Metal nickel / crystalline metal oxide hydrogen evolution catalyst, preparation method and application
By growing crystalline metal oxides on the surface of a nickel mesh to form a nickel/crystalline metal oxide catalyst, the problems of catalytic activity and stability were solved, and a highly efficient hydrogen production effect from water electrolysis was achieved.
Patent Information
- Application Number
- CN202410659114.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-05-24
- Publication Date
- 2026-01-23
AI Technical Summary
Existing catalysts exhibit poor catalytic activity and low stability during water electrolysis for hydrogen production. In particular, nickel catalysts have few active interfaces, and amorphous metal oxide catalysts are easily dissolved in the electrolyte, resulting in poor long-term stability.
By roughening the surface of the nickel mesh, spraying nickel-aluminum alloy and using alkaline etching, combined with hydrothermal synthesis and heat treatment, crystalline metal oxides are grown on the surface of metallic nickel to form a metallic nickel/crystalline metal oxide catalyst, which enhances the reaction interface and stability.
This improved the hydrogen evolution activity and long-term stability of the catalyst, reduced mass transfer resistance, and achieved a highly efficient electrocatalytic hydrogen evolution effect.
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Figure CN121372431A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of catalysts, in particular to a metal nickel / crystalline metal oxide hydrogen evolution catalyst, a preparation method and an application. BACKGROUND
[0002] The depletion of fossil fuels and the deterioration of environmental problems make the development and application of renewable energy extremely urgent. Hydrogen energy has become the ideal energy for human beings in the future because of its high energy density, wide sources and non-polluting combustion products.
[0003] Water electrolysis hydrogen production, as the reverse reaction of hydrogen combustion, uses water as the only raw material, realizes close hydrogen circulation and zero carbon emission, and is considered as a green and sustainable hydrogen production method. A major challenge faced by the large-scale application of water electrolysis hydrogen production is the lack of high-activity, low-cost and high-stability catalysts. Although noble metals are considered as the most effective catalysts for improving the hydrogen evolution reaction due to their unique catalytic performance, the high cost and limited supply of noble metal-based catalysts constitute a major obstacle to their widespread application in commerce. Therefore, there is an urgent need to develop low-cost non-noble metal-based water electrolysis hydrogen evolution reaction catalysts.
[0004] At present, in the industrialized alkaline water electrolysis hydrogen production technology, the commonly used catalysts are metal nickel catalysts and amorphous metal oxide catalysts. The metal nickel catalyst has low activity due to its small active interface and active site, which ultimately affects the application of the metal nickel catalyst. The amorphous metal oxide catalyst has good electrocatalytic activity, and the amorphous metal oxide catalyst is considered as the most promising catalyst due to its composition diversity, environmental friendliness and controllable structure. However, the crystal lattice of the amorphous metal oxide catalyst has uncertainty, which leads to its easy dissolution in the electrolyte, thereby making the long-term stability of the amorphous metal oxide catalyst poor.
[0005] Therefore, there is an urgent need to provide a new catalyst to solve the above problems. SUMMARY
[0006] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, the present application provides a metal nickel / crystalline metal oxide hydrogen evolution catalyst, a preparation method and an application, which can solve the problems of poor catalytic activity and low stability of the existing catalysts.
[0007] In a first aspect, the present application provides a preparation method of a metal nickel / crystalline metal oxide hydrogen evolution catalyst, which comprises:
[0008] Roughening the surface of the nickel mesh to obtain a first intermediate product;
[0009] Spraying the nickel-aluminum alloy on the surface of the first intermediate product, and obtaining a nickel mesh containing metal nickel on the surface by alkali etching.
[0010] dissolving a precursor salt of metal oxide in a solvent as a precursor solution, placing the nickel mesh with metal nickel on the surface in the precursor solution, growing the metal oxide on the surface of the metal nickel by a hydrothermal synthesis method, and obtaining a second intermediate product after washing and drying;
[0011] heat-treating the second intermediate product in an atmosphere of inert gas, and obtaining the metal nickel / crystalline metal oxide hydrogen evolution catalyst after washing and drying.
[0012] Further, the roughening treatment of the surface of the nickel mesh to obtain the first intermediate product comprises:
[0013] roughening the surface of the nickel mesh by first acid washing and then alkali washing to obtain the first intermediate product.
[0014] Further, the nickel-aluminum alloy comprises Raney nickel.
[0015] Further, the metal oxide comprises at least one of chromium oxide, tin oxide, indium oxide, tungsten oxide, vanadium oxide, magnesium oxide, lanthanide oxide, manganese oxide, scandium oxide, yttrium oxide, and the lanthanide oxide comprises at least one of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, promethium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, and lutetium oxide.
[0016] Preferably, the solvent is N,N-dimethylformamide (DMF) or a mixture of N,N-dimethylformamide (DMF) and water.
[0017] Further, the concentration of the precursor solution is 0.1-0.8 mol / L.
[0018] Further, the reaction temperature of the hydrothermal synthesis is 100-150°C.
[0019] Further, the temperature of the heat treatment is 300-500°C.
[0020] Further, the temperature of the drying is 60-80°C.
[0021] In a second aspect, the present application further provides a metal nickel / crystalline metal oxide hydrogen evolution catalyst, which is prepared according to the above-mentioned method for preparing a metal nickel / crystalline metal oxide hydrogen evolution catalyst.
[0022] In a third aspect, the present application further provides an application of a metal nickel / crystalline metal oxide hydrogen evolution catalyst, and the metal nickel / crystalline metal oxide hydrogen evolution catalyst is used for water electrolysis hydrogen evolution reaction.
[0023] Preferably, the metal nickel / crystalline metal oxide hydrogen evolution catalyst is used for electrocatalytic hydrogen evolution reaction in an alkaline electrolyte.
[0024] The one or more embodiments of the present application have at least one or more of the following beneficial effects:
[0025] The present application provides a metal nickel / crystalline metal oxide hydrogen evolution catalyst, a preparation method and an application. The metal nickel / crystalline metal oxide hydrogen evolution catalyst with different reaction interfaces is prepared based on the growth of crystalline metal oxide on the surface of metal nickel, and has excellent hydrogen evolution catalytic activity and long-term stability, and can achieve excellent hydrogen production effect in the process of electrocatalytic hydrogen evolution. Specifically, the crystalline metal oxide used in the present application has high crystallinity, and the crystal lattice is stable during the reaction, which can reduce lattice reconstruction, particle agglomeration and element dissolution, and is not easy to be reduced. At the same time, the crystalline metal oxide and the metal can fully form an interface, thereby reducing the mass transfer resistance in the catalytic process, and thus facilitating the efficient and long-term stable operation of the catalyst.
[0026] Further, the preparation method of the metal nickel / crystalline metal oxide hydrogen evolution catalyst provided by the present application is simple and easy to realize large-scale production. The metal nickel / crystalline metal oxide hydrogen evolution catalyst prepared by the method provided by the present application has potential application value in the field of water electrolysis hydrogen production, and is expected to become an important breakthrough in water electrolysis hydrogen production technology, and promote the development of clean energy field.
[0027] Additional aspects and advantages of the present application will be in part apparent and in part pointed out hereinafter. BRIEF DESCRIPTION OF DRAWINGS
[0028] The disclosure of the present application will become more readily apparent from the following description of the present application. As will be readily appreciated by one skilled in the art, the present application is susceptible to capricious embodiments and, therefore, the following description of the present application is not meant to limit the scope of the present application. Furthermore, like reference numerals are intended to denote like parts throughout the figures, in which:
[0029] Figure 1 is a flow chart of the preparation method of the metal nickel / crystalline metal oxide hydrogen evolution catalyst provided by the present application;
[0030] Figure 2 is a LSV test curve graph of the metal nickel / crystalline metal oxide hydrogen evolution catalyst prepared by the present application in a 6 mol / L KOH solution;
[0031] Figure 3Stability results of the metal nickel / crystalline metal oxide hydrogen evolution catalyst prepared in Embodiment 1-5 of the present application at a current density of 200 mA / cm2. DETAILED DESCRIPTION
[0032] Some embodiments of the present application will be described below with reference to the accompanying drawings. Those skilled in the art will understand that these embodiments are only used to explain the technical principles of the present application and are not intended to limit the protection scope of the present application.
[0033] As shown in the background, in the industrialized alkaline electrolysis water hydrogen production technology, the commonly used catalysts are metal nickel catalyst and amorphous metal oxide catalyst. The metal nickel catalyst has low activity due to its small active interface and active site, which ultimately affects the application of the metal nickel catalyst. Although the amorphous metal oxide catalyst has good electrocatalytic activity, the crystal lattice of the amorphous metal oxide catalyst has uncertainty, which leads to its easy dissolution in the electrolyte, thereby making its catalytic long-term stability poor.
[0034] To this end, the present application creatively proposes a metal nickel / crystalline metal oxide hydrogen evolution catalyst, a preparation method and an application, which is based on the growth of crystalline metal oxide on the surface of metal nickel, thereby preparing a metal nickel / crystalline metal oxide hydrogen evolution catalyst with different reaction interfaces, which has excellent hydrogen evolution catalytic activity and long-term stability, and can achieve excellent hydrogen production effect in the process of electrocatalytic hydrogen evolution.
[0035] The following is an optional technical solution of the present application, but not as a limitation of the technical solutions provided by the present application. Through the following optional technical solution, the technical purpose and beneficial effects of the present application can be better achieved and realized.
[0036] In a first aspect, the present application provides a preparation method of a metal nickel / crystalline metal oxide hydrogen evolution catalyst, as shown in Figure 1 The preparation method comprises:
[0037] S1: roughening the surface of a nickel mesh to obtain a first intermediate product.
[0038] Specifically, roughening the surface of the nickel mesh to obtain the first intermediate product comprises: roughening the surface of the nickel mesh by first acid washing and then alkali washing to obtain the first intermediate product.
[0039] In a specific embodiment, the surface of the nickel mesh is roughened by first acid washing with a 0.1 mol / L sulfuric acid solution and then alkali washing with a 1 mol / L KOH solution to obtain the first intermediate product.
[0040] S2: Spraying nickel-aluminum alloy on the surface of the first intermediate product, and etching the surface with alkali to obtain a nickel mesh containing metallic nickel on the surface.
[0041] The nickel-aluminum alloy includes Raney nickel, which has very high catalytic activity and can improve the reaction efficiency. In addition, Raney nickel also has very high stability and can maintain its activity during long-term use.
[0042] In a specific embodiment, the surface of the first intermediate product can be etched with a KOH solution to obtain a nickel mesh containing metallic nickel on the surface.
[0043] S3: Dissolving a precursor salt for forming a metal oxide in a solvent to obtain a precursor solution, placing the nickel mesh containing metallic nickel on the surface in the precursor solution, growing the metal oxide on the surface of the metallic nickel by hydrothermal synthesis, and obtaining a second intermediate product after washing and drying.
[0044] The metal oxide includes at least one of chromium oxide, tin oxide, indium oxide, tungsten oxide, vanadium oxide, magnesium oxide, lanthanide oxide, manganese oxide, scandium oxide, yttrium oxide, and the lanthanide oxide includes at least one of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, promethium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, and lutetium oxide.
[0045] In the present application, N,N-dimethylformamide (DMF) or a mixture of N,N-dimethylformamide (DMF) and water is used as a solvent to dissolve the precursor salt for forming a metal oxide. The concentration of the precursor solution is 0.1-0.8 mol / L, and more specifically, the concentration of the precursor solution can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 mol / L, and specific point values between the above point values. Due to the limited space and for the sake of simplicity, the present application will not list the specific point values included in the range.
[0046] The reaction temperature of the hydrothermal synthesis is 100-150°C, and more specifically, the reaction temperature of the hydrothermal synthesis can be 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, and specific point values between the above point values. Due to the limited space and for the sake of simplicity, the present application will not list the specific point values included in the range.
[0047] In a specific embodiment, the metal oxide is grown on the surface of the metallic nickel by hydrothermal synthesis, the impurities on the surface are removed by washing with deionized water and anhydrous ethanol, and then the second intermediate product is obtained by drying at 60-80°C.
[0048] S4: heat-treating the second intermediate product under an atmosphere of inert gas, and then obtaining the metal nickel / crystalline metal oxide hydrogen evolution catalyst after washing and drying.
[0049] In the present application, the crystalline metal oxide adopted has high crystallinity, and the crystal lattice is stable during the reaction, which can reduce lattice reconstruction, particle agglomeration, element dissolution, and is not easy to be reduced. At the same time, the crystalline metal oxide can fully form an interface with the metal, thereby reducing the mass transfer resistance in the catalytic process, and thus being conducive to the efficient and long-time stable operation of the catalyst.
[0050] In the present application, the inert gas includes argon, helium, nitrogen, and preferably argon.
[0051] In a specific embodiment, the temperature of the heat treatment is 300-500°C, and more specifically, the temperature of the heat treatment can be 300°C, 350°C, 400°C, 450°C, 500°C, and specific point values between the above-mentioned point values. Due to the limitation of the length and the consideration of simplicity, the present application does not list the specific point values included in the range.
[0052] In another specific embodiment, after the heat treatment of the second intermediate product under the atmosphere of inert gas, the impurities on the surface of the second intermediate product are removed by washing with deionized water and anhydrous ethanol, and then the second intermediate product is dried under vacuum to obtain the metal nickel / crystalline metal oxide hydrogen evolution catalyst. The temperature of the drying is 60-80°C.
[0053] It should be noted that the metal nickel / crystalline metal oxide hydrogen evolution catalyst mentioned in the present application is the metal nickel and the crystalline metal oxide attached to the surface of the nickel mesh. The nickel mesh and the metal nickel / crystalline metal oxide hydrogen evolution catalyst attached to the surface of the nickel mesh are a metal nickel / crystalline metal oxide composite electrode. The "metal nickel / crystalline metal oxide" means "metal nickel and crystalline metal oxide", and more specifically, the "metal nickel / crystalline metal oxide" means that the metal nickel is attached with the crystalline metal oxide on the surface.
[0054] The preparation method of the metal nickel / crystalline metal oxide hydrogen evolution catalyst provided by the present application is simple and easy to realize large-scale production. The metal nickel / crystalline metal oxide hydrogen evolution catalyst prepared by the method provided by the present application has potential application value in the field of water electrolysis hydrogen production, and is expected to become an important breakthrough in water electrolysis hydrogen production technology, and promote the development of clean energy field.
[0055] In a second aspect, the present application also provides a metal nickel / crystalline metal oxide hydrogen evolution catalyst, which is prepared according to the above-mentioned preparation method of the metal nickel / crystalline metal oxide hydrogen evolution catalyst.
[0056] The application discloses a metal nickel / crystalline metal oxide hydrogen evolution catalyst with different reaction interfaces, which is prepared by growing crystalline metal oxides on the surface of metal nickel, and has excellent hydrogen evolution catalytic activity and long-time stability, and can achieve excellent hydrogen production effect in the process of electrocatalytic hydrogen evolution.
[0057] In a third aspect, the application also provides the application of the metal nickel / crystalline metal oxide hydrogen evolution catalyst, which is used for water electrolysis hydrogen evolution reaction. Preferably, the metal nickel / crystalline metal oxide hydrogen evolution catalyst is used for electrocatalytic hydrogen evolution reaction in an alkaline electrolyte.
[0058] The embodiments of the application will be described in more detail below by way of examples. However, the embodiments of the application are not limited only to these examples.
[0059] The examples described below are illustrative only and are not intended to limit the application. Unless otherwise indicated, the techniques or conditions described in the examples are not limiting of the application. The examples do not indicate the specific technical or conditions, which are described in the literature in the art or according to the product manual. The reagents or instruments used are not indicated by the manufacturer, which are all conventional products that can be obtained commercially.
[0060] In the application, the specific reaction device and external setting are not particularly limited. For example, the common solution reaction device includes but is not limited to a beaker, a flask or other containers; the heating device can adopt a heating furnace, and the common heating furnace includes but is not limited to an electric resistance heating furnace, a microwave heating furnace, an induction heating furnace, a radiation heating furnace and the like; the corresponding raw material holding device or container or reaction site is not particularly limited, and the common raw material holding device includes but is not limited to a crucible, a glass, a quartz and the like; the external device for providing a reaction atmosphere can adopt an existing self-made or commercial device, which is not limited herein.
[0061] Example 1
[0062] The nickel mesh is first subjected to acid washing by a 0.1 mol / L sulfuric acid solution, and then subjected to alkali washing by a 1 mol / L KOH solution, so that the surface is roughened to obtain a first intermediate product;
[0063] The Raney nickel is sprayed on the surface of the first intermediate product by means of plasma spraying, and the surface containing metal nickel is obtained by adopting 3 mol / L KOH solution for alkali etching.
[0064] 0.06 mol of chromium nitrate is dissolved in 0.1 L of DMF as a precursor solution, the precursor solution is placed in a hydrothermal reaction kettle, and the nickel mesh containing metal nickel on the surface is cut into 1*2 cm 2The nickel mesh with the surface containing the metal nickel is cut into 1*2 cm2specimen, and the cut nickel mesh with the surface containing the metal nickel is placed in the precursor solution, a temperature is set to 120°C, and chromium hydroxide is grown on the surface of the metal nickel by a hydrothermal synthesis. After the reaction ends, the second intermediate product is obtained by washing with deionized water and anhydrous ethanol and drying.
[0065] The second intermediate product is heat-treated at 300°C for 1h in an argon atmosphere, and then dried after washing with deionized water and anhydrous ethanol, so as to obtain the metal nickel / crystalline metal chromium oxide composite electrode.
[0066] The metal nickel / crystalline metal chromium oxide composite electrode is used as a working electrode, the nickel mesh is used as a counter electrode, and 6 mol / L of KOH is used as an electrolyte to perform a hydrogen evolution experiment of electrolytic water.
[0067] Example 2
[0068] The nickel mesh is first acid-washed by a 0.1 mol / L sulfuric acid solution, and then alkali-washed by a 1 mol / L KOH solution, so as to perform roughening treatment on the surface of the nickel mesh to obtain a first intermediate product;
[0069] Raney nickel is sprayed on the surface of the first intermediate product by a plasma spraying method, and alkali etching is performed by using a 3 mol / L KOH solution, so as to obtain the nickel mesh with the surface containing the metal nickel.
[0070] 0.06 mol of magnesium nitrate is dissolved in 0.1 L of DMF to obtain a precursor solution, the cut nickel mesh with the surface containing the metal nickel is placed in the precursor solution, a temperature is set to 150°C, and magnesium hydroxide is grown on the surface of the metal nickel by a hydrothermal synthesis. 2 The nickel mesh with the surface containing the metal nickel is cut into 1*2 cm2specimen, and the cut nickel mesh with the surface containing the metal nickel is placed in the precursor solution, a temperature is set to 120°C, and chromium hydroxide is grown on the surface of the metal nickel by a hydrothermal synthesis. After the reaction ends, the second intermediate product is obtained by washing with deionized water and anhydrous ethanol and drying.
[0071] The second intermediate product is heat-treated at 300°C for 1h in an argon atmosphere, and then dried after washing with deionized water and anhydrous ethanol, so as to obtain the metal nickel / crystalline metal chromium oxide composite electrode.
[0072] The metal nickel / crystalline metal chromium oxide composite electrode is used as a working electrode, the nickel mesh is used as a counter electrode, and 6 mol / L of KOH is used as an electrolyte to perform a hydrogen evolution experiment of electrolytic water.
[0073] Example 3
[0074] The nickel mesh is first acid-washed by a 0.1 mol / L sulfuric acid solution, and then alkali-washed by a 1 mol / L KOH solution, so as to perform roughening treatment on the surface of the nickel mesh to obtain a first intermediate product;
[0075] Raney nickel is sprayed on the surface of the first intermediate product by plasma spraying, and an alkali etching is performed using a 3 mol / L KOH solution to obtain a nickel mesh containing metal nickel on the surface;
[0076] 0.03 mol of stannous sulfate is dissolved in 0.1 L of a mixed solvent of DMF and water as a precursor solution, the precursor solution is placed in a hydrothermal reaction kettle, the nickel mesh containing metal nickel on the surface is cut into a 1*2 cm2specimen, the cut nickel mesh containing metal nickel on the surface is placed in the precursor solution, the temperature is set to 120℃, and tin hydroxide is grown on the surface of the metal nickel by hydrothermal synthesis. After the reaction, the second intermediate product is obtained after washing with deionized water and anhydrous ethanol and drying.
[0077] The second intermediate product is heat-treated at 500℃ for 2h in an argon atmosphere, and then dried after washing with deionized water and anhydrous ethanol to obtain a metal nickel / crystalline metal tin oxide composite electrode.
[0078] The above metal nickel / crystalline metal tin oxide composite electrode is used as a working electrode, a nickel mesh is used as a counter electrode, and a 6 mol / L KOH solution is used as an electrolyte to perform a hydrogen evolution experiment by electrolysis.
[0079] Example 4
[0080] The nickel mesh is first acid-washed by a 0.1 mol / L sulfuric acid solution, and then alkali-washed by a 1 mol / L KOH solution to roughen the surface and obtain a first intermediate product;
[0081] Raney nickel is sprayed on the surface of the first intermediate product by plasma spraying, and an alkali etching is performed using a 3 mol / L KOH solution to obtain a nickel mesh containing metal nickel on the surface;
[0082] 0.08 mol of manganese acetate is dissolved in 0.1 L of a mixed solvent of DMF and water as a precursor solution, the precursor solution is placed in a hydrothermal reaction kettle, the nickel mesh containing metal nickel on the surface is cut into a 1*2 cm 2 specimen, the cut nickel mesh containing metal nickel on the surface is placed in the precursor solution, the temperature is set to 150℃, and manganese hydroxide is grown on the surface of the metal nickel by hydrothermal synthesis. After the reaction, the second intermediate product is obtained after washing with deionized water and anhydrous ethanol and drying.
[0083] The second intermediate product is heat-treated at 400℃ for 2h in an argon atmosphere, and then dried after washing with deionized water and anhydrous ethanol to obtain a metal nickel / crystalline metal manganese oxide composite electrode.
[0084] The metal nickel / crystalline metal manganese oxide composite electrode is used as a working electrode, a nickel mesh is used as a counter electrode, and 6 mol / L of KOH is used as an electrolyte to perform an electrolytic water hydrogen evolution experiment.
[0085] Example 5
[0086] The nickel mesh is first subjected to acid washing by using a 0.1 mol / L sulfuric acid solution, and then subjected to alkali washing by using a 1 mol / L KOH solution, so as to perform roughening treatment on the surface of the nickel mesh to obtain a first intermediate product;
[0087] Raney nickel is sprayed on the surface of the first intermediate product by using a plasma spraying method, and alkali etching is performed by using a 3 mol / L KOH solution, so as to obtain a nickel mesh containing metal nickel on the surface;
[0088] 0.01 mol of yttrium nitrate is dissolved in 0.1 L of a mixed solvent of DMF and water to obtain a precursor solution, the nickel mesh containing metal nickel on the surface is cut into a 1*2 cm 2 specification, and the cut nickel mesh containing metal nickel on the surface is placed in the precursor solution, and the temperature is set to 180℃. After yttrium hydroxide is grown on the surface of the metal nickel by hydrothermal synthesis, the second intermediate product is washed by using deionized water and anhydrous ethanol and then dried, so as to obtain a second intermediate product.
[0089] The second intermediate product is subjected to heat treatment at 500℃ for 2 h in an argon atmosphere, and then washed by using deionized water and anhydrous ethanol and dried, so as to obtain a metal nickel / crystalline metal yttrium oxide composite electrode.
[0090] The metal nickel / crystalline metal yttrium oxide composite electrode is used as a working electrode, a nickel mesh is used as a counter electrode, and 6 mol / L of KOH is used as an electrolyte to perform an electrolytic water hydrogen evolution experiment.
[0091] From the test results of Figure 2 and Figure 3 , it can be known that the metal nickel / crystalline metal oxide hydrogen evolution catalyst prepared in the application has excellent hydrogen evolution catalytic activity and long-term stability.
[0092] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.
[0093] Furthermore, the terms "first", "second", etc. are used only for descriptive purposes and do not connote or imply relative importance or a quantity of the indicated technical features. Thus, a feature defined with "first", "second", etc. can include at least one of the features implicitly or explicitly. In the description of the present application, the meaning of "a plurality" is at least two, for example, two, three, etc., unless otherwise specifically defined.
[0094] Although the embodiments of the present application have been shown and described above, it is understood that the above-described embodiments are exemplary and are not to be construed as limiting the present application, and that changes, modifications, substitutions and variations can be made by those skilled in the art without departing from the scope of the present application.
Claims
1. A process for the preparation of a hydrogen-evolution catalyst of metallic nickel / crystalline metal oxide characterized in that, The preparation method comprises: roughening the surface of a nickel mesh to obtain a first intermediate product; spraying a nickel-aluminum alloy on the surface of the first intermediate product and obtaining a nickel mesh containing metallic nickel on the surface by alkali etching; dissolving a precursor salt forming a metal oxide in a solvent as a precursor solution, placing the nickel mesh containing metallic nickel on the surface in the precursor solution, growing the metal oxide on the surface of the metallic nickel by hydrothermal synthesis, and obtaining a second intermediate product after washing and drying; heat treating the second intermediate product in an atmosphere of an inert gas, and obtaining the metallic nickel / crystalline metal oxide hydrogen evolution catalyst after washing and drying.
2. The preparation method of the nickel / crystalline metal oxide hydrogen evolution catalyst according to claim 1, characterized in that, The roughening of the surface of the nickel mesh to obtain the first intermediate product comprises: roughening the surface of the nickel mesh by first acid washing and then alkali washing to obtain the first intermediate product.
3. The preparation method of the nickel / crystalline metal oxide hydrogen evolution catalyst according to claim 1, characterized in that, The nickel-aluminum alloy comprises Raney nickel.
4. The preparation method of the nickel / crystalline metal oxide hydrogen evolution catalyst according to claim 1, characterized in that, The metal oxide comprises at least one of chromium oxide, tin oxide, indium oxide, tungsten oxide, vanadium oxide, magnesium oxide, lanthanide oxide, manganese oxide, scandium oxide, yttrium oxide, and the lanthanide oxide comprises at least one of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, promethium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, and lutetium oxide.
5. The method of producing a metal nickel / crystalline metal oxide hydrogen evolution catalyst according to any one of claims 1 to 4, characterized by, The concentration of the precursor solution is 0.1-0.8 mol / L.
6. The method of producing a metal nickel / crystalline metal oxide hydrogen evolution catalyst according to any one of claims 1 to 4, characterized by, The reaction temperature of the hydrothermal synthesis is 100-150 ℃.
7. The method of producing a metal nickel / crystalline metal oxide hydrogen evolution catalyst according to any one of claims 1 to 4, characterized by, The temperature of the heat treatment is 300-500 ℃.
8. The method of producing a metal nickel / crystalline metal oxide hydrogen evolution catalyst according to any one of claims 1 to 4, characterized by, The temperature of the drying is 60-80 ℃.
9. A hydrogen evolution catalyst of metallic nickel / crystalline metal oxide, characterized in that, The metallic nickel / crystalline metal oxide hydrogen evolution catalyst is prepared according to the preparation method of the metallic nickel / crystalline metal oxide hydrogen evolution catalyst according to any one of claims 1 to 8.
10. Use of the hydrogen evolution catalyst of crystalline metal oxide on metal nickel according to claim 9, characterized in that, The metallic nickel / crystalline metal oxide hydrogen evolution catalyst is used for water electrolysis hydrogen evolution reaction.