Amorphous metal hydrogen evolution catalyst, preparation method and application

Abstract

The invention belongs to the technical field of hydrogen evolution catalysts, and particularly relates to an amorphous metal hydrogen evolution catalyst, a preparation method and application. The preparation method comprises the steps that metal nickel serves as a working electrode, binary alloy powder of different proportions serves as a precursor, the binary alloy powder is sprayed to the surface of the metal nickel, and a first intermediate electrode is obtained; reducing the binary alloy powder on the surface of the metallic nickel into metal to obtain a second intermediate electrode; taking the second intermediate electrode as a substrate to obtain a metallic nickel loaded binary metal / amorphous metal electrode; the binary metal / amorphous metal loaded on the metallic nickel in the metallic nickel loaded binary metal / amorphous metal electrode is the amorphous metal hydrogen evolution catalyst. The problems that an existing hydrogen evolution catalyst is high in cost, poor in hydrogen evolution catalytic activity and low in stability are solved, the prepared amorphous metal hydrogen evolution catalyst has excellent hydrogen evolution catalytic activity and long-time stability, and the excellent hydrogen production effect can be achieved in the electro-catalysis hydrogen evolution process.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogen evolution catalysts, and in particular relates to an amorphous metal hydrogen evolution catalyst, a preparation method and an application thereof. Background Art

[0002] As a clean energy carrier with a high specific energy density, hydrogen is currently the best alternative to fossil fuels. Hydrogen can be produced primarily from fossil fuels, industrial by-product hydrogen, and water electrolysis. Water electrolysis is the most commonly used hydrogen production technology.

[0003] In the technology of hydrogen production by water electrolysis, electrocatalysts are the key to hydrogen production by water electrolysis. Currently, the most outstanding hydrogen evolution electrocatalysts are precious metal platinum (Pt) and platinum-based alloys. However, they have problems such as high price, low natural abundance and poor cycle stability, which seriously hinder the commercialization process of hydrogen production by water electrolysis. Oxide catalysts have poor conductivity and large interfacial mass transfer resistance, which affect their catalytic activity. They are also easily dissolved by the electrolyte, resulting in insufficient stability.

[0004] Therefore, the development of highly active, highly stable and low-cost electrocatalysts is of great significance for promoting the industrialization of hydrogen production by water electrolysis. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention provides an amorphous metal hydrogen evolution catalyst, a preparation method, and an application thereof, which can solve the problems of high cost, poor hydrogen evolution catalytic activity, and low stability of existing hydrogen evolution catalysts.

[0006] The technical solution adopted by the present invention to solve its technical problem is:

[0007] The present invention provides a method for preparing an amorphous metal hydrogen evolution catalyst, comprising the following steps:

[0008] Step 1: Using nickel metal as the working electrode and binary alloy powders in different proportions as precursors, the binary alloy powders are sprayed onto the surface of the nickel metal by plasma spraying, and then washed and dried to obtain the first intermediate electrode;

[0009] Step 2: heat-treating the first intermediate electrode in a hydrogen atmosphere to reduce the binary alloy powder on the surface of the metallic nickel into metal, thereby obtaining a second intermediate electrode, wherein the second intermediate electrode is a metallic nickel-loaded binary metal electrode;

[0010] Step 3: Using the metal nickel-loaded binary metal electrode as a substrate, depositing an amorphous metal on the surface of the metal nickel-loaded binary metal electrode by chemical deposition, and washing and drying to obtain a metal nickel-loaded binary metal / amorphous metal electrode;

[0011] The binary metal / amorphous metal supported on the metallic nickel in the metallic nickel-supported binary metal / amorphous metal electrode is an amorphous metal hydrogen evolution catalyst.

[0012] Specifically, the binary alloy powder includes any one of nickel-cobalt alloy powder, nickel-chromium alloy powder, nickel-copper alloy powder, cobalt-copper alloy powder, cobalt-iron alloy powder, and copper-iron alloy powder;

[0013] Or / and, the mass ratio of the two metals in the binary alloy powder is 1:1-4:1.

[0014] Specifically, the amorphous metal includes at least one of amorphous nickel, amorphous cobalt, amorphous tin, amorphous chromium, amorphous indium, amorphous copper, amorphous iron, amorphous ruthenium, amorphous platinum, amorphous rhodium, amorphous palladium, and amorphous lanthanide.

[0015] Specifically, the amorphous lanthanum series includes at least one of amorphous lanthanum, amorphous cerium, amorphous praseodymium, amorphous neodymium, amorphous promethium, amorphous samarium, amorphous europium, amorphous gadolinium, and amorphous terbium.

[0016] Specifically, depositing the amorphous metal on the surface of the second intermediate electrode by chemical deposition specifically includes:

[0017] dissolving an electroless plating reduction metal precursor to form a precursor solution;

[0018] Under ice bath conditions, placing the second intermediate electrode in the precursor solution and allowing it to stand for 1-2 hours;

[0019] A reducing agent is added dropwise into the precursor solution to deposit the amorphous metal on the surface of the second intermediate electrode, thereby forming an amorphous metal structure on the metal nickel / two-element metal electrode.

[0020] Specifically, the reducing agent is a sodium borohydride solution;

[0021] Or / and, the concentration of the reducing agent is 0.1 mol / L to 1 mol / L.

[0022] Specifically, heat treating the first intermediate electrode in a hydrogen atmosphere includes the following steps:

[0023] S1: placing the first intermediate electrode in a hydrogen atmosphere furnace;

[0024] S2: Controlling the heat treatment equipment to heat, wherein the heat treatment temperature is 300° C. to 500° C., and the heat treatment time is 1 to 2 hours.

[0025] Specifically, the drying temperature of the first intermediate electrode obtained after washing and drying is 60° C. to 80° C., and the drying time is 1 to 2 hours.

[0026] The present invention also provides an amorphous metal hydrogen evolution catalyst, which is prepared by the above-mentioned preparation method of the amorphous metal hydrogen evolution catalyst.

[0027] Specifically, the amorphous metal hydrogen evolution catalyst includes a binary metal and an amorphous metal; the binary metal and the amorphous metal are sequentially loaded on the outer surface of the metallic nickel.

[0028] The present invention also provides an application of the amorphous metal hydrogen evolution catalyst obtained as described above, wherein the amorphous metal hydrogen evolution catalyst is used for hydrogen evolution reaction by electrolysis of water.

[0029] The beneficial effects of the amorphous metal hydrogen evolution catalyst, preparation method and application of the present invention are:

[0030] The present invention uses metallic nickel as a working electrode, and sequentially prepares a first intermediate electrode, a second intermediate electrode, and a metallic nickel-loaded two-element metal / amorphous metal electrode. Based on the metallic nickel-loaded two-element metal / amorphous metal, a metallic nickel-loaded two-element metal / amorphous metal hydrogen evolution catalyst with different reaction interfaces is prepared. The catalyst has excellent hydrogen evolution catalytic activity and long-term stability, and can achieve excellent hydrogen production effects during electrocatalytic hydrogen evolution. Specifically, the metallic nickel-loaded two-element metal / amorphous metal has a large specific surface area and many active sites, and can fully form an interface with the metal, reducing the mass transfer resistance during the catalytic process, thereby improving the catalyst's hydrogen evolution catalytic activity. At the same time, the gold metallic nickel-loaded two-element metal / amorphous metal has a dynamic regeneration phenomenon, which is beneficial to improving the long-term stability of the catalyst.

[0031] The preparation method of the amorphous metal hydrogen evolution catalyst of the present invention comprises the following steps: spraying alloy powder onto the surface of metallic nickel to form a first intermediate electrode, reducing the alloy powder on the surface of the metallic nickel to form a second intermediate electrode, and then depositing an amorphous metal on the surface of the second intermediate electrode to form a metallic nickel-loaded binary metal / amorphous metal electrode. The binary metal / amorphous metal loaded on the metallic nickel in the metallic nickel-loaded binary metal / amorphous metal electrode is the amorphous metal hydrogen evolution catalyst. The entire preparation process adopts relatively easy-to-implement procedures, is simple and reliable, is easy to carry out on a large scale, and has great application value and promotion value. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0033] Figure 1 The present invention provides a flow chart of the method for preparing the amorphous metal hydrogen evolution catalyst.

[0034] Figure 2 This is a comparison chart of the stability results of the amorphous metal hydrogen evolution catalysts prepared in Examples 1-6 of the present application and Comparative Examples 1-2 at a current density of 200 mA / cm2. DETAILED DESCRIPTION

[0035] The present invention will now be described in further detail with reference to the accompanying drawings, which are simplified schematic diagrams that illustrate the basic structure of the present invention in a schematic manner.

[0036] like Figure 1 The specific embodiment of the method for preparing an amorphous metal hydrogen evolution catalyst of the present invention includes the following contents:

[0037] Step 1: Using nickel metal as the working electrode and binary alloy powders in different proportions as precursors, the binary alloy powders are sprayed onto the surface of the nickel metal by plasma spraying, and then washed and dried to obtain the first intermediate electrode;

[0038] Step 2: heat-treating the first intermediate electrode in a hydrogen atmosphere to reduce the binary alloy powder on the surface of the metallic nickel into metal, thereby obtaining a second intermediate electrode, which is a metallic nickel-loaded binary metal electrode;

[0039] Step 3: Use the metal nickel loaded binary metal electrode as the substrate, dissolve the chemical plating reduction metal precursor, add a reducing agent, and deposit the amorphous metal on the surface of the second intermediate electrode by chemical deposition. After washing and drying, the metal nickel loaded binary metal / amorphous metal electrode is obtained.

[0040] Specifically, the two-element metal / amorphous metal loaded on the metal nickel in the metal nickel-loaded two-element metal / amorphous metal electrode is an amorphous metal hydrogen evolution catalyst. The two-element metal / amorphous metal loaded on the metal nickel prepared by the present invention is an amorphous metal hydrogen evolution catalyst with excellent hydrogen evolution catalytic activity and long-term stability, and can achieve excellent hydrogen production effect in the electrocatalytic hydrogen evolution process. The metal nickel-loaded two-element metal / amorphous metal has a large specific surface area and many active sites, and can fully form an interface with the metal, reducing the mass transfer resistance in the catalytic process, thereby improving the hydrogen evolution catalytic activity of the catalyst. At the same time, there is a dynamic regeneration phenomenon in the gold metal nickel-loaded two-element metal / amorphous metal, which is conducive to improving the long-term stability of the catalyst.

[0041] The preparation method of the amorphous metal hydrogen evolution catalyst of the present invention comprises the following steps: spraying alloy powder onto the surface of metallic nickel to form a first intermediate electrode, reducing the alloy powder on the surface of the metallic nickel to form a second intermediate electrode, and then depositing an amorphous metal on the surface of the second intermediate electrode to form a metallic nickel-loaded binary metal / amorphous metal electrode. The binary metal / amorphous metal loaded on the metallic nickel in the metallic nickel-loaded binary metal / amorphous metal electrode is the amorphous metal hydrogen evolution catalyst. The entire preparation process adopts relatively easy-to-implement procedures, is simple and reliable, is easy to carry out on a large scale, and has great application value and promotion value.

[0042] It is further explained that in step 1 of this embodiment, nickel mesh is used as the metallic nickel of the working electrode. The nickel mesh has a large specific surface area, can provide more reaction interfaces, increase the contact area between the reactants and the electrode, and is conducive to the occurrence of the catalytic reaction, thereby improving the electrolysis efficiency. The binary alloy powder in step 1 includes any one of nickel-cobalt alloy powder, nickel-chromium alloy powder, nickel-copper alloy powder, cobalt-copper alloy powder, cobalt-iron alloy powder, and copper-iron alloy powder. Preferably, the mass ratio of the two metals in the binary alloy powder is 1:1-4:1. It should be understood that, in specific use, depending on the preparation requirements and preparation conditions, the mass ratio of the two metals in the binary alloy powder can be any specific point value within the above-mentioned mass ratio range, which will not be listed here one by one.

[0043] When the binary alloy powder is sprayed onto the surface of metallic nickel by plasma spraying, the specific spraying parameters are as follows: a spraying distance of 60 mm to 100 mm, a spraying angle of 30° to 45°, hydrogen as the combustion gas, a gas supply pressure of 0.8 MPa to 1.0 MPa, argon as the main powder supply gas, nitrogen as the auxiliary powder supply gas, a flow rate of 300 L / h to 500 L / h, a spraying current of 300 A to 400 A, and a spraying voltage of 40 V to 50 V. After spraying onto the metallic nickel surface, the electrode sprayed with metallic nickel is first cleaned at least once with deionized water and / or anhydrous ethanol, and then dried at a drying temperature of 60° C. to 80° C. for 1 to 2 hours to obtain a first intermediate electrode.

[0044] In step 2, heat treatment of the first intermediate electrode in a hydrogen atmosphere includes the following steps:

[0045] S101: placing the first intermediate electrode in a hydrogen atmosphere furnace;

[0046] S102: Control the heat treatment equipment to heat, the heat treatment temperature is 300° C. to 500° C., and the heat treatment time is 1 to 2 hours.

[0047] It should be understood that the heat treatment temperature in this embodiment can be 300°C or 500°C, as well as other specific point values ​​between 300°C and 500°C, and the heat treatment time can also be adaptively adjusted within 1 to 2 hours according to specific needs.

[0048] In step three, the chemical plating reduction metal precursor uses cobalt nitrate or copper nitrate, and the concentration of the reaction solution obtained by dissolving it is 0.1 mol / L. The reducing agent in the present invention uses sodium borohydride solution, and its concentration is 0.1 mol / L to 1 mol / L. It should be understood that the concentration of the reaction solution and the reducing agent concentration can be adaptively selected within the specified range. The specific values ​​of the reaction solution concentration and the reducing agent concentration are not listed one by one here.

[0049] It is further specified that the amorphous metal used in step 3 includes one or more combinations of amorphous nickel, amorphous cobalt, amorphous tin, amorphous chromium, amorphous indium, amorphous copper, amorphous iron, amorphous ruthenium, amorphous platinum, amorphous rhodium, amorphous palladium, and amorphous lanthanides, and the amorphous lanthanides include at least one of amorphous lanthanum, amorphous cerium, amorphous praseodymium, amorphous neodymium, amorphous promethium, amorphous samarium, amorphous europium, amorphous gadolinium, and amorphous terbium. The use of any one or more of the above amorphous metals shall fall within the scope of protection of this application.

[0050] The step of depositing the amorphous metal on the surface of the second intermediate electrode by chemical deposition specifically includes:

[0051] S301: dissolving the chemical plating reduction metal precursor to form a precursor solution;

[0052] S302: placing the second intermediate electrode in the precursor solution under ice bath conditions and allowing it to stand for 1-2 hours;

[0053] S303: adding a reducing agent dropwise into the precursor solution to deposit the amorphous metal on the surface of the second intermediate electrode, thereby forming an amorphous metal structure on the metal nickel / two-element metal electrode.

[0054] Specifically, the metal electrode is placed in a precursor solution for a set time under ice bath conditions, and then a reducing agent is slowly added dropwise to deposit the amorphous metal on the surface of the metal electrode to form an amorphous metal structure.

[0055] It should be understood that there is no particular limitation on the specific reaction device and external furnishings. Examples include common solution reaction devices including but not limited to beakers, flasks or other containers; the heating device may be a heating furnace, common heating furnaces include but are not limited to resistance heating furnaces, microwave heating furnaces, induction heating furnaces, radiation heating furnaces, etc.; the corresponding raw material holding device or container or reaction site is not specifically limited, common raw material placement devices include but are not limited to crucibles, glass, quartz and other materials; the peripheral device for providing the reaction atmosphere may be existing self-built or commercial equipment, which is not limited here.

[0056] It is further explained here that the present application also provides an amorphous metal hydrogen evolution catalyst, which is prepared based on the above preparation method. The amorphous metal hydrogen evolution catalyst includes a binary metal and an amorphous metal, and the binary metal and the amorphous metal are sequentially loaded on the outer surface of the metal nickel.

[0057] The present application also provides an application of an amorphous metal hydrogen evolution catalyst prepared by the above preparation method, which is used for hydrogen evolution reaction by electrolysis of water.

[0058] Specifically, a metal nickel-loaded binary metal / amorphous metal electrode is used as a working electrode, and a nickel mesh is used as a counter electrode, and placed in an alkaline electrolyte to carry out a water electrolysis hydrogen evolution reaction.

[0059] Example 1

[0060] Load nickel-cobalt alloy powder with a mass ratio of 1:1 into the sample barrel of the plasma spray equipment;

[0061] 1*2cm 2 A nickel mesh substrate was prepared by spraying nickel-cobalt alloy powder onto the surface of the metal nickel mesh at a spray distance of 60 mm, a spray angle of 30°, hydrogen as the combustion gas, a gas supply pressure of 0.8 MPa, argon as the main powder supply gas, nitrogen as the auxiliary powder supply gas, a flow rate of 500 L / h, a spray current of 300 A, and a spray voltage of 40 V. The powder was then washed with deionized water and dried to obtain the first intermediate electrode.

[0062] The first intermediate electrode is placed in a hydrogen atmosphere furnace for heat treatment to reduce the partially oxidized nickel-cobalt alloy on the surface of the metal nickel mesh into nickel-cobalt alloy to obtain a metal nickel-loaded nickel-cobalt metal electrode, namely the second intermediate electrode, wherein the furnace temperature of the hydrogen atmosphere furnace is set to 400°C.

[0063] Dissolve 0.01 mol of copper nitrate in 100 mL of water in a reactor as the reaction solution. Place the nickel-loaded nickel-cobalt metal electrode as the substrate. After standing for 1 hour, place the reactor in an ice bath and slowly add 0.1 mol / L of sodium borohydride to the reaction solution. Deposit amorphous copper on the surface of the nickel-loaded nickel-cobalt metal electrode. After the reaction, wash the electrode twice with water and ethanol, respectively, and dry it at 60°C for 1 hour to prepare the nickel-loaded nickel-cobalt / amorphous copper electrode.

[0064] The above-prepared metal nickel-loaded nickel-cobalt / amorphous copper electrode was used as a working electrode, a nickel mesh was used as a counter electrode, and 6 mol / L KOH was used as an electrolyte to carry out a water electrolysis hydrogen evolution experiment.

[0065] Example 2

[0066] Load nickel-copper alloy powder with a mass ratio of 1:1 into the sample barrel of the plasma spray equipment;

[0067] 1*2cm 2 A nickel mesh substrate was prepared by spraying nickel-copper alloy powder onto the surface of the metal nickel mesh at a spraying distance of 100 mm, a spraying angle of 45°, hydrogen as the combustion gas, a gas supply pressure of 1.0 MPa, argon as the main powder supply gas, nitrogen as the auxiliary powder supply gas, a flow rate of 500 L / h, a spraying current of 400 A, and a spraying voltage of 50 V. The powder was then washed with deionized water and dried to obtain an intermediate product.

[0068] The intermediate product is placed in a hydrogen atmosphere furnace for heat treatment to reduce the partially oxidized nickel-copper alloy on the surface of the metal nickel mesh into a nickel-cobalt alloy to obtain a metal nickel-loaded nickel-cobalt metal electrode, wherein the furnace temperature of the hydrogen atmosphere furnace is set to 300°C.

[0069] 0.01 mol of cobalt nitrate was dissolved in 100 mL of water in a reactor as the reaction solution. The above-mentioned nickel-loaded nickel-copper metal electrode was used as the substrate. After standing for 1 hour, the reactor was placed in an ice bath and 0.1 mol / L of sodium borohydride was slowly added dropwise to the reaction solution. Amorphous cobalt was deposited on the surface of the nickel-loaded nickel-copper metal electrode. After the reaction, the electrode was washed twice with water and ethanol respectively, and dried at 60°C for 1 hour to prepare a nickel-loaded nickel-copper / amorphous cobalt electrode.

[0070] The above-prepared metal nickel-loaded nickel-copper / amorphous cobalt electrode was used as a working electrode, a nickel mesh was used as a counter electrode, and 6 mol / L KOH was used as an electrolyte to carry out a water electrolysis hydrogen evolution experiment.

[0071] Example 3

[0072] Load nickel-iron alloy powder with a mass ratio of 1:1 into the sample barrel of the plasma spray equipment;

[0073] 1*2cm 2 A nickel mesh substrate was prepared by spraying nickel-iron alloy powder onto the surface of the metal nickel mesh at a spraying distance of 80 mm, a spraying angle of 40°, hydrogen as the combustion gas, a gas supply pressure of 1 MPa, argon as the main powder supply gas, nitrogen as the auxiliary powder supply gas, a flow rate of 500 L / h, a spraying current of 400 A, and a spraying voltage of 45 V. The powder was then washed with deionized water and dried to obtain an intermediate product.

[0074] The intermediate product is placed in a hydrogen atmosphere furnace for heat treatment to reduce the partially oxidized nickel-iron alloy on the surface of the metal nickel mesh into nickel-iron alloy to obtain a metal nickel-loaded nickel-iron metal electrode, wherein the furnace temperature of the hydrogen atmosphere furnace is set to 400°C.

[0075] 0.01 mol of cobalt nitrate was dissolved in 100 mL of water in a reactor as the reaction solution. The nickel-loaded nickel-iron metal electrode was used as the substrate. After standing for 1 hour, the reactor was placed in an ice bath and 0.1 mol / L of sodium borohydride was slowly added dropwise to the reaction solution. Amorphous cobalt was deposited on the surface of the nickel-loaded nickel-iron metal electrode. After the reaction, the electrode was washed twice with water and ethanol respectively, and dried at 60°C for 1.5 hours to prepare the nickel-loaded nickel-iron / amorphous cobalt electrode.

[0076] The above-prepared metal nickel-loaded nickel-iron / amorphous cobalt electrode was used as a working electrode, a nickel mesh was used as a counter electrode, and 6 mol / L KOH was used as an electrolyte to carry out a water electrolysis hydrogen evolution experiment.

[0077] Example 4

[0078] Load nickel-iron alloy powder with a mass ratio of 1:1 into the sample barrel of the plasma spray equipment;

[0079] 1*2cm 2 A nickel mesh substrate was prepared by spraying nickel-iron alloy powder onto the surface of the metal nickel mesh at a spraying distance of 60 mm, a spraying angle of 30°, hydrogen as the combustion gas, a gas supply pressure of 0.9 MPa, argon as the main powder supply gas, nitrogen as the auxiliary powder supply gas, a flow rate of 500 L / h, a spraying current of 400 A, and a spraying voltage of 50 V. The powder was then washed with deionized water and dried to obtain an intermediate product.

[0080] The intermediate product is placed in a hydrogen atmosphere furnace for heat treatment to reduce the partially oxidized nickel-iron alloy on the surface of the metal nickel mesh into nickel-iron alloy to obtain a metal nickel-loaded nickel-iron metal electrode, wherein the furnace temperature of the hydrogen atmosphere furnace is set to 400°C.

[0081] 0.01 mol of copper nitrate was dissolved in 100 mL of water in a reactor as the reaction solution. The nickel-loaded nickel-iron metal electrode described above was used as the substrate. After standing for 1 hour, the reactor was placed in an ice bath and 0.1 mol / L of sodium borohydride was slowly added dropwise to the reaction solution. Amorphous copper was deposited on the surface of the nickel-loaded nickel-iron metal electrode. After the reaction, the electrode was washed twice with water and ethanol, respectively, and dried at 60°C for 2 hours to prepare the nickel-loaded nickel-iron / amorphous copper electrode.

[0082] The above-prepared metal nickel-loaded nickel-iron / amorphous copper electrode was used as a working electrode, a nickel mesh was used as a counter electrode, and 6 mol / L KOH was used as an electrolyte to carry out a water electrolysis hydrogen evolution experiment.

[0083] Example 5

[0084] Load nickel-chromium alloy powder with a mass ratio of 1:1 into the sample barrel of the plasma spray equipment;

[0085] 1*2cm 2 A nickel mesh substrate was prepared by spraying nickel-chromium alloy powder onto the surface of the metal nickel mesh at a spraying distance of 100 mm, a spraying angle of 45°, hydrogen as the combustion gas, a gas supply pressure of 1.0 MPa, argon as the main powder supply gas, nitrogen as the auxiliary powder supply gas, a flow rate of 300 L / h, a spraying current of 300 A, and a spraying voltage of 40 V. The powder was then washed with deionized water and dried to obtain an intermediate product.

[0086] The intermediate product is placed in a hydrogen atmosphere furnace for heat treatment to reduce the partially oxidized nickel-chromium alloy on the surface of the metal nickel mesh into nickel-chromium alloy to obtain a metal nickel-loaded nickel-chromium metal electrode, wherein the furnace temperature of the hydrogen atmosphere furnace is set to 400°C.

[0087] Dissolve 0.01 mol of copper nitrate in 50 mL of water in a reactor as the reaction solution. Place the nickel-loaded nickel-chromium electrode as the substrate. After standing for 1 hour, place the reactor in an ice bath and slowly add 0.1 mol / L of sodium borohydride to the reaction solution. Deposit amorphous copper on the surface of the nickel-loaded nickel-chromium electrode. After the reaction, wash the electrode twice with water and ethanol, respectively, and dry it at 60°C for 1 hour to prepare the nickel-loaded nickel-chromium / amorphous copper electrode.

[0088] The above-prepared metal nickel-loaded nickel-chromium / amorphous copper electrode was used as a working electrode, a nickel mesh was used as a counter electrode, and 6 mol / L KOH was used as an electrolyte to carry out a water electrolysis hydrogen evolution experiment.

[0089] Example 6

[0090] Load nickel-chromium alloy powder with a mass ratio of 1:1 into the sample barrel of the plasma spray equipment;

[0091] 1*2cm 2 A nickel mesh substrate was prepared by spraying nickel-chromium alloy powder onto the surface of the metal nickel mesh at a spraying distance of 60 mm, a spraying angle of 45°, hydrogen as the combustion gas, a gas supply pressure of 0.8 MPa, argon as the main powder supply gas, nitrogen as the auxiliary powder supply gas, a flow rate of 300 L / h, a spraying current of 300 A, and a spraying voltage of 40 V. The powder was then washed with deionized water and dried to obtain an intermediate product.

[0092] The intermediate product is placed in a hydrogen atmosphere furnace for heat treatment to reduce the partially oxidized nickel-chromium alloy on the surface of the metal nickel mesh into nickel-chromium alloy to obtain a metal nickel-loaded nickel-chromium metal electrode, wherein the furnace temperature of the hydrogen atmosphere furnace is set to 400°C.

[0093] Dissolve 0.01 mol of cobalt nitrate in 100 mL of water in a reactor as the electrolyte. Place the nickel-loaded nickel-chromium electrode as the substrate. After standing for 1 hour, place the reactor in an ice bath and slowly add 0.1 mol / L of sodium borohydride to the reaction solution. Amorphous cobalt is deposited on the surface of the nickel-loaded nickel-chromium electrode. After the reaction, wash the electrode twice with water and ethanol, respectively, and dry it at 60°C for 1 hour to prepare a nickel-loaded nickel-chromium / amorphous cobalt electrode.

[0094] The above-prepared metal nickel-loaded nickel-chromium / amorphous cobalt electrode was used as a working electrode, a nickel mesh was used as a counter electrode, and 6 mol / L KOH was used as an electrolyte to carry out a water electrolysis hydrogen evolution experiment.

[0095] Comparative Example 1

[0096] Comparative Example 1 discloses a method of using a metal catalyst in the prior art to conduct an electrolytic water hydrogen evolution experiment. Specifically, a 1*2 cm 2A nickel mesh substrate was prepared by depositing nickel-aluminum alloy powder onto the surface of the metal nickel mesh at a spraying distance of 90 mm, a spraying angle of 45°, hydrogen as the combustion gas, a gas supply pressure of 1.0 MPa, argon as the main powder supply gas, nitrogen as the auxiliary powder supply gas, a flow rate of 500 L / h, a spraying current of 400 A, and a spraying voltage of 50 V. The powder was then washed with deionized water and dried to obtain a metal electrode. The metal electrode was then activated in 4 mol / L KOH. After activation, the electrode was washed twice with water and ethanol, respectively, and dried at 60°C for 1 hour to prepare a nickel metal electrode.

[0097] The obtained nickel metal electrode was used as the working electrode, the nickel mesh was used as the counter electrode, and 6 mol / L KOH was used as the electrolyte to carry out the water electrolysis hydrogen evolution experiment.

[0098] Comparative Example 2

[0099] Comparative Example 2 discloses an experiment of electrolyzing water and releasing hydrogen using an oxide catalyst in the prior art. Specifically, a 1*2 cm 2 A nickel mesh substrate was prepared by depositing nickel-aluminum alloy powder onto the surface of the metal nickel mesh at a spray distance of 90 mm and a spray angle of 45°, using hydrogen as the combustion gas, a gas supply pressure of 1.0 MPa, argon as the main powder supply gas, nitrogen as the auxiliary powder supply gas, a flow rate of 500 L / h, a spray current of 400 A, and a spray voltage of 50 V. The powder was then washed with deionized water and dried to obtain a metal electrode. The metal electrode was activated in 4 mol / L KOH, washed twice with water and ethanol, and dried at 60°C for 1 hour to prepare a nickel metal electrode. The nickel metal electrode was then heat-treated in an air atmosphere furnace to oxidize the nickel on the surface of the metal nickel mesh to obtain a nickel oxide electrode.

[0100] The obtained nickel oxide electrode was used as the working electrode, the nickel mesh was used as the counter electrode, and 6 mol / L KOH was used as the electrolyte to carry out the hydrogen evolution experiment by electrolysis of water.

[0101] Depend on Figure 2 The test results clearly show that at the same time, the voltages of Comparative Examples 1 and 2 are in the range of 2V to 2.4V, which are significantly higher than the voltage values ​​of Examples 1-6, indicating that the amorphous metal hydrogen evolution catalyst prepared in the present application has excellent hydrogen evolution catalytic activity. The voltage value curve within 70 hours shows that Examples 1-6 are more stable, and the amorphous metal hydrogen evolution catalyst prepared in the present application has long-term stability.

[0102] It should be understood that the specific embodiments described above are only used to explain the present invention and are not intended to limit the present invention. Obvious changes or modifications derived from the spirit of the present invention are still within the scope of protection of the present invention.

Claims

1. A method for preparing an amorphous metal hydrogen evolution catalyst, characterized in that: Includes the following: Step 1: Using nickel as the working electrode and binary alloy powders in different proportions as precursors, the binary alloy powders are sprayed onto the surface of the nickel by plasma spraying, and then washed and dried to obtain the first intermediate electrode; Step 2: heat-treating the first intermediate electrode in a hydrogen atmosphere to reduce the binary alloy powder on the surface of the metallic nickel into metal, thereby obtaining a second intermediate electrode, wherein the second intermediate electrode is a metallic nickel-loaded binary metal electrode; Step 3: Using the second intermediate electrode as a substrate, depositing an amorphous metal on the surface of the second intermediate electrode by chemical deposition, and washing and drying to obtain a nickel-loaded binary metal / amorphous metal electrode; The binary metal / amorphous metal supported on the metallic nickel in the metallic nickel-supported binary metal / amorphous metal electrode is an amorphous metal hydrogen evolution catalyst.

2. The method for preparing an amorphous metal hydrogen evolution catalyst according to claim 1, wherein: The binary alloy powder includes any one of nickel-cobalt alloy powder, nickel-chromium alloy powder, nickel-copper alloy powder, cobalt-copper alloy powder, cobalt-iron alloy powder, and copper-iron alloy powder; Or / and, the mass ratio of the two metals in the binary alloy powder is 1:1-4:

1.

3. The method for preparing an amorphous metal hydrogen evolution catalyst according to claim 1, wherein: The amorphous metal includes one or more combinations of amorphous nickel, amorphous cobalt, amorphous tin, amorphous chromium, amorphous indium, amorphous copper, amorphous iron, amorphous ruthenium, amorphous platinum, amorphous rhodium, amorphous palladium, and amorphous lanthanide.

4. The method for preparing an amorphous metal hydrogen evolution catalyst according to claim 3, wherein: The amorphous lanthanide series includes at least one of amorphous lanthanum, amorphous cerium, amorphous praseodymium, amorphous neodymium, amorphous promethium, amorphous samarium, amorphous europium, amorphous gadolinium, and amorphous terbium.

5. The method for preparing an amorphous metal hydrogen evolution catalyst according to claim 1, wherein: The step of depositing the amorphous metal on the surface of the second intermediate electrode by chemical deposition specifically includes: dissolving an electroless plating reduction metal precursor to form a precursor solution; Under ice bath conditions, placing the second intermediate electrode in the precursor solution and allowing it to stand for 1-2 hours; A reducing agent is added dropwise into the precursor solution to deposit the amorphous metal on the surface of the second intermediate electrode, thereby forming an amorphous metal structure on the metal nickel / two-element metal electrode.

6. The method for preparing an amorphous metal hydrogen evolution catalyst according to claim 1, wherein: The reducing agent is sodium borohydride solution; Or / and, the concentration of the reducing agent is 0.1 mol / L to 1 mol / L.

7. The method for preparing an amorphous metal hydrogen evolution catalyst according to claim 1, wherein: The heat treatment of the first intermediate electrode in a hydrogen atmosphere includes the following steps: S1: placing the first intermediate electrode in a hydrogen atmosphere furnace; S2: Controlling the heat treatment equipment to heat, wherein the heat treatment temperature is 300° C. to 500° C., and the heat treatment time is 1 to 2 hours.

8. The method for preparing an amorphous metal hydrogen evolution catalyst according to claim 1, wherein: The drying temperature of the first intermediate electrode obtained after washing and drying is 60°C to 80°C; Or / and, the drying time is 1 to 2 hours.

9. An amorphous metal hydrogen evolution catalyst, characterized in that The catalyst is prepared by the method for preparing the amorphous metal hydrogen evolution catalyst according to any one of claims 1 to 7.

10. The amorphous metal hydrogen evolution catalyst according to claim 8, characterized in that: The amorphous metal hydrogen evolution catalyst comprises a binary metal and an amorphous metal; the binary metal and the amorphous metal are sequentially loaded on the outer surface of the metallic nickel.

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