metal salt is ferric nitrate with the concentration of 0.025 g/mL;
the using amount of the methanol in the step (2) is 40mL, the hydrothermal temperature of the first step is 180 ℃, and the reaction time is 6 h;
the dosage of thiourea in the step (2) is 0.05M, the hydrothermal temperature in the second step is 150 ℃, and the reaction time is 6 h;
and (3): preparing a plating solution: weighing and mixing metal salts, a reducing agent, a complexing agent, a buffering agent and deionized water in different proportions according to a certain proportion to obtain a prepared plating solution;
in the step (3), cobalt nitrate is selected as the metal salt, and the concentration of the cobalt nitrate is 0.15 g/L; the reducing agent is selected from sodium hypophosphite and dimethylamino borane, and the concentration of the sodium hypophosphite and the concentration of the dimethylamino borane are respectively 0.01g/L and 0.072 g/L; the complexing agent is sodium succinate with the concentration of 0.25 g/L; the buffer agent is sodium sulfate with the concentration of 0.15 g/L;
and (4): chemical plating experiment: immersing the honeycomb nickel-based sulfide nanosheet substrate into the chemical plating solution prepared in the step (3), performing chemical plating reaction at a certain temperature for a certain time, taking out the catalyst after the reaction is finished, repeatedly washing the catalyst for a plurality of times by using absolute ethyl alcohol and deionized water, and drying the catalyst at a certain temperature to obtain the catalyst with a heterostructure;
in the step (4), the chemical plating reaction temperature is 50 ℃, and the reaction time is 30 min.
Example 2
This example is the same as example 1, except for the following parameters:
in the step (2), the metal salt is copper nitrate with the concentration of 0.025 g/mL;
the using amount of methanol in the step (2) is 30mL, the hydrothermal temperature of the first step is 120 ℃, and the reaction time is 6 h;
in the step (3), the metal salt is nickel nitrate with the concentration of 0.25 g/L; sodium hypophosphite is selected as a reducing agent, and the concentration of the sodium hypophosphite is 0.01 g/L;
in the step (4), the chemical plating reaction temperature is 30 ℃, and the reaction time is 90 min.
Example 3
This example is the same as example 1, except for the following parameters:
in the step (2), the metal salt is molybdenum nitrate with the concentration of 0.025 g/mL;
the using amount of methanol in the step (2) is 50mL, the hydrothermal temperature of the first step is 160 ℃, and the reaction time is 6 h;
in the step (3), the metal salt is nickel nitrate and cobalt nitrate, and the concentration of the metal salt is 0.25 g/L; the reducing agent is selected from dimethylamino borane, and the concentration of the dimethylamino borane is 0.072 g/L;
in the step (4), the chemical plating reaction temperature is 40 ℃, and the reaction time is 60 min.
The present invention may be embodied in other specific forms, and various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method and application of a high-efficiency and bifunctional heterostructure full-electrolysis water-electricity catalyst are characterized by comprising the following steps:
(1) the metal foam substrate pretreatment process comprises the following steps: the metal foam substrate is ultrasonically cleaned in an acidic solution, an organic solvent and deionized water for several times to remove oxides and impurities on the surface thereof.
(2) Preparing heteroatom-doped nickel-based sulfide by a hydrothermal method: weighing urea, nickel nitrate and a metal salt by taking metal foam as a carrier, weighing and mixing the urea, the nickel nitrate and the metal salt according to a proportion, dissolving the mixture in a methanol solution, preparing the honeycomb nickel-based hydroxide composite nanosheet by adopting a hydrothermal reaction, and performing a secondary hydrothermal reaction on the reacted substance in a thiourea solution to finally obtain the honeycomb nickel-based sulfide nanosheet.
(3) Preparing a plating solution: the metal salt, the reducing agent, the complexing agent, the buffering agent and the deionized water in different proportions are weighed and mixed according to a certain proportion to obtain the prepared plating solution.
(4) Chemical plating experiment: immersing the honeycomb nickel-based sulfide nanosheet substrate into the chemical plating solution obtained in the step (3), carrying out chemical plating reaction at a certain temperature for a certain time, taking out the catalyst after the reaction is finished, repeatedly washing the catalyst for a plurality of times by using absolute ethyl alcohol and deionized water, and drying the catalyst at a certain temperature to obtain the catalyst with the heterostructure.
(5) And (3) taking the prepared heterostructure catalyst as a self-supporting electrode, and carrying out performance test of hydrogen evolution and oxygen evolution by electrolysis and water evolution.
2. The preparation method and the application of the high-efficiency and bifunctional heterostructure full-electrolysis hydro-electric catalyst according to claim 1 are characterized in that: the metal foam substrate in the step (1) is one or two selected from titanium foam, cobalt foam, nickel foam, copper foam, iron foam and stainless steel mesh.
3. The preparation method and the application of the high-efficiency and bifunctional heterostructure full-electrolysis hydro-electric catalyst according to claim 1 are characterized in that: the acid solution in the step (1) is one or more of hydrochloric acid, sulfuric acid, nitric acid and oxalic acid, and the concentration of the acid solution is 1-3M; the organic solvent is acetone and absolute ethyl alcohol solution.
4. The preparation method and the application of the high-efficiency and bifunctional heterostructure full-electrolysis hydro-electric catalyst according to claim 1 are characterized in that: the cation of the metal salt selected in the hydrothermal reaction in the step (2) is selected from one or a mixture of more of iron, molybdenum, tungsten, manganese, copper and platinum, and the anion is selected from C1-，SO4 2-，NO3 -，HClO-The concentration of the metal salt is 0.005 g/mL-0.01 g/mL.
5. The preparation method and the application of the high-efficiency and bifunctional heterostructure full-electrolysis hydro-electric catalyst according to claim 1 are characterized in that: in the step (2), the concentration of urea is 0.01-0.05 g/mL, and the concentration of nickel nitrate is 0.01-0.05 g/mL.
6. The preparation method and the application of the high-efficiency and bifunctional heterostructure full-electrolysis hydro-electric catalyst according to claim 1 are characterized in that: the using amount of the methanol solution in the step (2) is 20-80 mL.
7. The preparation method and the application of the high-efficiency and bifunctional heterostructure full-electrolysis hydro-electric catalyst according to claim 1 are characterized in that: the hydrothermal temperature for preparing the honeycomb nickel-based hydroxide composite nanosheet through the hydrothermal reaction in the step (2) is 100-200 ℃.
8. The preparation method and the application of the high-efficiency and bifunctional heterostructure full-electrolysis hydro-electric catalyst according to claim 1 are characterized in that: and (3) when the honeycomb nickel-based sulfide nanosheet is prepared in the step (2), the hydrothermal temperature is 100-200 ℃.
9. The preparation method and the application of the high-efficiency and bifunctional heterostructure full-electrolysis hydro-electric catalyst according to claim 1 are characterized in that: in the chemical plating process in the step (3), the metal salt cation in the chemical plating solution is selected from Fe2+、Co2+、Ni2+、W2+、Sn2+One or more of them, and anion is selected from CI-、SO4 -2、NO3 -、PO4 3-(ii) a The concentration of the metal salt is 0.1-5 g/L; the reducing agent is selected from borohydride and hypophosphite; wherein the borohydride is selected from one or more of sodium borohydride, ammonia borane and amine borane compoundAn agent; the hypophosphite cation is selected from one or more of sodium, potassium, magnesium and calcium: the concentration of the reducing agent is 0.01 g/L-1 g/L; the complexing agent is a compound capable of coordinating with metal salt, and is selected from ammonia water, amine, sodium citrate, sodium acetate, sodium lactate and sodium malonate, and the concentration of the complexing agent is 0.01-0.5 g/L; the buffering agent is selected from one of sodium acetate, boric acid, ammonium chloride and sodium sulfate, and the concentration of the buffering agent is 0.01-0.3 g/L.
10. The preparation method and the application of the high-efficiency and bifunctional heterostructure full-electrolysis hydro-electric catalyst according to claim 1 are characterized in that: the reaction temperature in the step (4) is 10-80 ℃; the reaction time is 10-90 min; the catalyst was dried in a vacuum oven at 60 ℃.
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