Electrode for hydrogen evolution, preparation method thereof and hydrogen evolution reaction device

Abstract

The invention relates to an electrode for hydrogen evolution, a preparation method thereof and a hydrogen evolution reaction device, and the electrode is prepared by the following steps: preparing a solution of a soluble compound of ruthenium or platinum or rhodium or palladium or iridium, preparing a carrier of the electrode, the method comprises the following steps: preparing a solution of the same element of a soluble compound of a metal material which is the same as the metal material of a carrier forming an electrode, and controlling the atomic percentage of any one or combination of any two of ruthenium, platinum, rhodium, palladium or iridium to be 20-40% and the atomic percentage of the same element to be 60-80%. The invention aims to provide a catalyst which has a large contact area with an electrolyte, can rapidly generate a hydrogen evolution reaction, enables hydrogen to be rapidly desorbed and desorbed on a smooth and compact catalyst surface, has lower hydrogen evolution overpotential, longer service life and stronger hydrogen evolution catalytic capability under harsh acid and alkali conditions, and further facilitates reduction of electrolysis energy consumption and reduction of electrolysis energy consumption. The electrode for hydrogen evolution, the preparation method thereof and the hydrogen evolution reaction device are provided.

Description

Technical Field

[0001] The invention relates to the field of electrocatalytic hydrogen evolution, and in particular to an electrode for hydrogen evolution and a preparation method thereof, and a hydrogen evolution reaction device. Background Art

[0002] The key condition for the realization of electrocatalytic hydrogen production is the development and application of efficient hydrogen evolution catalysts. Hydrogen evolution catalysts include metal-based catalysts and non-metal-based catalysts. Non-metal-based catalysts can effectively improve catalytic performance by regulating the intrinsic electronic structure and chemical environment of the substrate through laboratory doping, and have become a research hotspot in universities and research institutes. However, due to the limitations of technical conditions, equipment precision and scale, the process of realizing industrial application is still difficult. The research on metal catalysts in hydrogen evolution catalysts has a history of nearly half a century and has been industrialized. The early research and application of hydrogen evolution catalysts focused on the Raney nickel alloy coated cathode used in chlor-alkali batteries, mainly focusing on how to realize and control the cost of hydrogen evolution reaction. In the 1990s, research on stainless steel cathodes and their surface doping improvements began, and some research on perovskite catalysts was conducted to improve the efficiency of hydrogen evolution catalysts and reduce costs.

[0003] The grain size and shape of traditional hydrogen evolution catalysts are irregular, and their arrangement is irregular. They have different electron-binding abilities for hydrogen ions and atoms in the electrolyte, which leads to inconsistent hydrogen evolution reaction rates. The catalyst also has different dissolution and consumption rates due to electron transfer during the reaction. At the same time, traditional catalysts and their manufacturing processes are prone to crystal agglomeration. After crystal agglomeration, the adsorption and desorption surface of the hydrogen evolution reaction is reduced. After the hydrogen evolution reaction occurs on a larger surface of the crystal, the hydrogen aggregation becomes larger, the desorption rate slows down, the solution resistance increases, and the energy consumption of the hydrogen evolution reaction increases. The crystals after agglomeration have irregular shapes. After the hydrogen evolution reaction occurs on the surface, the hydrogen aggregation has an increased impact on the irregular crystals, which accelerates the peeling of the catalytic crystals and shortens the service life of the catalyst. In locations where the catalytic crystals are less covered, the energy consumption of the hydrogen evolution reaction is relatively large and the speed is relatively slow. The amount of hydrogen produced in the electrolyte is different and the distribution is uneven, resulting in uneven solution resistance and high local energy and heat generation of the catalyst. The catalytic energy consumption increases while the catalyst life is shortened.

[0004] In addition, catalysts made by traditional processes are prone to agglomeration due to uneven catalyst growth, which may form cracks of varying degrees on the surface of the carrier. Although these cracks increase the surface area of ​​the catalytic reaction to a certain extent, in acid-base corrosive electrolytes, the cracks will accelerate the peeling of the catalyst from the matrix, which is not conducive to extending the service life of the catalyst.

[0005] Among the numerous noble metal hydrogen evolution catalysts, platinum-based noble metal catalysts have excellent HER activity, but they are susceptible to poisoning, and their catalytic activity and tolerance in acidic and alkaline media are also different, which greatly limits the application of platinum-based noble metal catalysts. In order to overcome the technical defects of unstable HER activity, short service life in acidic media, and easy poisoning and inactivation of platinum-based noble metal catalysts, the present invention combines the research on industrial production conditions and the action mechanism of the catalytic activity of hydrogen evolution of platinum-based catalysts, and through the control of the production process of platinum-based noble metal catalysts, develops a corrosion-resistant hydrogen evolution catalyst that can be industrialized, can be stably exerted in both acidic and alkaline media for a long time, has no inactivation of hydrogen evolution catalytic action, and has a lower hydrogen evolution overpotential. After the corrosion-resistant hydrogen evolution catalyst is double-layered, the catalyst can be tightly combined with the carrier, making the conductivity more excellent and the service life longer. Summary of the invention

[0006] The present invention aims to provide an electrode for hydrogen evolution, a preparation method thereof, and a hydrogen evolution reaction device, which has a large contact area with an electrolyte, allows a hydrogen evolution reaction to occur rapidly, allows hydrogen to be rapidly desorbed and desorbed on a smooth and dense catalyst surface, has a lower hydrogen evolution overpotential under harsh acid and alkaline conditions, has a longer service life, and has a stronger hydrogen evolution catalytic ability, thereby helping to reduce electrolysis energy consumption and improve economic benefits.

[0007] The corrosion-resistant hydrogen evolution catalyst of the present invention is prepared by the following steps:

[0008] A. Prepare a solution of a soluble compound of ruthenium or platinum or rhodium or palladium or iridium, prepare an electrode carrier, the electrode carrier is a metal material, prepare a solution of the same element of a soluble compound of the same metal material as the metal material constituting the electrode carrier, according to the ratio of the atomic percentage of any one or any two of ruthenium or platinum or rhodium or palladium or iridium is 20%-40%, the ratio of the atomic percentage of the same element is 60%-80%, prepare a multi-catalyst layer mixed solution according to the ratio of the atomic percentage, the metal mass concentration of any one or any two of ruthenium or platinum or rhodium or palladium or iridium in the multi-catalyst layer mixed solution is 100g / L-150g / L, after the multi-catalyst layer mixed solution is prepared in proportion, stir the multi-catalyst layer mixed solution under the condition of -25°C to 4°C to mix the multi-catalyst layer mixed solution evenly, then transfer the multi-catalyst layer mixed solution into a sealed container, and store it under the condition of -4°C to 10°C for standby use;

[0009] B. Clean the electrode carrier to remove dirt on the surface of the electrode carrier, apply the multi-catalyst layer mixed solution obtained in step A to the electrode carrier, and then calcine the electrode carrier at 400° C. to 600° C. for 0.5 h to 1.0 h;

[0010] C. Repeat step B several times to make the loading of the multi-catalytic layer composed of precious metals and their oxides on the electrode carrier reach 10-22g / m 2 , obtaining a carrier coated with a multi-catalyst layer;

[0011] D. Prepare a mixed solution using a soluble platinum compound and a soluble ruthenium compound, according to a ratio of 0.5% to 60% of ruthenium atomic percentage and a ratio of 40% to 99.5% of platinum atomic percentage, wherein the metal mass concentration of ruthenium and platinum in the mixed solution is 100 g / L to 150 g / L. After the mixed solution is prepared in proportion, stir the mixed solution at room temperature to mix the mixed solution evenly, thereby obtaining a mixed solution of soluble ruthenium and platinum compounds;

[0012] E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container, and calcine it at 350°C-550°C for 0.5h-2.0h to obtain ruthenium and platinum catalyst powder;

[0013] F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable container for sealed storage for later use;

[0014] G. Add ruthenium platinum catalyst powder into an aqueous solution containing 0.1%-1% fluorocarbon surfactant, and then vibrate the aqueous solution using ultrasonic waves for 2h-4h.

[0015] H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.1h-0.5h, then reduce the ultrasonic frequency for 0.1h-0.5h until the ultrasonic vibration stops, and then let it stand for more than 0.2h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 75°C-90°C, and then calcine the carrier coated with the multi-catalyst layer at 350°C-550°C in an atmosphere for 0.5h-1.0h;

[0016] The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density, which is composed of nano-materials aggregated, after being fired for 0.5h-1.0h in an atmosphere of 350℃-550℃;

[0017] I. Repeat steps G and H for multiple times to make the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer greater than 1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

[0018] Preferably, in step A, the atomic percentage ratio of any one or any two of ruthenium, platinum, rhodium, palladium or iridium is 25%-35%, and the atomic percentage ratio of the same element is 65%-75%. A multi-catalytic layer mixed solution is prepared according to the atomic percentage ratio, and the metal mass concentration of any one or any two of ruthenium, platinum, rhodium, palladium or iridium in the multi-catalytic layer mixed solution is 110g / L-140g / L;

[0019] In the step B, the electrode carrier is calcined at 450° C. to 550° C. for 0.5 h to 1.0 h;

[0020] In step C, step B is repeated several times to allow the loading of the multi-catalyst layer composed of the precious metals and their oxides on the electrode carrier to reach 12-20 g / m 2 ;

[0021] In the step D, a mixed solution is prepared using a soluble compound of platinum and a soluble compound of ruthenium, with the atomic percentage of ruthenium being 5% to 50% and the atomic percentage of platinum being 50% to 95%, and the metal mass concentration of ruthenium and platinum in the mixed solution being 110 g / L to 140 g / L;

[0022] In the step E, a mixed solution of ruthenium and platinum soluble compounds is placed in a high temperature resistant container and calcined at 375° C. to 500° C. for 0.8 h to 1.8 h to obtain a ruthenium and platinum catalyst powder;

[0023] In the step G, weighing ruthenium platinum catalyst powder and dissolving it in an aqueous solution containing 0.2%-0.8% fluorocarbon surfactant, and then using ultrasonic vibration to vibrate the aqueous solution for 2.5h-3.5h, the frequency of the ultrasonic vibration is 80KHz-100KHz;

[0024] In the step H, the carrier coated with the multi-catalyst layer obtained in step C is placed in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.15h-0.25h, the distance between the carrier and the liquid surface of the ruthenium platinum catalyst solution is greater than 50mm, and then the ultrasonic frequency is reduced for 0.15h-0.25h until the ultrasonic vibration stops, and then it is allowed to stand for 0.25h-0.5h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then the carrier coated with the multi-catalyst layer is dried at 80°C-85°C, and then the carrier coated with the multi-catalyst layer is calcined at 400°C-525°C for 0.6h-0.9h;

[0025] In step I, steps G and H are repeated multiple times to allow the loading of ruthenium and platinum on the surface of the support coated with the multi-catalyst layer to be greater than 1.2 g / m 2 .

[0026] Preferably, in step A, the atomic percentage ratio of any one or any two of ruthenium, platinum, rhodium, palladium or iridium is 28%-32%, and the atomic percentage ratio of the same element is 68%-72%. A multi-catalytic layer mixed solution is prepared according to the atomic percentage ratio, and the metal mass concentration of any one or any two of ruthenium, platinum, rhodium, palladium or iridium in the multi-catalytic layer mixed solution is 120g / L-130g / L;

[0027] In the step B, the electrode carrier is calcined at 475° C. to 525° C. for 0.6 h to 0.9 h;

[0028] In step C, step B is repeated several times to allow the loading of the multi-catalyst layer composed of the precious metals and their oxides on the electrode carrier to reach 15-17 g / m 2 ;

[0029] In the step D, a mixed solution is prepared using a soluble compound of platinum and a soluble compound of ruthenium, with the atomic percentage of ruthenium being 10%-40% and the atomic percentage of platinum being 60%-90%, and the metal mass concentration of ruthenium and platinum in the mixed solution being 120g / L-130g / L;

[0030] In the step E, a mixed solution of ruthenium and platinum soluble compounds is placed in a high temperature resistant container and calcined at 400° C. to 475° C. for 1.0 h to 1.5 h to obtain a ruthenium and platinum catalyst powder;

[0031] In the step G, weighing ruthenium platinum catalyst powder and dissolving it in an aqueous solution containing 0.4%-0.6% fluorocarbon surfactant, and then using ultrasonic vibration to vibrate the aqueous solution for 2.8h-3.2h, the frequency of the ultrasonic vibration is 85KHz-95KHz;

[0032] In the step H, the carrier coated with the multi-catalyst layer obtained in step C is placed in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.18h-0.23h, the distance between the carrier and the liquid surface of the ruthenium platinum catalyst solution is greater than 60mm, and then the ultrasonic frequency is reduced for 0.18h-0.23h until the ultrasonic vibration stops, and then it is allowed to stand for 0.30h-0.45h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then the carrier coated with the multi-catalyst layer is dried at 82°C-83°C, and then the carrier coated with the multi-catalyst layer is calcined at 425°C-475°C for 0.7h-0.8h;

[0033] In step I, steps G and H are repeated multiple times to allow the loading of ruthenium and platinum on the surface of the support coated with the multi-catalyst layer to be greater than 1.5 g / m 2 .

[0034] Preferably, the surface of the ultrasonic compaction catalyst layer has a plurality of pyramid-shaped protrusions composed of nanocrystals.

[0035] The method for preparing the corrosion-resistant hydrogen evolution catalyst of the present invention comprises the following steps:

[0036] A. Prepare a solution of a soluble compound of ruthenium or platinum or rhodium or palladium or iridium, prepare an electrode carrier, the electrode carrier is a metal material, prepare a solution of the same element of a soluble compound of the same metal material as the metal material constituting the electrode carrier, according to the ratio of the atomic percentage of any one or any two of ruthenium or platinum or rhodium or palladium or iridium is 20%-40%, the ratio of the atomic percentage of the same element is 60%-80%, prepare a multi-catalyst layer mixed solution according to the ratio of the atomic percentage, the metal mass concentration of any one or any two of ruthenium or platinum or rhodium or palladium or iridium in the multi-catalyst layer mixed solution is 100g / L-150g / L, after the multi-catalyst layer mixed solution is prepared in proportion, stir the multi-catalyst layer mixed solution under the condition of -25°C to 4°C to mix the multi-catalyst layer mixed solution evenly, then transfer the multi-catalyst layer mixed solution into a sealed container, and store it under the condition of -4°C to 10°C for standby use;

[0037] B. Clean the electrode carrier to remove dirt on the surface of the electrode carrier, apply the multi-catalyst layer mixed solution obtained in step A to the electrode carrier, and then calcine the electrode carrier at 400° C. to 600° C. for 0.5 h to 1.0 h;

[0038] C. Repeat step B several times to make the loading of the multi-catalytic layer composed of precious metals and their oxides on the electrode carrier reach 10-22g / m 2 , obtaining a carrier coated with a multi-catalyst layer;

[0039] D. Prepare a mixed solution using a soluble platinum compound and a soluble ruthenium compound, according to a ratio of 0.5% to 60% of ruthenium atomic percentage and a ratio of 40% to 99.5% of platinum atomic percentage, wherein the metal mass concentration of ruthenium and platinum in the mixed solution is 100 g / L to 150 g / L. After the mixed solution is prepared in proportion, stir the mixed solution at room temperature to mix the mixed solution evenly, thereby obtaining a mixed solution of soluble ruthenium and platinum compounds;

[0040] E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container, and calcine it at 350°C-550°C for 0.5h-2.0h to obtain ruthenium and platinum catalyst powder;

[0041] F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable container for sealed storage for later use;

[0042] G. Add ruthenium platinum catalyst powder into an aqueous solution containing 0.1%-1% fluorocarbon surfactant, and then vibrate the aqueous solution using ultrasonic waves for 2h-4h.

[0043] H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.1h-0.5h, then reduce the ultrasonic frequency for 0.1h-0.5h until the ultrasonic vibration stops, and then let it stand for more than 0.2h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 75°C-90°C, and then calcine the carrier coated with the multi-catalyst layer at 350°C-550°C in an atmosphere for 0.5h-1.0h;

[0044] The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density, which is composed of nano-materials aggregated, after being fired for 0.5h-1.0h in an atmosphere of 350℃-550℃;

[0045] I. Repeat steps G and H for multiple times to make the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer greater than 1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

[0046] Preferably, in step A, the atomic percentage ratio of any one or any two of ruthenium, platinum, rhodium, palladium or iridium is 25%-35%, and the atomic percentage ratio of the same element is 65%-75%. A multi-catalytic layer mixed solution is prepared according to the atomic percentage ratio, and the metal mass concentration of any one or any two of ruthenium, platinum, rhodium, palladium or iridium in the multi-catalytic layer mixed solution is 110g / L-140g / L;

[0047] In the step B, the electrode carrier is calcined at 450° C. to 550° C. for 0.5 h to 1.0 h;

[0048] In step C, step B is repeated several times to allow the loading of the multi-catalyst layer composed of the precious metals and their oxides on the electrode carrier to reach 12-20 g / m 2 ;

[0049] In the step D, a mixed solution is prepared using a soluble compound of platinum and a soluble compound of ruthenium, with the atomic percentage of ruthenium being 5% to 50% and the atomic percentage of platinum being 50% to 95%, and the metal mass concentration of ruthenium and platinum in the mixed solution being 110 g / L to 140 g / L;

[0050] In the step E, a mixed solution of ruthenium and platinum soluble compounds is placed in a high temperature resistant container and calcined at 375° C. to 500° C. for 0.8 h to 1.8 h to obtain a ruthenium and platinum catalyst powder;

[0051] In the step G, weighing ruthenium platinum catalyst powder and dissolving it in an aqueous solution containing 0.2%-0.8% fluorocarbon surfactant, and then using ultrasonic vibration to vibrate the aqueous solution for 2.5h-3.5h, the frequency of the ultrasonic vibration is 80KHz-100KHz;

[0052] In the step H, the carrier coated with the multi-catalyst layer obtained in step C is placed in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.15h-0.25h, the distance between the carrier and the liquid surface of the ruthenium platinum catalyst solution is greater than 50mm, and then the ultrasonic frequency is reduced for 0.15h-0.25h until the ultrasonic vibration stops, and then it is allowed to stand for 0.25h-0.5h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then the carrier coated with the multi-catalyst layer is dried at 80°C-85°C, and then the carrier coated with the multi-catalyst layer is calcined at 400°C-525°C for 0.6h-0.9h;

[0053] In step I, steps G and H are repeated multiple times to allow the loading of ruthenium and platinum on the surface of the support coated with the multi-catalyst layer to be greater than 1.2 g / m 2 .

[0054] Preferably, in step A, the atomic percentage ratio of any one or any two of ruthenium, platinum, rhodium, palladium or iridium is 28%-32%, and the atomic percentage ratio of the same element is 68%-72%. A multi-catalytic layer mixed solution is prepared according to the atomic percentage ratio, and the metal mass concentration of any one or any two of ruthenium, platinum, rhodium, palladium or iridium in the multi-catalytic layer mixed solution is 120g / L-130g / L;

[0055] In the step B, the electrode carrier is calcined at 475° C. to 525° C. for 0.6 h to 0.9 h;

[0056] In step C, step B is repeated several times to allow the loading of the multi-catalyst layer composed of the precious metals and their oxides on the electrode carrier to reach 15-17 g / m 2 ;

[0057] In the step D, a mixed solution is prepared using a soluble compound of platinum and a soluble compound of ruthenium, with the atomic percentage of ruthenium being 10%-40% and the atomic percentage of platinum being 60%-90%, and the metal mass concentration of ruthenium and platinum in the mixed solution being 120g / L-130g / L;

[0058] In the step E, a mixed solution of ruthenium and platinum soluble compounds is placed in a high temperature resistant container and calcined at 400° C. to 475° C. for 1.0 h to 1.5 h to obtain a ruthenium and platinum catalyst powder;

[0059] In the step G, weighing ruthenium platinum catalyst powder and dissolving it in an aqueous solution containing 0.4%-0.6% fluorocarbon surfactant, and then using ultrasonic vibration to vibrate the aqueous solution for 2.8h-3.2h, the frequency of the ultrasonic vibration is 85KHz-95KHz;

[0060] In the step H, the carrier coated with the multi-catalyst layer obtained in step C is placed in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.18h-0.23h, the distance between the carrier and the liquid surface of the ruthenium platinum catalyst solution is greater than 60mm, and then the ultrasonic frequency is reduced for 0.18h-0.23h until the ultrasonic vibration stops, and then it is allowed to stand for 0.30h-0.45h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then the carrier coated with the multi-catalyst layer is dried at 82°C-83°C, and then the carrier coated with the multi-catalyst layer is calcined at 425°C-475°C for 0.7h-0.8h;

[0061] In step I, steps G and H are repeated multiple times to allow the loading of ruthenium and platinum on the surface of the support coated with the multi-catalyst layer to be greater than 1.5 g / m 2 .

[0062] Preferably, the surface of the ultrasonic compaction catalyst layer has a plurality of pyramid-shaped protrusions composed of nanocrystals.

[0063] The corrosion-resistant hydrogen evolution electrode of the present invention comprises a carrier, a multi-catalyst layer and an anti-corrosion catalyst layer, wherein the multi-catalyst layer is used to connect the carrier and the anti-corrosion catalyst layer, and the anti-corrosion catalyst layer is an ultrasonic compaction catalyst layer composed of one or two of platinum, ruthenium and their oxides, and the metal and oxide loading in the ultrasonic compaction catalyst layer is ≥1g / m 2 .

[0064] Preferably, the ultrasonic compaction catalyst layer is composed of catalytic crystals in the shape of a geometric combination of uniform shape and size, the catalytic crystals have a slightly convex upper surface and a slightly concave lower surface, and the vertical surface is flat, and there is a mosaic connection between the catalytic crystals in the geometric combination.

[0065] Preferably, the multi-catalyst layer is formed by thermal oxidation of one or two metal elements selected from ruthenium, platinum, rhodium, palladium and iridium mixed with an element that is the same as the carrier component.

[0066] Preferably, the multi-catalyst layer is formed by thermal oxidation of one or two metal elements selected from ruthenium, platinum, rhodium, palladium and iridium mixed with an element that is the same as the carrier component.

[0067] Preferably, one or two of the metal elements selected from ruthenium, platinum, rhodium, palladium and iridium account for 20% to 40% of the atoms in the multi-catalyst layer.

[0068] Preferably, one or two of the metal elements selected from ruthenium, platinum, rhodium, palladium and iridium account for 23% to 38% of the atoms in the multi-catalyst layer.

[0069] Preferably, the electrode is a cathode.

[0070] The multi-element catalyst layer of the present invention is prepared by the following steps:

[0071] A. Prepare a solution of a soluble compound of ruthenium or platinum or rhodium or palladium or iridium, prepare an electrode carrier, the electrode carrier is a metal material, prepare a solution of the same element of a soluble compound of the same metal material as the metal material constituting the electrode carrier, according to the ratio of the atomic percentage of any one or any two of ruthenium or platinum or rhodium or palladium or iridium is 20%-40%, the ratio of the atomic percentage of the same element is 60%-80%, prepare a multi-catalyst layer mixed solution according to the ratio of the atomic percentage, the metal mass concentration of any one or any two of ruthenium or platinum or rhodium or palladium or iridium in the multi-catalyst layer mixed solution is 100g / L-150g / L, after the multi-catalyst layer mixed solution is prepared in proportion, stir the multi-catalyst layer mixed solution under the condition of -25°C to 4°C to mix the multi-catalyst layer mixed solution evenly, then transfer the multi-catalyst layer mixed solution into a sealed container, and store it under the condition of -4°C to 10°C for standby use;

[0072] B. Clean the electrode carrier to remove dirt on the surface of the electrode carrier, apply the multi-catalyst layer mixed solution obtained in step A to the electrode carrier, and then calcine the electrode carrier at 400° C. to 600° C. for 0.5 h to 1.0 h;

[0073] C. Repeat step B several times to allow the loading amount of the multi-catalytic layer composed of the precious metals and their oxides on the electrode carrier to reach 10-22 g / m2, that is, to form a multi-catalytic layer on the surface of the carrier.

[0074] The ultrasonic compaction catalyst layer of the present invention is prepared by the following steps:

[0075] The electrode carrier is placed in a solution containing a catalyst under ultrasonic vibration for 0.1h-0.5h, and then the ultrasonic frequency is reduced for 0.1h-0.5h until the ultrasonic vibration stops, and then it is left to stand for more than 0.2h to allow the catalyst to be evenly deposited on the surface of the carrier, and then the carrier is dried at 75℃-90℃, and then the carrier is calcined at 350℃-550℃ atmosphere for 0.5h-1.0h;

[0076] The catalyst layer deposited on the surface of the carrier under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density, which is composed of nano-materials, after being fired in an atmosphere of 350℃-550℃ for 0.5h-1.0h.

[0077] Repeat the above steps for several times to make the catalyst loading on the surface of the carrier greater than 1.0 g / m2, that is, to form an ultrasonic compacted catalyst layer on the surface of the carrier.

[0078] A corrosion-resistant electrode for hydrogen evolution prepared by the preparation method according to any one of claims 9 to 15.

[0079] A corrosion-resistant electrode for hydrogen evolution prepared using the ultrasonic compaction catalyst layer as claimed in claim 17.

[0080] A hydrogen evolution reaction device of the present invention uses the corrosion-resistant hydrogen evolution electrode as claimed in any one of claims 9 to 15, 18 and 19.

[0081] The electrode for hydrogen evolution and the preparation method thereof, as well as the hydrogen evolution reaction device of the present invention aim at the problems existing in the catalytic activity of conventional catalysts for hydrogen evolution. By adopting ruthenium platinum metal and its oxide, and utilizing a catalyst layer deposited on the surface of a carrier coated with a multi-catalytic layer under the action of ultrasonic vibration, after being calcined for 0.5h-1.0h in an atmosphere of 350°C-550°C, an ultrasonic compaction catalyst layer with uniform crystal distribution, compact combination and density formed by aggregation of nano materials can be formed on the surface of the carrier, so that the crystal particles of the corrosion-resistant hydrogen evolution catalyst of the present invention are uniform and small, and the surface is smooth and flat, and the number of overall active points of the catalyst is increased, so that the catalyst has a lower hydrogen evolution overpotential under harsh acid and alkaline conditions, a longer service life and a stronger hydrogen evolution catalytic ability. Such structural features, on the one hand, greatly increase the contact area with the electrolyte, allowing the hydrogen evolution reaction to occur rapidly, allowing hydrogen to be rapidly desorbed and desorbed on the smooth and dense catalyst surface. On the other hand, the ultrasonic compaction catalyst layer has a dense structure with uniform, fine crystal particles and a smooth and flat surface, which reduces the acid-base corrosive electrolyte from penetrating into the cracks generated by catalyst agglomeration to corrode the matrix material inside, thereby effectively improving the service life of the hydrogen evolution catalyst working in the acid-base corrosive liquid. In addition, the nanocrystalline ultrasonic compaction catalyst layer composed of ruthenium platinum metal and its oxides and the multi-catalyst layer connecting the ultrasonic compaction catalyst layer and the carrier together constitute the corrosion-resistant hydrogen evolution catalyst of this patent. The multi-catalyst layer connecting the ultrasonic compaction catalyst layer and the carrier adds the same elements as the carrier and precious metal components with hydrogen evolution catalytic effect, so that the two and the carrier form a stable and firm enamel solid solution, while increasing the active components of the hydrogen evolution catalyst, the coating and the interface bonding force between the coating and the substrate can be strengthened, thereby effectively extending the service life of the hydrogen evolution catalyst.

[0082] The corrosion-resistant hydrogen evolution catalyst of the present invention is in an acidic electrolyte with a hydrogen ion concentration of 2 mol / L and a hydrogen evolution reaction rate of 20 KA / m 2 After electrolysis in acidic electrolyte for 1000h, the effective components of the corrosion-resistant hydrogen evolution catalyst remain ≥30%; in alkaline electrolyte with a hydroxide ion concentration of 10mol / L, 20KA / m 2 After 1000h of electrolysis in alkaline electrolyte, the effective components of the corrosion-resistant hydrogen evolution catalyst remain ≥60%, and the hydrogen evolution overpotential is lower; in an acidic electrolyte with a hydrogen ion concentration of 2mol / L, 5KA / m 2 The overpotential of hydrogen evolution is ≤68mV, in an alkaline electrolyte with a hydroxide ion concentration of 10mol / L, 5KA / m 2 The hydrogen evolution overpotential is ≤75mV.

[0083] The corrosion-resistant hydrogen evolution catalyst of the present invention can react with the hydrogen ion concentration of 2 mol / L in an acidic electrolyte at 5 KA / m 2 The hydrogen evolution overpotential is ≤58mV at the current density of 20KA / m 2The effective components of the catalyst remain ≥35% after electrolysis for 1000h in acidic electrolyte and 5KA / m in alkaline electrolyte with 10mol / L hydroxide ion concentration. 2 The hydrogen evolution overpotential is ≤65mV at the current density of 20KA / m 2 After 1000h of electrolysis in alkaline electrolyte, the residual effective components of the catalyst shall be ≥70%.

[0084] Therefore, the electrode for hydrogen evolution and the preparation method thereof, as well as the hydrogen evolution reaction device of the present invention have a large contact area with the electrolyte, which allows the hydrogen evolution reaction to occur rapidly, allowing hydrogen to be rapidly desorbed and desorbed on the smooth and dense catalyst surface, and has the characteristics of lower hydrogen evolution overpotential, longer application life, and stronger hydrogen evolution catalytic ability under harsh acid and alkaline conditions.

[0085] Other details and features of the electrode for hydrogen evolution and the preparation method thereof, and the hydrogen evolution reaction device of the present invention can be clearly understood by reading the embodiments described in detail below. DETAILED DESCRIPTION

[0086] The corrosion-resistant hydrogen evolution catalyst of the present invention is prepared by the following steps:

[0087] A. Prepare a solution of a soluble compound of ruthenium or platinum or rhodium or palladium or iridium, prepare an electrode carrier, the electrode carrier is a metal material, prepare a solution of the same element of a soluble compound of the same metal material as the metal material constituting the electrode carrier, according to the ratio of the atomic percentage of any one or any two of ruthenium or platinum or rhodium or palladium or iridium is 20%-40%, the ratio of the atomic percentage of the same element is 60%-80%, prepare a multi-catalyst layer mixed solution according to the ratio of the atomic percentage, the metal mass concentration of any one or any two of ruthenium or platinum or rhodium or palladium or iridium in the multi-catalyst layer mixed solution is 100g / L-150g / L, after the multi-catalyst layer mixed solution is prepared in proportion, stir the multi-catalyst layer mixed solution under the condition of -25°C to 4°C to mix the multi-catalyst layer mixed solution evenly, then transfer the multi-catalyst layer mixed solution into a sealed container, and store it under the condition of -4°C to 10°C for standby use;

[0088] B. Clean the electrode carrier to remove dirt on the surface of the electrode carrier, apply the multi-catalyst layer mixed solution obtained in step A to the electrode carrier, and then calcine the electrode carrier at 400° C. to 600° C. for 0.5 h to 1.0 h;

[0089] C. Repeat step B several times to make the loading of the multi-catalytic layer composed of precious metals and their oxides on the electrode carrier reach 10-22g / m 2 , obtaining a carrier coated with a multi-catalyst layer;

[0090] D. Prepare a mixed solution using a soluble platinum compound and a soluble ruthenium compound, according to a ratio of 0.5% to 60% of ruthenium atomic percentage and a ratio of 40% to 99.5% of platinum atomic percentage, wherein the metal mass concentration of ruthenium and platinum in the mixed solution is 100 g / L to 150 g / L. After the mixed solution is prepared in proportion, stir the mixed solution at room temperature to mix the mixed solution evenly, thereby obtaining a mixed solution of soluble ruthenium and platinum compounds;

[0091] E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container, and calcine it at 350°C-550°C for 0.5h-2.0h to obtain ruthenium and platinum catalyst powder;

[0092] F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable container for sealed storage for later use;

[0093] G. Add ruthenium platinum catalyst powder into an aqueous solution containing 0.1%-1% fluorocarbon surfactant, and then vibrate the aqueous solution using ultrasonic waves for 2h-4h.

[0094] H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.1h-0.5h, then reduce the ultrasonic frequency for 0.1h-0.5h until the ultrasonic vibration stops, and then let it stand for more than 0.2h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 75°C-90°C, and then calcine the carrier coated with the multi-catalyst layer at 350°C-550°C in an atmosphere for 0.5h-1.0h;

[0095] The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density, which is composed of nano-materials aggregated, after being fired for 0.5h-1.0h in an atmosphere of 350℃-550℃;

[0096] I. Repeat steps G and H for multiple times to make the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer greater than 1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

[0097] As a further improvement of the present invention, in the above step A, the atomic percentage ratio of any one or any two of ruthenium, platinum, rhodium, palladium or iridium is 25%-35%, and the atomic percentage ratio of the same element is 65%-75%. A multi-catalytic layer mixed solution is prepared according to the atomic percentage ratio, and the metal mass concentration of any one or any two of ruthenium, platinum, rhodium, palladium or iridium in the multi-catalytic layer mixed solution is 110g / L-140g / L;

[0098] In the step B, the electrode carrier is calcined at 450° C. to 550° C. for 0.5 h to 1.0 h;

[0099] In step C, step B is repeated several times to allow the loading of the multi-catalyst layer composed of the precious metals and their oxides on the electrode carrier to reach 12-20 g / m 2 ;

[0100] In the step D, a mixed solution is prepared using a soluble compound of platinum and a soluble compound of ruthenium, with the atomic percentage of ruthenium being 5% to 50% and the atomic percentage of platinum being 50% to 95%, and the metal mass concentration of ruthenium and platinum in the mixed solution being 110 g / L to 140 g / L;

[0101] In the step E, a mixed solution of ruthenium and platinum soluble compounds is placed in a high temperature resistant container and calcined at 375° C. to 500° C. for 0.8 h to 1.8 h to obtain a ruthenium and platinum catalyst powder;

[0102] In the step G, weighing ruthenium platinum catalyst powder and dissolving it in an aqueous solution containing 0.2%-0.8% fluorocarbon surfactant, and then using ultrasonic vibration to vibrate the aqueous solution for 2.5h-3.5h, the frequency of the ultrasonic vibration is 80KHz-100KHz;

[0103] In the step H, the carrier coated with the multi-catalyst layer obtained in step C is placed in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.15h-0.25h, the distance between the carrier and the liquid surface of the ruthenium platinum catalyst solution is greater than 50mm, and then the ultrasonic frequency is reduced for 0.15h-0.25h until the ultrasonic vibration stops, and then it is allowed to stand for 0.25h-0.5h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then the carrier coated with the multi-catalyst layer is dried at 80°C-85°C, and then the carrier coated with the multi-catalyst layer is calcined at 400°C-525°C for 0.6h-0.9h;

[0104] In step I, steps G and H are repeated multiple times to allow the loading of ruthenium and platinum on the surface of the support coated with the multi-catalyst layer to be greater than 1.2 g / m 2 .

[0105] As a further improvement of the present invention, in the above step A, the atomic percentage ratio of any one or any two of ruthenium, platinum, rhodium, palladium or iridium is 28%-32%, and the atomic percentage ratio of the same element is 68%-72%. A multi-catalytic layer mixed solution is prepared according to the atomic percentage ratio, and the metal mass concentration of any one or any two of ruthenium, platinum, rhodium, palladium or iridium in the multi-catalytic layer mixed solution is 120g / L-130g / L;

[0106] In the step B, the electrode carrier is calcined at 475° C. to 525° C. for 0.6 h to 0.9 h;

[0107] In step C, step B is repeated several times to allow the loading of the multi-catalyst layer composed of the precious metals and their oxides on the electrode carrier to reach 15-17 g / m 2 ;

[0108] In the step D, a mixed solution is prepared using a soluble compound of platinum and a soluble compound of ruthenium, with the atomic percentage of ruthenium being 10%-40% and the atomic percentage of platinum being 60%-90%, and the metal mass concentration of ruthenium and platinum in the mixed solution being 120g / L-130g / L;

[0109] In the step E, a mixed solution of ruthenium and platinum soluble compounds is placed in a high temperature resistant container and calcined at 400° C. to 475° C. for 1.0 h to 1.5 h to obtain a ruthenium and platinum catalyst powder;

[0110] In the step G, weighing ruthenium platinum catalyst powder and dissolving it in an aqueous solution containing 0.4%-0.6% fluorocarbon surfactant, and then using ultrasonic vibration to vibrate the aqueous solution for 2.8h-3.2h, the frequency of the ultrasonic vibration is 85KHz-95KHz;

[0111] In the step H, the carrier coated with the multi-catalyst layer obtained in step C is placed in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.18h-0.23h, the distance between the carrier and the liquid surface of the ruthenium platinum catalyst solution is greater than 60mm, and then the ultrasonic frequency is reduced for 0.18h-0.23h until the ultrasonic vibration stops, and then it is allowed to stand for 0.30h-0.45h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then the carrier coated with the multi-catalyst layer is dried at 82°C-83°C, and then the carrier coated with the multi-catalyst layer is calcined at 425°C-475°C for 0.7h-0.8h;

[0112] In step I, steps G and H are repeated multiple times to allow the loading of ruthenium and platinum on the surface of the support coated with the multi-catalyst layer to be greater than 1.5 g / m 2 .

[0113] As a further improvement of the present invention, the surface of the ultrasonic compaction catalyst layer has a plurality of pyramidal protrusions composed of nanocrystals.

[0114] The method for preparing the corrosion-resistant hydrogen evolution catalyst of the present invention comprises the following steps:

[0115] A. Prepare a solution of a soluble compound of ruthenium or platinum or rhodium or palladium or iridium, prepare an electrode carrier, the electrode carrier is a metal material, prepare a solution of the same element of a soluble compound of the same metal material as the metal material constituting the electrode carrier, according to the ratio of the atomic percentage of any one or any two of ruthenium or platinum or rhodium or palladium or iridium is 20%-40%, the ratio of the atomic percentage of the same element is 60%-80%, prepare a multi-catalyst layer mixed solution according to the ratio of the atomic percentage, the metal mass concentration of any one or any two of ruthenium or platinum or rhodium or palladium or iridium in the multi-catalyst layer mixed solution is 100g / L-150g / L, after the multi-catalyst layer mixed solution is prepared in proportion, stir the multi-catalyst layer mixed solution under the condition of -25°C to 4°C to mix the multi-catalyst layer mixed solution evenly, then transfer the multi-catalyst layer mixed solution into a sealed container, and store it under the condition of -4°C to 10°C for standby use;

[0116] B. Clean the electrode carrier to remove dirt on the surface of the electrode carrier, apply the multi-catalyst layer mixed solution obtained in step A to the electrode carrier, and then calcine the electrode carrier at 400° C. to 600° C. for 0.5 h to 1.0 h;

[0117] C. Repeat step B several times to make the loading of the multi-catalytic layer composed of precious metals and their oxides on the electrode carrier reach 10-22g / m 2 , obtaining a carrier coated with a multi-catalyst layer;

[0118] D. Prepare a mixed solution using a soluble platinum compound and a soluble ruthenium compound, according to a ratio of 0.5% to 60% of ruthenium atomic percentage and a ratio of 40% to 99.5% of platinum atomic percentage, wherein the metal mass concentration of ruthenium and platinum in the mixed solution is 100 g / L to 150 g / L. After the mixed solution is prepared in proportion, stir the mixed solution at room temperature to mix the mixed solution evenly, thereby obtaining a mixed solution of soluble ruthenium and platinum compounds;

[0119] E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container, and calcine it at 350°C-550°C for 0.5h-2.0h to obtain ruthenium and platinum catalyst powder;

[0120] F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable container for sealed storage for later use;

[0121] G. Add ruthenium platinum catalyst powder into an aqueous solution containing 0.1%-1% fluorocarbon surfactant, and then vibrate the aqueous solution using ultrasonic waves for 2h-4h.

[0122] H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.1h-0.5h, then reduce the ultrasonic frequency for 0.1h-0.5h until the ultrasonic vibration stops, and then let it stand for more than 0.2h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 75°C-90°C, and then calcine the carrier coated with the multi-catalyst layer at 350°C-550°C in an atmosphere for 0.5h-1.0h;

[0123] The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density, which is composed of nano-materials aggregated, after being fired for 0.5h-1.0h in an atmosphere of 350℃-550℃;

[0124] I. Repeat steps G and H for multiple times to make the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer greater than 1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

[0125] As a further improvement of the present invention, in the above step A, the atomic percentage ratio of any one or any two of ruthenium, platinum, rhodium, palladium or iridium is 25%-35%, and the atomic percentage ratio of the same element is 65%-75%. A multi-catalytic layer mixed solution is prepared according to the atomic percentage ratio, and the metal mass concentration of any one or any two of ruthenium, platinum, rhodium, palladium or iridium in the multi-catalytic layer mixed solution is 110g / L-140g / L;

[0126] In the step B, the electrode carrier is calcined at 450° C. to 550° C. for 0.5 h to 1.0 h;

[0127] In step C, step B is repeated several times to allow the loading of the multi-catalyst layer composed of the precious metals and their oxides on the electrode carrier to reach 12-20 g / m 2 ;

[0128] In the step D, a mixed solution is prepared using a soluble compound of platinum and a soluble compound of ruthenium, with the atomic percentage of ruthenium being 5% to 50% and the atomic percentage of platinum being 50% to 95%, and the metal mass concentration of ruthenium and platinum in the mixed solution being 110 g / L to 140 g / L;

[0129] In the step E, a mixed solution of ruthenium and platinum soluble compounds is placed in a high temperature resistant container and calcined at 375° C. to 500° C. for 0.8 h to 1.8 h to obtain a ruthenium and platinum catalyst powder;

[0130] In the step G, weighing ruthenium platinum catalyst powder and dissolving it in an aqueous solution containing 0.2%-0.8% fluorocarbon surfactant, and then using ultrasonic vibration to vibrate the aqueous solution for 2.5h-3.5h, the frequency of the ultrasonic vibration is 80KHz-100KHz;

[0131] In the step H, the carrier coated with the multi-catalyst layer obtained in step C is placed in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.15h-0.25h, the distance between the carrier and the liquid surface of the ruthenium platinum catalyst solution is greater than 50mm, and then the ultrasonic frequency is reduced for 0.15h-0.25h until the ultrasonic vibration stops, and then it is allowed to stand for 0.25h-0.5h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then the carrier coated with the multi-catalyst layer is dried at 80°C-85°C, and then the carrier coated with the multi-catalyst layer is calcined at 400°C-525°C for 0.6h-0.9h;

[0132] In step I, steps G and H are repeated multiple times to allow the loading of ruthenium and platinum on the surface of the support coated with the multi-catalyst layer to be greater than 1.2 g / m 2 .

[0133] As a further improvement of the present invention, in the above step A, the atomic percentage ratio of any one or any two of ruthenium, platinum, rhodium, palladium or iridium is 28%-32%, and the atomic percentage ratio of the same element is 68%-72%. A multi-catalytic layer mixed solution is prepared according to the atomic percentage ratio, and the metal mass concentration of any one or any two of ruthenium, platinum, rhodium, palladium or iridium in the multi-catalytic layer mixed solution is 120g / L-130g / L;

[0134] In the step B, the electrode carrier is calcined at 475° C. to 525° C. for 0.6 h to 0.9 h;

[0135] In step C, step B is repeated several times to allow the loading of the multi-catalyst layer composed of the precious metals and their oxides on the electrode carrier to reach 15-17 g / m 2 ;

[0136] In the step D, a mixed solution is prepared using a soluble compound of platinum and a soluble compound of ruthenium, with the atomic percentage of ruthenium being 10%-40% and the atomic percentage of platinum being 60%-90%, and the metal mass concentration of ruthenium and platinum in the mixed solution being 120g / L-130g / L;

[0137] In the step E, a mixed solution of ruthenium and platinum soluble compounds is placed in a high temperature resistant container and calcined at 400° C. to 475° C. for 1.0 h to 1.5 h to obtain a ruthenium and platinum catalyst powder;

[0138] In the step G, weighing ruthenium platinum catalyst powder and dissolving it in an aqueous solution containing 0.4%-0.6% fluorocarbon surfactant, and then using ultrasonic vibration to vibrate the aqueous solution for 2.8h-3.2h, the frequency of the ultrasonic vibration is 85KHz-95KHz;

[0139] In the step H, the carrier coated with the multi-catalyst layer obtained in step C is placed in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.18h-0.23h, the distance between the carrier and the liquid surface of the ruthenium platinum catalyst solution is greater than 60mm, and then the ultrasonic frequency is reduced for 0.18h-0.23h until the ultrasonic vibration stops, and then it is allowed to stand for 0.30h-0.45h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then the carrier coated with the multi-catalyst layer is dried at 82°C-83°C, and then the carrier coated with the multi-catalyst layer is calcined at 425°C-475°C for 0.7h-0.8h;

[0140] In step I, steps G and H are repeated multiple times to allow the loading of ruthenium and platinum on the surface of the support coated with the multi-catalyst layer to be greater than 1.5 g / m 2 .

[0141] As a further improvement of the present invention, the surface of the ultrasonic compaction catalyst layer has a plurality of pyramidal protrusions composed of nanocrystals.

[0142] The corrosion-resistant hydrogen evolution electrode of the present invention comprises a carrier, a multi-catalyst layer and an anti-corrosion catalyst layer, wherein the multi-catalyst layer is used to connect the carrier and the anti-corrosion catalyst layer, and the anti-corrosion catalyst layer is an ultrasonic compaction catalyst layer composed of one or two of platinum, ruthenium and their oxides, and the metal and oxide loading in the ultrasonic compaction catalyst layer is ≥1g / m 2 .

[0143] As a further improvement of the present invention, the ultrasonic compaction catalyst layer is composed of catalytic crystals in the shape of a geometric combination of uniform shape and size, the upper surface of the catalytic crystals is slightly convex and the lower surface is slightly concave, the vertical surface is flat, and there is a mosaic connection between the catalytic crystals in the geometric combination.

[0144] As a further improvement of the present invention, the multi-catalyst layer is formed by thermal oxidation of one or two metal elements selected from ruthenium, platinum, rhodium, palladium and iridium mixed with an element identical to the carrier component.

[0145] As a further improvement of the present invention, the multi-catalyst layer is formed by thermal oxidation of one or two metal elements selected from ruthenium, platinum, rhodium, palladium and iridium mixed with an element identical to the carrier component.

[0146] As a further improvement of the present invention, one or two metal elements selected from the above ruthenium, platinum, rhodium, palladium and iridium elements account for 20%-40% of the atoms in the multi-catalyst layer.

[0147] As a further improvement of the present invention, one or two metal elements selected from the above ruthenium, platinum, rhodium, palladium and iridium elements account for 23% to 38% of atoms in the multi-catalyst layer.

[0148] As a further improvement of the present invention, the above-mentioned electrode is a cathode.

[0149] The multi-element catalyst layer of the present invention is prepared by the following steps:

[0150] A. Prepare a solution of a soluble compound of ruthenium or platinum or rhodium or palladium or iridium, prepare an electrode carrier, the electrode carrier is a metal material, prepare a solution of the same element of a soluble compound of the same metal material as the metal material constituting the electrode carrier, according to the ratio of the atomic percentage of any one or any two of ruthenium or platinum or rhodium or palladium or iridium is 20%-40%, the ratio of the atomic percentage of the same element is 60%-80%, prepare a multi-catalyst layer mixed solution according to the ratio of the atomic percentage, the metal mass concentration of any one or any two of ruthenium or platinum or rhodium or palladium or iridium in the multi-catalyst layer mixed solution is 100g / L-150g / L, after the multi-catalyst layer mixed solution is prepared in proportion, stir the multi-catalyst layer mixed solution under the condition of -25°C to 4°C to mix the multi-catalyst layer mixed solution evenly, then transfer the multi-catalyst layer mixed solution into a sealed container, and store it under the condition of -4°C to 10°C for standby use;

[0151] B. Clean the electrode carrier to remove dirt on the surface of the electrode carrier, apply the multi-catalyst layer mixed solution obtained in step A to the electrode carrier, and then calcine the electrode carrier at 400° C. to 600° C. for 0.5 h to 1.0 h;

[0152] C. Repeat step B several times to make the loading of the multi-catalytic layer composed of precious metals and their oxides on the electrode carrier reach 10-22g / m 2 , that is, a multi-catalyst layer is formed on the surface of the carrier.

[0153] The ultrasonic compaction catalyst layer of the present invention is prepared by the following steps:

[0154] The electrode carrier is placed in a solution containing a catalyst under ultrasonic vibration for 0.1h-0.5h, and then the ultrasonic frequency is reduced for 0.1h-0.5h until the ultrasonic vibration stops, and then it is left to stand for more than 0.2h to allow the catalyst to be evenly deposited on the surface of the carrier, and then the carrier is dried at 75℃-90℃, and then the carrier is calcined at 350℃-550℃ atmosphere for 0.5h-1.0h;

[0155] The catalyst layer deposited on the surface of the carrier under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density, which is composed of nano-materials, after being fired in an atmosphere of 350℃-550℃ for 0.5h-1.0h.

[0156] Repeat the above steps several times to make the catalyst loading on the carrier surface greater than 1.0 g / m 2 , that is, an ultrasonic compaction catalyst layer is formed on the surface of the carrier.

[0157] A corrosion-resistant electrode for hydrogen evolution prepared by the preparation method according to any one of claims 9 to 15.

[0158] A corrosion-resistant electrode for hydrogen evolution prepared using the ultrasonic compaction catalyst layer as claimed in claim 17.

[0159] A hydrogen evolution reaction device using the corrosion-resistant hydrogen evolution electrode according to any one of claims 9 to 15, 18 and 19.

[0160] Example 1

[0161] The preparation method of the corrosion-resistant hydrogen evolution catalyst of the present invention is as follows:

[0162] A. When the electrode carrier is made of metallic titanium, a multi-catalyst layer mixed solution is prepared with a solution of a soluble ruthenium compound (ruthenium trichloride) and a solution of a soluble titanium compound (titanium tetrachloride, tetrabutyl titanate) in a ratio of 40% atomic percentage of ruthenium and 60% atomic percentage of titanium, and the concentration of ruthenium and titanium in the multi-catalyst layer mixed solution is 100 g / l. After the multi-catalyst layer mixed solution is prepared in proportion, the multi-catalyst layer mixed solution is stirred at -25°C to 4°C for 3 hours to mix the solution of the soluble ruthenium compound (ruthenium trichloride) and the solution of the soluble titanium compound (titanium tetrachloride, tetrabutyl titanate) evenly to obtain a multi-catalyst layer mixed solution, and then the multi-catalyst layer mixed solution is transferred into a sealed container and stored at -4°C to 10°C;

[0163] B. Clean the carrier of the electrode made of metal titanium to remove the surface dirt of the carrier, then apply an appropriate amount of the multi-catalyst layer mixed solution obtained in step a on the carrier, and then sinter the carrier at a high temperature of 450°C for 0.5h, that is, to allow the coated catalyst to adhere to the substrate or the upper layer of catalyst through sintering. Firing is a thermal oxidation process;

[0164] If the carrier of the above-mentioned electrode is made of metallic nickel, then when preparing the multi-catalyst layer mixed solution, the soluble compound of titanium can be replaced by the soluble compound of nickel, and the other treatment methods remain unchanged.

[0165] C. Repeat step B 8-12 times to make the loading of precious metals and their oxides in the multi-catalytic layer on the carrier reach 15.0±3.0g / m 2 , obtaining a carrier coated with a multi-catalyst layer;

[0166] D. Prepare a ruthenium-platinum soluble compound mixed solution using a soluble compound of platinum and a soluble compound of ruthenium, according to a ratio of 60% atomic percentage of ruthenium and 40% atomic percentage of platinum, wherein the concentration of ruthenium and platinum in the ruthenium-platinum soluble compound mixed solution is 100 g / l. After the ruthenium-platinum soluble compound mixed solution is prepared in proportion, stir the ruthenium-platinum soluble compound mixed solution at room temperature for 3 hours to uniformly mix the soluble compound of platinum and the soluble compound of ruthenium;

[0167] E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container, and calcine at 500° C. for 1.0 h to obtain ruthenium and platinum catalyst powder;

[0168] F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable glass container for sealed storage for later use;

[0169] G. Weigh the ruthenium platinum catalyst powder and dissolve it in an aqueous solution containing 1% fluorocarbon surfactant, that is, 1 liter of fluorocarbon surfactant in 99 liters of water, and then ultrasonically vibrate the aqueous solution containing 1% fluorocarbon surfactant for 2h-4h.

[0170] H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium-platinum catalyst solution under ultrasonic vibration for 0.2 h, with the distance between the carrier and the liquid level of the ruthenium-platinum catalyst solution greater than 60 mm, then reduce the ultrasonic frequency for 0.2 h until the ultrasonic vibration stops, and then stand for 0.35 h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 85° C. for 10 min, and then sinter the carrier coated with the multi-catalyst layer in an atmosphere of 350° C. for 0.5 h;

[0171] The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density, which is composed of nano-materials aggregated, after being fired at 350°C for 0.5h.

[0172] I. Repeat steps G and H for a total of 4 times, so that the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer is 2.0±1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

[0173] The above-mentioned corrosion-resistant hydrogen evolution catalyst is in an acidic electrolyte with a hydrogen ion concentration of 2 mol / L and 5 KA / m 2 The overpotential of hydrogen evolution by electrolysis was 57mV at a current density of 20KA / m 2 After electrolysis in an acidic electrolyte at a current density of 1000 h, the effective component of the catalyst remained 34%; the corrosion-resistant hydrogen evolution catalyst remained 5KA / m in an alkaline electrolyte with a hydroxide ion concentration of 10 mol / L. 2 The hydrogen evolution overpotential was 71mV at a current density of 20KA / m 2 After electrolysis in alkaline electrolyte for 1000 hours at a current density of 1.5, the residual effective components of the catalyst were determined to be 72%.

[0174] In the present invention, all "firing" refers to allowing the coated catalyst to adhere to the substrate or the upper layer of catalyst through sintering. Firing is a thermal oxidation process.

[0175] Example 2

[0176] The corrosion-resistant hydrogen evolution catalyst of the present invention is prepared by the following steps:

[0177] A. Prepare solutions of soluble compounds of ruthenium (ruthenium trichloride) and soluble compounds of titanium (titanium tetrachloride, tetrabutyl titanate), prepare a carrier of an electrode, the carrier of the electrode is a titanium metal material, prepare a multi-catalyst layer mixed solution according to a ratio of ruthenium atomic percentage of 20% and titanium atomic percentage of 80%, the metal mass concentration of ruthenium and titanium in the multi-catalyst layer mixed solution is 100g / L, after the multi-catalyst layer mixed solution is prepared in proportion, stir the multi-catalyst layer mixed solution at -25°C to 4°C for 3h, mix the solution of soluble compound of ruthenium (ruthenium trichloride) and the solution of soluble compound of titanium (titanium tetrachloride, tetrabutyl titanate) evenly, and obtain a multi-catalyst layer mixed solution, then transfer the multi-catalyst layer mixed solution into a sealed container and store it at -4°C to 10°C for standby use;

[0178] B. Clean the support of the electrode made of metal titanium to remove the surface dirt of the support, then apply an appropriate amount of the multi-catalyst layer mixed solution obtained in step A on the support, and then calcine the support of the electrode at a high temperature of 450° C. for 0.5 h;

[0179] If the support of the above-mentioned electrode is made of metallic nickel, the soluble compound of titanium should be replaced by a soluble compound of nickel when preparing the mixed solution of the multi-catalyst layer, and the other steps remain unchanged.

[0180] C. Repeat step B twelve times to make the loading of the multi-catalytic layer composed of precious metals and their oxides on the electrode carrier reach 15.0±3.0g / m 2 , obtaining a carrier coated with a multi-catalyst layer;

[0181] D. Prepare a ruthenium-platinum soluble compound mixed solution with a soluble compound of platinum and a soluble compound of ruthenium, according to a ratio of 60% atomic percentage of ruthenium and 40% atomic percentage of platinum, wherein the concentration of ruthenium and platinum in the ruthenium-platinum soluble compound mixed solution is 100 g / l. After the ruthenium-platinum soluble compound mixed solution is prepared in proportion, stir the ruthenium-platinum soluble compound mixed solution at room temperature for 3 hours to uniformly mix the soluble compound of platinum and the soluble compound of ruthenium;

[0182] E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container and calcine at 450° C. for 1.0 h to obtain ruthenium and platinum catalyst powder;

[0183] F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable glass container for sealed storage for later use;

[0184] G. Weigh the ruthenium platinum catalyst powder and dissolve it in a pure water solution containing 1% fluorocarbon surfactant, 99 liters of water and 1 liter of fluorocarbon surfactant, and ultrasonically vibrate for 2 hours, 3 hours or 4 hours.

[0185] H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.1h-0.5h, then reduce the ultrasonic frequency for 0.1h-0.5h until the ultrasonic vibration stops, and then let it stand for 0.3h to allow the catalyst to be evenly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 75°C-90°C, and then calcine the carrier coated with the multi-catalyst layer at 350°C in an atmosphere for 0.5h;

[0186] The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density, which is composed of nano-materials aggregated, after being fired at 350°C for 0.5h.

[0187] I. Repeat steps G and H for a total of 4 times to make the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer 2.0±1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

[0188] The above-mentioned corrosion-resistant hydrogen evolution catalyst is in an acidic electrolyte with a hydrogen ion concentration of 2 mol / L and 5 KA / m 2 Electrolytic determination of hydrogen evolution overpotential 68mV at current density 20KA / m 2 After electrolysis in an acidic electrolyte at a current density of 5 KA / m, the effective component of the catalyst remained 30%. The corrosion-resistant hydrogen evolution catalyst was electrolyzed in an alkaline electrolyte with a hydroxide ion concentration of 10 mol / L at 5 KA / m 2 The hydrogen evolution overpotential was measured at a current density of 75mV and 20KA / m 2 After electrolysis in alkaline electrolyte for 1000 hours at a current density of 1.5, the residual effective components of the catalyst were 60%.

[0189] Example 3

[0190] The preparation method of the corrosion-resistant hydrogen evolution catalyst of the present invention is as follows:

[0191] A. When the electrode carrier is made of metallic titanium, a multi-catalyst layer mixed solution is prepared with a solution of a soluble compound of ruthenium (ruthenium trichloride), a solution of a soluble compound of platinum and a solution of a soluble compound of titanium (titanium tetrachloride, tetrabutyl titanate) according to a ratio of 15% atomic percentage of ruthenium, 15% atomic percentage of platinum and 70% atomic percentage of titanium. The concentration of ruthenium, platinum and titanium in the multi-catalyst layer mixed solution is 100 g / l. After the multi-catalyst layer mixed solution is prepared in proportion, the multi-catalyst layer mixed solution is stirred at -25°C to 4°C for 3 hours to mix the solution of the soluble compound of ruthenium, the solution of the soluble compound of platinum and the solution of the soluble compound of titanium uniformly to obtain a multi-catalyst layer mixed solution. The multi-catalyst layer mixed solution is then transferred into a sealed container and stored at -4°C to 10°C.

[0192] B. Clean the carrier of the electrode made of metal titanium to remove the surface dirt of the carrier, then apply an appropriate amount of the multi-catalyst layer mixed solution obtained in step a on the carrier, and then sinter the carrier at a high temperature of 500°C for 0.6h, that is, to allow the coated catalyst to adhere to the substrate or the upper layer of catalyst through sintering. Firing is a thermal oxidation process;

[0193] If the carrier of the above-mentioned electrode is made of metallic nickel, then when preparing the multi-catalyst layer mixed solution, the soluble compound of titanium can be replaced by the soluble compound of nickel, and the other treatment methods remain unchanged.

[0194] C. Repeat step B 10 times to make the loading of precious metals and their oxides in the multi-catalytic layer on the carrier reach 15.0±2.0g / m 2 , obtaining a carrier coated with a multi-catalyst layer;

[0195] D. Prepare a ruthenium-platinum soluble compound mixed solution using a soluble compound of platinum and a soluble compound of ruthenium, according to a ratio of 10.0% atomic percentage of ruthenium and 90.0% atomic percentage of platinum, wherein the concentration of ruthenium and platinum in the ruthenium-platinum soluble compound mixed solution is 100 g / l. After the ruthenium-platinum soluble compound mixed solution is prepared in proportion, stir the ruthenium-platinum soluble compound mixed solution at room temperature for 3 hours to uniformly mix the soluble compound of platinum and the soluble compound of ruthenium;

[0196] E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container, and calcine at 500° C. for 1.0 h to obtain ruthenium and platinum catalyst powder;

[0197] F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable glass container for sealed storage for later use;

[0198] G. Weigh the ruthenium platinum catalyst powder and dissolve it in an aqueous solution containing 0.2% fluorocarbon surfactant, that is, 0.2 liters of fluorocarbon surfactant in 99.8 liters of water, and then ultrasonically vibrate the aqueous solution containing 0.2% fluorocarbon surfactant for 2h-4h.

[0199] H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium-platinum catalyst solution under ultrasonic vibration for 0.2 h, with the distance between the carrier and the liquid level of the ruthenium-platinum catalyst solution greater than 60 mm, then reduce the ultrasonic frequency for 0.2 h until the ultrasonic vibration stops, and then stand for 0.35 h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 85° C. for 10 min, and then sinter the carrier coated with the multi-catalyst layer in an atmosphere of 350° C. for 0.5 h;

[0200] The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density, which is composed of nano-materials aggregated, after being fired at 350°C for 0.5h.

[0201] I. Repeat steps G and H for 1-2 times in total, so that the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer is 2.0±1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

[0202] The corrosion-resistant hydrogen evolution catalyst is in an acidic electrolyte with a hydrogen ion concentration of 2 mol / L and at a temperature of 5 KA / m 2 The overpotential of hydrogen evolution by electrolysis was 53mV at a current density of 20KA / m 2 After electrolysis in an acidic electrolyte at a current density of 500 kJ / min for 1000 h, the effective component of the catalyst remained at 51%. The corrosion-resistant hydrogen evolution catalyst was electrolyzed in an alkaline electrolyte with a hydroxide ion concentration of 10 mol / L at a current density of 5 kJ / min. 2 The hydrogen evolution overpotential was 59mV at a current density of 20KA / m 2 After electrolysis in alkaline electrolyte for 1000 hours at a current density of 1.5, the residual effective components of the catalyst were determined to be 78%.

[0203] Example 4

[0204] The preparation method of the corrosion-resistant hydrogen evolution catalyst of the present invention is as follows:

[0205] A. When the electrode carrier is made of titanium metal, a multi-catalyst layer mixed solution is prepared with a solution of a soluble compound of ruthenium, a solution of a soluble compound of rhodium and a solution of a soluble compound of titanium, according to a ratio of 10% atomic percentage of ruthenium, 10% atomic percentage of platinum and 80% atomic percentage of titanium, wherein the concentrations of ruthenium, rhodium and titanium in the multi-catalyst layer mixed solution are 100 g / l. After the multi-catalyst layer mixed solution is prepared in proportion, the multi-catalyst layer mixed solution is stirred at -25°C to 4°C for 3 h to uniformly mix the solution of the soluble compound of ruthenium, the solution of the soluble compound of platinum and the solution of the soluble compound of titanium to obtain a multi-catalyst layer mixed solution, and then the multi-catalyst layer mixed solution is transferred into a sealed container and stored at -4°C to 10°C;

[0206] B. Clean the carrier of the electrode made of metal titanium to remove the surface dirt of the carrier, then apply an appropriate amount of the multi-catalyst layer mixed solution obtained in step a on the carrier, and then sinter the carrier at a high temperature of 450°C for 1 hour, that is, to allow the coated catalyst to adhere to the substrate or the upper layer of catalyst through sintering. Firing is a thermal oxidation process;

[0207] If the carrier of the above-mentioned electrode is made of metallic nickel, then when preparing the multi-catalyst layer mixed solution, the soluble compound of titanium can be replaced by the soluble compound of nickel, and the other treatment methods remain unchanged.

[0208] C. Repeat step B 6 times to make the loading of precious metals and their oxides in the multi-catalytic layer on the carrier reach 15.0±2.0g / m 2 , obtaining a carrier coated with a multi-catalyst layer;

[0209] D. Prepare a ruthenium-platinum soluble compound mixed solution using a soluble compound of platinum and a soluble compound of ruthenium, according to a ratio of 60% atomic percentage of ruthenium and 40% atomic percentage of platinum, wherein the concentration of ruthenium and platinum in the ruthenium-platinum soluble compound mixed solution is 100 g / l. After the ruthenium-platinum soluble compound mixed solution is prepared in proportion, stir the ruthenium-platinum soluble compound mixed solution at room temperature for 3 hours to uniformly mix the soluble compound of platinum and the soluble compound of ruthenium;

[0210] E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container, and calcine at 550° C. for 1.0 h to obtain ruthenium and platinum catalyst powder;

[0211] F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable glass container for sealed storage for later use;

[0212] G. Weigh the ruthenium platinum catalyst powder and dissolve it in an aqueous solution containing 0.2% fluorocarbon surfactant, that is, 0.2 liters of fluorocarbon surfactant in 99.8 liters of water, and then ultrasonically vibrate the aqueous solution containing 0.2% fluorocarbon surfactant for 2h-4h.

[0213] H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium-platinum catalyst solution under ultrasonic vibration for 0.2 h, with the distance between the carrier and the liquid level of the ruthenium-platinum catalyst solution greater than 60 mm, then reduce the ultrasonic frequency for 0.2 h until the ultrasonic vibration stops, and then let it stand for 0.35 h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 85° C. for 10 min, and then sinter the carrier coated with the multi-catalyst layer in an atmosphere of 450° C. for 0.5 h;

[0214] The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density composed of nano-materials after being fired at 450°C for 0.5h.

[0215] I. Repeat steps G and H for 1-2 times in total, so that the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer is 2.0±1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

[0216] The above corrosion-resistant hydrogen evolution catalyst is in an acidic electrolyte with a hydrogen ion concentration of 2 mol / L and a 5KA / m 2 Electrolytic determination of hydrogen evolution overpotential 61mV at current density 20KA / m 2 After electrolysis in an acidic electrolyte for 1000 hours, the effective components of the catalyst remained at 37%; the corrosion-resistant hydrogen evolution catalyst was electrolyzed in an alkaline electrolyte with a hydroxide ion concentration of 10 mol / L and a concentration of 5KA / m 2 At the current density of 20KA / m, the hydrogen evolution overpotential was measured to be 72mV. 2 After electrolysis in alkaline electrolyte with a current density of 1.5477 W for 1000 h, the effective components of the catalyst remained at 67%.

[0217] Example 5

[0218] The preparation method of the corrosion-resistant hydrogen evolution catalyst of the present invention is as follows:

[0219] A. When the electrode carrier is made of titanium metal, a multi-catalyst layer mixed solution is prepared with a solution of a soluble compound of ruthenium, a solution of a soluble compound of platinum and a solution of a soluble compound of titanium, according to a ratio of 16% atomic percentage of ruthenium, 16% atomic percentage of platinum and 68% atomic percentage of titanium, wherein the concentration of ruthenium, platinum and titanium in the multi-catalyst layer mixed solution is 100 g / l. After the multi-catalyst layer mixed solution is prepared in proportion, the multi-catalyst layer mixed solution is stirred at -25°C to 4°C for 3 hours to mix the solution of the soluble compound of ruthenium, the solution of the soluble compound of platinum and the solution of the soluble compound of titanium uniformly to obtain a multi-catalyst layer mixed solution, and then the multi-catalyst layer mixed solution is transferred into a sealed container and stored at -4°C to 10°C;

[0220] B. Clean the carrier of the electrode made of metal titanium to remove the surface dirt of the carrier, then apply an appropriate amount of the multi-catalyst layer mixed solution obtained in step a on the carrier, and then sinter the carrier at a high temperature of 500°C for 0.5h, that is, to allow the coated catalyst to adhere to the substrate or the upper layer of catalyst through sintering. Firing is a thermal oxidation process;

[0221] If the carrier of the above-mentioned electrode is made of metallic nickel, then when preparing the multi-catalyst layer mixed solution, the soluble compound of titanium can be replaced by the soluble compound of nickel, and the other treatment methods remain unchanged.

[0222] C. Repeat step B 9 times to make the loading of precious metals and their oxides in the multi-catalytic layer on the carrier reach 15.0±3.0g / m 2 , obtaining a carrier coated with a multi-catalyst layer;

[0223] D. Prepare a ruthenium-platinum soluble compound mixed solution using a soluble compound of platinum and a soluble compound of ruthenium, according to a ratio of 32% atomic percentage of ruthenium and 68% atomic percentage of platinum, wherein the concentration of ruthenium and platinum in the ruthenium-platinum soluble compound mixed solution is 100 g / l. After the ruthenium-platinum soluble compound mixed solution is prepared in proportion, stir the ruthenium-platinum soluble compound mixed solution at room temperature for 3 hours to uniformly mix the soluble compound of platinum and the soluble compound of ruthenium;

[0224] E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container, and calcine at 500° C. for 0.9 h to obtain ruthenium and platinum catalyst powder;

[0225] F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable glass container for sealed storage for later use;

[0226] G. Weigh the ruthenium platinum catalyst powder and dissolve it in an aqueous solution containing 0.2% fluorocarbon surfactant, that is, 0.2 liters of fluorocarbon surfactant in 99.8 liters of water, and then ultrasonically vibrate the aqueous solution containing 0.2% fluorocarbon surfactant for 2h-4h.

[0227] H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium-platinum catalyst solution under ultrasonic vibration for 0.2 h, with the distance between the carrier and the liquid level of the ruthenium-platinum catalyst solution being greater than 60 mm, then reduce the ultrasonic frequency for 0.2 h until the ultrasonic vibration stops, and then let it stand for 0.35 h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 85° C. for 10 min, and then sinter the carrier coated with the multi-catalyst layer in an atmosphere of 500° C. for 0.5 h;

[0228] The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density composed of nano-materials after being fired at 500℃ for 0.5h.

[0229] I. Repeat steps G and H for a total of 3 times, so that the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer is 2.0±1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

[0230] The above-mentioned corrosion-resistant hydrogen evolution catalyst is in an acidic electrolyte with a hydrogen ion concentration of 2 mol / L and 5 KA / m 2 Electrolytic determination of hydrogen evolution overpotential 45mV at current density 20KA / m 2 After electrolysis in an acidic electrolyte for 1000 hours, it was determined that the effective components of the catalyst remained at 65%; the corrosion-resistant hydrogen evolution catalyst remained at 5KA / m in an alkaline electrolyte with a hydroxide ion concentration of 10 mol / L. 2 The hydrogen evolution overpotential was 51mV at a current density of 20KA / m 2 After electrolysis in alkaline electrolyte for 1000 hours, the residual effective components of the catalyst were determined to be 87%.

[0231] Example 6

[0232] The preparation method of the corrosion-resistant hydrogen evolution catalyst of the present invention is as follows:

[0233] A. When the support of the electrode is made of metallic titanium, a solution of a soluble compound of ruthenium (ruthenium trichloride), a solution of a soluble compound of iridium and a solution of a soluble compound of titanium (titanium tetrachloride, tetrabutyl titanate) are used to prepare a multi-catalyst layer mixed solution according to a ratio of 10% atomic percentage of ruthenium, 10% atomic percentage of iridium and 80% atomic percentage of titanium. The concentration of ruthenium, iridium and titanium in the multi-catalyst layer mixed solution is 100 g / l. After the multi-catalyst layer mixed solution is prepared in proportion, the multi-catalyst layer mixed solution is stirred at -25°C to 4°C for 3 hours to mix the solution of the soluble compound of ruthenium, the solution of the soluble compound of iridium and the solution of the soluble compound of titanium uniformly to obtain a multi-catalyst layer mixed solution. The multi-catalyst layer mixed solution is then transferred into a sealed container and stored at -4°C to 10°C.

[0234] B. Clean the carrier of the electrode made of metal titanium to remove the surface dirt of the carrier, then apply an appropriate amount of the multi-catalyst layer mixed solution obtained in step a on the carrier, and then sinter the carrier at a high temperature of 500°C for 0.5h, that is, to allow the coated catalyst to adhere to the substrate or the upper layer of catalyst through sintering. Firing is a thermal oxidation process;

[0235] If the carrier of the above-mentioned electrode is made of metallic nickel, then when preparing the multi-catalyst layer mixed solution, the soluble compound of titanium can be replaced by the soluble compound of nickel, and the other treatment methods remain unchanged.

[0236] C. Repeat step B 8 times to make the loading of precious metals and their oxides in the multi-catalytic layer on the carrier reach 15.0±3.0g / m 2 , obtaining a carrier coated with a multi-catalyst layer;

[0237] D. Prepare a ruthenium-platinum soluble compound mixed solution using a soluble compound of platinum and a soluble compound of ruthenium, according to a ratio of 60% atomic percentage of ruthenium and 40% atomic percentage of platinum, wherein the concentration of ruthenium and platinum in the ruthenium-platinum soluble compound mixed solution is 100 g / l. After the ruthenium-platinum soluble compound mixed solution is prepared in proportion, stir the ruthenium-platinum soluble compound mixed solution at room temperature for 3 hours to uniformly mix the soluble compound of platinum and the soluble compound of ruthenium;

[0238] E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container, and calcine at 550° C. for 0.5 h to obtain ruthenium and platinum catalyst powder;

[0239] F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable glass container for sealed storage for later use;

[0240] G. Weigh the ruthenium platinum catalyst powder and dissolve it in an aqueous solution containing 0.1% fluorocarbon surfactant, that is, 0.1 liter of fluorocarbon surfactant in 99.9 liters of water, and then ultrasonically vibrate the aqueous solution containing 0.1% fluorocarbon surfactant for 2h-4h.

[0241] H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium-platinum catalyst solution under ultrasonic vibration for 0.25 h, the distance between the carrier and the liquid level of the ruthenium-platinum catalyst solution is greater than 60 mm, then reduce the ultrasonic frequency for 0.25 h until the ultrasonic vibration stops, and then stand for 0.45 h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 80° C. for 10 min, and then sinter the carrier coated with the multi-catalyst layer in an atmosphere of 500° C. for 0.5 h;

[0242] The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density composed of nano-materials after being fired at 500℃ for 0.5h.

[0243] I. Repeat steps G and H for a total of 4 times, so that the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer is 2.0±1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

[0244] The above-mentioned corrosion-resistant hydrogen evolution catalyst is in an acidic electrolyte with a hydrogen ion concentration of 2 mol / L and 5 KA / m 2 The overpotential of hydrogen evolution by electrolysis was 74mV at a current density of 20KA / m 2 After electrolysis in an acidic electrolyte for 1000 hours, the effective components of the catalyst remained at 63%. The corrosion-resistant hydrogen evolution catalyst remained at 5KA / m in an alkaline electrolyte with a hydroxide ion concentration of 10 mol / L. 2 The hydrogen evolution overpotential was 74mV at a current density of 20KA / m 2 After electrolysis in alkaline electrolyte for 1000 hours, the residual effective components of the catalyst were determined to be 63%.

[0245] Example 7

[0246] The preparation method of the corrosion-resistant hydrogen evolution catalyst of the present invention is as follows:

[0247] A. When the electrode carrier is made of metallic titanium, a multi-catalyst layer mixed solution is prepared with a solution of a soluble compound of ruthenium (ruthenium trichloride), a solution of a soluble compound of palladium and a solution of a soluble compound of titanium, according to a ratio of 10% atomic percentage of ruthenium, 10% atomic percentage of palladium and 80% atomic percentage of titanium, wherein the concentration of ruthenium, palladium and titanium in the multi-catalyst layer mixed solution is 100 g / l. After the multi-catalyst layer mixed solution is prepared in proportion, the multi-catalyst layer mixed solution is stirred at -25°C to 4°C for 3 h to mix the solution of the soluble compound of ruthenium, the solution of the soluble compound of iridium and the solution of the soluble compound of titanium uniformly to obtain a multi-catalyst layer mixed solution, and then the multi-catalyst layer mixed solution is transferred into a sealed container and stored at -4°C to 10°C;

[0248] B. Clean the carrier of the electrode made of metal titanium to remove the surface dirt of the carrier, then apply an appropriate amount of the multi-catalyst layer mixed solution obtained in step a on the carrier, and then sinter the carrier at a high temperature of 500°C for 1 hour, that is, to allow the coated catalyst to adhere to the substrate or the upper layer of catalyst through sintering. Firing is a thermal oxidation process;

[0249] If the carrier of the above-mentioned electrode is made of metallic nickel, then when preparing the multi-catalyst layer mixed solution, the soluble compound of titanium can be replaced by the soluble compound of nickel, and the other treatment methods remain unchanged.

[0250] C. Repeat step B 6 times to make the loading of precious metals and their oxides in the multi-catalytic layer on the carrier reach 15.0±3.0g / m 2 , obtaining a carrier coated with a multi-catalyst layer;

[0251] D. Prepare a ruthenium-platinum soluble compound mixed solution using a soluble compound of platinum and a soluble compound of ruthenium, according to a ratio of 60% atomic percentage of ruthenium and 40% atomic percentage of platinum, wherein the concentration of ruthenium and platinum in the ruthenium-platinum soluble compound mixed solution is 100 g / l. After the ruthenium-platinum soluble compound mixed solution is prepared in proportion, stir the ruthenium-platinum soluble compound mixed solution at room temperature for 3 hours to uniformly mix the soluble compound of platinum and the soluble compound of ruthenium;

[0252] E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container and calcine at 350° C. for 0.5 h to obtain ruthenium and platinum catalyst powder;

[0253] F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable glass container for sealed storage for later use;

[0254] G. Weigh the ruthenium platinum catalyst powder and dissolve it in an aqueous solution containing 0.2% fluorocarbon surfactant, and then ultrasonically vibrate the aqueous solution containing 0.2% fluorocarbon surfactant for 2h-4h.

[0255] H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium-platinum catalyst solution under ultrasonic vibration for 0.35 h, the distance between the carrier and the liquid level of the ruthenium-platinum catalyst solution is greater than 60 mm, then reduce the ultrasonic frequency for 0.35 h until the ultrasonic vibration stops, and then let it stand for 0.40 h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 80° C. for 10 min, and then sinter the carrier coated with the multi-catalyst layer in an atmosphere of 500° C. for 1 h;

[0256] The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density composed of nano-materials after being fired at 500℃ for 1 hour.

[0257] I. Repeat steps G and H for a total of 2 times, so that the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer is 2.0±1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

[0258] The above-mentioned corrosion-resistant hydrogen evolution catalyst is in an acidic electrolyte with a hydrogen ion concentration of 2 mol / L and 5 KA / m 2 The overpotential of hydrogen evolution by electrolysis was 59mV at a current density of 20KA / m 2 After electrolysis in an acidic electrolyte for 1000 hours, the effective components of the catalyst remained at 30%; the corrosion-resistant hydrogen evolution catalyst remained at 5KA / m in an alkaline electrolyte with a hydroxide ion concentration of 10 mol / L. 2 The hydrogen evolution overpotential was 71mV at a current density of 20KA / m 2 After electrolysis in alkaline electrolyte for 1000 hours, the residual effective components of the catalyst were determined to be 61%.

[0259] Example 8

[0260] The preparation method of the corrosion-resistant hydrogen evolution catalyst of the present invention is as follows:

[0261] A. When the electrode carrier is made of metallic nickel, a multi-catalyst layer mixed solution is prepared with a solution of a soluble compound of ruthenium (ruthenium trichloride) and a solution of a soluble compound of nickel, with the atomic percentage of ruthenium being 40% and the atomic percentage of nickel being 60%, and the concentration of ruthenium and nickel in the multi-catalyst layer mixed solution is 100 g / l. After the multi-catalyst layer mixed solution is prepared in proportion, the multi-catalyst layer mixed solution is stirred at -25°C to 4°C for 3 hours to mix the solution of the soluble compound of ruthenium, the solution of the soluble compound of iridium and the solution of the soluble compound of titanium evenly to obtain a multi-catalyst layer mixed solution, and then the multi-catalyst layer mixed solution is transferred into a sealed container and stored at -4°C to 10°C;

[0262] B. Clean the support of the electrode made of metal nickel to remove the surface dirt of the support, then apply an appropriate amount of the multi-catalyst layer mixed solution obtained in step a on the support, and then sinter the support at a high temperature of 550°C for 0.5h, that is, to allow the coated catalyst to adhere to the substrate or the upper layer of catalyst through sintering. Firing is a thermal oxidation process;

[0263] C. Repeat step B 8 times to make the loading of precious metals and their oxides in the multi-catalytic layer on the carrier reach 15.0±3.0g / m 2 , obtaining a carrier coated with a multi-catalyst layer;

[0264] D. Prepare a ruthenium-platinum soluble compound mixed solution using a soluble compound of platinum and a soluble compound of ruthenium, according to a ratio of 6% atomic percentage of ruthenium and 94% atomic percentage of platinum, wherein the concentration of ruthenium and platinum in the ruthenium-platinum soluble compound mixed solution is 100 g / l. After the ruthenium-platinum soluble compound mixed solution is prepared in proportion, stir the ruthenium-platinum soluble compound mixed solution at room temperature for 3 hours to uniformly mix the soluble compound of platinum and the soluble compound of ruthenium;

[0265] E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container, and calcine at 500° C. for 1 hour to obtain ruthenium and platinum catalyst powder;

[0266] F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable glass container for sealed storage for later use;

[0267] G. Weigh the ruthenium platinum catalyst powder and dissolve it in an aqueous solution containing 0.2% fluorocarbon surfactant, and then ultrasonically vibrate the aqueous solution containing 0.2% fluorocarbon surfactant for 2h-4h.

[0268] H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium-platinum catalyst solution under ultrasonic vibration for 0.35 h, the distance between the carrier and the liquid level of the ruthenium-platinum catalyst solution is greater than 60 mm, then reduce the ultrasonic frequency for 0.35 h until the ultrasonic vibration stops, and then let it stand for 0.40 h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 80° C. for 10 min, and then sinter the carrier coated with the multi-catalyst layer in an atmosphere of 500° C. for 1 h;

[0269] The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density composed of nano-materials after being fired at 500℃ for 1 hour.

[0270] I. Repeat steps G and H for a total of 2 times, so that the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer is 2.0±1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

[0271] The above-mentioned corrosion-resistant hydrogen evolution catalyst is in an acidic electrolyte with a hydrogen ion concentration of 2 mol / L and 5 KA / m 2 The overpotential of hydrogen evolution by electrolysis was 59mV at a current density of 20KA / m 2 After electrolysis in an acidic electrolyte for 1000 hours, the effective components of the catalyst remained at 30%; the corrosion-resistant hydrogen evolution catalyst remained at 5KA / m in an alkaline electrolyte with a hydroxide ion concentration of 10 mol / L. 2 The hydrogen evolution overpotential was 56mV at a current density of 20KA / m 2 After electrolysis in alkaline electrolyte for 1000 hours, the effective components of the catalyst remained at 75%.

[0272] Comparative Example 1

[0273] The hydrogen evolution catalyst is prepared as follows:

[0274] a. Select a solution prepared with a soluble salt of ruthenium and a titanium solution of the same metal as the catalyst carrier, and prepare a multi-catalyst layer mixed solution according to the ratio of ruthenium atoms of 40% and the ratio of metal titanium atoms of the same carrier of 60%. The metal mass concentration in the solution is 100g / l, and the mixture is stirred for 3h to mix evenly, and then transferred into a sealed container and stored at -4℃-10℃;

[0275] b. Apply an appropriate amount of multi-catalyst solution on the carrier and calcine at 450℃ for 0.5h;

[0276] c. Repeat step b 12 times, and the loading amount of precious metals and their oxides in the multi-catalytic layer is 15.0±3.0g / m 2 , that is, the preparation of the hydrogen evolution catalyst layer of the comparative example is completed.

[0277] d. The hydrogen evolution catalyst of the comparative example was subjected to 5KA / m 2 Under the current density of 20KA / m, the overpotential of hydrogen evolution was 83mV by electrolysis. 2 After electrolysis in an acidic electrolyte for 100 h, the catalyst active ingredient remained at 21%. The hydrogen evolution catalyst of the comparative example remained at 5KA / m in an alkaline electrolyte with a hydroxide ion concentration of 10 mol / L. 2 The hydrogen evolution overpotential was determined to be 71mV at a current density of 20KA / m 2 After 8 hours of electrolysis in alkaline electrolyte, the residual effective components of the catalyst were 36%.

[0278] Comparative Example 2

[0279] The hydrogen evolution catalyst is prepared as follows:

[0280] a. Select a solution prepared with a ruthenium soluble salt and a titanium solution that is the same as the catalyst carrier metal titanium. Prepare a multi-catalyst layer mixed solution according to the ratio of ruthenium atoms to 35% and the ratio of metal titanium atoms to the carrier to 65%. The metal mass concentration in the solution is 100g / l. Stir for 3 hours to mix evenly, and then transfer to a sealed container and store at -4℃-10℃;

[0281] b. Apply an appropriate amount of multi-catalyst solution on the carrier and calcine at 500℃ for 0.5h;

[0282] c. Repeat step b 12 times, and the loading amount of precious metals and their oxides in the multi-catalytic layer is 15.0±3.0g / m 2 , that is, the production of the multi-catalytic layer is completed.

[0283] d. Select a platinum solution with a metal mass concentration of 100 g / l, apply it to the multi-catalyst layer carrier, dry it at 85°C for 10 minutes, and then burn it in an atmosphere at 500°C for 0.5 h.

[0284] e. Repeat the above step d twice to make the loading amount of precious metals and their oxides 2.0±1.0g / m 2 , that is, the preparation of the hydrogen evolution catalyst of the comparative example is completed.

[0285] f. The hydrogen evolution catalyst of the comparative example was 5KA / m 2 Under the current density of 20KA / m, the overpotential of hydrogen evolution was determined by electrolysis at 73mV. 2After electrolysis in an acidic electrolyte for 300 hours, the catalyst active ingredient remained 35%; the hydrogen evolution catalyst of the comparative example remained 5KA / m in an alkaline electrolyte with a hydroxide ion concentration of 10 mol / L. 2 At the current density of 20KA / m, the hydrogen evolution overpotential was measured to be 68mV. 2 After electrolysis in alkaline electrolyte for 12 hours, the residual effective components of the catalyst were determined to be 48%.

[0286] The data of the above-mentioned embodiments and comparative examples show that the electrode for hydrogen evolution and the preparation method thereof, as well as the hydrogen evolution reaction device of the present invention have a large contact area with the electrolyte, which allows the hydrogen evolution reaction to occur rapidly, and allows hydrogen to be rapidly desorbed and desorbed on the smooth and dense catalyst surface. Under harsh acid and alkaline conditions, the hydrogen evolution overpotential is lower, the application life is longer, and the hydrogen evolution catalytic ability is stronger, which is conducive to reducing the energy consumption of electrolysis and improving the economic benefits.

[0287] The above-mentioned embodiments are merely descriptions of the preferred implementation modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary engineering and technical personnel in the field shall fall within the protection scope determined by the claims of the present invention.

Claims

1. A corrosion-resistant hydrogen evolution catalyst, characterized in that Made in the following steps: A. Prepare a solution of a soluble compound of ruthenium or platinum or rhodium or palladium or iridium, prepare an electrode carrier, the electrode carrier is a metal material, prepare a solution of the same element of a soluble compound of the same metal material as the metal material constituting the electrode carrier, according to the ratio of the atomic percentage of any one or any two of ruthenium or platinum or rhodium or palladium or iridium is 20%-40%, the ratio of the atomic percentage of the same element is 60%-80%, prepare a multi-catalyst layer mixed solution according to the ratio of the atomic percentage, the metal mass concentration of any one or any two of ruthenium or platinum or rhodium or palladium or iridium in the multi-catalyst layer mixed solution is 100g / L-150g / L, after the multi-catalyst layer mixed solution is prepared in proportion, stir the multi-catalyst layer mixed solution under the condition of -25°C to 4°C to mix the multi-catalyst layer mixed solution evenly, then transfer the multi-catalyst layer mixed solution into a sealed container, and store it under the condition of -4°C to 10°C for standby use; B. Clean the electrode carrier to remove dirt on the surface of the electrode carrier, apply the multi-catalyst layer mixed solution obtained in step A to the electrode carrier, and then calcine the electrode carrier at 400° C. to 600° C. for 0.5 h to 1.0 h; C. Repeat step B several times to make the loading of the multi-catalytic layer composed of precious metals and their oxides on the electrode carrier reach 10-22g / m 2 , obtaining a carrier coated with a multi-catalyst layer; D. Prepare a mixed solution using a soluble platinum compound and a soluble ruthenium compound, according to a ratio of 0.5% to 60% of ruthenium atomic percentage and a ratio of 40% to 99.5% of platinum atomic percentage, wherein the metal mass concentration of ruthenium and platinum in the mixed solution is 100 g / L to 150 g / L. After the mixed solution is prepared in proportion, stir the mixed solution at room temperature to mix the mixed solution evenly, thereby obtaining a mixed solution of soluble ruthenium and platinum compounds; E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container, and calcine it at 350°C-550°C for 0.5h-2.0h to obtain ruthenium and platinum catalyst powder; F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable container for sealed storage for later use; G. Add ruthenium platinum catalyst powder into an aqueous solution containing 0.1%-1% fluorocarbon surfactant, and then vibrate the aqueous solution using ultrasonic waves for 2h-4h. H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.1h-0.5h, then reduce the ultrasonic frequency for 0.1h-0.5h until the ultrasonic vibration stops, and then let it stand for more than 0.2h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 75°C-90°C, and then calcine the carrier coated with the multi-catalyst layer at 350°C-550°C in an atmosphere for 0.5h-1.0h; The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density, which is composed of nano-materials aggregated, after being fired for 0.5h-1.0h in an atmosphere of 350℃-550℃; I. Repeat steps G and H for multiple times to make the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer greater than 1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

2. The corrosion-resistant hydrogen evolution catalyst according to claim 1, characterized in that: In the step A, the atomic percentage ratio of any one or any two of ruthenium, platinum, rhodium, palladium or iridium is 25%-35%, and the atomic percentage ratio of the same element is 65%-75%. A multi-catalyst layer mixed solution is prepared according to the atomic percentage ratio, and the metal mass concentration of any one or any two of ruthenium, platinum, rhodium, palladium or iridium in the multi-catalyst layer mixed solution is 110g / L-140g / L; In the step B, the electrode carrier is calcined at 450° C. to 550° C. for 0.5 h to 1.0 h; In step C, step B is repeated several times to allow the loading of the multi-catalyst layer composed of the precious metals and their oxides on the electrode carrier to reach 12-20 g / m 2 ; In the step D, a mixed solution is prepared using a soluble compound of platinum and a soluble compound of ruthenium, with the atomic percentage of ruthenium being 5% to 50% and the atomic percentage of platinum being 50% to 95%, and the metal mass concentration of ruthenium and platinum in the mixed solution being 110 g / L to 140 g / L; In the step E, a mixed solution of ruthenium and platinum soluble compounds is placed in a high temperature resistant container and calcined at 375° C. to 500° C. for 0.8 h to 1.8 h to obtain a ruthenium and platinum catalyst powder; In the step G, weighing ruthenium platinum catalyst powder and dissolving it in an aqueous solution containing 0.2%-0.8% fluorocarbon surfactant, and then using ultrasonic vibration to vibrate the aqueous solution for 2.5h-3.5h, the frequency of the ultrasonic vibration is 80KHz-100KHz; In the step H, the carrier coated with the multi-catalyst layer obtained in step C is placed in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.15h-0.25h, the distance between the carrier and the liquid surface of the ruthenium platinum catalyst solution is greater than 50mm, and then the ultrasonic frequency is reduced for 0.15h-0.25h until the ultrasonic vibration stops, and then it is allowed to stand for 0.25h-0.5h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then the carrier coated with the multi-catalyst layer is dried at 80°C-85°C, and then the carrier coated with the multi-catalyst layer is calcined at 400°C-525°C for 0.6h-0.9h; In step I, steps G and H are repeated multiple times to allow the loading of ruthenium and platinum on the surface of the support coated with the multi-catalyst layer to be greater than 1.2 g / m 2 .

3. The corrosion-resistant hydrogen evolution catalyst according to claim 2, characterized in that: In the step A, the atomic percentage ratio of any one or any two of ruthenium, platinum, rhodium, palladium or iridium is 28%-32%, and the atomic percentage ratio of the same element is 68%-72%. A multi-catalyst layer mixed solution is prepared according to the atomic percentage ratio, and the metal mass concentration of any one or any two of ruthenium, platinum, rhodium, palladium or iridium in the multi-catalyst layer mixed solution is 120g / L-130g / L; In the step B, the electrode carrier is calcined at 475° C. to 525° C. for 0.6 h to 0.9 h; In step C, step B is repeated several times to allow the loading of the multi-catalyst layer composed of the precious metals and their oxides on the electrode carrier to reach 15-17 g / m 2 ; In the step D, a mixed solution is prepared using a soluble compound of platinum and a soluble compound of ruthenium, with the atomic percentage of ruthenium being 10%-40% and the atomic percentage of platinum being 60%-90%, and the metal mass concentration of ruthenium and platinum in the mixed solution being 120g / L-130g / L; In the step E, a mixed solution of ruthenium and platinum soluble compounds is placed in a high temperature resistant container and calcined at 400° C. to 475° C. for 1.0 h to 1.5 h to obtain a ruthenium and platinum catalyst powder; In the step G, weighing ruthenium platinum catalyst powder and dissolving it in an aqueous solution containing 0.4%-0.6% fluorocarbon surfactant, and then using ultrasonic vibration to vibrate the aqueous solution for 2.8h-3.2h, the frequency of the ultrasonic vibration is 85KHz-95KHz; In the step H, the carrier coated with the multi-catalyst layer obtained in step C is placed in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.18h-0.23h, the distance between the carrier and the liquid surface of the ruthenium platinum catalyst solution is greater than 60mm, and then the ultrasonic frequency is reduced for 0.18h-0.23h until the ultrasonic vibration stops, and then it is allowed to stand for 0.30h-0.45h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then the carrier coated with the multi-catalyst layer is dried at 82°C-83°C, and then the carrier coated with the multi-catalyst layer is calcined at 425°C-475°C for 0.7h-0.8h; In step I, steps G and H are repeated multiple times to allow the loading of ruthenium and platinum on the surface of the support coated with the multi-catalyst layer to be greater than 1.5 g / m 2 .

4. The corrosion-resistant hydrogen evolution catalyst according to claim 1, 2 or 3, characterized in that: The surface of the ultrasonic compaction catalyst layer has a plurality of pyramid-shaped protrusions composed of nanocrystals.

5. A method for preparing a corrosion-resistant hydrogen evolution catalyst, characterized in that The steps include: A. Prepare a solution of a soluble compound of ruthenium or platinum or rhodium or palladium or iridium, prepare an electrode carrier, the electrode carrier is a metal material, prepare a solution of the same element of a soluble compound of the same metal material as the metal material constituting the electrode carrier, according to the ratio of the atomic percentage of any one or any two of ruthenium or platinum or rhodium or palladium or iridium is 20%-40%, the ratio of the atomic percentage of the same element is 60%-80%, prepare a multi-catalyst layer mixed solution according to the ratio of the atomic percentage, the metal mass concentration of any one or any two of ruthenium or platinum or rhodium or palladium or iridium in the multi-catalyst layer mixed solution is 100g / L-150g / L, after the multi-catalyst layer mixed solution is prepared in proportion, stir the multi-catalyst layer mixed solution under the condition of -25°C to 4°C to mix the multi-catalyst layer mixed solution evenly, then transfer the multi-catalyst layer mixed solution into a sealed container, and store it under the condition of -4°C to 10°C for standby use; B. Clean the electrode carrier to remove dirt on the surface of the electrode carrier, apply the multi-catalyst layer mixed solution obtained in step A to the electrode carrier, and then calcine the electrode carrier at 400° C. to 600° C. for 0.5 h to 1.0 h; C. Repeat step B several times to make the loading of the multi-catalytic layer composed of precious metals and their oxides on the electrode carrier reach 10-22g / m 2 , obtaining a carrier coated with a multi-catalyst layer; D. Prepare a mixed solution using a soluble platinum compound and a soluble ruthenium compound, according to a ratio of 0.5% to 60% of ruthenium atomic percentage and a ratio of 40% to 99.5% of platinum atomic percentage, wherein the metal mass concentration of ruthenium and platinum in the mixed solution is 100 g / L to 150 g / L. After the mixed solution is prepared in proportion, stir the mixed solution at room temperature to mix the mixed solution evenly, thereby obtaining a mixed solution of soluble ruthenium and platinum compounds; E. Put the mixed solution of ruthenium and platinum soluble compounds into a high temperature resistant container, and calcine it at 350°C-550°C for 0.5h-2.0h to obtain ruthenium and platinum catalyst powder; F. The ruthenium platinum catalyst powder obtained after the high temperature calcination is moved into a grinder for grinding, and then the ground ruthenium platinum catalyst is transferred into a sealable container for sealed storage for later use; G. Add ruthenium platinum catalyst powder into an aqueous solution containing 0.1%-1% fluorocarbon surfactant, and then vibrate the aqueous solution using ultrasonic waves for 2h-4h. H. Place the carrier coated with the multi-catalyst layer obtained in step C in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.1h-0.5h, then reduce the ultrasonic frequency for 0.1h-0.5h until the ultrasonic vibration stops, and then let it stand for more than 0.2h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then dry the carrier coated with the multi-catalyst layer at 75°C-90°C, and then calcine the carrier coated with the multi-catalyst layer at 350°C-550°C in an atmosphere for 0.5h-1.0h; The catalyst layer deposited on the surface of the carrier coated with the multi-catalyst layer under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density, which is composed of nano-materials aggregated, after being fired for 0.5h-1.0h in an atmosphere of 350℃-550℃; I. Repeat steps G and H for multiple times until the loading amount of ruthenium and platinum on the surface of the carrier coated with the multi-catalyst layer is greater than 1.0 g / m 2 , the surface of the carrier coated with the multi-catalyst layer is repeatedly coated with an ultrasonic compaction catalyst layer to obtain a corrosion-resistant hydrogen evolution catalyst.

6. The method for preparing the corrosion-resistant hydrogen evolution catalyst according to claim 5, characterized in that: In the step A, the atomic percentage ratio of any one or any two of ruthenium, platinum, rhodium, palladium or iridium is 25%-35%, and the atomic percentage ratio of the same element is 65%-75%. A multi-catalyst layer mixed solution is prepared according to the atomic percentage ratio, and the metal mass concentration of any one or any two of ruthenium, platinum, rhodium, palladium or iridium in the multi-catalyst layer mixed solution is 110g / L-140g / L; In the step B, the electrode carrier is calcined at 450° C. to 550° C. for 0.5 h to 1.0 h; In step C, step B is repeated several times to allow the loading of the multi-catalyst layer composed of the precious metals and their oxides on the electrode carrier to reach 12-20 g / m 2 ; In the step D, a mixed solution is prepared using a soluble compound of platinum and a soluble compound of ruthenium, with the atomic percentage of ruthenium being 5% to 50% and the atomic percentage of platinum being 50% to 95%, and the metal mass concentration of ruthenium and platinum in the mixed solution being 110 g / L to 140 g / L; In the step E, a mixed solution of ruthenium and platinum soluble compounds is placed in a high temperature resistant container and calcined at 375° C. to 500° C. for 0.8 h to 1.8 h to obtain a ruthenium and platinum catalyst powder; In the step G, weighing ruthenium platinum catalyst powder and dissolving it in an aqueous solution containing 0.2%-0.8% fluorocarbon surfactant, and then using ultrasonic vibration to vibrate the aqueous solution for 2.5h-3.5h, the frequency of the ultrasonic vibration is 80KHz-100KHz; In the step H, the carrier coated with the multi-catalyst layer obtained in step C is placed in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.15h-0.25h, the distance between the carrier and the liquid surface of the ruthenium platinum catalyst solution is greater than 50mm, and then the ultrasonic frequency is reduced for 0.15h-0.25h until the ultrasonic vibration stops, and then it is allowed to stand for 0.25h-0.5h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then the carrier coated with the multi-catalyst layer is dried at 80°C-85°C, and then the carrier coated with the multi-catalyst layer is calcined at 400°C-525°C for 0.6h-0.9h; In step I, steps G and H are repeated multiple times to allow the loading of ruthenium and platinum on the surface of the support coated with the multi-catalyst layer to be greater than 1.2 g / m 2 .

7. The method for preparing the corrosion-resistant hydrogen evolution catalyst according to claim 6, characterized in that: In the step A, the atomic percentage ratio of any one or any two of ruthenium, platinum, rhodium, palladium or iridium is 28%-32%, and the atomic percentage ratio of the same element is 68%-72%. A multi-catalyst layer mixed solution is prepared according to the atomic percentage ratio, and the metal mass concentration of any one or any two of ruthenium, platinum, rhodium, palladium or iridium in the multi-catalyst layer mixed solution is 120g / L-130g / L; In the step B, the electrode carrier is calcined at 475° C. to 525° C. for 0.6 h to 0.9 h; In step C, step B is repeated several times to allow the loading of the multi-catalyst layer composed of the precious metals and their oxides on the electrode carrier to reach 15-17 g / m 2 ; In the step D, a mixed solution is prepared using a soluble compound of platinum and a soluble compound of ruthenium, with the atomic percentage of ruthenium being 10%-40% and the atomic percentage of platinum being 60%-90%, and the metal mass concentration of ruthenium and platinum in the mixed solution being 120g / L-130g / L; In the step E, a mixed solution of ruthenium and platinum soluble compounds is placed in a high temperature resistant container and calcined at 400° C. to 475° C. for 1.0 h to 1.5 h to obtain a ruthenium and platinum catalyst powder; In the step G, weighing ruthenium platinum catalyst powder and dissolving it in an aqueous solution containing 0.4%-0.6% fluorocarbon surfactant, and then using ultrasonic vibration to vibrate the aqueous solution for 2.8h-3.2h, the frequency of the ultrasonic vibration is 85KHz-95KHz; In the step H, the carrier coated with the multi-catalyst layer obtained in step C is placed in the ruthenium platinum catalyst solution under ultrasonic vibration for 0.18h-0.23h, the distance between the carrier and the liquid surface of the ruthenium platinum catalyst solution is greater than 60mm, and then the ultrasonic frequency is reduced for 0.18h-0.23h until the ultrasonic vibration stops, and then it is allowed to stand for 0.30h-0.45h to allow the catalyst to be uniformly deposited on the surface of the carrier coated with the multi-catalyst layer, and then the carrier coated with the multi-catalyst layer is dried at 82°C-83°C, and then the carrier coated with the multi-catalyst layer is calcined at 425°C-475°C for 0.7h-0.8h; In step I, steps G and H are repeated multiple times to allow the loading of ruthenium and platinum on the surface of the support coated with the multi-catalyst layer to be greater than 1.5 g / m 2 .

8. The method for preparing the corrosion-resistant hydrogen evolution catalyst according to claim 5, 6 or 7, characterized in that: The surface of the ultrasonic compaction catalyst layer has a plurality of pyramid-shaped protrusions composed of nanocrystals.

9. An electrode for corrosion-resistant hydrogen evolution, comprising a carrier, a multi-catalyst layer and an anti-corrosion catalyst layer, wherein the multi-catalyst layer is used to connect the carrier and the anti-corrosion catalyst layer, and characterized in that: The anti-corrosion catalyst layer is an ultrasonic compaction catalyst layer composed of one or two of platinum, ruthenium and their oxides, and the metal and oxide loading in the ultrasonic compaction catalyst layer is ≥1g / m 2 .

10. The corrosion-resistant electrode for hydrogen evolution according to claim 9, characterized in that: The ultrasonic compaction catalyst layer is composed of catalytic crystals in the shape of a geometric combination of uniform shape and size. The catalytic crystals have a slightly convex upper surface and a slightly concave lower surface, a flat vertical surface, and a mosaic-like combination of catalytic crystals.

11. The corrosion-resistant electrode for hydrogen evolution according to claim 9 or 10, characterized in that: The multi-element catalytic layer is formed by mixing one or two metal elements among ruthenium, platinum, rhodium, palladium and iridium with an element that is the same as the carrier component and then thermally oxidizing the mixture.

12. The corrosion-resistant electrode for hydrogen evolution according to claim 11, characterized in that: The multi-element catalytic layer is formed by mixing one or two metal elements among ruthenium, platinum, rhodium, palladium and iridium with an element that is the same as the carrier component and then thermally oxidizing the mixture.

13. The corrosion-resistant electrode for hydrogen evolution according to claim 12, characterized in that: One or two metal elements among ruthenium, platinum, rhodium, palladium and iridium account for 20%-40% of atoms in the multi-catalyst layer.

14. The corrosion-resistant electrode for hydrogen evolution according to claim 13, characterized in that: One or two metal elements among ruthenium, platinum, rhodium, palladium and iridium account for 23% to 38% of atoms in the multi-catalyst layer.

15. The corrosion-resistant electrode for hydrogen evolution according to claim 9 or 10, characterized in that: The electrode is a cathode.

16. A multi-component catalytic layer, characterized in that: It is made by the following steps: A. Prepare a solution of a soluble compound of ruthenium or platinum or rhodium or palladium or iridium, prepare an electrode carrier, the electrode carrier is a metal material, prepare a solution of the same element of a soluble compound of the same metal material as the metal material constituting the electrode carrier, according to the ratio of the atomic percentage of any one or any two of ruthenium or platinum or rhodium or palladium or iridium is 20%-40%, the ratio of the atomic percentage of the same element is 60%-80%, prepare a multi-catalyst layer mixed solution according to the ratio of the atomic percentage, the metal mass concentration of any one or any two of ruthenium or platinum or rhodium or palladium or iridium in the multi-catalyst layer mixed solution is 100g / L-150g / L, after the multi-catalyst layer mixed solution is prepared in proportion, stir the multi-catalyst layer mixed solution under the condition of -25°C to 4°C to mix the multi-catalyst layer mixed solution evenly, then transfer the multi-catalyst layer mixed solution into a sealed container, and store it under the condition of -4°C to 10°C for standby use; B. Clean the electrode carrier to remove dirt on the surface of the electrode carrier, apply the multi-catalyst layer mixed solution obtained in step A to the electrode carrier, and then calcine the electrode carrier at 400° C. to 600° C. for 0.5 h to 1.0 h; C. Repeat step B several times to make the loading of the multi-catalytic layer composed of precious metals and their oxides on the electrode carrier reach 10-22g / m 2 , that is, a multi-catalyst layer is formed on the surface of the carrier.

17. Ultrasonic compaction of the catalyst layer, characterized in that: It is made by the following steps: The electrode carrier is placed in a solution containing a catalyst under ultrasonic vibration for 0.1h-0.5h, and then the ultrasonic frequency is reduced for 0.1h-0.5h until the ultrasonic vibration stops, and then it is left to stand for more than 0.2h to allow the catalyst to be evenly deposited on the surface of the carrier, and then the carrier is dried at 75℃-90℃, and then the carrier is calcined at 350℃-550℃ atmosphere for 0.5h-1.0h; The catalyst layer deposited on the surface of the carrier under the action of ultrasonic vibration can form an ultrasonic compacted catalyst layer on the surface of the carrier with uniform crystal distribution, compact combination and density, which is composed of nano-materials, after being fired in an atmosphere of 350℃-550℃ for 0.5h-1.0h. Repeat the above steps several times to make the catalyst loading on the carrier surface greater than 1.0 g / m 2 , that is, an ultrasonic compaction catalyst layer is formed on the surface of the carrier.

18. A corrosion-resistant electrode for hydrogen evolution prepared by the preparation method according to any one of claims 9 to 15.

19. A corrosion-resistant electrode for hydrogen evolution prepared using the ultrasonic compaction catalyst layer according to claim 17.

20. A hydrogen evolution reaction device, characterized in that: A hydrogen evolution reaction device using the corrosion-resistant hydrogen evolution electrode according to any one of claims 9 to 15, 18 and 19.