Nanowire nickel oxide-copper nitride loaded graphene composite material, preparation method thereof and application of nanowire nickel oxide-copper nitride loaded graphene composite material in catalysis of ammonia borane hydrolysis for hydrogen production
Through the preparation of nanowire nickel oxide-copper nitride-supported graphene composite materials, the synergistic effect of NiO-Cu3N heterojunction and graphene is used to solve the problem of easy deactivation of catalyst active sites and insufficient interface regulation, achieving the dual improvement of the catalyst, and is suitable for efficient catalysis of hydrogen production by ammonia borane hydrolysis.
Patent Information
- Application Number
- CN202510217951.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-26
- Publication Date
- 2025-06-13
AI Technical Summary
In the catalytic ammonia borane hydrolysis reaction, existing non-precious metal catalysts have problems such as prone to inactivation of active sites, insufficient regulation of heterojunction interfaces, and weak binding strength of carrier-active components, which is difficult to meet the needs of efficient catalytic hydrogen.
The preparation method of nanowire nickel oxide-copper nitride-supported graphene composite material is adopted to enhance the activity and stability of the catalyst through the electron synergistic effect of NiO-Cu3N heterojunction and the strong anchoring effect of graphene.
The dual improvement of the catalyst has been achieved, which not only improves the catalytic activity but also enhances the cycle stability. It is suitable for industrial production and efficient catalysis of hydrogen production by ammonia borane hydrolysis.
Smart Images
Figure CN120132882A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of catalytic hydrogen production, and particularly relates to a preparation method of a composite material of nickel oxide nanowire - copper nitride supported on graphene and its application in catalytic hydrolysis of ammonia borane for hydrogen production. Background Art
[0002] As an efficient and clean secondary energy carrier, the large - scale production and safe storage and transportation of hydrogen energy are the core. Ammonia borane (NH 3 BH 3 ) is regarded as a highly potential chemical hydrogen storage material due to its high hydrogen storage density (19.6 wt%) and controllable hydrolysis characteristics under mild conditions. However, the hydrolysis reaction of ammonia borane (NH 3 BH 3 +2H 2 O→NH 4 BO 2 +3H 2 ↑) needs to be driven by an efficient catalyst. However, traditional noble metal - based catalysts (such as Pt, Ru) are limited by scarcity and cost problems and are difficult to meet the actual application requirements. Therefore, the development of transition metal - based catalysts with high activity, high stability and low cost has become a research hotspot in this field.
[0003] In recent years, nickel - based and copper - based catalysts have attracted much attention due to their catalytic potential for ammonia borane hydrolysis. However, single metal oxides (such as NiO) or nitrides (such as Cu 3 N) have problems such as insufficient exposure of active sites, low electron transfer efficiency and poor cycle stability. Research shows that by constructing a heterojunction interface, the electronic structure of catalytic materials can be effectively regulated. For example, the combination of nickel oxide (NiO) and copper nitride (Cu 3 N) can form a heterojunction, induce the redistribution of interface charges, optimize the adsorption / desorption energy barriers of reaction intermediates, and thus significantly improve the catalytic activity. In addition, the heterojunction structure can promote the kinetic processes of key steps (such as H 2 O molecule activation and B - N bond cleavage) in the hydrolysis reaction through a synergistic effect, further breaking through the performance bottleneck of single components.
[0004] The selection of the catalyst support is crucial for its stability and dispersion. Graphene is considered an ideal catalyst support due to its ultra - high specific surface area, excellent electrical conductivity and chemical stability. Compared with traditional carbon materials (such as activated carbon, carbon nanotubes), the two - dimensional layered structure of graphene can provide rich anchoring sites for metal nanoparticles, inhibit the migration and agglomeration of active components during the reaction through strong metal - support interaction (SMSI), and thus improve the cycle stability of the catalyst. In addition, the oxygen - containing functional groups on the surface of graphene can further promote the adsorption of reactants through chemical bonding, thereby promoting the reaction.
[0005] Although existing studies have explored the composite systems of metal oxides / nitrides and graphene, the co - design of NiO - Cu 3 N heterojunction and graphene has not been reported yet. In the prior art, non - noble metal catalysts still face problems such as easy inactivation of active sites, insufficient regulation of heterojunction interfaces, and weak binding force between carriers and active components.
[0006] Therefore, developing a method for preparing a nanowire nickel oxide - copper nitride supported graphene composite material, using the interfacial effect of nickel oxide - copper nitride to synergistically enhance the catalytic performance of ammonia borane hydrolysis for hydrogen production, and using the strong anchoring effect of the graphene carrier to inhibit the structural collapse of nanowires in the cyclic reaction, so as to achieve a double improvement in catalytic stability and activity, is the problem that this invention is committed to solving. Summary of the Invention
[0007] The purpose of this invention is to provide a preparation method for a nanowire nickel oxide - copper nitride supported graphene composite material. This invention has the advantages of simple synthesis method, mild conditions, and regular morphology of the obtained nickel oxide - copper nitride / graphene target product.
[0008] The inventors of this application found that compounding nickel oxide and copper nitride into a nickel oxide - copper nitride / graphene composite for catalytic reactions can produce a synergistic catalytic effect, enhancing the reaction activity and stability. Therefore, developing a method for preparing nickel oxide - copper nitride composites with a simple preparation process, low cost, and excellent product performance that can be applied to industrial production is the problem that this invention is committed to solving.
[0009] To solve the above - mentioned technical problems, this invention adopts the following technical solution: A preparation method for a nanosheet nickel oxide - copper nitride supported graphene composite material, comprising the following steps:
[0010] (1) Dissolve soluble copper salts and nickel salts in ultrapure water according to a ratio to prepare a mixed salt solution A;
[0011] (2) Ultrasonically disperse the carrier graphene in ultrapure water;
[0012] (3) Slowly drop the graphene dispersion into solution A under magnetic stirring to form solution B;
[0013] (4) Slowly drop an alkaline solution into solution B to form solution C; the alkaline solution is selected from one or more of urea, sodium hydroxide, potassium hydroxide, ammonia water, and hexamethylenetetramine;
[0014] (5) Transfer solution C to a reaction kettle, react at 100 - 180 °C for 6 - 12 h, filter and wash, collect the product, and dry it.
[0015] (6) Place the sample in a muffle furnace and calcine it at 350 °C for 2 h. After the reaction is completed, collect the sample;
[0016] (7) Using ammonia gas as the ammonia source, place the sample in step (6) upstream of the tubular furnace and calcine it for 0.5 - 5 h under an ammonia atmosphere at 300 - 400 °C for partial nitridation treatment.
[0017] Preferably, the soluble copper salt in step (1) is selected from one or more of copper acetate monohydrate, copper sulfate pentahydrate, copper nitrate hexahydrate, and copper chloride dihydrate, and the soluble nickel salt is selected from one or more of nickel acetate tetrahydrate, nickel sulfate hexahydrate, nickel nitrate hexahydrate, and nickel chloride hexahydrate.
[0018] Preferably, the soluble copper salt and nickel salt in step (1) are dissolved in ultrapure water in any ratio between 1:10 and 10:1.
[0019] Preferably, the amount of the base added in step (4) is 10 - 50 times the amount of the metal ions in terms of the amount of substance.
[0020] The present invention also discloses the application of the nickel oxide - copper nitride composite material prepared by the above method in catalyzing the hydrolysis of ammonia borane to produce hydrogen.
[0021] The "nanowire nickel oxide - copper nitride supported graphene composite material" proposed by the present invention breaks through the technical bottleneck through the following innovative points: (1) Utilize the electron synergy effect of the NiO - Cu 3 N heterojunction to optimize the intrinsic catalytic activity of the active sites; (2) The nanowire structure provides a high specific surface area and abundant exposed active sites; (3) The graphene support inhibits the structural collapse of the nanowires in the cyclic reaction through strong anchoring, achieving a double improvement in catalytic stability and activity. This design provides a new idea for the development of highly efficient and stable catalysts for the hydrolysis of ammonia borane to produce hydrogen.
[0022] In summary, the preparation method of the present invention has the following beneficial effects:
[0023] 1. By precisely adjusting the nitridation time and the feeding amounts of nickel salt and copper salt, nickel oxide - copper nitride supported graphene composite catalysts with different ratios can be obtained.
[0024] 2. The nickel oxide - copper nitride supported graphene composite material prepared by the present invention has obvious electron synergy effect and metal - support interaction, and shows a synergistic effect in catalyzing the hydrolysis of ammonia borane to produce hydrogen.
[0025] 3. The present invention adopts a simple hydrothermal synthesis method and step - by - step calcination to achieve partial nitridation, and successfully prepares the nickel oxide - copper nitride supported graphene composite material. The whole preparation process is simple, environmentally friendly, has very good experimental reproducibility, low cost, and is easy for industrial production, and can produce the nickel oxide - copper nitride supported graphene composite material on a large scale. Brief Description of the Drawings
[0026] Figure 1 SEM image of the nickel oxide - copper nitride supported graphene composite prepared according to the present invention;
[0027] Figure 2 XRD pattern of the nickel oxide - copper nitride supported graphene composite prepared according to the present invention;
[0028] Figure 3 BET diagram of the nickel oxide - copper nitride supported graphene composite prepared according to the present invention;
[0029] Figure 4 Hydrogen production performance diagram of the nickel oxide - copper nitride supported graphene composite prepared according to the present invention;
[0030] Figure 5 Hydrogen production performance diagram of the nickel oxide - copper nitride supported graphene composites prepared with different feed ratios according to the present invention;
[0031] Figure 6 Hydrogen production performance diagram of the nickel oxide - copper nitride supported graphene composites prepared with different nitridation times according to the present invention. Detailed Description of the Invention
[0032] The above - mentioned inventive content of the present invention will be further described in detail below in conjunction with the specific embodiments. However, it should not be understood that the scope of the above - mentioned subject matter of the present invention is only limited to the following embodiments. Without departing from the above - mentioned technical idea of the present invention, various substitutions, changes, and improvements made according to the common general knowledge and conventional means in the art should all be included within the scope of the present invention.
[0033] Example 1
[0034] Weigh 100 mg of rGO and dissolve it in 60 mL of ultrapure water, and ultrasonically disperse it for 10 minutes. Separately, weigh 4 mmol of Cu(Ac)₂ and 20 mmol of hexamethylenetetramine and dissolve them in 20 mL of ultrapure water, stir magnetically until dissolved, pour it into the rGO dispersion and continue stirring to obtain solution A. Transfer the obtained solution to a reaction kettle and react at 120 °C for 8 h. After the reaction is completed, collect the sample, wash it with water 2 - 3 times, wash it with ethanol 2 - 3 times, and dry it. Calcinate it in a muffle furnace, heat it up to 350 °C and calcinate it for 2 h. After the reaction is completed, collect the sample. Weigh 0.1 g of the sample calcined in the muffle furnace and place it in a porcelain boat, then place it in a tube furnace. Use ammonia gas as the ammonia source and calcine it in the tube furnace at 350 °C in an ammonia atmosphere for 1 h for nitridation treatment to obtain the target product, the copper nitride supported graphene composite catalyst.
[0035] Example 2
[0036] Weigh 100 mg of rGO and dissolve it in 60 mL of ultrapure water, then ultrasonically disperse it for 10 minutes. Separately, weigh 4 mmol of Ni(Ac)₂ and 20 mmol of hexamethylenetetramine, dissolve them in 20 mL of ultrapure water, stir magnetically until dissolved, pour it into the rGO dispersion and continue stirring to obtain Solution A. Transfer the obtained solution to a reaction kettle and react at 120 °C for 8 h. After the reaction is completed, collect the sample, wash it with water 2 - 3 times, wash it with ethanol 2 - 3 times, and dry it. Calcinate it in a muffle furnace, raise the temperature to 350 °C and calcinate for 2 h. After the reaction is completed, collect the sample. Weigh 0.1 g of the sample calcined in the muffle furnace, place it in a porcelain boat, put it into a tube furnace, use ammonia gas as the ammonia source, and calcinate it in the tube furnace at 350 °C under an ammonia atmosphere for 1 h for nitridation treatment to obtain the target product, nickel oxide supported graphene composite catalyst.
[0037] Example 3
[0038] Weigh 100 mg of rGO and dissolve it in 60 mL of ultrapure water, then ultrasonically disperse it for 10 minutes. Separately, weigh 2 mmol of Ni(Ac)₂, 2 mmol of Cu(Ac)₂ and 20 mmol of hexamethylenetetramine, dissolve them in 20 mL of ultrapure water, stir magnetically until dissolved, pour it into the rGO dispersion and continue stirring to obtain Solution A. Transfer the obtained solution to a reaction kettle and react at 120 °C for 8 h. After the reaction is completed, collect the sample, wash it with water 2 - 3 times, wash it with ethanol 2 - 3 times, and dry it. Calcinate it in a muffle furnace, raise the temperature to 350 °C and calcinate for 2 h. After the reaction is completed, collect the sample. Weigh 0.1 g of the sample calcined in the muffle furnace, place it in a porcelain boat, put it into a tube furnace, use ammonia gas as the ammonia source, and calcinate it in the tube furnace at 350 °C under an ammonia atmosphere for 1 h for nitridation treatment to obtain the target product, nickel oxide - copper nitride supported graphene composite catalyst.
[0039] Example 4
[0040] Weigh 100 mg of rGO and dissolve it in 60 mL of ultrapure water, then ultrasonically disperse it for 10 minutes. Separately, weigh 3 mmol of Ni(Ac)₂, 1 mmol of Cu(Ac)₂ and 20 mmol of hexamethylenetetramine, dissolve them in 20 mL of ultrapure water, stir magnetically until dissolved, pour it into the rGO dispersion and continue stirring to obtain Solution A. Transfer the obtained solution to a reaction kettle and react at 120 °C for 8 h. After the reaction is completed, collect the sample, wash it with water 2 - 3 times, wash it with ethanol 2 - 3 times, and dry it. Calcinate it in a muffle furnace, raise the temperature to 350 °C and calcinate for 2 h. After the reaction is completed, collect the sample. Weigh 0.1 g of the sample calcined in the muffle furnace, place it in a porcelain boat, put it into a tube furnace, use ammonia gas as the ammonia source, and calcinate it in the tube furnace at 350 °C under an ammonia atmosphere for 1 h for nitridation treatment to obtain the target product, nickel oxide - copper nitride supported graphene composite catalyst.
[0041] Example 5
[0042] Weigh 100 mg of rGO and dissolve it in 60 mL of ultrapure water, then ultrasonically disperse it for 10 minutes. Separately, weigh 1 mmol of Ni(Ac)₂, 3 mmol of Cu(Ac)₂, and 20 mmol of hexamethylenetetramine, dissolve them in 20 mL of ultrapure water by magnetic stirring, pour the solution into the rGO dispersion and continue stirring to obtain solution A. Transfer the obtained solution to a reaction kettle and react at 120 °C for 8 h. After the reaction is completed, collect the sample, wash it with water 2 - 3 times, wash it with ethanol 2 - 3 times, and then dry it. Calcinate it in a muffle furnace, raise the temperature to 350 °C and calcinate for 2 h. After the reaction is completed, collect the sample. Weigh 0.1 g of the sample calcined in the muffle furnace and place it in a porcelain boat, then place it in a tubular furnace. Use ammonia gas as the ammonia source and calcine it in the tubular furnace at 350 °C in an ammonia atmosphere for 1 h for nitridation treatment to obtain the target product, the nickel oxide - copper nitride supported graphene composite catalyst.
[0043] Cu 3 There is a synergistic effect between N and NiO. Adjusting the appropriate Cu 3 N and NiO ratio is beneficial to improving the catalyst performance. Comparative Example 1 and Comparative Example 2 were designed to reveal that Cu 3 The N and NiO ratio between 1:10 - 10:1 can obtain better catalytic performance.
[0044] Comparative Example 1
[0045] Weigh 100 mg of rGO and dissolve it in 60 mL of ultrapure water, then ultrasonically disperse it for 10 minutes. Separately, weigh 1 mmol of Ni(Ac)₂, 11 mmol of Cu(Ac)₂, and 20 mmol of hexamethylenetetramine, dissolve them in 20 mL of ultrapure water by magnetic stirring, pour the solution into the rGO dispersion and continue stirring to obtain solution A. Transfer the obtained solution to a reaction kettle and react at 120 °C for 8 h. After the reaction is completed, collect the sample, wash it with water 2 - 3 times, wash it with ethanol 2 - 3 times, and then dry it. Calcinate it in a muffle furnace, raise the temperature to 350 °C and calcinate for 2 h. After the reaction is completed, collect the sample. Weigh 0.1 g of the sample calcined in the muffle furnace and place it in a porcelain boat, then place it in a tubular furnace. Use ammonia gas as the ammonia source and calcine it in the tubular furnace at 350 °C in an ammonia atmosphere for 1 h for nitridation treatment to obtain the target product, the nickel oxide - copper nitride supported graphene composite catalyst.
[0046] Comparative Example 2
[0047] Weigh 100 mg of rGO and dissolve it in 60 mL of ultrapure water, then ultrasonically disperse it for 10 minutes. Separately, weigh 11 mmol of Ni(Ac)₂, 1 mmol of Cu(Ac)₂ and 20 mmol of hexamethylenetetramine, dissolve them in 20 mL of ultrapure water, stir magnetically until dissolved, pour it into the rGO dispersion and continue stirring to obtain Solution A. Transfer the obtained solution to a reaction kettle and react at 120 °C for 8 h. After the reaction is completed, collect the sample, wash it with water 2 - 3 times, wash it with ethanol 2 - 3 times, and dry it. Calcinate it in a muffle furnace, raise the temperature to 350 °C and calcinate for 2 h. After the reaction is completed, collect the sample. Weigh 0.1 g of the sample calcined in the muffle furnace and place it in a porcelain boat, then place it in a tube furnace. Use ammonia gas as the ammonia source and calcine it in the tube furnace at 350 °C in an ammonia gas atmosphere for 1 h for nitridation treatment to obtain the target product, the nickel oxide - copper nitride supported graphene composite catalyst.
[0048] The ammonia gas nitridation treatment time will affect the ratio of Cu 3 N to NiO. Adjust the appropriate nitridation time to further adjust the ratio of Cu 3 N to NiO, which is beneficial to improving the performance of the catalyst. Comparative Example 3 and Comparative Example 4 were designed to reveal that better catalytic performance can be obtained when the nitridation time is between 0.5 h and 5 h.
[0049] Comparative Example 3
[0050] Weigh 100 mg of rGO and dissolve it in 60 mL of ultrapure water, then ultrasonically disperse it for 10 minutes. Separately, weigh 2 mmol of Ni(Ac)₂, 2 mmol of Cu(Ac)₂ and 20 mmol of hexamethylenetetramine, dissolve them in 20 mL of ultrapure water, stir magnetically until dissolved, pour it into the rGO dispersion and continue stirring to obtain Solution A. Transfer the obtained solution to a reaction kettle and react at 120 °C for 8 h. After the reaction is completed, collect the sample, wash it with water 2 - 3 times, wash it with ethanol 2 - 3 times, and dry it. Calcinate it in a muffle furnace, raise the temperature to 350 °C and calcinate for 2 h. After the reaction is completed, collect the sample. Weigh 0.1 g of the sample calcined in the muffle furnace and place it in a porcelain boat, then place it in a tube furnace. Use ammonia gas as the ammonia source and calcinate it in the tube furnace at 350 °C in an ammonia gas atmosphere for 0.4 h for nitridation treatment to obtain the target product, the nickel oxide - copper nitride supported graphene composite catalyst.
[0051] Comparative Example 4
[0052] Weigh 100 mg of rGO and dissolve it in 60 mL of ultrapure water, then ultrasonically disperse it for 10 minutes. Separately, weigh 2 mmol of Ni(Ac)₂, 2 mmol of Cu(Ac)₂, and 20 mmol of hexamethylenetetramine and dissolve them in 20 mL of ultrapure water. Stir magnetically until dissolved, then pour it into the rGO dispersion and continue stirring to obtain Solution A. Transfer the obtained solution to a reaction kettle and react at 120 °C for 8 h. After the reaction, collect the sample, wash it with water 2 - 3 times, wash it with ethanol 2 - 3 times, and then dry it. Calcine it in a muffle furnace, heat it to 350 °C and calcine for 2 h. After the reaction, collect the sample. Weigh 0.1 g of the sample calcined in the muffle furnace and place it in a porcelain boat, then place it in a tubular furnace. Use ammonia gas as the ammonia source and calcine it in the tubular furnace at 350 °C in an ammonia atmosphere for 5.5 h for nitridation treatment to obtain the target product, the nickel oxide - copper nitride supported graphene composite catalyst.
[0053] Next, analyze and test the structure and properties of the nickel oxide - copper nitride supported graphene composite prepared in Example 4 of the present invention.
[0054] 1. SEM analysis
[0055] Figure 1 This is the SEM image of the nickel oxide - copper nitride supported graphene prepared in the present invention. It can be seen from the scanning electron microscope image that the morphology of the synthesized nickel oxide - copper nitride supported graphene composite is nanowires grown on nanosheets, and the diameter of the nanowires is about 100 nm.
[0056] 2. XRD analysis
[0057] Figure 2 This is the XRD test of the nickel oxide - copper nitride supported graphene prepared in the present invention. The results show that nickel and copper exist in the composite as NiO (JCPDS 47 - 1049) and Cu 3 N (JCPDS 47 - 1088) respectively.
[0058] 3. Pore structure and specific surface area analysis
[0059] Figure 3 This is the BET test of the nickel oxide - copper nitride supported graphene prepared in the present invention, and the BET area is as high as 113 m 2 / g.
[0060] 4. Test of catalytic hydrogen production performance
[0061] Test the catalytic hydrogen production performance of the catalysts prepared in Example 1, Example 2, and Example 4 and Comparative Example 1, Example 2, Example 3, and Example 4;
[0062] Figure 4 、 Figure 5 、 Figure 6This is the performance test for preparing nickel oxide - copper nitride supported on graphene as a catalyst for catalytic hydrolysis of ammonia borane to produce hydrogen in the present invention. The amount of NH 3 BH 3 is 3 mmol, the amount of NaOH is 10 mmol, and the amount of the catalyst is 10 mg. The hydrogen production rate curve of nickel oxide - copper nitride / graphene catalytic ammonia borane at 25 °C was measured.
[0063] The above are the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements are also regarded as the protection scope of the present invention.
Claims
1. A method for preparing a nanowire nickel oxide-copper nitride loaded graphene composite material, characterized in that: The following steps are involved: (1) dissolving soluble copper salt and nickel salt in ultrapure water in proportion to prepare a mixed salt solution A; (2) ultrasonically dispersing the carrier graphene in ultrapure water; (3) slowly adding the graphene dispersion into solution A under magnetic stirring to form solution B; (4) Slowly add alkali solution to solution B to form solution C; (5) Transfer solution C to a reactor, react at 100-180°C for 6-12 hours, filter and wash, collect the product, and dry; (6) Place the sample in a muffle furnace and calcine at 350 °C for 2 h. After the reaction is completed, collect the sample; (7) Using ammonia as the ammonia source, place the sample in step (6) upstream of a tube furnace and calcine it at 300-400° C. in an ammonia atmosphere for 0.5-5 h to perform partial nitridation treatment.
2. The method for preparing a nanowire nickel oxide-copper nitride loaded graphene composite material according to claim 1, characterized in that: The ratio of the soluble copper salt to the nickel salt in step (1) is 1:10-10:
1.
3. The method for preparing a nanowire nickel oxide-copper nitride loaded graphene composite material according to claim 1, characterized in that: The soluble copper salt in step (1) is selected from one or more of copper acetate monohydrate, copper sulfate pentahydrate, copper nitrate hexahydrate, and copper chloride dihydrate.
4. The method for preparing a nanowire nickel oxide-copper nitride loaded graphene composite material according to claim 1, characterized in that: The soluble nickel salt in step (1) is selected from one or more of nickel acetate tetrahydrate, nickel sulfate hexahydrate, nickel nitrate hexahydrate, and nickel chloride hexahydrate.
5. The method for preparing a nanowire nickel oxide-copper nitride loaded graphene composite material according to claim 1, characterized in that: The soluble copper salt in step (1) is copper acetate monohydrate, and the soluble nickel salt is nickel acetate tetrahydrate.
6. The method for preparing a nanowire nickel oxide-copper nitride loaded graphene composite material according to claim 1, characterized in that: The alkaline solution in step (4) is selected from one or more of urea, sodium hydroxide, potassium hydroxide, ammonia water, and hexamethylenetetramine.
7. The method for preparing a nanowire nickel oxide-copper nitride loaded graphene composite material according to claim 1, characterized in that: The amount of the alkali substance added in step (4) is 10 to 50 times that of the metal ion.
8. A nanowire nickel oxide-copper nitride loaded graphene composite material, characterized in that: Prepared according to the method according to any one of claims 1 to 7.
9. Use of the nanowire nickel oxide-copper nitride supported graphene composite material prepared by the preparation method according to any one of claims 1 to 7 as a catalyst in catalyzing the hydrolysis of ammonia borane to produce hydrogen.