阅读说明：本技术 一种Co3O4纳米多孔阴极涂层的制备方法及其应用 (Co3O4Preparation method and application of nano-porous cathode coating ) 是由 王建国 张世杰 包志康 丁磊 季文凯 于 2020-12-07 设计创作，主要内容包括：本发明公开了一种Co-3O-4纳米多孔阴极涂层的制备方法及其应用。该方法是以Ni或雷尼镍为基底,将Co-3O-4与Al进行混合,涂覆在磁控溅射的靶材上,通过磁控溅射的方式将混合物涂负于基底上,形成一种致密的混合物涂层,然后用碱液对其表面进行刻蚀,清洗干燥后得到多孔的Co-3O-4纳米涂层。该发明一方面提高阴极电极的化学稳定性,使其在反应过程中不容易腐蚀,另一方面由于是多孔材料,不会影响其反应进程。该方法不仅可以降低电极腐蚀产生的成本,还可以避免因腐蚀带来的电解液的不纯导致的性能降低,有着很大的应用前景。(The invention discloses a Co 3 O 4 A preparation method and application of a nano-porous cathode coating. The method takes Ni or Raney nickel as a substrate and Co 3 O 4 Mixing with Al, coating on the target material of magnetron sputtering, coating the mixture on a substrate in a magnetron sputtering mode to form a compact mixture coating, etching the surface of the compact mixture coating with alkali liquor, cleaning and drying to obtain porous Co 3 O 4 And (4) nano coating. The invention improves the chemical stability of the cathode electrode on one hand, so that the cathode electrode is not easy to corrode in the reaction process, and on the other hand, the reaction process is not influenced because the cathode electrode is made of porous material. The method can reduce the cost caused by electrode corrosion, avoid the performance reduction caused by the impurity of the electrolyte caused by corrosion, and has wide application prospect.)

1. Co₃O₄The preparation method of the nano-porous cathode coating is characterized by comprising the following steps:

1) selecting a substrate, cleaning the substrate by adopting water and ethanol, and drying the substrate for later use;

2) mixing Co₃O₄Mixing with Al, coating on the target material of magnetron sputtering, and performing magnetron sputtering to Co₃O₄Coating Al on the substrate in the step 1) to form a compact mixture coating;

3) purging the mixture coating prepared by step 2);

4) preparing a sodium hydroxide solution, and putting the mixture coating which is swept in the step 3) into the sodium hydroxide solution for etching;

5) ultrasonically cleaning the mixture coating etched in the step 4) by using deionized water, repeatedly cleaning for a certain number of times, and drying to obtain Co₃O₄A nanoporous cathode coating.

2. Co according to claim 1₃O₄The preparation method of the nano-porous cathode coating is characterized in that the substrate is Ni or Raney nickel, preferably the Raney nickel.

3. Co according to claim 1₃O₄The preparation method of the nano-porous cathode coating is characterized in that Co in the step 2)₃O₄The mass ratio to Al is 1: 0.5-1: 5, preferably 3: 2.

4. co according to claim 1₃O₄The preparation method of the nano porous cathode coating is characterized in that the sputtering time of the magnetron sputtering mode in the step 2) is 5-50 min, preferably 15 min; the sputtering current is 10-20A, preferably 13A, the operation is carried out by adopting a rotary sputtering mode, and the sputtering amount per minute is the same.

5. Co according to claim 1₃O₄Method for producing a nanoporous cathode coating, characterized in that the purging in step 3) is performed with an inert gas, preferably N₂。

6. Co according to claim 1₃O₄The preparation method of the nano porous cathode coating is characterized in that the concentration of sodium hydroxide in the step 4) is 3-8M, preferably 5M; heating and etching are carried out, wherein the temperature is 40-80 ℃, and preferably 60 ℃.

7. According to the rightCo of claim 1₃O₄The preparation method of the nano porous cathode coating is characterized in that the ultrasonic power of the ultrasonic wave in the step 5) is 350-700W, preferably 500W; the time is 5-10 min, preferably 7 min; the number of times of repeated washing is 3 to 8, preferably 5.

8. Co according to claim 1₃O₄The preparation method of the nano porous cathode coating is characterized in that the drying in the step 5) is drying in an oven at 50-80 ℃ for 6-12 h, the temperature is preferably 60 ℃, and the time is preferably 10 h.

9. Co as claimed in claim 1₃O₄The application of the nano-porous cathode coating is characterized by comprising the following operation steps: to coating with Co₃O₄Performing electrolytic deuterium evolution performance test on the electrode of the nano-porous cathode coating, and testing the deuterium evolution performance by adopting a three-electrode system to coat Co₃O₄The electrode of the nano-porous cathode coating is used as a working electrode, Ag/AgCl is used as a reference electrode, a stone grinding rod is used as a comparison electrode, the electrolyte used for testing is 1M NaOD solution, and electrolysis is carried out at normal temperature and normal pressure.

Technical Field

The invention belongs to the technical field of catalyst electrode preparation, and particularly relates to Co₃O₄A preparation method and application of a nano-porous cathode coating.

Background

With the advance of human science and technology, various electrode catalysis technologies come out endlessly! The general trend is still towards "nanocrystallization", that is, the microstructure of the catalytic material is controlled by various ways and means, and the development and the change are carried out towards the direction expected by people, so as to realize the excellent performance of the microstructure of the catalytic material. Currently, although research has led to the acquisition of a number of methods for the nanocrystallization of catalytic materials, such as: laser ablation, chemical vapor deposition, thermal vapor deposition, templating, hydrothermal methods, and the like, but are subject to industrial applications. Especially, there are many problems in terms of mass production, large-scale production and assembly process with the electrode. The magnetron sputtering process is a common physical deposition mode for preparing the nano film, the method has wide selectivity range on the substrate of the deposited film, and the ultrathin film of dozens of nanometers can be prepared on the substrate.

In the field of catalysis, the catalyst can be used for coating by vapor deposition, and as a preparation method of the catalyst, in the machining industry, the surface deposition technology of a surface functional film, a superhard film and a self-lubricating film is greatly developed since the emergence of the technology, and the surface hardness, the composite toughness, the wear resistance and the high-temperature resistance chemical stability can be effectively improved, so that the service life of a coating product is greatly prolonged.

Disclosure of the invention

In order to adapt to batch and large-scale processing, the thickness of the coating is effectively controlled within 100nm, the technical method which causes complicated and expensive process flow in the forming process of the porous nano coating is avoided, the technical process is simple and efficient, and the pores of the coating are simple and efficientFine and uniform, the invention provides a Co₃O₄A preparation method and application of a nano-porous cathode coating.

One kind of Co₃O₄The preparation method of the nano-porous cathode coating is characterized by comprising the following steps:

1) selecting a substrate, cleaning the substrate by adopting water and ethanol, and drying the substrate for later use;

2) mixing Co₃O₄Mixing with Al, coating on the target material of magnetron sputtering, and performing magnetron sputtering to Co₃O₄Coating Al on the substrate in the step 1) to form a compact mixture coating;

3) purging the mixture coating prepared by step 2);

4) preparing a sodium hydroxide solution, and putting the mixture coating which is swept in the step 3) into the sodium hydroxide solution for etching;

5) ultrasonically cleaning the mixture coating etched in the step 4) by using deionized water, repeatedly cleaning for a certain number of times, and drying to obtain Co₃O₄A nanoporous cathode coating.

One kind of Co₃O₄The preparation method of the nano-porous cathode coating is characterized in that the substrate is Ni or Raney nickel, preferably the Raney nickel.

One kind of Co₃O₄The preparation method of the nano-porous cathode coating is characterized in that Co in the step 2)₃O₄The mass ratio to Al is 1: 0.5-1: 5, preferably 3: 2.

one kind of Co₃O₄The preparation method of the nano porous cathode coating is characterized in that the sputtering time of the magnetron sputtering mode in the step 2) is 5-50 min, preferably 15 min; the sputtering current is 10-20A, preferably 13A, the operation is carried out by adopting a rotary sputtering mode, and the sputtering amount per minute is the same.

One kind of Co₃O₄Method for producing a nanoporous cathode coating, characterized in that the purging in step 3) is performed with an inert gas, preferably N₂。

One kind of Co₃O₄The preparation method of the nano porous cathode coating is characterized in that the concentration of sodium hydroxide in the step 4) is 3-8M, preferably 5M; heating and etching are carried out, wherein the temperature is 40-80 ℃, and preferably 60 ℃.

One kind of Co₃O₄The preparation method of the nano porous cathode coating is characterized in that the ultrasonic power of the ultrasonic wave in the step 5) is 350-700W, preferably 500W; the time is 5-10 min, preferably 7 min; the number of times of repeated washing is 3 to 8, preferably 5.

One kind of Co₃O₄The preparation method of the nano porous cathode coating is characterized in that the drying in the step 5) is drying in an oven at 50-80 ℃ for 6-12 h, the temperature is preferably 60 ℃, and the time is preferably 10 h.

Co₃O₄The application of the nano-porous cathode coating is characterized by comprising the following operation steps: to coating with Co₃O₄Performing electrolytic deuterium evolution performance test on the electrode of the nano-porous cathode coating, and testing the deuterium evolution performance by adopting a three-electrode system to coat Co₃O₄The electrode of the nano-porous cathode coating is used as a working electrode, Ag/AgCl is used as a reference electrode, a stone grinding rod is used as a comparison electrode, the electrolyte used for testing is 1M NaOD solution, and electrolysis is carried out at normal temperature and normal pressure.

Co of the invention₃O₄The preparation method of the nano porous cathode coating has the following effects:

1) the coating thickness of the invention is controlled to be about 60nm, the surface presents a porous appearance, the specific surface area is large, the combination with the nickel electrode substrate is firm, the chemical stability of the cathode electrode can be well improved, and the cathode electrode is not easy to corrode in the reaction process.

2) The coating is a porous material, and is used as an electrode for electrolytic rehydration deuterium evolution reaction, and deuterium gas can well permeate through pores, so that the reaction process is not influenced.

3) The coating method of the coating can reduce the cost caused by electrode corrosion, can avoid the performance reduction caused by the impurity of electrolyte brought by corrosion, and has good social and economic benefits.

Drawings

FIG. 1 is a schematic view of the magnetron sputtering principle;

FIG. 2 is a SEM image of a surface of pure Raney nickel;

FIG. 3 shows Co-containing pellets prepared in example 2₃O₄SEM image of raney nickel of the coating;

FIG. 4 shows a pure Raney nickel electrode and Co prepared in example 2₃O₄Deuterium evolution stability test pattern of coated raney nickel.

Detailed Description

The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.

Example 1

Taking a piece of Raney nickel as a substrate, cleaning the substrate by using a mixed solution of water and ethanol, and drying the substrate for later use. Mixing Co₃O₄And Al in a mass ratio of 1: 0.5 g of the mixture is taken to coat the mixture of 5g on a target material for magnetron sputtering, and Co is coated on the target material by the way of magnetron sputtering₃O₄Spin-sputter coating the substrate with a mixture of Al for 5min at a sputter current of 10A to form a dense coating of the mixture, and then applying N₂Purging is carried out; preparing a NaOH solution with the concentration of 3M, putting 100ml of the NaOH solution into a beaker, immersing the Raney nickel with the coating into the beaker for etching, and continuously stirring for 3 hours by magnetic force, wherein the heating temperature is 40 ℃; cleaning the etched Raney nickel, placing the Raney nickel in a clean beaker, adding deionized water, then placing the Raney nickel in an ultrasonic pool for ultrasonic operation with the ultrasonic power of 350W for 5min, then taking out the Raney nickel, replacing the deionized water in the beaker, repeating the cleaning operation for 3 times, then drying in an oven at 50 ℃ for 6h to finally obtain Co₃O₄A raney nickel electrode with a nanoporous cathode coating.

And (3) carrying out electrolytic deuterium evolution performance test on the prepared electrode: 1 x 1cm²Co of (A)₃O₄And washing the Raney nickel electrode with the nano-porous cathode coating with water and ethanol, and naturally drying. Using a three-electrode systemThe performance of deuterium evolution is tested, the prepared electrode is used as a working electrode, Ag/AgCl is used as a reference electrode, a millstone rod is used as a comparison electrode, a test electrolyte is a 1M NaOD solution, the activity of the catalyst is judged at normal temperature and normal pressure through the change of current density along with voltage, and the test results are shown in Table 1.

Example 2

Taking a piece of Raney nickel as a substrate, cleaning the substrate by using a mixed solution of water and ethanol, and drying the substrate for later use. Mixing Co₃O₄And Al according to a mass ratio of 3:2, mixing, coating 5g of the mixture on a magnetron sputtering target material, and carrying out magnetron sputtering on Co₃O₄Spin-sputter coating the substrate with Al for 15min at a sputter current of 13A to form a dense coating of the mixture, and then applying N₂Purging, preparing a NaOH solution with the concentration of 5M, putting 100ml of the solution into a beaker, immersing the Raney nickel with the coating into the beaker for etching, continuously magnetically stirring for 3 hours, heating to 60 ℃, cleaning the etched Raney nickel, putting the Raney nickel into a clean beaker, adding deionized water, then putting the Raney nickel into an ultrasonic pool for ultrasonic operation with the ultrasonic power of 500W and the time of 7min, taking out the Raney nickel, replacing the deionized water in the beaker, repeating the cleaning operation for 5 times, drying for 10 hours in an oven with the temperature of 60 ℃, and finally obtaining Co₃O₄A raney nickel electrode with a nanoporous cathode coating.

And (3) carrying out electrolytic deuterium evolution performance test on the prepared electrode: 1 x 1cm²Co of (A)₃O₄And washing the Raney nickel electrode with the nano-porous cathode coating with water and ethanol, and naturally drying. The three-electrode system is adopted to test the performance of deuterium evolution, the prepared electrode is used as a working electrode, Ag/AgCl is used as a reference electrode, a graphite grinding rod is used as a comparison electrode, the test electrolyte is 1M NaOD solution, the activity of the catalyst is judged at normal temperature and normal pressure through the change of current density along with voltage, and the test results are shown in Table 1.

Example 3

Taking a piece of Raney nickel as a substrate, and carrying out the process by using a mixed solution of water and ethanolCleaning and drying for later use. Mixing Co₃O₄Mixing with Al according to the mass ratio of 1:5, coating 5g of the mixture on a magnetron sputtering target material, and carrying out magnetron sputtering on Co₃O₄Spin-sputter coating with Al on the substrate for 20min at a sputter current of 20A to form a dense mixture coating, and then applying N₂Purging, preparing NaOH solution with the concentration of 8M, putting 100ml of the solution into a beaker, immersing the Raney nickel with the coating into the beaker for etching, continuously magnetically stirring for 3 hours, heating to 80 ℃, cleaning the etched Raney nickel, putting the Raney nickel into a clean beaker, adding deionized water, then putting the Raney nickel into an ultrasonic pool for ultrasonic operation with the ultrasonic power of 700W and the time of 10 minutes, then taking out the Raney nickel, replacing the deionized water in the beaker, repeating the cleaning operation for 8 times, then drying in an oven with the temperature of 80 ℃ for 12 hours, and finally obtaining Co₃O₄A raney nickel electrode with a nanoporous cathode coating.

And (3) carrying out electrolytic deuterium evolution performance test on the prepared electrode: 1 x 1cm²Co of (A)₃O₄And washing the Raney nickel electrode with the nano-porous cathode coating with water and ethanol, and naturally drying. The three-electrode system is adopted to test the performance of deuterium evolution, the prepared electrode is used as a working electrode, Ag/AgCl is used as a reference electrode, a graphite grinding rod is used as a comparison electrode, the test electrolyte is 1M NaOD solution, the activity of the catalyst is judged at normal temperature and normal pressure through the change of current density along with voltage, and the test results are shown in Table 1.

Example 4

Taking a piece of Raney nickel as a substrate, cleaning the substrate by using a mixed solution of water and ethanol, and drying the substrate for later use. Mixing Co₃O₄Mixing with Al according to the mass ratio of 3:2, coating 5g of the mixture on a magnetron sputtering target material, and carrying out magnetron sputtering on Co₃O₄Spin-sputter coating the substrate with a mixture of Al for 5min at a sputter current of 13A to form a dense coating of the mixture, and then applying N₂Purging is carried out; preparing 5M NaOH solution, placing 100ml of the NaOH solution in a beaker, and coating the NaOH solutionSoaking raney nickel into a beaker for etching, continuously magnetically stirring for 3 hours at the heating temperature of 60 ℃, cleaning the etched raney nickel, putting the raney nickel into a clean beaker, adding deionized water, then putting the beaker into an ultrasonic pool for ultrasonic operation with the ultrasonic power of 500W and the ultrasonic time of 7min, then taking out the raney nickel, replacing the deionized water in the beaker, repeating the cleaning operation for 5 times, then drying the beaker in a 60 ℃ oven for 10 hours to finally obtain Co₃O₄A raney nickel electrode with a nanoporous cathode coating.

And (3) carrying out electrolytic rehydration deuterium evolution performance test on the prepared electrode: 1 x 1cm²Co of (A)₃O₄And washing the Raney nickel electrode with the nano-porous cathode coating with water and ethanol, and naturally drying. The three-electrode system is adopted to test the performance of deuterium evolution, the prepared electrode is used as a working electrode, Ag/AgCl is used as a reference electrode, a graphite grinding rod is used as a comparison electrode, the test electrolyte is 1M NaOD solution, the activity of the catalyst is judged at normal temperature and normal pressure through the change of current density along with voltage, and the test results are shown in Table 1.

Example 5

Taking a piece of Raney nickel as a substrate, cleaning the substrate by using a mixed solution of water and ethanol, and drying the substrate for later use. Mixing Co₃O₄Mixing with Al according to the mass ratio of 3:2, coating 5g of the mixture on a magnetron sputtering target material, and carrying out magnetron sputtering on Co₃O₄Spin-sputter coating the substrate with a mixture of Al for 25min at a sputter current of 13A to form a dense coating of the mixture, and then applying N₂Purging is carried out; preparing NaOH solution with the concentration of 5M, putting 100ml of the solution into a beaker, immersing the Raney nickel with the coating into the beaker for etching, continuously magnetically stirring for 3 hours, heating to 60 ℃, cleaning the etched Raney nickel, putting the Raney nickel into a clean beaker, adding deionized water, then putting the Raney nickel into an ultrasonic pool for ultrasonic operation with the ultrasonic power of 500W and the time of 7min, then taking out the Raney nickel, replacing the deionized water in the beaker, repeating the cleaning operation for 5 times, and then drying in an oven at 60 ℃ for 10 hours to finally obtain Co₃O₄A raney nickel electrode with a nanoporous cathode coating.

And (3) carrying out electrolytic rehydration deuterium evolution performance test on the prepared electrode: 1 x 1cm²Co of (A)₃O₄And washing the Raney nickel electrode with the nano-porous cathode coating with water and ethanol, and naturally drying. The three-electrode system is adopted to test the performance of deuterium evolution, the prepared electrode is used as a working electrode, Ag/AgCl is used as a reference electrode, a graphite grinding rod is used as a comparison electrode, the test electrolyte is 1M NaOD solution, the activity of the catalyst is judged at normal temperature and normal pressure through the change of current density along with voltage, and the test results are shown in Table 1.

Example 6

Taking a piece of Raney nickel as a substrate, cleaning the substrate by using a mixed solution of water and ethanol, and drying the substrate for later use. Mixing Co₃O₄Mixing with Al according to the mass ratio of 3:2, coating 5g of the mixture on a magnetron sputtering target material, and carrying out magnetron sputtering on Co₃O₄Coating the mixture with Al on a substrate by rotary sputtering for 50min at a sputtering current of 13A to form a compact mixture coating, and then purging with N2; preparing NaOH solution with the concentration of 5M, putting 100ml of the solution into a beaker, immersing the Raney nickel with the coating into the beaker for etching, continuously magnetically stirring for 3 hours, heating to 60 ℃, cleaning the etched Raney nickel, putting the Raney nickel into a clean beaker, adding deionized water, then putting the Raney nickel into an ultrasonic pool for ultrasonic operation with the ultrasonic power of 500W and the time of 7min, then taking out the Raney nickel, replacing the deionized water in the beaker, repeating the cleaning operation for 5 times, and then drying in an oven at 60 ℃ for 10 hours to finally obtain Co₃O₄A raney nickel electrode with a nanoporous cathode coating.

And (3) carrying out electrolytic deuterium evolution performance test on the prepared electrode: 1 x 1cm²Co of (A)₃O₄And washing the Raney nickel electrode with the nano-porous cathode coating with water and ethanol, and naturally drying. Testing deuterium evolution performance by adopting a three-electrode system, taking the prepared electrode as a working electrode, taking Ag/AgCl as a reference electrode, and grinding with a stone millThe rod was used as a comparative electrode, the test electrolyte was a 1M NaOD solution, the activity of the catalyst was judged by the change of current density with voltage at normal temperature and pressure, and the test results are shown in table 1.

Example 7

Taking a piece of nickel as a substrate, cleaning the nickel by using a mixed solution of water and ethanol, and drying the nickel for later use. Mixing Co₃O₄Mixing with Al according to the mass ratio of 3:2, coating 5g of the mixture on a magnetron sputtering target material, and carrying out magnetron sputtering on Co₃O₄Spin-sputter coating the substrate with a mixture of Al for 50min at a sputter current of 13A to form a dense coating of the mixture, and then applying N₂Purging is carried out; preparing NaOH solution with the concentration of 5M, putting 100ml of the solution into a beaker, immersing the nickel with the coating into the beaker for etching, continuously stirring the solution by magnetic force for 3 hours at the heating temperature of 60 ℃, cleaning the etched nickel, putting the nickel into a clean beaker, adding deionized water, then putting the beaker into an ultrasonic pool for ultrasonic operation with the ultrasonic power of 500W and the time of 7min, then taking out the nickel, replacing the deionized water in the beaker, repeating the cleaning operation for 5 times, then drying the beaker in an oven at the temperature of 60 ℃ for 10 hours to finally obtain Co₃O₄A nickel electrode coated with a nanoporous cathode.

And (3) carrying out electrolytic rehydration deuterium evolution performance test on the prepared electrode: 1 x 1cm²Co of (A)₃O₄And (3) washing the nickel electrode with the nano-porous cathode coating with water and ethanol, and naturally drying. The three-electrode system is adopted to test the performance of deuterium evolution, the prepared electrode is used as a working electrode, Ag/AgCl is used as a reference electrode, a graphite grinding rod is used as a comparison electrode, the test electrolyte is 1M NaOD solution, the activity of the catalyst is judged at normal temperature and normal pressure through the change of current density along with voltage, and the test results are shown in Table 1.

Example 8

And (3) carrying out electrolytic rehydration deuterium evolution performance test on the electrode: 1 x 1cm²The Raney nickel electrode is washed by water and ethanol and naturally dried. The three-electrode system is adopted to test the performance of deuterium evolution, pure Raney nickel is taken as a working electrode, Ag/AgCl is taken as a referenceThe specific electrode and the graphite rod are used as the comparative electrode, the test electrolyte is 1M NaOD solution, the activity of the catalyst is judged through the change of current density along with voltage at normal temperature and normal pressure, and the test results are shown in Table 1.

Example 9

And (3) carrying out electrolytic rehydration deuterium evolution performance test on the electrode: 1 x 1cm²The nickel electrode is washed by water and ethanol and naturally dried. A three-electrode system is adopted to test the deuterium evolution performance, pure nickel is used as a working electrode, Ag/AgCl is used as a reference electrode, a stone grinding rod is used as a comparison electrode, a test electrolyte is a 1M NaOD solution, the activity of the catalyst is judged at normal temperature and normal pressure through the change of current density along with voltage, and the test results are shown in Table 1.

FIG. 1 shows the magnetron sputtering scheme, Co₃O₄The mixture of Al and the target material falls off to a substrate rotating at a constant speed in a magnetron sputtering mode to form uniform Co₃O₄And a plating layer of Al; FIG. 2 is a surface SEM image of pure Raney nickel; FIG. 3 is an SEM image of example 2, comparing with FIG. 2, showing the porous surface structure of example 2, which is favorable for the overflow of deuterium gas generated by electrolytic test. FIG. 4 shows the Raney nickel surface coating Co₃O₄From the stability graphs before and after, it can be seen that the reaction produced a current fluctuation at 4.8h without the coating, indicating its catalytic instability, while the coated raney ni showed a very small current density fluctuation at 9h of the test condition, indicating its performance as a stable catalyst.

TABLE 1 comparison of the properties of magnetron sputtered Co3O4 coatings under different conditions

Test of	Catalyst numbering	Sputtering time (min)	Sputtering current (A)	η/100 mA·cm -2	D2Yield/ml/h
						Example 1	Co3O4Raney nickel	5	10	245	23.3
Example 2	Co3O4Raney nickel	15	13	235	28.7
						Example 3	Co3O4Raney nickel	20	20	273	18.5
Example 4	Co3O4Raney nickel	5	13	240	21.3
						Example 5	Co3O4Raney nickel	25	13	248	20.4
Example 6	Co3O4Raney nickel	50	13	286	20.7
						Example 7	Co3O4Nickel/nickel alloy	50	13	288	14.5
Example 8	Raney nickel	0	0	238	28.3
						Example 9	Nickel (II)	0	0	283	16.5

In Table 1, η -_{100 mA·cm} ^-2Indicates a current density of 100 mA/cm²Lower overpotential. The performance test data for the different catalysts are shown in table 1, with the same amount of sputtering per second, as can be seen from table 1:

1) examples 1-3 compare different magnetron sputtering times and current versus final Co₃O₄Raney nickel electrolytic rehydration deuterium performance of the coating. As can be seen from the table, different sputtering times and currents have large changes on deuterium evolution performance, and show better catalytic activity under the sputtering conditions of 15min and 13A, and the excessive sputtering time and the excessive current can cause Co3O4 to cover the surface of Raney nickel, thereby affecting the activity of the Raney nickel.

2) Examples 4-6 and 2 compare the influence of different magnetron sputtering times on the catalytic performance, and find that the sputtering time is too long and the performance is reduced, which indicates that Co sputtering is performed₃O₄The thickness of (a) increases, affecting the exposure of the raney nickel active sites and thus their activity.

3) In the comparative test of example 2 and pure raney nickel, no great difference in deuterium evolution performance was found between the two, indicating that the coating under this condition has no great influence on the deuterium evolution performance of raney nickel.

The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.