CN117552041A - Preparation method and application of rhenium oxysulfide@nickel hydroxide/foam nickel hydrogen evolution catalytic material - Google Patents
Preparation method and application of rhenium oxysulfide@nickel hydroxide/foam nickel hydrogen evolution catalytic material Download PDFInfo
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- CN117552041A CN117552041A CN202311597633.0A CN202311597633A CN117552041A CN 117552041 A CN117552041 A CN 117552041A CN 202311597633 A CN202311597633 A CN 202311597633A CN 117552041 A CN117552041 A CN 117552041A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 116
- 239000006260 foam Substances 0.000 title claims abstract description 110
- 239000000463 material Substances 0.000 title claims abstract description 56
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 52
- 239000001257 hydrogen Substances 0.000 title claims abstract description 52
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- SNBOIOXFQPEEGS-UHFFFAOYSA-N S(=O)=[Re] Chemical compound S(=O)=[Re] SNBOIOXFQPEEGS-UHFFFAOYSA-N 0.000 title description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 41
- 238000004070 electrodeposition Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000009713 electroplating Methods 0.000 claims abstract description 22
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 5
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 230000005611 electricity Effects 0.000 abstract 1
- 239000002659 electrodeposit Substances 0.000 abstract 1
- USBWXQYIYZPMMN-UHFFFAOYSA-N rhenium;heptasulfide Chemical compound [S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[Re].[Re] USBWXQYIYZPMMN-UHFFFAOYSA-N 0.000 abstract 1
- 238000004506 ultrasonic cleaning Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 19
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229910052702 rhenium Inorganic materials 0.000 description 5
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009812 interlayer coupling reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- -1 sulfur ions Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Classifications
-
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
-
- 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 and application of a rhenium sulfide@nickel hydroxide/foam nickel hydrogen evolution catalytic material, and aims to solve the problems that noble metal materials except platinum are less in application in water and electricity catalytic decomposition and low in electrocatalytic hydrogen evolution performance. The preparation method comprises the following steps: 1. ultrasonic cleaning is carried out on the foam nickel substrate; 2. adding the cleaned foam nickel, ammonium perrhenate and thioacetamide into ammonia water, immersing the foam nickel serving as a working electrode into electroplating solution, performing first electrodeposition treatment at 40-50 ℃ by adopting a cyclic voltammetry, and performing second electrodeposition treatment after 10-14 hours in a constant-temperature water bath at 40-50 ℃. The invention adopts cyclic voltammetry to electrodeposit the structure on the foam nickelBuild Re 1‑x O x S 2 The nano block electrocatalyst for hydrogen evolution of nickel hydroxide/foam nickel can obviously change the electronic property of a space charge region, promote electron transfer, enhance hydrogen evolution reaction and show excellent catalytic performance in terms of HER.
Description
Technical Field
The invention belongs to the field of electrocatalytic materials, and in particular relates to Re 1-x O x S 2 Preparation method of nickel hydroxide/foam nickel hydrogen evolution catalytic material.
Background
In recent years, with the continuous development of industrialization and city, the demand of human beings for energy has been in a straight line trend, and accordingly, energy and environmental problems have been increasingly emphasized, and it is imperative to develop clean energy and reduce environmental pollution. Therefore, the search of a novel energy source which is green, safe and renewable also becomes a hot spot for competitive research of domestic and foreign scientific researchers, wherein the hydrogen energy source is used as a novel energy source with zero emission and no pollution, and the wide research and report of people are caused. Development of an electrocatalytic water splitting catalyst with abundant earth resources and high efficiency is a precondition for realizing a hydrogen energy society, and a water electrolysis process needs higher activation energy, so that a proper catalyst needs to be found for improving the efficiency.
Electrocatalytically decomposing water includes both Hydrogen Evolution (HER) and Oxygen Evolution (OER) half reactions, HER and OER requiring the use of an electrocatalyst to reduce the overpotential required for the electrochemical reaction. The higher the overpotential, the higher the voltage that should be applied, and the more energy that is consumed. Therefore, it is important to develop a high-efficiency hydrogen evolution catalyst capable of significantly reducing hydrogen evolution overpotential. Currently, noble metal platinum (Pt) and its alloys are widely used as the most effective cathode catalytic material for electrolysis of water. However, the research on Pt-based catalysts has been relatively mature, and the application development and research on other noble metal materials in the catalytic decomposition of water is still very small. Therefore, other types of noble metal-based water electrolytic materials have been receiving attention from researchers in recent years.
Rhenium (Re) has received considerable attention for its excellent plastic, mechanical properties, creep resistance, good wear and corrosion resistance. Rhenium-based catalysts are stable, non-toxic and reasonably priced materials with great potential in the fields of catalysis, sensing, electrochemistry and environmental correlation. ReS (ReS) 2 As TMDs materialOne of the materials, not only has optimal binding energy for adsorption and desorption of protons, but also has distorted 1T structure and low lattice structure symmetry, and is receiving a great deal of attention due to its unusual anisotropic electrical and optical properties, interlayer coupling and non-layer dependence. There are many methods for preparing rhenium-based catalysts, and the electrodeposition method is an efficient and time-saving preparation method, and has a broad prospect in the aspect of preparing the catalysts on a large scale. In addition, the electrodeposition method can tightly bond the catalyst and the substrate to reduce the resistance between the catalyst and the substrate. Wherein, in-situ electrodeposition on the foam nickel not only avoids the use of a binder, but also improves the conductivity and the electron transfer rate of the catalyst. The result shows that the rhenium-based catalyst prepared by the electrodeposition method is a high-efficiency stable catalyst and has great practical application potential.
Disclosure of Invention
The invention aims to solve the problems that noble metal materials except platinum have less application in the water electrolysis catalytic decomposition and the electrocatalytic hydrogen evolution performance is lower, and provides a Re 1-x O x S 2 Preparation method and application of nickel hydroxide/foam nickel hydrogen evolution catalytic material.
Re of the present invention 1-x O x S 2 The preparation method of the @ nickel hydroxide/foam nickel hydrogen evolution catalytic material is realized according to the following steps:
sequentially using hydrochloric acid, absolute ethyl alcohol and deionized water to ultrasonically clean a foam nickel substrate, and drying to obtain two clean foam nickel sheets;
step two, adding the cleaned foam nickel, ammonium perrhenate and thioacetamide into ammonia water, stirring uniformly to obtain electroplating solution and pretreated foam nickel, immersing the foam nickel serving as a working electrode into the electroplating solution, performing first electrodeposition treatment at 40-50 ℃ by adopting cyclic voltammetry, after the electrodeposition is finished, placing the foam nickel into the electroplating solution for 10-14 hours in a constant-temperature water bath at 40-50 ℃, replacing a second cleaned foam nickel, performing second electrodeposition treatment, wherein the technological conditions of the first electrodeposition treatment and the second electrodeposition treatment are the same, and finally washing and drying to obtain the productRe 1-x O x S 2 Nickel hydroxide/foam nickel hydrogen evolution catalytic material;
wherein the concentration of ammonium perrhenate in the electroplating solution in the second step is 0.02-0.03 mol/L, and the concentration of thioacetamide is 0.1-0.2 mol/L.
In the second step of the invention, the secondary electrodeposition treatment is adopted, the foam nickel is placed in ammonia water to be dissolved to a certain extent, so that the electroplating solution contains free nickel ions, the pH value of the solution is reduced while no chemical reagent is additionally added, and proper ions (Ni 2+ ，OH - ) Concentration. Thereby being capable of providing more Ni (OH) in the second electrodeposition process 2 A substrate.
Re of the present invention 1-x O x S 2 The application of the catalyst material for hydrogen evolution of nickel hydroxide/foam nickel is to apply the Re 1-x O x S 2 The nickel hydroxide/foam nickel hydrogen evolution catalytic material is applied to Hydrogen Evolution Reaction (HER) as an electrolytic water catalytic reaction electrode.
The invention successfully constructs Re through electrodeposition on foam nickel 1-x O x S 2 Nickel hydroxide/Nickel Foam (NF) nano-block electrocatalysts can significantly change the electronic properties of the space charge region, promoting electron transfer. According to the invention, thioacetamide (TAA) is adopted to assist electrodeposition, the hydrolysis process induced by the TAA is crucial for adjusting the composition of the surface of the electrode material, and the Thioacetamide (TAA) is taken as a sulfur source, so that the pH value of the solution can be adjusted, thereby adjusting the reaction kinetics of metal ions and sulfur ions, and further adjusting the crystalline phase of metal sulfide. The material is used for enhancing hydrogen evolution reaction through interfacial charge transfer and redistribution of the nano-array electrocatalyst, and a HER catalyst with ion and electron transmission paths, high exposed active sites and high reaction activity is constructed. The preparation method comprises the steps of electrodepositing a rhenium-based catalyst on foam nickel by a cyclic voltammetry technology, and then washing, drying and standby.
Compared with the prior art, the Re of the invention 1-x O x S 2 The preparation method and application of the nickel hydroxide/foam nickel hydrogen evolution catalytic material have the following beneficial effects:
(1) Re prepared by the invention 1-x O x S 2 The nickel hydroxide/foam nickel hydrogen evolution catalytic material is applied to the technical field of electrocatalytic materials, and is expected to improve energy and environmental problems.
(2) The electrocatalytic active material prepared by the invention fully exposes active sites, has good catalytic performance and has good application prospect in the technical field of electrocatalytic materials.
(3) The electrocatalytic active material prepared by the invention has the advantages that the close-packed nano block structure is beneficial to increasing the specific surface area, increasing the active site, promoting the electron transfer, improving the electron transmission rate and promoting the wide application of transition metal compounds in other fields.
(4) The foam nickel is used as the electrode substrate, the material directly grows on the foam nickel, the complex step of pasting by using conductive adhesive is omitted, the foam nickel is not easy to fall off, and the conductive efficiency is improved.
Drawings
FIG. 1 is an SEM image of various multiples of the original nickel foam in the examples, (a) a low magnification SEM image, and (b) a high magnification SEM image;
FIG. 2 is Re obtained in the examples 1-x O x S 2 SEM images of nickel hydroxide/foam nickel hydrogen evolution catalytic material at different multiples, (a) low-magnification SEM image, (b) high-magnification SEM image;
FIG. 3 is Re in the examples 1-x O x S 2 Raman spectrum diagram of nickel hydroxide/foam nickel hydrogen evolution catalytic material;
FIG. 4 is Re in the examples 1-x O x S 2 XRD spectrum of nickel hydroxide/foam nickel hydrogen evolution catalytic material;
FIG. 5 is the original foam nickel and Re in the examples 1-x O x S 2 Material object diagram of nickel hydroxide/foam nickel hydrogen evolution catalytic material, (a) is original foam nickel, and (b) is Re 1-x O x S 2 Nickel hydroxide/foam nickel hydrogen evolution catalytic material;
FIG. 6 is Re in the examples 1-x O x S 2 The catalyst material for hydrogen evolution of nickel hydroxide/foam nickel is 10mA/cm 2 Linear sweep voltammogram at current density;
FIG. 7 is raw foam nickel and Re 1-x O x S 2 Tafel slope plot of @ nickel hydroxide/nickel foam, wherein 1 represents Re 1- x O x S 2 Nickel hydroxide/foam nickel hydrogen evolution catalytic material, 2 represents foam nickel;
FIG. 8 is Re in the examples 1-x O x S 2 Stability test chart for nickel hydroxide/foam nickel hydrogen evolution catalytic material.
Detailed Description
The first embodiment is as follows: this embodiment of the invention Re 1-x O x S 2 The preparation method of the nickel hydroxide/foam nickel hydrogen evolution catalytic material is implemented according to the following steps:
sequentially using hydrochloric acid, absolute ethyl alcohol and deionized water to ultrasonically clean a foam nickel substrate, and drying to obtain two clean foam nickel sheets;
step two, adding the cleaned foam nickel, ammonium perrhenate and thioacetamide into ammonia water, stirring uniformly to obtain electroplating solution and pretreated foam nickel, immersing the foam nickel serving as a working electrode into the electroplating solution, performing first electrodeposition treatment at 40-50 ℃ by adopting cyclic voltammetry, after the electrodeposition is finished, placing the foam nickel into the electroplating solution for 10-14 hours in a constant-temperature water bath at 40-50 ℃, replacing a second cleaned foam nickel, performing second electrodeposition treatment, wherein the technological conditions of the first electrodeposition treatment and the second electrodeposition treatment are the same, and finally washing and drying to obtain Re 1-x O x S 2 Nickel hydroxide/foam nickel hydrogen evolution catalytic material;
wherein the concentration of ammonium perrhenate in the electroplating solution in the second step is 0.02-0.03 mol/L, and the concentration of thioacetamide is 0.1-0.2 mol/L.
In the embodiment, the secondary electrodeposition is adopted, the pH value in the electroplating solution is reduced through the primary electrodeposition, the ions in the solution reach more proper concentration, and the secondary foam nickel is used for continuous electrodeposition on the basis, so that the best catalytic effect is obtained.
The embodiment prepares Re 1-x O x S 2 The nickel hydroxide/foam nickel hydrogen evolution catalytic material has excellent catalytic performance in terms of HER, excellent electrochemical performance and wide application prospect in the technical field of water electrolysis hydrogen production catalyst materials.
The second embodiment is as follows: the difference between the embodiment and the specific embodiment is that hydrochloric acid, absolute ethyl alcohol and deionized water are used for respectively ultrasonically cleaning the foam nickel substrate for 10min in the first step.
In this embodiment, the concentration of hydrochloric acid is 3mol/L.
And a third specific embodiment: this embodiment differs from the first or second embodiments in that the drying temperature in the first step is 60 ℃.
The specific embodiment IV is as follows: the difference between this embodiment and the first to third embodiments is that the concentration of ammonium perrhenate in the plating solution in the second step is 0.025mol/L and the concentration of thioacetamide is 0.15mol/L.
Fifth embodiment: the difference between the present embodiment and the first to fourth embodiments is that the mass concentration of the ammonia water in the second step is 25% -28%.
The ammonia water of the embodiment adjusts the pH value of the plating solution and promotes Ni (OH) 2 Is a growth of (a).
Specific embodiment six: the difference between the embodiment and the specific embodiment is that in the second step, the cleaned foam nickel, ammonium perrhenate and thioacetamide are sequentially dissolved in ammonia water, and the solution is respectively stirred magnetically for 10min,6min and 10min at room temperature until the solution is uniformly mixed.
Seventh embodiment: the difference between the embodiment and the first to sixth embodiments is that the cyclic voltammetry is adopted in the second step, ag/AgCl is used as a reference electrode, pt sheets are used as a counter electrode, and pretreated foam nickel is used as a working electrode.
Eighth embodiment: the difference between the embodiment and the first to seventh embodiments is that in the second step, cyclic voltammetry is adopted, the scanning potential window of electrodeposition is selected from-1.4V to-0.2V, the scanning speed is 10mV/s, and the electroplating solution is continuously circulated for 20 to 40 times for electrodeposition treatment.
Detailed description nine: the embodiment is different from one of the first to eighth embodiments in that the second step is performed by using a constant temperature water bath at 45 ℃ for 10 to 12 hours.
Detailed description ten: the difference between the present embodiment and one of the first to ninth embodiments is that the washing in the second step is to wash 3 to 5 times with deionized water, and the drying is to dry in a drying oven at 60 ℃.
Examples: this example Re 1-x O x S 2 The preparation method of the nickel hydroxide/foam nickel hydrogen evolution catalytic material is implemented according to the following steps:
step one, taking two tablets with the size of 1 x 2cm 2 Sequentially using 3mol/L hydrochloric acid, absolute ethyl alcohol and deionized water to ultrasonically clean the foam nickel substrate for 10min respectively, and drying at 60 ℃ for 6h to obtain two cleaned foam nickel sheets;
firstly, putting the cleaned foam nickel into 30ml of ammonia water (the mass concentration of the ammonia water is 25% -28%), stirring for 10min at room temperature, sequentially adding ammonium perrhenate and thioacetamide, magnetically stirring for 6min and 10min at room temperature until the solution is uniformly mixed to obtain electroplating solution and pretreated foam nickel, wherein one piece of foam nickel is used as a working electrode to be immersed into the electroplating solution, the other piece of foam nickel is repeatedly washed for 3 times by deionized water, and drying for 6h at 60 ℃ to obtain the pretreated foam nickel; selecting Ag/AgCl as a reference electrode, pt sheets as a counter electrode, foamed nickel as a working electrode, performing first electrodeposition treatment at 45 ℃ by adopting cyclic voltammetry, selecting-1.4V to-0.2V for an electrodeposited scanning potential window, performing continuous cyclic voltammetry on electroplating solution for 30 times at a scanning rate of 10mV/s, performing constant-temperature water bath at 45 ℃ for 11 hours after the electrodeposition, replacing a second foamed nickel sheet for second electrodeposition treatment, performing second electrodeposition treatment under the same technological conditions, repeatedly flushing with deionized water for 3 times, and drying at 60 ℃ for 6 hours to obtain Re 1-x O x S 2 Nickel hydroxide/foam nickel hydrogen evolution catalytic material (second electrodeposited product);
wherein the concentration of ammonium perrhenate in the electroplating solution in the second step is 0.025mol/L, and the concentration of thioacetamide is 0.15mol/L.
The SEM image of the pretreated nickel foam in this example is shown in fig. 1, and the nickel foam without supported catalyst has a smooth surface. FIG. 2 is Re 1-x O x S 2 SEM images of nickel hydroxide/nickel foam catalytic material grown on the nickel foam surface, it can be clearly seen that three-dimensional lumps are generated on the nickel foam surface and are closely aligned, in sharp contrast to the smooth surface of the original nickel foam. The three-dimensional block structure formed on the surface is favorable for the full contact of the electrolyte and the catalyst, and is favorable for the discharge of bubbles during the hydrogen evolution reaction, so that the hydrogen evolution reaction is promoted. FIG. 3 is Re 1-x O x S 2 Raman spectrum chart of nickel hydroxide/foam nickel catalytic material, and Raman spectrum is 160cm -1 、304cm -1 And 434cm -1 There are three characteristic peaks, the peak positions of which are similar to those of ReS 2 The vibration peaks correspond. The spectrogram is displayed at 342cm -1 Has a characteristic peak corresponding to Re 2 O 7 Vibration peaks. Finally at 460cm -1 Characteristic peak at the location and Ni (OH) 2 The characteristic peaks correspond. FIG. 4 is Re 1-x O x S 2 XRD patterns of nickel hydroxide/foam nickel catalytic materials, peaks of elemental Ni can be seen according to comparison with standard PDF cards. FIG. 5 is a pictorial representation of the original nickel foam and the electrodeposited catalytic material, showing that the prepared material grows more uniformly, and the nickel foam without the supported catalyst has a smooth surface and is silvery white; re grown on the surface of foam nickel by electrodeposition 1-x O x S 2 Nickel hydroxide/foam nickel, the foam nickel surface was covered with a layer of black material, demonstrating Re 1-x O x S 2 Nickel hydroxide/nickel foam was successfully supported on a nickel foam substrate. FIG. 6 is a raw foam nickel and Re 1-x O x S 2 The current density of the @ nickel hydroxide/foam nickel catalytic material is 10mA/cm 2 Linear sweep voltammogram at 10mA/cm with IR correction 2 The time overpotential is 82mV, which shows the electrocatalytic performance of the electrode material is far better than the original oneCatalytic performance of the initial foam nickel. At the same time, original foam nickel and Re 1-x O x S 2 The tafel slopes of the @ nickel hydroxide/nickel foam electrode material correspond to 158.5mV/dec and 85.9mV/dec, respectively (as shown in fig. 7), and the tafel slope of the electrode material is much less than that of the original nickel foam material, indicating Re 1-x O x S 2 Nickel hydroxide/nickel foam has a faster electron transfer rate. FIG. 8 is Re 1-x O x S 2 Stability pattern of nickel hydroxide/foam nickel catalytic material, it can be seen that over potential only shows slight loss in stability test up to 72h, proving the Re 1-x O x S 2 The nickel hydroxide/foam nickel hydrogen evolution catalytic material has good stability.
Claims (10)
1.Re 1-x O x S 2 The preparation method of the hydrogen evolution catalytic material of nickel hydroxide/foam nickel is characterized by comprising the following steps:
sequentially using hydrochloric acid, absolute ethyl alcohol and deionized water to ultrasonically clean a foam nickel substrate, and drying to obtain two clean foam nickel sheets;
step two, adding the cleaned foam nickel, ammonium perrhenate and thioacetamide into ammonia water, stirring uniformly to obtain electroplating solution and pretreated foam nickel, immersing the foam nickel serving as a working electrode into the electroplating solution, performing first electrodeposition treatment at 40-50 ℃ by adopting cyclic voltammetry, after the electrodeposition is finished, placing the foam nickel into the electroplating solution for 10-14 hours in a constant-temperature water bath at 40-50 ℃, replacing a second cleaned foam nickel, performing second electrodeposition treatment, wherein the technological conditions of the first electrodeposition treatment and the second electrodeposition treatment are the same, and finally washing and drying to obtain Re 1-x O x S 2 Nickel hydroxide/foam nickel hydrogen evolution catalytic material;
wherein the concentration of ammonium perrhenate in the electroplating solution in the second step is 0.02-0.03 mol/L, and the concentration of thioacetamide is 0.1-0.2 mol/L.
2. According to claimRe as described in 1 1-x O x S 2 The preparation method of the nickel hydroxide/foam nickel hydrogen evolution catalytic material is characterized in that hydrochloric acid, absolute ethyl alcohol and deionized water are used for respectively ultrasonically cleaning a foam nickel substrate for 10min in the first step.
3. Re according to claim 1 1-x O x S 2 The preparation method of the nickel hydroxide/foam nickel hydrogen evolution catalytic material is characterized in that the drying temperature in the first step is 60 ℃.
4. Re according to claim 1 1-x O x S 2 The preparation method of the nickel hydroxide/foam nickel hydrogen evolution catalytic material is characterized in that the concentration of ammonium perrhenate in the electroplating solution in the second step is 0.025mol/L, and the concentration of thioacetamide is 0.15mol/L.
5. Re according to claim 1 1-x O x S 2 The preparation method of the nickel hydroxide/foam nickel hydrogen evolution catalytic material is characterized in that the mass concentration of ammonia water in the second step is 25% -28%.
6. Re according to claim 1 1-x O x S 2 The preparation method of the nickel hydroxide/foamed nickel hydrogen evolution catalytic material is characterized in that in the second step, the cleaned foamed nickel, ammonium perrhenate and thioacetamide are sequentially dissolved in ammonia water, and are respectively magnetically stirred for 10min,6min and 10min at room temperature until the solutions are uniformly mixed.
7. Re according to claim 1 1-x O x S 2 The preparation method of the nickel hydroxide/foam nickel hydrogen evolution catalytic material is characterized in that in the second step, cyclic voltammetry is adopted, ag/AgCl is used as a reference electrode, pt sheets are used as a counter electrode, and pretreated foam nickel is used as a working electrode.
8. Re according to claim 1 1-x O x S 2 Nickel hydroxideThe preparation method of the foam nickel hydrogen evolution catalytic material is characterized in that in the second step, a cyclic voltammetry is adopted, a scanning potential window of electrodeposition is selected from minus 1.4V to minus 0.2V, the scanning speed is 10mV/s, and electroplating solution is continuously circulated for 20-40 times for electrodeposition treatment.
9. Re according to claim 1 1-x O x S 2 The preparation process of hydrogen evolution catalytic nickel hydroxide/foamed nickel material features that in the second step, water bath at 45 deg.c is performed for 10-12 hr.
10. Re prepared according to claim 1 1-x O x S 2 Application of nickel hydroxide/foam nickel hydrogen evolution catalytic material is characterized in that Re is prepared by 1-x O x S 2 The nickel hydroxide/foam nickel hydrogen evolution catalytic material is used as an electrolytic water catalytic reaction electrode to be applied to hydrogen evolution reaction.
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