NiRuM / C catalyst for water electrolysis of anion exchange membrane as well as preparation method and application of NiRuM / C catalyst

Abstract

The invention belongs to the technical field of water electrolysis hydrogen production, and particularly relates to a NiRuM / C catalyst for anion exchange membrane water electrolysis as well as a preparation method and application of the NiRuM / C catalyst. The NiRuM / C hydrogen evolution catalyst is prepared by adopting two ways: one way is a coprecipitation method: firstly coating a carbon carrier with amorphous nickel salt by utilizing coprecipitation, and then preparing the NiRuM / C catalyst by utilizing precipitation dissolution equilibrium movement; and 2, a group anchoring method: dispersing metal salts such as nickel, ruthenium and the like and the dopamine hydrochloride surface functionalized carbon material in a polar solvent, and preparing the NiRuM / C catalyst through coordination interaction and self-polymerization reaction of dopamine molecules. The invention provides two preparation ways of the NiRuM / C material with alkaline hydrogen evolution performance better than that of a platinum-based material, and the NiRuM / C material is applied to anion exchange membrane water electrolysis hydrogen production, so that the problems of complex process, high price, low hydrogen production efficiency, poor durability and the like of the existing preparation technology are solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogen production by electrolyzing water with an anion exchange membrane, and particularly relates to a NiRuM / C catalyst for anion exchange membrane water electrolysis, a preparation method thereof, and an application thereof. Background Art

[0002] As a key driving force for the national energy transformation and strategic security, hydrogen energy, with its dual attributes of unique industrial raw materials and energy, has great strategic value for promoting the optimization of China's energy structure and building a safe, efficient, clean, and low-carbon modern energy system. Traditional hydrogen energy sources mainly rely on the reforming of fossil fuels with high carbon emissions, which does not conform to the concept of sustainable development. In contrast, the electrolysis water hydrogen production technology is an indispensable green hydrogen production technology with very broad application prospects. Therefore, the research and development of efficient and low-cost electrolysis water technology is crucial for the development of the hydrogen energy economy. However, the hydrogen evolution catalyst is the key to hydrogen evolution in electrolyzing water. The Pt-group noble metals are recognized as the optimal catalysts for HER, but their limited reserves and high prices limit their wide application. Therefore, the development of low-cost and efficient electrocatalysts is of great significance. Summary of the Invention

[0003] The purpose of the present invention is to provide a NiRuM / C catalyst for anion exchange membrane water electrolysis, a preparation method thereof, and an application thereof. Using a carbon material as a carrier, the NiRuM / C catalyst is prepared by a coprecipitation method or a group anchoring method, and has hydrogen evolution performance superior to that of a commercial platinum-carbon catalyst and excellent stability.

[0004] To achieve the above purpose, the first aspect of the present invention provides a preparation method of a NiRuM / C catalyst, including the following steps:

[0005] S1. Disperse the carbon material in a solvent, then add dopamine and polymerize it under alkaline conditions to perform surface treatment on the carbon material, and then perform suction filtration, washing, and drying to obtain a modified carbon material;

[0006] S2. Add nickel salt and sodium bicarbonate to deionized water to form a suspension, then introduce CO 2 until the solution becomes clear, then add the modified carbon material described in step S1, continue to introduce CO 2 and stir and react, and then successively perform suction filtration, washing, and drying to obtain a carbon material coated with nickel salt;

[0007] S3. Disperse the carbon material coated with nickel salt obtained in step S2 in deionized water, then add ruthenium salt and metal M salt, stir evenly at room temperature, and after successively performing suction filtration, washing, and drying, heat-treat the obtained dry powder in a reducing atmosphere to obtain a NiRuM / C catalyst;

[0008] Among them, the metal M salt is one or more of Cu salt, Cr salt, Ce salt, and Pt salt.

[0009] Further, in step S1, the carbon material is one or more of carbon black, carbon nanotubes, carbon spheres, and graphene; the alkaline condition is regulated by adding sodium hydroxide or ammonia water; the carbon black is preferably VULCAN XC72 or Ketjenblack. The solvent is water and / or ethanol. Dopamine is preferably dopamine hydrochloride.

[0010] The mass ratio of the carbon material to dopamine is (1-30):1, preferably (10-20):1.

[0011] Further, in step S2, the molar ratio of sodium bicarbonate to nickel salt is (2-4):1; the dosage ratio of nickel salt to modified carbon material is (0.3-5) mmol:0.2 g, preferably (3-5) mmol:0.2 g.

[0012] Further, in step S3, the molar ratio of nickel salt to ruthenium salt is (1-50):1, preferably (30-50):1; the molar ratio of nickel salt to metal M salt is (1-10):1, preferably (1-5):1. The nickel salt is any one of nickel nitrate, nickel chloride, nickel sulfate, and nickel acetate, and the type of metal M salt is any one of nitrate, chlorate, sulfate, and acetate.

[0013] Further, in step S3, the reducing atmosphere is a mixed atmosphere of hydrogen and argon or a mixed atmosphere of hydrogen and nitrogen, the temperature of the heat treatment is 200-1000 °C, preferably 500-1000 °C, and the time of the heat treatment is 1-5 h.

[0014] The second aspect of the present invention provides a method for preparing a NiRuM / C catalyst, comprising the following steps:

[0015] (1) Disperse dopamine hydrochloride in a solvent, then add a carbon material, and perform ultrasonic treatment to obtain a suspension;

[0016] (2) Add a nickel salt, a ruthenium salt, and a metal M salt to the black suspension obtained in step (1), then heat and stir, evaporate all the solvent, and grind to obtain a black solid powder; the metal M salt is one or more of Cu salt, Cr salt, Ce salt, and Pt salt;

[0017] (3) Heat-treat the black solid powder in step (2) under a reducing atmosphere to obtain a NiRuM / C catalyst.

[0018] Further, in step (1), the mass ratio of the carbon material to dopamine hydrochloride is (1 - 30):1, preferably (10 - 20):1; the carbon material is one or more of carbon black, carbon nanotubes, carbon spheres, and graphene; the solvent is water and / or ethanol.

[0019] In step (2), the dosage ratio of the nickel salt to the carbon material is (0.5 - 3) mmol:0.1 g; the molar ratio of the nickel salt to the ruthenium salt is (1 - 50):1, preferably (1 - 10):1;

[0020] The molar ratio of the nickel salt to the metal M salt is (1 - 10):1, preferably (1 - 5):1.

[0021] Further, in step (3), the reducing atmosphere is a mixed atmosphere of hydrogen and argon or a mixed atmosphere of hydrogen and nitrogen; the temperature of the heat treatment is 200 - 1000 °C, and the time of the heat treatment is 1 - 5 h.

[0022] When the metal M salt contains a Pt salt, its preparation method can be as follows: first, obtain the NiRuM / C catalyst (M does not include Pt) according to the above method, then disperse the NiRuM / C catalyst in ethanol, reflux at 110 °C for 1 - 3 h, cool to room temperature, add H 2 PtCl 6 ethanol solution, and then add NaOH. Heat the mixture to 80 °C and keep it for 2 hours. Cool the mixture to room temperature, filter and wash with water, and dry to obtain the Pt@NiRuM / C catalyst.

[0023] Further, the NiRuM / C catalyst prepared by the present invention is NiRuCuCr / C, NiRuCu / C, NiRuCr / C, Pt@NiRuCuCr / C, or NiRuCuCe / C. The molar content of element M is 1% - 50% of the total content of Ni and Ru, preferably 10% - 35%, such as 15%, 18%, 20%, 25%, 28%, 30%, 32%, 35%, etc.

[0024] The third aspect of the present invention provides a NiRuM / C catalyst obtained by the preparation method described in any one of the above.

[0025] The fourth aspect of the present invention provides an application of the above-mentioned NiRuM / C catalyst in anion exchange membrane electrolysis of water.

[0026] Generally speaking, compared with the prior art through the above technical solutions conceived by the present invention, the following technical advantages are mainly possessed:

[0027] 1. The present invention uses a surface-modified carbon material as a carrier and prepares a NiRuM / C hydrogen evolution catalyst by a coprecipitation method or a group anchoring method. Metal particles can be evenly dispersed on the carbon carrier. At the same time, through the synergistic effect of multiple metal elements, the hydrogen evolution catalyst not only exhibits excellent activity and stability in a three-electrode test, but also shows performance and stability comparable to that of a proton exchange membrane electrolyzed water device in an anion exchange membrane electrolyzed water device.

[0028] 2. The preparation method of the NiRuM / C hydrogen evolution catalyst provided by the present invention can flexibly adjust the types and proportions of metals, thereby accelerating the hydrogen desorption process, improving the intrinsic activity of the catalyst, making it exhibit hydrogen evolution performance far superior to that of commercial platinum-carbon catalysts, and at the same time improving stability.

[0029] 3. After the NiRuM / C cathode hydrogen evolution catalyst provided by the present invention is used as the cathode material for anion exchange membrane electrolyzed water, it shows a higher hydrogen production efficiency than commercial platinum-carbon and has excellent stability.

[0030] 4. When the NiRuM / C hydrogen evolution catalyst contains an appropriate amount of platinum, the overpotentials at 10 mA / cm 2 and 100 mA / cm 2 are as low as 12 mV and 45 mV respectively, and the hydrogen evolution performance and stability are better. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 is a schematic diagram of an anion exchange membrane electrolytic cell assembled with the hydrogen evolution catalyst of the present invention.

[0032] Figure 2 In (a) is a transmission electron microscope image of the NiRuCuCr / C hydrogen evolution catalyst prepared in Example 1 of the present invention, and (b) is the corresponding particle size estimation.

[0033] Figure 3 is the polarization curve of the NiRuCuCr / C hydrogen evolution catalyst prepared in Example 1 of the present invention in a three-electrode system.

[0034] Figure 4 is the potential-time curve of the NiRuCuCr / C hydrogen evolution catalyst prepared in Example 1 of the present invention operating stably at a current density of 100 mA cm -2 for 1000 h in a three-electrode system.

[0035] Figure 5 is the polarization curve of the NiRuCuCr / C hydrogen evolution catalyst prepared in Example 1 of the present invention in an AEMWE when the anode supplies 1 M KOH.

[0036] Figure 6For the NiRuCuCr / C hydrogen evolution catalyst prepared in Example 1 of the present invention in an AEMWE, when 1 M KOH is supplied to the anode, the potential-time curve at a stable operating current density of 1000 mA cm -2 for 200 h.

[0037] Figure 7 The polarization curve of the NiRuCuCr / C hydrogen evolution catalyst prepared in Example 1 of the present invention in an AEMWE when pure water is supplied to the anode.

[0038] Figure 8 For the NiRuCuCr / C hydrogen evolution catalyst prepared in Example 1 of the present invention in an AEMWE, when pure water is supplied to the anode, the potential-time curve at a stable operating current density of 500 mA cm -2 for 1000 h.

[0039] Figure 9 The polarization curve of the NiRuCr / C hydrogen evolution catalyst prepared in Example 2 of the present invention in a three-electrode system.

[0040] Figure 10 The polarization curve of the NiRuCu / C hydrogen evolution catalyst prepared in Example 3 of the present invention in an AEMWE in a three-electrode system.

[0041] Figure 11 The polarization curve of the NiRu / C hydrogen evolution catalyst prepared in Example 4 of the present invention in a three-electrode system.

[0042] Figure 12 The polarization curve of the NiRuCuCr / C hydrogen evolution catalyst prepared in Example 5 of the present invention in a three-electrode system.

[0043] Figure 13 The polarization curve of the Pt@NiRuCuCr / C hydrogen evolution catalyst prepared in Example 6 of the present invention in a three-electrode system.

[0044] Figure 14 For the Pt@NiRuCuCr / C hydrogen evolution catalyst prepared in Example 6 of the present invention in a three-electrode system, the potential-time curve at a stable operating current density of 100 mA cm -2 for 1000 h.

[0045] Figure 15 The polarization curve of the Pt@NiRuCuCr / C hydrogen evolution catalyst prepared in Example 6 of the present invention in an AEMWE when 1 M KOH is supplied to the anode.

[0046] Figure 16 The polarization curve of the Pt@NiRuCuCr / C hydrogen evolution catalyst prepared in Example 6 of the present invention in an AEMWE when pure water is supplied to the anode.

[0047] Figure 17 For the Pt@NiRuCuCr / C hydrogen evolution catalyst prepared in Example 6 of the present invention in an AEMWE, when pure water is supplied to the anode, at a current density of 500 mA cm -2 The potential-time curve of stable operation for 1000 h.

[0048] Figure 18 The polarization curve of the NiRuCuCe / C hydrogen evolution catalyst prepared in Example 7 of the present invention in a three-electrode system. Detailed implementation manners

[0049] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0050] Example 1

[0051] Preparation of NiRuCuCr / C hydrogen evolution catalyst by co-precipitation method

[0052] 1) Disperse 2 g of VULCAN XC72 in 100 ml of pure water containing 0.1 g of dopamine hydrochloride, add 5 - 10 ml of ammonia water for the polymerization of dopamine to perform surface treatment on the carbon material; after reacting for 12 h, filter the product by suction, wash it, and freeze-dry it.

[0053] Add 0.9 g of NiCl 2 ·6H 2 O and 0.7 g of NaHCO 3 to 200 ml of pure water to form a suspension, and continuously introduce CO 2 into the suspension until the solution becomes clear, then add 0.2 g of XC72 treated with dopamine, disperse it evenly to obtain a black suspension, and then continue to introduce CO for 10 - 20 min 2 (to ensure gas saturation), then stir overnight at room temperature, and successively filter by suction, wash, and dry to obtain a carbon material coated with nickel salt.

[0054] 2) Add 300 mg of Cr(NO 3 ) 3 ·9H 2 O, 20 mg of RuCl 3 ·3H 2 O, and 50 mg of Cu(NO 3 ) 2 ·3H 2O, after uniform dispersion, the obtained nickel salt-coated carbon material was then dispersed in this solution, stirred at room temperature until the filtrate was nearly colorless, and after suction filtration, washing, and drying in sequence, the obtained black powder was placed in a tube furnace and treated under a mixed atmosphere of H 2 / Ar (volume ratio 1:9) at 500 °C for 1 h with a heating rate of 5 °C / min. After the reaction was completed, the NiRuCuCr / C hydrogen evolution catalyst was obtained.

[0055] Figure 2 In (a) is the transmission electron microscope (TEM) image of the NiRuCuCr / C hydrogen evolution catalyst prepared in Example 1 of the present invention. From Figure 2 In (b), it can be seen that the metals in NiRuCuCr / C mainly exist in the form of particles, and the particle size is about 2.5 nm.

[0056] Application test

[0057] a) The alkaline hydrogen evolution performance of the NiRuCuCr / C catalyst prepared in Example 1 was tested and evaluated using a Chenhua electrochemical workstation. Figure 3 The polarization curve obtained from the test and evaluation in 1 M KOH solution shows that the overpotentials of this catalyst at 10 mA / cm 2 and 100 mA / cm 2 are 17 mV and 70 mV respectively, far lower than 38 mV and 188 mV of commercial platinum carbon (20 wt%). And (using the catalyst as the working electrode, Hg / HgO as the reference electrode, and a carbon rod as the counter electrode) in the three-electrode system, it can operate stably at a current density of 100 mA cm -2 for 1000 h (as Figure 4 ).

[0058] b) Assembly and performance evaluation of AEMWE: Using the NiRuCuCr / C catalyst as the cathode and the self-made self-supported nickel iron oxyhydroxide as the anode. The anode, anion exchange membrane, cathode, gas diffusion layer, flow channel plate, and end plate were assembled into an AEMWE electrolytic cell in sequence, and the structure of the electrolytic cell device is as Figure 1 shown. The effective area of the membrane electrode is 5 cm 2 , 1 M KOH is supplied to the anode, and the test temperature is 25 °C - 80 °C.

[0059] c) Using the NiRuCuCr / C powder catalyst prepared in Example 1 as the cathode of AEMWE (anion exchange membrane water electrolysis) and supplying 1 M KOH to the anode, the polarization curve is as Figure 5 shown. At a voltage of 1.8 V, the current density can reach 2.3 A / cm 2 , and at a voltage of 2.0 V, it reaches 3.9 A / cm 2 , which is better than 1.76 A / cm 2and 3.2 A / cm 2 . Under alkaline conditions, it can operate stably for 200 h, as Figure 6 shown.

[0060] d) The NiRuCuCr / C powder catalyst prepared in Example 1 was used as the cathode of AEMWE, and pure water was supplied to the anode. The polarization curve is as Figure 7 shown. At a voltage of 1.8 V, the current density can reach 840 mA / cm 2 , and at 2.0 V, it reaches 1640 mA / cm 2 , which is better than 600 mA / cm of commercial platinum-carbon 2 and 1400 mA / cm 2 . And it can operate stably for 1000 h under pure water conditions, as Figure 8 shown.

[0061] Example 2

[0062] Preparation of NiRuCr / C hydrogen evolution catalyst by co-precipitation method

[0063] The preparation method was the same as that in Example 1, except that Cu(NO 3 ) 2 ·3H 2 O was not added in step 2). The test result of the three-electrode system showed that the overpotential at 10 mA cm -2 was 31 mV, and the catalytic performance decreased compared with that in Example 1, as Figure 9 shown.

[0064] Example 3

[0065] Preparation of NiRuCu / C hydrogen evolution catalyst by co-precipitation method

[0066] The preparation method was the same as that in Example 1, except that Cr(NO 3 ) 3 ·9H 2 O was not added in step 2). The test result of the three-electrode system showed that the overpotential at 10 mA cm -2 was 105 mV, and the catalytic performance decreased significantly compared with that in Example 1, as Figure 10 shown.

[0067] Example 4

[0068] Preparation of NiRu / C hydrogen evolution catalyst by co-precipitation method

[0069] The preparation method was the same as that in Example 1, except that Cu(NO 3 ) 2 ·3H 2 O and Cr(NO 3 ) 3 ·9H2 O. The overpotential of the three - electrode system test result at 10 mA cm -2 is 122 mV, indicating that the synchronous doping of Cr and Cu is more conducive to improving the hydrogen evolution catalytic performance, as Figure 11 shown.

[0070] Example 5

[0071] Preparation of NiRuCuCr / C hydrogen evolution catalyst by group anchoring method

[0072] Disperse 0.1 g of dopamine hydrochloride in 100 mL of ethanol, then add 1 g of VULCAN XC - 72 to the solution and ultrasonically treat for 5 minutes. Then add 10 mL of an ethanol solution containing RuCl 3 ·3H 2 O (0.3 g), NiCl 2 ·6H 2 O (0.4 g), Cu(NO 3 ) 2 ·3H 2 O (0.1 g) and Cr(NO 3 ) 3 ·9H 2 O (0.2 g). Then place the suspension in an oil bath and stir at a constant temperature of 40 °C until all the ethanol has evaporated to obtain a black powder. Then, under an H 2 / Ar atmosphere at 800 °C, anneal the powder at a heating rate of 10 °C / min for 1 - 3 h to obtain the NiRuCuCr / C hydrogen evolution catalyst. The overpotential of the three - electrode system test result at 10 mA cm -2 is 18 mV, as Figure 12 shown.

[0073] Example 6

[0074] Preparation of Pt@NiRuCuCr / C catalyst by group anchoring method

[0075] Take 1 g of the NiRuCuCr / C synthesized in Example 5 and disperse it in 100 mL of ethanol, and reflux at 110 °C for 1 h. After cooling to room temperature, add 8 ml of 50 mM H 2 PtCl 6 ethanol solution, then add 800 μmol of NaOH, and stir vigorously to ensure uniform dispersion. Heat the mixture to 80 °C and keep it for 2 hours. Cool the mixture to room temperature, filter, wash with a large amount of water, and dry to obtain the Pt@NiRuCuCr / C catalyst.

[0076] Application test

[0077] a) The alkaline hydrogen evolution performance of the Pt@NiRuCuCr / C catalyst prepared in Example 6 was tested and evaluated using an electrochemical workstation. Figure 13 The polarization curve obtained from the test and evaluation in 1 M KOH solution shows that the overpotentials of this catalyst at 10 mA / cm 2 and 100 mA / cm 2 are 12 mV and 45 mV respectively, which are much lower than 38 mV and 188 mV of commercial platinum carbon (20 wt%). And it can stably operate at a current density of 100 mA cm -2 for 1000 h in a three-electrode system (as shown in Figure 14 ).

[0078] b) Assembly and performance evaluation of AEMWE: Using the Pt@NiRuCuCr / C catalyst as the cathode and a self-made self-supporting nickel iron oxyhydroxide as the anode. The anode, anion exchange membrane, cathode, gas diffusion layer, flow channel plate and end plate were assembled into an AEMWE electrolytic cell in sequence, and the structure of the electrolytic cell device is as shown in Figure 2 . The effective area of the membrane electrode is 5 cm 2 , 1 M KOH is supplied to the anode, and the test temperature is 25 °C - 80 °C.

[0079] c) Using the Pt@NiRuCuCr / C powder catalyst prepared in Example 6 as the cathode of AEMWE and supplying 1 M KOH to the anode, the polarization curve is as shown in Figure 15 . The current density can reach 2.2 A / cm 2 at a voltage of 1.8 V and 3.9 A / cm 2 at a voltage of 2.0 V, which is better than 1.76 A / cm 2 and 3.2 A / cm 2 of commercial platinum carbon.

[0080] d) Using the Pt@NiRuCuCr / C powder catalyst prepared in Example 6 as the cathode of AEMWE and supplying pure water to the anode, the polarization curve is as shown in Figure 16 . The current density can reach 700 mA / cm 2 at a voltage of 1.8 V and 1580 mA / cm 2 at a voltage of 2.0 V, which is better than 600 mA / cm 2 and 1400 mA / cm 2 of commercial platinum carbon. And it can stably operate for 1000 h under pure water conditions, as shown in Figure 17 .

[0081] Example 7

[0082] Preparation of NiRuCuCe / C catalyst by group anchoring method

[0083] Disperse 0.1 g of dopamine hydrochloride in 100 mL of ethanol, and then add 1 g of VULCAN XC-72 to the solution and sonicate for 5 minutes. Then add 10 mL of an ethanol solution containing RuCl 3 ·3H 2 O (0.3 g), NiCl 2 ·6H 2 O (0.4 g), Cu(NO 3 ) 2 ·3H 2 O (0.05 g) and Ce(C 2 H 3 O 2 ) 3 ·4H 2 O (0.4 g). Then place the suspension in an oil bath and stir at a constant temperature of 40 °C to evaporate all the ethanol to obtain a black powder. Then anneal the powder at a heating rate of 10 °C / min for 1 h in an H 2 / Ar atmosphere at 600 °C. The overpotential measured by the three-electrode system is 26 mV at 10 mA cm -2 , as shown in Figure 18 .

[0084] It is easy for those skilled in the art to understand that the above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a NiRuM / C catalyst, characterized in that: The following steps are involved: S1, dispersing the carbon material in a solvent, then adding dopamine and polymerizing under alkaline conditions to treat the surface of the carbon material, then filtering, washing, and drying to obtain a modified carbon material; S2, adding nickel salt and sodium bicarbonate to deionized water to prepare a suspension, then passing CO2 to clarify the solution, then adding the modified carbon material described in step S1, continuing to pass CO2 to stir the reaction, and then filtering, washing, and drying in sequence to obtain a nickel salt-coated carbon material; S3, dispersing the nickel salt-coated carbon material obtained in step S2 in deionized water, then adding ruthenium salt and metal M salt, stirring evenly at room temperature, filtering, washing, and drying in sequence, and heat-treating the obtained dry powder under a reducing atmosphere to obtain a NiRuM / C catalyst; Wherein, the metal M salt is one or more of Cu salt, Cr salt, Ce salt and Pt salt.

2. The preparation method according to claim 1, characterized in that: In step S1, the carbon material is one or more of carbon black, carbon tubes, carbon spheres, and graphene; the alkaline condition is regulated by adding sodium hydroxide or ammonia water; The mass ratio of the carbon material to dopamine is (1-30):1, preferably (10-20):

1.

3. The preparation method according to claim 1, characterized in that: In step S2, the molar ratio of the sodium bicarbonate to the nickel salt is (2-4):1; the usage ratio of the nickel salt to the modified carbon material is (0.3-5) mmol:0.2 g, preferably (3-5) mmol:0.2 g.

4. The preparation method according to claim 1, characterized in that: In step S3, the molar ratio of the nickel salt to the ruthenium salt is (1-50):1, preferably (30-50):1; The molar ratio of the nickel salt to the metal M salt is (1-10):1, preferably (1-5):

1.

5. The preparation method according to claim 1, characterized in that: In step S3, the reducing atmosphere is a mixed atmosphere of hydrogen and argon or a mixed atmosphere of hydrogen and nitrogen, the temperature of the heat treatment is 200-1000° C., and the time of the heat treatment is 1-5 hours.

6. A method for preparing a NiRuM / C catalyst, characterized in that: The following steps are involved: (1) dispersing dopamine hydrochloride in a solvent, then adding a carbon material, and ultrasonically treating the carbon material to obtain a suspension; (2) adding nickel salt, ruthenium salt and metal M salt to the black suspension obtained in step (1), then heating and stirring, evaporating all the solvent, and grinding to obtain a black solid powder; the metal M salt is one or more of Cu salt, Cr salt, Ce salt and Pt salt; (3) Heat treating the black solid powder in step (2) under a reducing atmosphere to obtain a NiRuM / C catalyst.

7. The preparation method according to claim 6, characterized in that: In step (1), the mass ratio of the carbon material to dopamine hydrochloride is (1-30):1, preferably (10-20):1; the carbon material is one or more of carbon black, carbon tubes, carbon spheres, and graphene; In step (2), the molar ratio of the nickel salt to the carbon material is (0.5-3) mmol:0.1 g; the molar ratio of the nickel salt to the ruthenium salt is (1-50):1, preferably (1-10):1; The molar ratio of the nickel salt to the metal M salt is (1-10):1, preferably (1-5):

1.

8. The preparation method according to claim 6, characterized in that: In step (3), the reducing atmosphere is a mixed atmosphere of hydrogen and argon or a mixed atmosphere of hydrogen and nitrogen; the heat treatment temperature is 200-1000° C., and the heat treatment time is 1-5 h.

9. A NiRuM / C catalyst obtained by the preparation method according to any one of claims 1 to 8.

10. Use of the NiRuM / C catalyst according to claim 9 in anion exchange membrane water electrolysis.

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