Tower-shaped nickel hydroxide catalytic material and preparation method thereof

Abstract

The invention relates to the technical field of electro-catalytic material synthesis, and particularly discloses a tower-shaped nickel hydroxide catalytic material and a preparation method thereof. The preparation method of the tower-shaped nickel hydroxide catalytic material comprises the following steps: (1) surface treatment of a nickel substrate: performing ultrasonic cleaning treatment on the nickel substrate, and performing vacuum drying to obtain the cleaned nickel substrate; and (2) synthesis of tower-shaped nickel hydroxide: dissolving phosphate to obtain a phosphate solution, adding hydrogen peroxide, stirring, adding the cleaned nickel substrate, and carrying out hydrothermal reaction to obtain a semi-finished product of tower-shaped nickel hydroxide. And (3) cleaning and drying the tower-shaped nickel hydroxide: cleaning the semi-finished product tower-shaped nickel hydroxide, and carrying out vacuum drying to obtain the tower-shaped nickel hydroxide catalytic material. The method is simple in process, relatively low in cost and easy for large-scale synthesis, and has a relatively good large-scale commercial application prospect; and the specific morphology effectively exposes active crystal faces and active sites, and as an excellent catalyst, the catalyst can improve the hydrogen production rate and the organic matter oxidation rate.

Description

Technical Field

[0001] The present invention relates to the technical field of electrocatalytic material synthesis, and in particular to a tower-shaped nickel hydroxide catalytic material and a preparation method thereof. Background Art

[0002] Hydrogen, with its high energy density and clean, pollution-free nature, is one of the most ideal secondary energy sources for the 21st century. Hydrogen production primarily involves fossil fuels, water electrolysis, industrial byproduct production, and renewable energy. Hydrogen produced from fossil fuels (i.e., gray hydrogen) accounts for approximately 96% of total hydrogen production, but this is accompanied by significant CO2 emissions. For example, for every kg of hydrogen produced from water gas, 16 kg of CO2 is emitted. This method is highly dependent on traditional fossil fuels and poses significant environmental risks. In recent years, water electrolysis has garnered widespread attention from scientists. Its key advantages include: the abundant raw material, water; mild preparation conditions; and a simple process flow. The entire process is environmentally friendly and pollution-free, making it one of the most promising and promising technologies for hydrogen production and considered the best path to a future "hydrogen economy."

[0003] However, the technology of hydrogen production by electrolysis of water involves two half-reactions, hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In particular, the anodic oxygen evolution reaction (OER) has slow kinetics and high power consumption, and the added value of O2 produced by OER is low. Therefore, improving energy conversion efficiency and reducing power loss are important breakthroughs for the large-scale application of hydrogen production by electrolysis of water. As an innovative design concept, the coupling of hydrogen production by electrolysis of water with organic oxidation is based on the principle of replacing OER with the anodic reaction of electrocatalytic oxidation of organic matter including alcohols (aromatic alcohols, furfuryl alcohol, sorbitol, etc.), aldehydes (hydroxymethylfurfural, etc.), sugars, etc. to produce high value-added chemicals; for example, the oxidation reaction of hydroxymethylfurfural replaces OER, and furandicarboxylic acid is generated at the same time, which can be used as a monomer to synthesize biomass PEF plastics. Not only does the product have high added value, but the synthesis method of anodic oxidation can also replace the petrochemical-derived synthesis method. This new approach to efficient hydrogen production by water electrolysis has the following advantages: (1) lower theoretical potential, which is lower than the 1.23V of water electrolysis; (2) improved energy conversion efficiency, with the theoretical efficiency of the anode reaching 100%; (3) reduced power loss, saving hydrogen production costs; and (4) production of high-value-added chemicals, resulting in additional economic benefits. In future research on water electrolysis hydrogen production systems, in addition to considering efficient hydrogen production rates, more attention should be paid to the comprehensive economic and environmental benefits of the entire reaction system. Therefore, the development of highly active and stable bifunctional electrocatalytic materials to improve the efficiency of hydrogen production and organic matter oxidation, reduce hydrogen production costs, and accelerate the industrialization of efficient water electrolysis hydrogen production coupled with organic matter oxidation has important practical value.

[0004] Currently, there is limited research on combining hydrogen production with organic oxidation, and no commercially viable bifunctional electrocatalytic materials have been developed. Therefore, how to adopt a simple method to prepare highly active bifunctional electrocatalytic materials is a key technical problem that urgently needs to be solved. The present invention proposes a tower-shaped nickel hydroxide catalytic material and a preparation method thereof. The obtained material has high catalytic activity, can reduce the overpotential for hydrogen production, increase the rate of organic oxidation, and greatly reduce the cost of hydrogen production. In addition, the synthesis method is simple and highly reproducible, which can achieve commercial production. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a tower-shaped nickel hydroxide catalytic material and a preparation method thereof. The obtained material has high catalytic activity, can reduce the overpotential of hydrogen production, increase the oxidation rate of organic matter, and greatly reduce the cost of hydrogen production; and the synthesis method is simple and highly reproducible, which can realize commercial production.

[0006] A first aspect of the present invention provides a method for preparing a tower-shaped nickel hydroxide catalytic material.

[0007] Specifically, the preparation method of the tower-shaped nickel hydroxide catalytic material comprises the following steps:

[0008] (1) Surface treatment of the nickel substrate: ultrasonically cleaning the nickel substrate and vacuum drying the nickel substrate to obtain a cleaned nickel substrate;

[0009] (2) Synthesis of tower-shaped nickel hydroxide: dissolving phosphate to obtain a phosphate solution, adding hydrogen peroxide, stirring, and then adding the cleaned nickel substrate to carry out a hydrothermal reaction to obtain a semi-finished tower-shaped nickel hydroxide;

[0010] (3) Cleaning and drying of tower-shaped nickel hydroxide: The semi-finished tower-shaped nickel hydroxide is cleaned and vacuum-dried to obtain a tower-shaped nickel hydroxide catalytic material.

[0011] Preferably, in step (1), the nickel substrate comprises at least one of nickel foam, nickel mesh, nickel wire, nickel sheet, and nickel block.

[0012] Preferably, in step (1), the ultrasonic cleaning treatment comprises the following steps: ultrasonically cleaning the nickel substrate with ethanol, dilute hydrochloric acid and double distilled water in sequence.

[0013] Preferably, in step (2), the phosphate includes at least one of monohydrogen phosphate, dihydrogen phosphate, phosphate, phosphoric acid, monohydrogen hypophosphite, dihydrogen hypophosphite, hypophosphite, monohydrogen phosphite, dihydrogen phosphite, and phosphite.

[0014] Preferably, in step (2), the concentration of the phosphate solution is 1 to 400 mg / mL.

[0015] Preferably, in step (2), the amount of hydrogen peroxide added is 1 to 20 mL.

[0016] Further preferably, in step (2), the amount of hydrogen peroxide added is 5 to 15 mL.

[0017] More preferably, in step (2), the amount of hydrogen peroxide added is 5 to 10 mL.

[0018] Preferably, in step (2), the temperature of the hydrothermal reaction is 80 to 280° C., and the time is 1 to 48 hours.

[0019] Further preferably, in step (2), the temperature of the hydrothermal reaction is 180-280° C., and the time is 12-48 hours.

[0020] More preferably, in step (2), the temperature of the hydrothermal reaction is 180-220° C., and the time is 12-24 h.

[0021] Preferably, in step (2), the pressure of the hydrothermal reaction is 0.1 to 20 MPa.

[0022] Preferably, in step (3), the cleaning comprises the following steps: cleaning the semi-finished tower-shaped nickel hydroxide with ethanol and double distilled water respectively.

[0023] Preferably, in step (3), the vacuum drying time is 12 to 36 hours.

[0024] Further preferably, in step (3), the vacuum drying time is 24 to 36 hours.

[0025] More preferably, in step (3), the vacuum drying time is 24 hours.

[0026] A second aspect of the present invention provides a tower-shaped nickel hydroxide catalytic material.

[0027] Specifically, the tower-shaped nickel hydroxide catalytic material is prepared by the preparation method provided in the first aspect.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) Energy saving: The method of the present invention uses the oxidation of small molecule alcohols or aldehydes at the anode, the oxidation of pollutants and other reactions instead of the O2 oxidation reaction, which reduces the energy consumption of the reaction system and improves the efficiency of electrocatalytic hydrogen synthesis. (2) Obtaining high value-added products: The oxidation reaction of alcohols or aldehydes at the anode can produce high value-added chemicals. (3) Products are easy to separate: The method of the present invention produces hydrogen at the cathode and liquid high value-added chemicals at the anode. The gas and liquid are naturally separated, which increases additional benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a scanning electron microscope image of the "tower-shaped" nickel hydroxide catalytic material B synthesized in Example 1;

[0031] Figure 2 are X-ray powder diffraction patterns of samples B, C, and D;

[0032] Figure 3 The hydrogen evolution performance diagram of samples A, B, C, and D;

[0033] Figure 4 This is the oxidation activity diagram of organic matter (furfural, etc.) of samples A, B, C, and D. DETAILED DESCRIPTION

[0034] In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the following examples are given for illustration. It should be noted that the following examples do not limit the scope of protection claimed by the present invention.

[0035] Unless otherwise specified, the raw materials, reagents, or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0036] Example 1

[0037] The preparation method of the tower-shaped nickel hydroxide catalytic material comprises the following steps:

[0038] (1) Surface treatment of commercial nickel foam substrate: The commercial nickel foam substrate was placed in ethanol, dilute hydrochloric acid and double distilled water in sequence, ultrasonically cleaned for 10 minutes and then vacuum dried for use. Vacuum drying can prevent secondary oxidation of the surface.

[0039] (2) Loading "tower-shaped" nickel hydroxide on the surface of a commercial nickel foam substrate: dissolve 5 mg of ammonium dihydrogen phosphate in 30 mL of water and stir for 10 minutes to completely dissolve it; then add 10 mL of hydrogen peroxide to the phosphate solution and continue stirring for 20 minutes; then add the nickel substrate cleaned in step (1) to the obtained solution, and after a hydrothermal reaction at 180°C for 24 hours, the "tower-shaped" nickel hydroxide grows on the nickel foam substrate to obtain a semi-finished tower-shaped nickel hydroxide.

[0040] (3) Cleaning and drying of the “tower-shaped” nickel hydroxide: The semi-finished tower-shaped nickel hydroxide was repeatedly rinsed in ethanol and double-distilled water, and then vacuum-dried for 24 hours to finally obtain the “tower-shaped” nickel hydroxide catalytic material, and the sample was named B.

[0041] Example 2

[0042] The preparation method of the tower-shaped nickel hydroxide catalytic material comprises the following steps:

[0043] (1) Surface treatment of commercial nickel mesh substrate: Place the commercial nickel mesh substrate in ethanol, dilute hydrochloric acid and double distilled water in turn, ultrasonically clean it for 10 minutes and then vacuum dry it for use. Vacuum drying can prevent secondary oxidation of its surface.

[0044] (2) Loading "tower-shaped" nickel hydroxide on the surface of a commercial nickel mesh substrate: dissolve 5 mg of ammonium dihydrogen phosphate in 30 mL of water and stir for 10 minutes to completely dissolve it; then add 10 mL of hydrogen peroxide to the phosphate solution and continue stirring for 20 minutes; then add the nickel mesh substrate cleaned in step (1) to the obtained solution, and after a hydrothermal reaction at 180°C for 24 hours, allow "tower-shaped" nickel hydroxide to grow on the nickel mesh substrate, thereby obtaining a semi-finished tower-shaped nickel hydroxide.

[0045] (3) Cleaning and drying of the “tower-shaped” nickel hydroxide: The semi-finished tower-shaped nickel hydroxide was repeatedly rinsed in ethanol and double-distilled water, and then vacuum-dried for 24 hours to finally obtain the “tower-shaped” nickel hydroxide catalytic material.

[0046] Example 3

[0047] The preparation method of the tower-shaped nickel hydroxide catalytic material comprises the following steps:

[0048] (1) Surface treatment of commercial nickel foam substrate: The commercial nickel foam substrate was placed in ethanol, dilute hydrochloric acid and double distilled water in sequence, ultrasonically cleaned for 10 minutes and then vacuum dried for use. Vacuum drying can prevent secondary oxidation of the surface.

[0049] (2) Loading "tower-shaped" nickel hydroxide on the surface of a commercial nickel foam substrate: dissolve 20 mg of ammonium dihydrogen phosphate in 30 mL of water and stir for 10 minutes to completely dissolve it; then add 5 mL of hydrogen peroxide to the phosphate solution and continue stirring for 20 minutes; then add the nickel foam substrate cleaned in step (1) to the obtained solution, and after a hydrothermal reaction at 180°C for 24 hours, the "tower-shaped" nickel hydroxide grows on the nickel foam substrate to obtain a semi-finished tower-shaped nickel hydroxide.

[0050] (3) Cleaning and drying of the “tower-shaped” nickel hydroxide: The semi-finished tower-shaped nickel hydroxide was repeatedly rinsed in ethanol and double-distilled water, and then vacuum-dried for 24 hours to finally obtain the “tower-shaped” nickel hydroxide catalytic material.

[0051] Example 4

[0052] The preparation method of the tower-shaped nickel hydroxide catalytic material comprises the following steps:

[0053] (1) Surface treatment of commercial nickel foam substrate: The commercial nickel foam substrate was placed in ethanol, dilute hydrochloric acid and double distilled water in sequence, ultrasonically cleaned for 10 minutes and then vacuum dried for use. Vacuum drying can prevent secondary oxidation of the surface.

[0054] (2) Loading "tower-shaped" nickel hydroxide on the surface of a commercial nickel foam substrate: dissolve 5 mg of ammonium dihydrogen phosphate in 30 mL of water and stir for 10 minutes to completely dissolve it; then add 10 mL of hydrogen peroxide to the phosphate solution and continue stirring for 20 minutes; then add the nickel foam substrate cleaned in step (1) to the obtained solution, and after a hydrothermal reaction at 180°C for 24 hours, the "tower-shaped" nickel hydroxide grows on the nickel foam substrate to obtain a semi-finished tower-shaped nickel hydroxide.

[0055] (3) Cleaning and drying of the “tower-shaped” nickel hydroxide: The semi-finished tower-shaped nickel hydroxide was repeatedly rinsed in ethanol and double-distilled water, and then vacuum-dried for 24 hours to finally obtain the “tower-shaped” nickel hydroxide catalytic material.

[0056] Example 5

[0057] The preparation method of the tower-shaped nickel hydroxide catalytic material comprises the following steps:

[0058] (1) Surface treatment of commercial nickel foam substrate: The commercial nickel foam substrate was placed in ethanol, dilute hydrochloric acid and double distilled water in sequence, ultrasonically cleaned for 10 minutes and then vacuum dried for use. Vacuum drying can prevent secondary oxidation of the surface.

[0059] (2) Loading "tower-shaped" nickel hydroxide on the surface of a commercial nickel foam substrate: dissolve 5 mg of potassium dihydrogen phosphate in 30 mL of water and stir for 10 minutes to completely dissolve it; then add 10 mL of hydrogen peroxide to the phosphate solution and continue stirring for 20 minutes; then add the nickel foam substrate cleaned in step (1) to the obtained solution, and after a hydrothermal reaction at 180°C for 24 hours, the "tower-shaped" nickel hydroxide grows on the nickel foam substrate to obtain a semi-finished tower-shaped nickel hydroxide.

[0060] (3) Cleaning and drying of the “tower-shaped” nickel hydroxide: The semi-finished tower-shaped nickel hydroxide was repeatedly rinsed in ethanol and double-distilled water, and then vacuum-dried for 24 hours to finally obtain the “tower-shaped” nickel hydroxide catalytic material.

[0061] Example 6

[0062] The preparation method of the tower-shaped nickel hydroxide catalytic material comprises the following steps:

[0063] (1) Surface treatment of commercial nickel foam substrate: The commercial nickel foam substrate was placed in ethanol, dilute hydrochloric acid and double distilled water in sequence, ultrasonically cleaned for 10 minutes and then vacuum dried for use. Vacuum drying can prevent secondary oxidation of the surface.

[0064] (2) Loading "tower-shaped" nickel hydroxide on the surface of a commercial nickel foam substrate: dissolve 5 mg of ammonium dihydrogen phosphate in 30 mL of water and stir for 10 minutes to completely dissolve it; then add 10 mL of hydrogen peroxide to the phosphate solution and continue stirring for 20 minutes; then add the nickel foam substrate cleaned in step (1) to the obtained solution, and after a hydrothermal reaction at 200°C for 18 hours, the "tower-shaped" nickel hydroxide grows on the nickel foam substrate to obtain a semi-finished tower-shaped nickel hydroxide.

[0065] (3) Cleaning and drying of the “tower-shaped” nickel hydroxide: The semi-finished tower-shaped nickel hydroxide was repeatedly rinsed in ethanol and double-distilled water, and then vacuum-dried for 24 hours to finally obtain the “tower-shaped” nickel hydroxide catalytic material.

[0066] Example 7

[0067] The preparation method of the tower-shaped nickel hydroxide catalytic material comprises the following steps:

[0068] (1) Surface treatment of commercial nickel foam substrate: The commercial nickel foam substrate was placed in ethanol, dilute hydrochloric acid and double distilled water in sequence, ultrasonically cleaned for 10 minutes and then vacuum dried for use. Vacuum drying can prevent secondary oxidation of the surface.

[0069] (2) Loading "tower-shaped" nickel hydroxide on the surface of a commercial nickel foam substrate: dissolve 5 mg of ammonium dihydrogen phosphate in 30 mL of water and stir for 10 minutes to completely dissolve it; then add 10 mL of hydrogen peroxide to the phosphate solution and continue stirring for 20 minutes; then add the nickel foam substrate cleaned in step (1) to the obtained solution, and after a hydrothermal reaction at 220°C for 12 hours, the "tower-shaped" nickel hydroxide grows on the nickel foam substrate to obtain a semi-finished tower-shaped nickel hydroxide.

[0070] (3) Cleaning and drying of the “tower-shaped” nickel hydroxide: The semi-finished tower-shaped nickel hydroxide was repeatedly rinsed in ethanol and double-distilled water, and then vacuum-dried for 24 hours to finally obtain the “tower-shaped” nickel hydroxide catalytic material.

[0071] Example 8

[0072] The preparation method of the tower-shaped nickel hydroxide catalytic material comprises the following steps:

[0073] (1) Surface treatment of commercial nickel foam substrate: The commercial nickel foam substrate was placed in ethanol, dilute hydrochloric acid and double distilled water in sequence, ultrasonically cleaned for 10 minutes and then vacuum dried for use. Vacuum drying can prevent secondary oxidation of the surface.

[0074] (2) Loading "tower-shaped" nickel hydroxide on the surface of a commercial nickel foam substrate: dissolve 5 mg of ammonium dihydrogen phosphite in 30 mL of water and stir for 10 minutes to completely dissolve it; then add 10 mL of hydrogen peroxide to the phosphate solution and continue stirring for 20 minutes; then add the nickel foam substrate cleaned in step (1) to the obtained solution, and after a hydrothermal reaction at 180°C for 24 hours, allow the "tower-shaped" nickel hydroxide to grow on the nickel foam substrate, thereby obtaining a semi-finished tower-shaped nickel hydroxide.

[0075] (3) Cleaning and drying of the “tower-shaped” nickel hydroxide: The semi-finished tower-shaped nickel hydroxide was repeatedly rinsed in ethanol and double-distilled water, and then vacuum-dried for 24 hours to finally obtain the “tower-shaped” nickel hydroxide catalytic material.

[0076] Comparative Example 1

[0077] Commercial nickel hydroxide was purchased from MacLean Reagent Co., Ltd. without any treatment and was named sample A.

[0078] Comparative Example 2

[0079] The preparation method of the tower-shaped nickel hydroxide catalytic material comprises the following steps:

[0080] (1) Surface treatment of commercial nickel foam substrate: The commercial nickel foam substrate was placed in ethanol, dilute hydrochloric acid and double distilled water in sequence, ultrasonically cleaned for 10 minutes and then vacuum dried for use. Vacuum drying can prevent secondary oxidation of the surface.

[0081] (2) Loading "tower-shaped" nickel hydroxide on the surface of a commercial nickel foam substrate: dissolve 5 mg of ammonium dihydrogen phosphate in 30 mL of water and stir for 10 minutes to completely dissolve it; then add 10 mL of hydrogen peroxide to the phosphate solution and continue stirring for 20 minutes; then add the nickel foam substrate cleaned in step (1) to the obtained solution, and react at room temperature for 24 hours to allow "tower-shaped" nickel hydroxide to grow on the nickel foam substrate, thereby obtaining a semi-finished tower-shaped nickel hydroxide.

[0082] (3) Cleaning and drying of the “tower-shaped” nickel hydroxide: The semi-finished tower-shaped nickel hydroxide was repeatedly rinsed in ethanol and double-distilled water, and then vacuum-dried for 24 hours to finally obtain the “tower-shaped” nickel hydroxide catalytic material, and the sample was named C.

[0083] Comparative Example 3

[0084] The preparation method of the tower-shaped nickel hydroxide catalytic material comprises the following steps:

[0085] (1) Surface treatment of commercial nickel foam substrate: The commercial nickel foam substrate was placed in ethanol, dilute hydrochloric acid and double distilled water in sequence, ultrasonically cleaned for 10 minutes and then vacuum dried for use. Vacuum drying can prevent secondary oxidation of the surface.

[0086] (2) Loading "tower-shaped" nickel hydroxide on the surface of a commercial nickel foam substrate: dissolve 5 mg of ammonium dihydrogen phosphate in 30 mL of water and stir for 10 minutes to completely dissolve it; then add 10 mL of deionized water to the phosphate solution and continue stirring for 20 minutes; then add the nickel foam substrate cleaned in step (1) to the obtained solution, and after a hydrothermal reaction at 180°C for 24 hours, the "tower-shaped" nickel hydroxide grows on the nickel foam substrate to obtain a semi-finished tower-shaped nickel hydroxide.

[0087] (3) Cleaning and drying of the “tower-shaped” nickel hydroxide: The semi-finished tower-shaped nickel hydroxide was repeatedly rinsed in ethanol and double-distilled water, and then vacuum-dried for 24 hours to finally obtain the “tower-shaped” nickel hydroxide catalytic material, and the sample was named D.

[0088] Performance testing:

[0089] Figure 1 This is a scanning electron microscope image of the "tower-shaped" nickel hydroxide catalyst material B synthesized in Example 1. Figure 1 As shown, a catalytic material with a "tower-like" morphology was grown on the surface of nickel foam, demonstrating the reliability of this method. In addition, the rough surface of the material can increase the catalytic active sites and facilitate the overflow of bubbles, thereby improving the catalytic activity of electrocatalytic water hydrogen production and organic oxidation. At the same time, due to the presence of phosphate, the synthesized material contains a small amount of phosphate, which can adjust the electronic structure of the material, optimize the adsorption and desorption free energy of hydrogen production and organic oxidation intermediates, and accelerate the kinetic process. Due to the above advantages, the "tower-shaped" nickel hydroxide catalytic material can reduce power loss, thereby significantly reducing the cost of electrolytic water hydrogen production and realizing the industrialization of electrolytic water coupled with organic oxidation.

[0090] Figure 2 is the X-ray powder diffraction pattern of samples B, C, and D. Figure 2 (a) shows that the phase structure of the synthesized tower-shaped nickel hydroxide B is β-Ni(OH)2, while in the comparative sample C, there are no other characteristics except the peak of the foam nickel base, indicating that Ni(OH)2 cannot be obtained by directly reacting at room temperature without undergoing a hydrothermal reaction; in addition, when hydrogen peroxide is not added to the reaction, the phase structure of the obtained sample D is two phases, namely α-Ni(OH)2 and Ni2P2O7, and there are other unknown impurity peaks, indicating that the phase structure of the synthesized sample is impure.

[0091] In alkaline solution, its electrochemical properties were tested, such as Figure 3 As shown, the hydrogen evolution performance of sample B is significantly better than that of samples A, C, and D. Figure 4 As for its organic small molecule oxidation performance, it can be clearly seen from the figure that sample B exhibits a larger current density at the same voltage, indicating that it has better organic small molecule oxidation performance; the electrochemical test results show that compared with samples C and D, the tower-shaped structure of sample B has the best electrochemical catalytic performance, which confirms that the hydrothermal reaction and hydrogen peroxide have a significant effect on the performance of the phase structure and its catalytic performance, and the catalytic performance of the tower-shaped structure of sample B is also better than that of commercial nickel hydroxide A.

[0092] In summary, the present invention effectively synthesizes for the first time a "tower-shaped" nickel hydroxide catalytic material with a unique morphology, which has high bifunctional catalytic reaction activity, can effectively improve the efficiency of hydrogen production by electrolysis of water, and reduce the cost of hydrogen production.

[0093] The above describes in detail the preferred embodiments of the present invention. It should be understood that those skilled in the art can make numerous modifications and variations based on the concepts of the present invention without inventive effort. Therefore, any technical solutions derived from modifications, equivalent substitutions, improvements, etc. made by those skilled in the art based on the concepts of the present invention through logical analysis, reasoning, or limited experimentation on the basis of the prior art shall be within the scope of protection defined by the claims.

Claims

1. A method for preparing a tower-shaped nickel hydroxide catalytic material, characterized in that: The following steps are involved: (1) Surface treatment of the nickel substrate: ultrasonically cleaning the nickel substrate and vacuum drying the nickel substrate to obtain a cleaned nickel substrate; (2) Synthesis of tower-shaped nickel hydroxide: dissolving phosphate to obtain a phosphate solution, adding hydrogen peroxide, stirring, and then adding the cleaned nickel substrate to carry out a hydrothermal reaction to obtain a semi-finished tower-shaped nickel hydroxide; (3) Cleaning and drying of tower-shaped nickel hydroxide: The semi-finished tower-shaped nickel hydroxide is cleaned and vacuum-dried to obtain a tower-shaped nickel hydroxide catalytic material.

2. The preparation method according to claim 1, characterized in that In step (1), the nickel substrate includes at least one of nickel foam, nickel mesh, nickel wire, nickel sheet, and nickel block.

3. The preparation method according to claim 1, characterized in that In step (1), the ultrasonic cleaning treatment comprises the following steps: ultrasonic cleaning the nickel substrate with ethanol, dilute hydrochloric acid and double distilled water in sequence.

4. The preparation method according to claim 1, characterized in that In step (2), the phosphate includes at least one of monohydrogen phosphate, dihydrogen phosphate, phosphate, phosphoric acid, monohydrogen hypophosphite, dihydrogen hypophosphite, hypophosphite, monohydrogen phosphite, dihydrogen phosphite, and phosphite.

5. The preparation method according to claim 1, characterized in that In step (2), the concentration of the phosphate solution is 1 to 400 mg / mL.

6. The preparation method according to claim 1, characterized in that In step (2), the amount of hydrogen peroxide added is 1 to 20 mL.

7. The preparation method according to claim 1, characterized in that In step (2), the temperature of the hydrothermal reaction is 80 to 280° C., and the time is 1 to 48 hours.

8. The preparation method according to claim 1, characterized in that In step (2), the pressure of the hydrothermal reaction is 0.1 to 20 MPa.

9. The preparation method according to claim 1, characterized in that In step (3), the cleaning comprises the following steps: cleaning the semi-finished tower-shaped nickel hydroxide with ethanol and double distilled water respectively.

10. A tower-shaped nickel hydroxide catalytic material, characterized in that: The tower-shaped nickel hydroxide catalytic material is prepared by the preparation method according to any one of claims 1 to 9.

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