CN117552031A - Preparation method of phosphorus-doped hydrogen evolution catalytic electrode - Google Patents
Preparation method of phosphorus-doped hydrogen evolution catalytic electrode Download PDFInfo
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- CN117552031A CN117552031A CN202311601367.4A CN202311601367A CN117552031A CN 117552031 A CN117552031 A CN 117552031A CN 202311601367 A CN202311601367 A CN 202311601367A CN 117552031 A CN117552031 A CN 117552031A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 38
- 239000001257 hydrogen Substances 0.000 title claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011574 phosphorus Substances 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004070 electrodeposition Methods 0.000 claims abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 44
- 238000009713 electroplating Methods 0.000 claims description 39
- 239000006260 foam Substances 0.000 claims description 37
- 238000000151 deposition Methods 0.000 claims description 33
- 230000008021 deposition Effects 0.000 claims description 32
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 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 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 7
- 229940078494 nickel acetate Drugs 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 7
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 7
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 5
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 229910000863 Ferronickel Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000000956 alloy Substances 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 229910001325 element alloy Inorganic materials 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000002779 inactivation Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910000756 V alloy Inorganic materials 0.000 description 8
- MXYAPMQTRLKMAI-UHFFFAOYSA-N [V].[Ni].[Cu] Chemical compound [V].[Ni].[Cu] MXYAPMQTRLKMAI-UHFFFAOYSA-N 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 235000014653 Carica parviflora Nutrition 0.000 description 2
- 241000243321 Cnidaria Species 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004210 cathodic protection Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 229940038773 trisodium citrate Drugs 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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
- C25B11/02—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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a preparation method of a phosphorus-doped hydrogen evolution catalytic electrode, which is characterized in that phosphorus is introduced into a multi-element alloy material containing nickel, copper and vanadium by a one-step electrodeposition method, so that an integral electrode with a three-dimensional coral-shaped surface structure is constructed. According to the invention, through the introduction of phosphorus, the cathode protection of the active electrode is realized, the oxidation and inactivation of the active electrode in a strong alkali environment are avoided, and the stability of the catalyst is enhanced; and the introduction of phosphorus further enhances the hydrogen evolution catalytic activity of the electrode. The method provides a new thought for improving the stability and activity of the catalyst, and is favorable for promoting the large-scale practical application of the integral electrolytic water cathode hydrogen evolution electrode material.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by water electrolysis, and particularly relates to a method for realizing cathodic protection of an active hydrogen evolution catalytic electrode and further improving electrochemical activity of the active hydrogen evolution catalytic electrode by electrodepositing phosphorus through a one-step method.
Background
Hydrogen is used as a clean energy carrier and an important chemical raw material, and is one of the necessary choices for realizing the 'double carbon' target in China. Solar, wind, tidal, and other renewable electrically driven electrochemical water splitting provides a viable and sustainable method to produce high purity hydrogen compared to traditional steam reforming and coal gasification. Pt group noble metals are well known Hydrogen Evolution Reaction (HER) benchmark catalysts with almost zero overpotential, but their widespread use is severely hampered by natural scarcity and high cost. Under the background, the development of the replaceable, high-cost-performance and high-activity non-noble metal hydrogen evolution electrocatalyst has important significance for promoting the industrialization of water electrolysis.
In response to the above problems, researchers have recently developed a range of active materials to catalyze the cathodic hydrogen evolution process. Among them, the transition metal-based catalytic material is considered as one of the catalytic materials with higher cost performance and better hydrogen evolution activity, and the performance of the material is even superior to that of noble metals and oxides thereof (Pt, irO 2 ，RuO 2 ) A catalyst. When nonmetallic elements including Se, S, B, P, C, N and the like are introduced into the nickel-copper-vanadium alloy material, the hydrogen evolution activity can be optimized. Wherein, the P doped material can obviously improve the characteristics of intrinsic activity, conductivity and the like of the material.
However, the non-metal P doping generally produces Transition Metal Phosphide (TMPs), which has limited space for improving the performance of the catalyst, and the stability of the catalytic material under the condition of long-time water electrolysis is not ideal, thus limiting the macro-preparation of large-area integral electrodes. Based on the above, a phosphorus doping method which is simple and efficient to operate needs to be explored to reduce the short plates of the phosphorus doping method, so that large-scale application is realized.
Disclosure of Invention
In order to obtain the high-efficiency and high-stability active cathode material for producing hydrogen by electrolyzing water, the invention prepares the phosphorus-doped multi-element alloy electrode by electrodeposition based on a cathode protection and synergistic effect mechanism. The activity is obviously improved in the hydrogen evolution of alkaline electrolyzed water, and the alkaline electrolyzed water can be operated under a larger current density. Due to the introduction of phosphorus, the oxidation reaction of Ni and Cu in the hydrogen separation process of alkaline electrolytic water is delayed, the deactivation of active sites is delayed, the cathode protection effect is realized, and the stability of the catalyst is enhanced to a certain extent.
The invention adopts the technical scheme that: and (3) placing the conductive porous metal substrate with the clean surface into electroplating solution, and performing electrodeposition under the constant potential of a three-electrode system or constant current of a two-electrode system to obtain the phosphorus doped hydrogen evolution catalytic electrode.
The electroplating solution is an aqueous solution containing a nickel source, a copper source, a vanadium source, a phosphorus source, boric acid and ammonium chloride.
The nickel source is any one of nickel sulfate, nickel nitrate, nickel acetate and nickel chloride. Further preferably, when the nickel source is nickel sulfate, the concentration of the nickel sulfate in the electroplating solution is 0.5-3 mol/L; when the nickel source is nickel acetate, the concentration of the nickel acetate in the electroplating solution is 0.1-1 mol/L; when the nickel source is nickel nitrate, the concentration of the nickel nitrate in the electroplating solution is 0.05-2.5 mol/L; when the nickel source is nickel chloride, the concentration of the nickel chloride in the electroplating solution is 0.16-1.3 mol/L.
The copper source is any one of copper sulfate, copper nitrate and copper chloride. Further preferably, when the copper source is copper sulfate, the concentration of the copper sulfate in the electroplating solution is 5-80 mmol/L; when the copper source is copper nitrate, the concentration of the copper nitrate in the electroplating solution is 10-90 mmol/L; when the copper source is copper chloride, the concentration of the copper chloride in the electroplating solution is 5-65 mmol/L.
The vanadium source is any one of vanadyl sulfate, ammonium metavanadate and sodium metavanadate. Further preferably, when the vanadium source is ammonium metavanadate, the concentration of the ammonium metavanadate in the electroplating solution is 1-18 mmol/L; when the vanadium source is vanadyl sulfate, the concentration of vanadyl sulfate in the electroplating solution is 0.2-4 mmol/L; when the vanadium source is sodium metavanadate, the concentration of sodium metavanadate in the electroplating solution is 1.4-12 mmol/L.
The phosphorus source is any one or more of dipotassium hydrogen phosphate, metaphosphoric acid and sodium hypophosphite. Further preferably, when the phosphorus source is dipotassium hydrogen phosphate, the concentration of the dipotassium hydrogen phosphate in the electroplating solution is 0.1-5 mol/L; when the phosphorus source is metaphosphoric acid, the concentration of metaphosphoric acid in the electroplating solution is 0.5-2.5 mol/L; when the phosphorus source is sodium hypophosphite, the concentration of sodium hypophosphite in the electroplating solution is 0.2-4 mol/L.
Further preferably, the concentration of boric acid in the electrolyte is 0.05-2 mol/L and the concentration of ammonium chloride is 0.1-1.2 mol/L.
The method for obtaining the conductive porous metal substrate with clean surface comprises the following steps: and sequentially placing the conductive porous metal substrate in dilute hydrochloric acid, deionized water, absolute ethyl alcohol and deionized water for ultrasonic treatment for 1-30 min, and then placing the conductive porous metal substrate in a vacuum drying oven for drying to obtain the conductive porous metal substrate with a clean surface. Wherein the conductive porous metal substrate is any one of foam nickel, foam copper, foam nickel-iron, foam nickel-copper, nickel net, copper net, nickel-copper alloy net and nickel-iron alloy net.
In the preparation method, the temperature for performing electrodeposition by the three-electrode constant potential is preferably 30-80 ℃, the counter electrode is graphite or nickel, the reference electrode is a saturated calomel electrode, the conductive porous metal substrate is a working electrode, the deposition potential is-0.1 to-2V vs. SCE, and the deposition time is 10-60 min.
In the preparation method, the temperature for carrying out electrodeposition by constant current of the two electrodes is preferably 5-30 ℃, the counter electrode is graphite or nickel, the conductive porous metal substrate is a working electrode, and the deposition current density is preferably 20-100 mA cm -2 The deposition time is 10-60 min.
The invention prepares an electrolytic water active electrode by a one-step electrodeposition phosphorus-doped cathodic protection method, wherein the active electrode is an integral material grown in a self-supporting form on a conductive carrier and comprises a conductive porous metal base material and a phosphorus-doped active catalytic material deposited on the surface of the conductive porous metal base material; the phosphorus-doped active catalytic material is a composite material formed by introducing nonmetallic element phosphorus into an alloy active material containing nickel, copper and vanadium, and the composite material has a three-dimensional coral-shaped structure.
The beneficial effects of the invention are as follows:
1. according to the invention, phosphorus is introduced into the nickel-copper-vanadium alloy electrode through one-step electrodeposition, so that the oxidation resistance of the active electrode material in a strong alkaline environment is improved, the oxidation hysteresis of Ni and Cu in the hydrogen evolution process of alkaline electrolytic water of the nickel-copper-vanadium multi-element alloy material is realized, the deactivation of active sites is delayed, the cathode protection effect is realized, and the stability of the catalyst is enhanced;
2. the integral catalytic electrode provided by the invention is suitable for hydrogen evolution catalytic reaction of alkaline electrolyzed water, has good electrochemical hydrogen evolution catalytic activity, improves the electrolyzed water efficiency, and reduces the hydrogen production energy consumption;
3. the integral catalytic electrode prepared by the phosphorus-doped cathode protection method has a three-dimensional coral structure, obviously improves the specific active surface area, and is beneficial to the mass transfer process of electrochemical reaction; and the cathode protection effect after phosphorus doping ensures that the catalyst has better stability;
4. the material provided by the invention is an integral electrode, and can be directly used for an alkaline water electrolysis hydrogen production electrolytic tank;
5. the catalytic material does not use noble metal elements, has low production cost, is simple to operate, has wide precursor sources, can realize macro preparation, and is easy for industrial production.
Drawings
FIG. 1 shows a scanning electron microscope microstructure of an electrode surface obtained in example 1.
FIG. 2 is a scanning electron microscope microstructure of the electrode surface obtained in example 2.
FIG. 3 is a scanning electron microscope microstructure of the electrode surface obtained in example 3.
FIG. 4 shows the scanning electron microscope microstructure of the electrode surface obtained in example 4.
FIG. 5 is a scanning electron microscope microstructure of the electrode surface obtained in comparative example 1.
FIG. 6 is a scanning electron microscope microstructure of the electrode surface obtained in comparative example 2.
FIG. 7 shows the activity test of the alkaline electrolysis water efficiency of the electrodes of examples 1 to 4 and comparative examples 1 to 2.
FIG. 8 is an electrode alkaline electrolyzed water stability test of example 3.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
Example 1
Preparation of phosphorus-doped nickel-copper-vanadium alloy electrode
Sequentially placing 3cm multiplied by 5cm of foam nickel into absolute ethyl alcohol, dilute hydrochloric acid, deionized water, absolute ethyl alcohol and deionized water for 30 minutes, and then placing the foam nickel into a vacuum drying oven for drying at 60 ℃ to obtain foam nickel with clean surfaces; placing the foam nickel with clean surface into 100mL of electroplating solution, performing electrodeposition under a three-electrode system, wherein a counter electrode is graphite, a reference electrode is a saturated calomel electrode, the foam nickel with clean surface is a working electrode, the deposition temperature is 30 ℃, the deposition potential is-1V vs. SCE, and the deposition time is 10min. Wherein the plating solution is an aqueous solution containing 0.7mol/L nickel sulfate, 10mmol/L copper sulfate, 9mmol/L sodium metavanadate, 0.6mol/L boric acid, 0.3mol/L sodium hypophosphite and 1mol/L ammonium chloride.
Example 2
Preparation of phosphorus-doped nickel-copper-vanadium alloy electrode
Sequentially placing 3cm multiplied by 5cm of foam nickel into absolute ethyl alcohol, dilute hydrochloric acid, deionized water, absolute ethyl alcohol and deionized water for 30 minutes, and then placing the foam nickel into a vacuum drying oven for drying at 60 ℃ to obtain foam nickel with clean surfaces; placing the foam nickel with clean surface into 100mL of electroplating solution, performing electrodeposition under a three-electrode system, wherein a counter electrode is graphite, a reference electrode is a saturated calomel electrode, the foam nickel with clean surface is a working electrode, the deposition temperature is 80 ℃, the deposition potential is-0.2V vs. SCE, and the deposition time is 60min. Wherein the plating solution is an aqueous solution containing 0.2mol/L nickel nitrate, 54mmol/L copper nitrate, 2mmol/L ammonium metavanadate, 0.1mol/L boric acid, 1mol/L sodium hypophosphite, 0.2mol/L dipotassium hydrogen phosphate and 0.2mol/L ammonium chloride.
Example 3
Preparation of phosphorus-doped nickel-copper-vanadium alloy electrode
Sequentially placing 3cm multiplied by 5cm of foam nickel into absolute ethyl alcohol, dilute hydrochloric acid, deionized water, absolute ethyl alcohol and deionized water for 30 minutes, and then placing the foam nickel into a vacuum drying oven for drying at 60 ℃ to obtain foam nickel with clean surfaces; placing foam nickel with clean surface into 100mL of electroplating solution, performing electrodeposition under a two-electrode system, wherein a counter electrode is graphite, the foam nickel with clean surface is a working electrode, the deposition temperature is 5 ℃, and the deposition current density is 60mA cm -2 The deposition time was 10min. Wherein the electroplating solutionIs an aqueous solution containing 0.2mol/L nickel acetate, 54mmol/L copper sulfate, 2mmol/L sodium metavanadate, 0.1mol/L boric acid, 1mol/L metaphosphoric acid and 0.2mol/L ammonium chloride.
Example 4
Preparation of phosphorus-doped nickel-copper-vanadium alloy electrode
Sequentially placing 3cm multiplied by 5cm of foam nickel into absolute ethyl alcohol, dilute hydrochloric acid, deionized water, absolute ethyl alcohol and deionized water for 30 minutes, and then placing the foam nickel into a vacuum drying oven for drying at 60 ℃ to obtain foam nickel with clean surfaces; placing foam nickel with clean surface into 100mL of electroplating solution, performing electrodeposition under a two-electrode system, wherein a counter electrode is graphite, the foam nickel with clean surface is a working electrode, the deposition temperature is 5 ℃, and the deposition current density is 10mA cm -2 Deposition time was 10min. Wherein the plating solution is an aqueous solution containing 0.2mol/L nickel chloride, 54mmol/L copper chloride, 2mmol/L vanadyl sulfate, 0.1mol/L boric acid, 1mol/L sodium hypophosphite and 0.2mol/L ammonium chloride.
Comparative example 1
Preparation of nickel-vanadium alloy electrode
Sequentially placing 3cm multiplied by 5cm of foam nickel into absolute ethyl alcohol, dilute hydrochloric acid, deionized water, absolute ethyl alcohol and deionized water for 30 minutes, and then placing the foam nickel into a vacuum drying oven for drying at 60 ℃ to obtain foam nickel with clean surfaces; placing foam nickel with clean surface into 100mL of electroplating solution, performing electrodeposition under a two-electrode system, wherein a counter electrode is graphite, the foam nickel with clean surface is a working electrode, the deposition temperature is 30 ℃, and the deposition current density is 10mA cm -2 The deposition time was 10min. Wherein the electroplating solution is an aqueous solution containing 0.8mol/L nickel chloride, 12mmol/L ammonium metavanadate, 1mol/L boric acid, 2mol/L trisodium citrate and 1mol/L ammonium chloride.
Comparative example 2
Preparation of nickel-copper-vanadium alloy electrode
Sequentially placing 3cm multiplied by 5cm of foam nickel into absolute ethyl alcohol, dilute hydrochloric acid, deionized water, absolute ethyl alcohol and deionized water for 30 minutes, and then placing the foam nickel into a vacuum drying oven for drying at 60 ℃ to obtain foam nickel with clean surfaces; placing the foam nickel with clean surface into 100mL of electroplating solution, performing electrodeposition under a three-electrode system, wherein a counter electrode is graphite, a reference electrode is a saturated calomel electrode, the foam nickel with clean surface is a working electrode, the deposition temperature is 37 ℃, the deposition potential is-0.2V vs. SCE, and the deposition time is 23min. Wherein the electroplating solution is an aqueous solution containing 0.7mol/L nickel chloride, 9mmol/L copper chloride, 6mmol/L ammonium metavanadate, 1.2mol/L boric acid, 2mol/L trisodium citrate and 1mol/L ammonium chloride.
The electrodes obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to scanning electron microscope characterization, and the results are shown in FIGS. 1 to 6. As can be seen from the graph, the electrode surfaces prepared in comparative examples 1 and 2 have nanoparticle morphology, and after phosphorus doping, the morphology of examples 1 to 4 is converted into three-dimensional coral structure, and the thickness of the two-dimensional nanometer film is about 5 to 10nm. Among them, the surface deposition particles of comparative example 1 are less than those of comparative example because it is difficult to achieve co-deposition of nickel and vanadium by such electrochemical method.
The electrodes obtained in examples 1 to 4 and comparative examples 1 to 2 were used to evaluate electrochemical hydrogen evolution activity under alkaline conditions. The analysis is carried out by adopting a standard three-electrode electrochemical linear voltammetry scanning method, the obtained electrode is an electrolyzed water hydrogen evolution cathode, the electrolyte is 1M KOH solution, the effective exposure area of the electrode is 0.5cm multiplied by 0.5cm, 95% iR compensation is carried out, and the voltammetry scanning rate is 5mV s -1 The test temperature was 25 ℃. The total efficiency of electrolyzed water is shown in FIG. 3: at a current density of less than 100mA cm -2 Example 3 when>Example 4>Example 2>Example 1>Comparative example 2>Comparative example 1. It is explained that the catalytic activity of the sample is significantly improved after the introduction of phosphorus, both potentiostatic and galvanostatic deposition. Under potentiostatic deposition conditions, the hydrogen evolution activity of example 2 was higher because of the higher phosphorus source and longer deposition time in the plating bath system of example 2. Under constant current deposition conditions, example 3 was highly catalytically active due to the greater deposition current density of example 3 and the greater loading of the final deposited sample.
The electrode obtained in example 3 was used for the stability test of electrocatalytic decomposition water under alkaline conditions. The analysis is carried out by adopting a standard three-electrode instant potential method, the obtained electrode is an electrolytic water hydrogen-separating cathode, and the electrolysis is carried outThe solution is 1M KOH solution, the effective exposure area of the electrode is 0.5cm multiplied by 0.5cm, and the effective exposure area is 1A cm -2 And (3) carrying out controllable current electrolysis under the condition of stable high current density, wherein the test temperature is 25 ℃. The stability test curves are shown in fig. 4: at high current densities, the water splitting voltage of example 3 without iR compensation was around-0.8V (vs. rhe) with no significant change in the potential profile over 250h of continuous catalytic water splitting.
Claims (10)
1. A preparation method of a phosphorus-doped hydrogen evolution catalytic electrode is characterized by comprising the following steps of: placing a conductive porous metal substrate with a clean surface into electroplating solution, and performing electrodeposition under the constant potential of a three-electrode system or constant current of a two-electrode system to obtain a phosphorus doped hydrogen evolution catalytic electrode;
the electroplating solution is an aqueous solution containing a nickel source, a copper source, a vanadium source, a phosphorus source, boric acid and ammonium chloride;
the nickel source is any one of nickel sulfate, nickel nitrate, nickel acetate and nickel chloride;
the copper source is any one of copper sulfate, copper nitrate and copper chloride;
the vanadium source is any one of vanadyl sulfate, ammonium metavanadate and sodium metavanadate;
the phosphorus source is any one or more of dipotassium hydrogen phosphate, metaphosphoric acid and sodium hypophosphite.
2. The method for preparing the phosphorus-doped hydrogen evolution catalytic electrode according to claim 1, wherein the method comprises the following steps: and sequentially placing the conductive porous metal substrate in dilute hydrochloric acid, deionized water, absolute ethyl alcohol and deionized water for ultrasonic treatment for 1-30 min, and then placing the conductive porous metal substrate in a vacuum drying oven for drying to obtain the conductive porous metal substrate with a clean surface.
3. The method for preparing a phosphorus-doped hydrogen evolution catalytic electrode according to claim 1 or 2, characterized in that: the conductive porous metal substrate is any one of foam nickel, foam copper, foam ferronickel, nickel net, copper net, nickel-copper alloy net and nickel-iron alloy net.
4. The method for preparing the phosphorus-doped hydrogen evolution catalytic electrode according to claim 1, wherein the method comprises the following steps: when the nickel source is nickel sulfate, the concentration of the nickel sulfate in the electroplating solution is 0.5-3 mol/L; when the nickel source is nickel acetate, the concentration of the nickel acetate in the electroplating solution is 0.1-1 mol/L; when the nickel source is nickel nitrate, the concentration of the nickel nitrate in the electroplating solution is 0.05-2.5 mol/L; when the nickel source is nickel chloride, the concentration of the nickel chloride in the electroplating solution is 0.16-1.3 mol/L.
5. The method for preparing the phosphorus-doped hydrogen evolution catalytic electrode according to claim 1, wherein the method comprises the following steps: when the copper source is copper sulfate, the concentration of the copper sulfate in the electroplating solution is 5-80 mmol/L; when the copper source is copper nitrate, the concentration of the copper nitrate in the electroplating solution is 10-90 mmol/L; when the copper source is copper chloride, the concentration of the copper chloride in the electroplating solution is 5-65 mmol/L.
6. The method for preparing the phosphorus-doped hydrogen evolution catalytic electrode according to claim 1, wherein the method comprises the following steps: when the vanadium source is ammonium metavanadate, the concentration of the ammonium metavanadate in the electroplating solution is 1-18 mmol/L; when the vanadium source is vanadyl sulfate, the concentration of vanadyl sulfate in the electroplating solution is 0.2-4 mmol/L; when the vanadium source is sodium metavanadate, the concentration of sodium metavanadate in the electroplating solution is 1.4-12 mmol/L.
7. The method for preparing the phosphorus-doped hydrogen evolution catalytic electrode according to claim 1, wherein the method comprises the following steps: when the phosphorus source is dipotassium hydrogen phosphate, the concentration of the dipotassium hydrogen phosphate in the electroplating solution is 0.1-5 mol/L; when the phosphorus source is metaphosphoric acid, the concentration of metaphosphoric acid in the electroplating solution is 0.5-2.5 mol/L; when the phosphorus source is sodium hypophosphite, the concentration of sodium hypophosphite in the electroplating solution is 0.2-4 mol/L.
8. The method for preparing the phosphorus-doped hydrogen evolution catalytic electrode according to claim 1, wherein the method comprises the following steps: the concentration of boric acid in the electrolyte is 0.05-2 mol/L, and the concentration of ammonium chloride is 0.1-1.2 mol/L.
9. The method for preparing the phosphorus-doped hydrogen evolution catalytic electrode according to claim 1, wherein the method comprises the following steps: the temperature of the three-electrode constant potential electro-deposition is 30-80 ℃, the counter electrode is graphite or nickel, the reference electrode is a saturated calomel electrode, the conductive porous metal substrate is a working electrode, the deposition potential is-0.1 to-2V vs. SCE, and the deposition time is 10-60 min.
10. The method for preparing the phosphorus-doped hydrogen evolution catalytic electrode according to claim 1, wherein the method comprises the following steps: the temperature of the constant current of the two electrodes for electrodeposition is 5-30 ℃, the counter electrode is graphite or nickel, the conductive porous metal substrate is a working electrode, and the deposition current density is 20-100 mA cm -2 The deposition time is 10-60 min.
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