Iron-based noble metal catalytic electrode for hydrogen evolution by electrolyzing water as well as preparation method and application of iron-based noble metal catalytic electrode

Abstract

The invention belongs to the technical field of electrochemical catalysis, and particularly relates to an iron-based precious metal catalytic electrode for hydrogen evolution through water electrolysis and a preparation method and application thereof.The preparation method comprises the steps that firstly, an iron-based material is pretreated, oxide and oil dirt on the surface of the iron-based material are removed, and acid pickling and etching are conducted; secondly, a plating solution containing precious metal is prepared, deionized water is adopted, electrolyte comprises potassium ions, sulfate ions, sulfite ions and at least two of platinum ions, iridium ions, ruthenium ions and palladium ions, and the pH value is adjusted to be 1-4; thirdly, the plating solution serves as electrolyte, the pretreated iron-based material serves as a cathode, a DSA electrode or a carbon-based electrode serves as an anode, and electro-deposition is conducted; the parameters are as follows: the temperature of the plating solution is 20-80 DEG C, the current density is 0.1-100 mA / cm < 2 >, the power-on time is 40-4000 s, and the time ratio of power-on to power-off is (1: 0)-(1: 100). The use amount of precious metal is remarkably reduced, and meanwhile excellent catalytic performance and long-term stability are guaranteed.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochemical catalysis, and in particular relates to an iron-based noble metal catalytic electrode for electrolyzing water to produce hydrogen, and a preparation method and application thereof. Background Art

[0002] Hydrogen production by water electrolysis is a clean energy technology that decomposes water into hydrogen and oxygen through electrical energy. The process is centered on electrochemical reactions and includes two main reactions: oxygen evolution reaction (OER) at the anode and hydrogen evolution reaction (HER) at the cathode. The hydrogen evolution reaction is a key step in the production of hydrogen during water electrolysis, and its efficiency directly affects the energy consumption and economy of the hydrogen production process. In theory, the hydrogen evolution reaction can proceed at zero voltage, but in actual operation, an additional voltage (i.e., overpotential) needs to be applied to overcome the reaction kinetic resistance, so a low hydrogen evolution overpotential needs to be achieved through electrodes with catalytic functions. Precious metals such as platinum (Pt), ruthenium (Ru), iridium (Ir) and palladium (Pd) are widely considered to be the best hydrogen evolution catalysts due to their low hydrogen evolution overpotential and high current density. These precious metals can provide fast electron transfer channels and low energy barriers on the electrode surface, thereby significantly increasing the rate of hydrogen evolution reaction. These properties make precious metal hydrogen evolution catalysts show excellent catalytic efficiency under laboratory conditions. However, this type of material also faces two significant limitations: high price and scarcity of resources.

[0003] Although precious metal catalysts have superior performance, their high price and resource scarcity in large-scale applications have prompted researchers to seek low-cost, high-performance alternative materials. At present, most of the research on precious metal hydrogen evolution catalytic electrodes focuses on material systems based on titanium (Ti) or nickel (Ni). Titanium and nickel are good alternative substrate materials due to their relatively low price and relatively abundant resources. For example, nickel-based materials show good hydrogen evolution catalytic performance in alkaline media, while titanium is widely used in acidic media due to its excellent corrosion resistance. However, from an economic point of view, iron (Fe)-based materials are obviously more cost-effective. Iron-based materials are low-cost, widely available, and have good mechanical properties and conductivity, making them an ideal substrate material. In addition, after appropriate surface modification, the hydrogen evolution catalytic performance of iron-based materials is expected to approach or even exceed that of titanium and nickel-based materials. Therefore, combining iron-based materials with precious metals has the potential to further reduce the cost of catalytic electrodes while ensuring excellent catalytic performance and stability.

[0004] On the other hand, most current research focuses on a single noble metal or the combination of a noble metal and a cheap substrate, and relatively few studies have been conducted on multiple noble metal alloys. Noble metal alloys can usually improve catalytic performance through synergistic effects, such as optimizing the surface electronic structure and reducing the free energy of hydrogen adsorption (ΔG). Therefore, exploring the combination of multiple noble metal alloys with iron-based materials and designing an efficient, stable, and low-cost hydrogen evolution catalytic electrode has important research value and application potential. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, the problem to be solved by the present invention is that the noble metal hydrogen evolution catalyst has excellent catalytic efficiency but high cost. The present invention provides an iron-based noble metal catalytic electrode for electrolysis of water for hydrogen evolution and a preparation method and application thereof, so as to prepare a hydrogen evolution catalytic electrode with good catalytic effect and stability.

[0006] In order to achieve the above object, the present invention provides a method for preparing an iron-based noble metal catalytic electrode for electrolysis of water for hydrogen evolution, comprising the following steps:

[0007] Step 1: Pre-treat the iron-based material to remove oxides and oil stains on the surface of the iron-based material, and perform pickling and etching;

[0008] The second step is to prepare a plating solution containing precious metals, using deionized water, the electrolyte including potassium ions, sulfate ions, sulfite ions, and at least two of the following: platinum ions, iridium ions, ruthenium ions, and palladium ions, and the pH value is adjusted to 1-4;

[0009] In the third step, the above-mentioned plating solution is used as the electrolyte, the above-mentioned pretreated iron-based material is used as the cathode, and the DSA electrode or the carbon-based electrode is used as the anode for electrodeposition; the parameters are as follows: the temperature of the plating solution is 20-80°C, the current density is 0.1-100mA / cm 2 The power-on time is 40-4000s, and the ratio of power-on to power-off time is 1:0-1:100.

[0010] According to another embodiment of the present invention or the preparation method of any of the aforementioned embodiments, the substrate is mesh stainless steel.

[0011] According to another embodiment of the present invention or a preparation method of any of the aforementioned embodiments, during the pretreatment of the iron-based material, grinding, water washing, alkali washing, water washing, pickling etching and water washing treatment are sequentially performed, and grinding the substrate with sandpaper or sandblasting can effectively remove dirt such as oxides on the surface of the substrate, and then alkali washing is performed after water washing, and ultrasonic cleaning is performed in a solution of potassium hydroxide or sodium hydroxide with a concentration of 1-5 mol / L for 1-30 minutes to remove oil stains on the surface of the substrate; after water washing, it is placed in 10-30% hydrochloric acid for pickling and etching for 2-30 minutes.

[0012] According to another embodiment of the present invention or the preparation method of any of the aforementioned embodiments, the plating solution comprises potassium sulfate K2SO4, potassium sulfite K2SO3, and at least two of the following: chloroplatinic acid H2PtCl6, chloroiridic acid H2IrCl6, ruthenium trichloride RuCl3, and palladium chloride PdCl2.

[0013] According to another embodiment of the present invention or the preparation method of any of the aforementioned embodiments, the concentration of potassium sulfate K2SO4 is 1-300 g / L, the concentration of potassium sulfite K2SO3 is 0.1-500 g / L, the concentration of chloroplatinic acid H2PtCl6 calculated as platinum metal is 100-10000 mg / L, the concentration of chloroiridic acid H2IrCl6 calculated as iridium metal is 100-12000 mg / L, the concentration of ruthenium trichloride RuCl3 calculated as ruthenium metal is 100-2500 mg / L, and the concentration of palladium chloride PdCl2 calculated as palladium metal is 100-4000 mg / L.

[0014] According to another embodiment of the present invention or any of the above-mentioned embodiments, in the step of preparing the plating solution, potassium sulfate K2SO4 and potassium sulfite K2SO3 are dissolved in deionized water, and after stirring and dissolving, chloroplatinic acid H2PtCl6, chloroiridic acid H2IrCl6, and ruthenium trichloride RuCl are added. 3、 Two or more precursors of palladium chloride PdCl2, when stirred.

[0015] According to a preparation method according to another embodiment of the present invention or any of the aforementioned embodiments, during the electrodeposition, a stirring bar is added for stirring.

[0016] Beneficial effects of the present invention:

[0017] The iron-based noble metal catalytic electrode for hydrogen evolution by electrolysis of water and its preparation method and application described in the present invention ensures excellent catalytic performance and long-term stability through the synergistic effect of the iron base material and the noble metal. Nano-noble metal elements or alloys can be effectively electrodeposited on the iron base to obtain a high-performance catalytic electrode. At the same time, the effect of the deposited noble metal can be fully exerted, the utilization rate of the noble metal can be improved, the amount of noble metal used can be reduced, and the manufacturing cost of the hydrogen evolution electrode can be reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a schematic diagram of the operation flow of the method for preparing an iron-based noble metal catalytic electrode for electrolysis of water for hydrogen evolution according to the present invention;

[0019] Figure 2 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 1 of the present invention;

[0020] Figure 3is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 1 of the present invention;

[0021] Figure 4 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 2 of the present invention;

[0022] Figure 5 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 2 of the present invention;

[0023] Figure 6 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 3 of the present invention;

[0024] Figure 7 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 3 of the present invention;

[0025] Figure 8 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 4 of the present invention;

[0026] Fig. 9 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 4 of the present invention;

[0027] Fig.10 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 5 of the present invention;

[0028] Fig.11 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 5 of the present invention;

[0029] Fig.12 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 6 of the present invention;

[0030] Fig.13 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 6 of the present invention;

[0031] Fig.14 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 7 of the present invention;

[0032] Fig.15 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 7 of the present invention;

[0033] Fig.16 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 8 of the present invention;

[0034] Fig.17is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 8 of the present invention;

[0035] Fig.18 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 9 of the present invention;

[0036] Fig.19 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 9 of the present invention;

[0037] Fig. 20 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 10 of the present invention;

[0038] Fig.21 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 10 of the present invention;

[0039] Fig. 22 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 11 of the present invention;

[0040] Fig.23 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 11 of the present invention;

[0041] Fig.24 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 12 of the present invention;

[0042] Fig.25 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 12 of the present invention;

[0043] Fig.26 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 13 of the present invention;

[0044] Fig. 27 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 13 of the present invention;

[0045] Fig.28 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 14 of the present invention;

[0046] Fig.29 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 14 of the present invention;

[0047] Fig.30 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 15 of the present invention;

[0048] Fig.31 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 15 of the present invention;

[0049] Fig.32 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 16 of the present invention;

[0050] Fig.33 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 16 of the present invention;

[0051] Fig.34 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 17 of the present invention;

[0052] Fig.35 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 17 of the present invention;

[0053] Fig.36 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 18 of the present invention;

[0054] Fig.37 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 18 of the present invention;

[0055] Fig.38 is a SEM image of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 19 of the present invention;

[0056] Fig.39 is a polarization curve diagram of the iron-based noble metal hydrogen evolution catalytic electrode prepared in Example 19 of the present invention; DETAILED DESCRIPTION

[0057] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0058] The invention provides an iron-based noble metal catalytic electrode for electrolyzing water for hydrogen evolution, and a preparation method and application thereof. The plating solution of the iron-based noble metal catalytic electrode for hydrogen evolution consists of potassium sulfate, potassium sulfite, hydrochloric acid, chloroplatinic acid, chloroiridic acid, ruthenium trichloride, palladium chloride and deionized water; the concentration of chloroplatinic acid is 100-10000 mg / L based on platinum; the concentration of chloroiridic acid H2IrCl6 is 100-12000 mg / L based on iridium, the concentration of ruthenium trichloride RuCl3 is 100-2500 mg / L based on ruthenium, and the concentration of palladium chloride PdCl2 is 100-4000 mg / L based on palladium; the concentration of sulfate is 1-300 g / L, and the concentration of sulfite is 0.1-500 g / L; the pH value of the plating solution is 1-4, and the balance is deionized water.

[0059] The plating solution used in the present invention uses two or more of chloroplatinic acid, chloroiridic acid, ruthenium trichloride and palladium chloride as main salts, and sulfite as an additive. During the electroplating process, the cathode reduces the noble metal ions, so that the noble metal is deposited on the cathode to form a plating layer, and the sulfate mainly plays the role of a conductive salt in the plating solution.

[0060] The iron-based material is ordinary carbon steel or stainless steel in mesh, plate, felt or foam form. Cleaning the surface of the iron-based material includes sequential grinding, water washing, alkali washing, water washing, acid etching and water washing.

[0061] Grinding the substrate with sandpaper or sandblasting can effectively remove dirt such as oxides on the surface of the substrate, and then washing with water and then alkali washing, ultrasonic cleaning in a solution of potassium hydroxide or sodium hydroxide at a concentration of 1-5 mol / L for 1-30 minutes can remove oil stains on the surface of the substrate. After washing with water, it is placed in 10-30% hydrochloric acid for pickling and etching for 2-30 minutes. In order to make the etching more uniform, this step needs to be carried out under ultrasound at 20-80°C. After the pickling and etching is completed, wash with water. The pretreated iron-based material not only has a high degree of cleanliness, but also has a high surface roughness, which allows the nano-metal particles to grow better and more tightly on the surface of the substrate.

[0062] Optionally, during the electroplating process, the bath temperature is 20-80°C, the pH value is 1-4, and the electroplating current density is 0.1-100 mA / cm 2 The power-on time is 40s-4000s, and the ratio of power-on time to power-off time is 1:0-1:100.

[0063] During the electrodeposition process, it is necessary to continuously add two or more solutions of selected chloroplatinic acid, chloroiridic acid, ruthenium trichloride and palladium chloride to maintain the concentration of the main salt in the plating solution. In the electroplating solution, the concentration of chloroplatinic acid solution is 100-10000 mg / L calculated as platinum. In the electroplating solution, the concentration of chloroiridic acid solution is 100-12000 mg / L calculated as iridium. In the electroplating solution, the concentration of ruthenium trichloride solution is 100-2500 mg / L calculated as ruthenium. In the electroplating solution, the concentration of palladium chloride solution is 100-4000 mg / L calculated as palladium.

[0064] Working principle of the present invention:

[0065] The present invention can effectively electro-deposit nano noble metal elements or alloys on an iron substrate to obtain a high-performance catalytic electrode, and can also give full play to the role of the deposited noble metals, improve the utilization rate of the noble metals, reduce the amount of noble metals used, and reduce the manufacturing cost of the hydrogen evolution electrode.

[0066] Since the iron surface is prone to form a passivation film, which affects the catalytic activity, its active surface area must be increased by surface modification technology (such as pickling, sandblasting or coating with a conductive layer). At the same time, the present invention designs the base into a mesh structure, and the porous characteristics enhance the loading amount and distribution uniformity of precious metal particles such as platinum (Pt), ruthenium (Ru), iridium (Ir) and palladium (Pd). The present invention can dissolve and remove these oxides through chemical reactions through polishing and pickling. The active metal is exposed on the surface of the substrate, thereby providing a clean and active surface for subsequent electrodeposition, and improving the bonding force and uniformity of the coating. Pickling and etching selectively dissolve the softer or active areas on the surface of the substrate, forming a microscopic concave-convex structure, thereby coarsening the surface, so that the nano-metal particles can grow better and more closely on the substrate surface. Increase the specific surface area of ​​the substrate, provide more catalytic reaction sites, and provide more attachment sites for the deposition of precious metals. At the same time, improve the adhesion of the coating and reduce the risk of coating peeling.

[0067] The plating solution used in the present invention is mainly composed of one of chloroplatinic acid, chloroiridic acid, ruthenium trichloride and palladium chloride or a combination of two or more thereof, and sulfite is used as an additive. In the electroplating process, the cathode reduces the noble metal ions, so that the noble metal is deposited on the cathode to form a coating, and the sulfate mainly plays the role of a conductive salt in the plating solution. Through the reasonable proportion of multiple noble metals, the electrode surface electronic structure can be optimized, thereby improving the efficiency of the hydrogen evolution reaction. For example, the alloy of platinum and ruthenium has a lower adsorption hydrogen free energy, and the alloy of iridium and palladium shows excellent corrosion resistance in the electrolyte. Combining these noble metal alloys with an iron substrate is expected to achieve dual optimization of performance and cost.

[0068] Example 1

[0069] In this embodiment, a stainless steel mesh in an iron-based material is used as a substrate, and nano-platinum particles are deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for an iron-based noble metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with chloroplatinic acid, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 800mg / L, potassium sulfate 50g / L, potassium sulfite 300mg / L, an appropriate amount of hydrochloric acid to adjust the pH to 2.5, and the balance is deionized water.

[0070] The electrodeposition method provided in this embodiment comprises the following steps:

[0071] Step 1: Sandblast the surface of the stainless steel mesh; then rinse it with deionized water.

[0072] Step 2: After rinsing the sandblasted stainless steel mesh, place it in a 1 mol / L potassium hydroxide solution for ultrasonic cleaning at room temperature for 5 minutes, and then rinse it with deionized water.

[0073] Step 3: Place the washed stainless steel mesh in a 12% hydrochloric acid solution, and perform pickling and etching under ultrasonic oscillation at 60° C. for 20 minutes. After etching, wash with deionized water.

[0074] Step 4: Place the etched stainless steel mesh in the electroplating solution for platinum electrodeposition. The composition of the plating solution is: 800 mg / L chloroplatinic acid (in terms of platinum), 50 g / L potassium sulfate, 300 mg / L potassium sulfite, appropriate amount of hydrochloric acid to adjust the pH, and the remainder is deionized water. The process parameters of the electrodeposition are: temperature 30°C, cathode current density 2 mA / cm 2 , the single pulse power-on time is 10s, the power-on and power-off time ratio is 1:4, and the anode is a DSA electrode.

[0075] Example 2

[0076] In this embodiment, a stainless steel mesh in an iron-based material is used as a substrate, and nano-platinum particles are deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for an iron-based noble metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with chloroplatinic acid, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 800mg / L, potassium sulfate 50g / L, potassium sulfite 800mg / L, an appropriate amount of hydrochloric acid to adjust the pH to 3, and the balance is deionized water.

[0077] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 60°C, cathode current density 1.5 mA / cm 2 , the single pulse power-on time is 1s, the power-on and power-off time ratio is 1:9, and the anode is a DSA electrode.

[0078] Example 3

[0079] In this embodiment, a stainless steel mesh in an iron-based material is used as a substrate, and nano-platinum particles are deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for an iron-based noble metal hydrogen evolution catalytic electrode provided in this embodiment is a mixture of chloroplatinic acid, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 120 mg / L, potassium sulfate 55 g / L, potassium sulfite 500 mg / L, an appropriate amount of hydrochloric acid to adjust the pH to 2.5, and the balance is deionized water.

[0080] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 60°C, cathode current density 3.5 mA / cm 2 , the single pulse power-on time is 1s, the power-on and power-off time ratio is 1:19, and the anode is a DSA electrode.

[0081] Example 4

[0082] In this embodiment, a stainless steel mesh in an iron-based material is used as a substrate, and nano-platinum particles are deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for the iron-based noble metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with chloroplatinic acid, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 160mg / L, potassium sulfate 65g / L, potassium sulfite 800mg / L, an appropriate amount of hydrochloric acid to adjust the pH to 3, and the balance is deionized water.

[0083] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 80°C, cathode current density 5 mA / cm 2 , the single pulse power-on time is 5s, the power-on and power-off time ratio is 1:6, and the anode is a DSA electrode.

[0084] Example 5

[0085] In this embodiment, a stainless steel mesh in an iron-based material is used as a substrate, and nano-platinum particles are deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for an iron-based noble metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with chloroplatinic acid, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: 600 mg / L of chloroplatinic acid (in terms of platinum), 80 g / L of potassium sulfate, 400 mg / L of potassium sulfite, an appropriate amount of hydrochloric acid to adjust the pH to 1, and the balance is deionized water.

[0086] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 60°C, cathode current density 2.5 mA / cm 2, the single pulse power-on time is 8s, the time ratio of power-on to power-off is 18, and the anode is a DSA electrode.

[0087] Example 6

[0088] In this embodiment, a stainless steel mesh in an iron-based material is used as a substrate, and nano-platinum particles are deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for the iron-based noble metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with chloroplatinic acid, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 800mg / L, potassium sulfate 60g / L, potassium sulfite 550mg / L, an appropriate amount of hydrochloric acid to adjust the pH to 1.5, and the balance is deionized water.

[0089] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 50°C, cathode current density 10 mA / cm 2 , the single pulse power-on time is 1s, the power-on and power-off time ratio is 1:5, and the anode is a DSA electrode.

[0090] Example 7

[0091] In this embodiment, a stainless steel mesh in an iron-based material is used as a substrate, and nano-platinum particles are deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for an iron-based noble metal hydrogen evolution catalytic electrode provided in this embodiment is a mixture of chloroplatinic acid, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 500mg / L, potassium sulfate 100g / L, potassium sulfite 25g / L, an appropriate amount of hydrochloric acid to adjust the pH to 3, and the balance is deionized water.

[0092] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 45°C, cathode current density 6 mA / cm 2 , the single pulse power-on time is 1s, the power-on and power-off time ratio is 1:4, and the anode is a DSA electrode.

[0093] Example 8

[0094] In this embodiment, a stainless steel mesh in an iron-based material is used as a substrate, and nano-platinum particles are deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for an iron-based noble metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with chloroplatinic acid, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 600mg / L, potassium sulfate 150g / L, potassium sulfite 20g / L, an appropriate amount of hydrochloric acid to adjust the pH to 2, and the balance is deionized water.

[0095] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 55°C, cathode current density 5.5 mA / cm 2 , the single pulse power-on time is 5s, the power-on and power-off time ratio is 1:9, and the anode is a DSA electrode.

[0096] Example 9

[0097] In this embodiment, a stainless steel mesh in an iron-based material is used as a substrate, and nano-platinum particles are deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for an iron-based noble metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with chloroplatinic acid, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: 300 mg / L of chloroplatinic acid (in terms of platinum), 5 g / L of potassium sulfate, 500 mg / L of potassium sulfite, an appropriate amount of hydrochloric acid to adjust the pH to 2, and the balance is deionized water.

[0098] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 60°C, cathode current density 15 mA / cm 2 , direct current is used for electrodeposition, and the anode is a DSA electrode.

[0099] Example 10

[0100] In this embodiment, a stainless steel mesh in an iron-based material is used as a substrate, and nano-platinum particles are deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for an iron-based noble metal hydrogen evolution catalytic electrode provided in this embodiment is a mixture of chloroplatinic acid, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 600 mg / L, potassium sulfate 125 g / L, potassium sulfite 600 mg / L, an appropriate amount of hydrochloric acid to adjust the pH to 2, and the balance is deionized water.

[0101] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 60°C, cathode current density 20 mA / cm 2 , the electrodeposition is carried out by direct current, and the anode is a DSA electrode.

[0102] Embodiment 11

[0103] The present embodiment uses the stainless steel mesh in the iron-based material as a substrate, and deposits platinum, iridium, ruthenium, palladium alloy particles thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for the iron-based precious metal hydrogen evolution catalytic electrode provided in the present embodiment is mixed with chloroplatinic acid, chloroiridic acid, ruthenium trichloride, palladium chloride, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 600mg / L, chloroiridic acid (in terms of iridium) 500mg / L, ruthenium trichloride (in terms of ruthenium) 500mg / L, palladium chloride (in terms of palladium) 600mg / L, potassium sulfate 50g / L, potassium sulfite 15g / L, appropriate amount of hydrochloric acid to adjust pH to 2.5, and the remainder is deionized water.

[0104] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 45°C, cathode current density 15 mA / cm 2 , the single pulse power-on time is 0.1s, the power-on and power-off time ratio is 1:9, and the anode is a DSA electrode.

[0105] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 60°C, cathode current density 20 mA / cm 2 , the single pulse power-on time is 5s, the power-on and power-off time ratio is 1:19, and the anode is a DSA electrode.

[0106] Example 12

[0107] In this embodiment, a stainless steel mesh among iron-based materials is used as a substrate, and nano-iridium particles are deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for the iron-based precious metal hydrogen evolution catalytic electrode provided in this embodiment is a mixture of chloroiridic acid, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroiridic acid (in terms of iridium) 600 mg / L, potassium sulfate 35 g / L, potassium sulfite 300 mg / L, an appropriate amount of hydrochloric acid to adjust the pH to 3, and the balance is deionized water.

[0108] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 60°C, cathode current density 0.5 mA / cm 2 , the single pulse power-on time is 1s, the power-on and power-off time ratio is 1:9, and the anode is a DSA electrode.

[0109] Embodiment 13

[0110] In this embodiment, a stainless steel mesh among iron-based materials is used as a substrate, and nano-ruthenium particles are deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for the iron-based noble metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with ruthenium trichloride, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: ruthenium trichloride (in terms of ruthenium) 500mg / L, potassium sulfate 50g / L, potassium sulfite 4.5g / L, an appropriate amount of hydrochloric acid to adjust the pH to 2, and the balance is deionized water.

[0111] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 65°C, cathode current density 0.5 mA / cm 2 , the single pulse power-on time is 1s, the power-on and power-off time ratio is 1:9, and the anode is a DSA electrode.

[0112] Embodiment 14

[0113] In this embodiment, a stainless steel mesh among iron-based materials is used as a substrate, and nano-palladium particles are deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for the iron-based precious metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with palladium chloride, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: palladium chloride (in terms of palladium) 600mg / L, potassium sulfate 25g / L, potassium sulfite 6g / L, an appropriate amount of hydrochloric acid to adjust the pH to 1.5, and the balance is deionized water.

[0114] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 70°C, cathode current density 4 mA / cm 2 , the single pulse power-on time is 1.5s, the power-on and power-off time ratio is 1:10, and the anode is a DSA electrode.

[0115] Embodiment 15

[0116] In this embodiment, a stainless steel mesh in an iron-based material is used as a substrate, and a platinum-iridium alloy is deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for an iron-based precious metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with chloroplatinic acid, chloroiridic acid, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 400mg / L, chloroiridic acid (in terms of iridium) 600mg / L, potassium sulfate 50g / L, potassium sulfite 15g / L, an appropriate amount of hydrochloric acid to adjust the pH to 2.5, and the balance is deionized water.

[0117] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 65°C, cathode current density 10 mA / cm 2 , the single pulse power-on time is 3s, the power-on and power-off time ratio is 1:5, and the anode is a DSA electrode.

[0118] Example 16

[0119] In this embodiment, a stainless steel mesh in an iron-based material is used as a substrate, and a platinum-ruthenium alloy is deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for an iron-based precious metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with chloroplatinic acid, ruthenium trichloride, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 600mg / L, ruthenium trichloride (in terms of ruthenium) 500mg / L, potassium sulfate 120g / L, potassium sulfite 25g / L, an appropriate amount of hydrochloric acid to adjust the pH to 1.5, and the balance is deionized water.

[0120] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 60°C, cathode current density 1 mA / cm 2 , the single pulse power-on time is 2s, the power-on and power-off time ratio is 1:5, and the anode is a DSA electrode.

[0121] Embodiment 17

[0122] In this embodiment, a stainless steel mesh in an iron-based material is used as a substrate, and a platinum-palladium alloy is deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for an iron-based precious metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with chloroplatinic acid, palladium chloride, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 800mg / L, palladium chloride (in terms of palladium) 600mg / L, potassium sulfate 60g / L, potassium sulfite 35g / L, an appropriate amount of hydrochloric acid to adjust the pH to 2.5, and the balance is deionized water.

[0123] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 60°C, cathode current density 1 mA / cm 2 , the single pulse power-on time is 2s, the power-on and power-off time ratio is 1:5, and the anode is a DSA electrode.

[0124] Embodiment 18

[0125] In this embodiment, a Q345 steel plate in an iron-based material is used as a substrate, and a platinum-iridium alloy is deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for an iron-based precious metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with chloroplatinic acid, chloroiridic acid, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 600mg / L, chloroiridic acid (in terms of iridium) 600mg / L, potassium sulfate 150g / L, potassium sulfite 25g / L, an appropriate amount of hydrochloric acid to adjust the pH to 2, and the balance is deionized water.

[0126] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 50°C, cathode current density 1 mA / cm 2 , the single pulse power-on time is 1s, the power-on and power-off time ratio is 1:6, and the anode is a DSA electrode.

[0127] Embodiment 19

[0128] In this embodiment, a 65Mn steel plate in an iron-based material is used as a substrate, and a platinum-palladium alloy is deposited thereon by an electrodeposition method to prepare a hydrogen evolution catalytic electrode. The plating solution for an iron-based precious metal hydrogen evolution catalytic electrode provided in this embodiment is mixed with chloroplatinic acid, palladium chloride, potassium sulfate, potassium sulfite and deionized water, and the content of each component in the electrolyte is: chloroplatinic acid (in terms of platinum) 600mg / L, palladium chloride (in terms of palladium) 600mg / L, potassium sulfate 70g / L, potassium sulfite 30g / L, an appropriate amount of hydrochloric acid to adjust the pH to 2.5, and the balance is deionized water.

[0129] The operation steps of this embodiment are similar to those of embodiment 1, except that the electrodeposition process parameters are changed to: temperature 50°C, cathode current density 1 mA / cm 2 , the single pulse power-on time is 1s, the power-on and power-off time ratio is 1:6, and the anode is a DSA electrode.

[0130] Comparative Example 1

[0131] This comparative example is a platinum sheet with a thickness of 0.1 mm. It is placed in a 1 mol / L potassium hydroxide solution. The platinum sheet is used as a cathode at 10 mA / cm 2 The overpotential relative to the standard hydrogen evolution electrode is 55mV, 350mA / cm 2 The overpotential is 190mV.

[0132] Comparative Example 2

[0133] This comparative example is a commercial hydrogen-evolving active cathode of a certain company. It is placed in a 1 mol / L potassium hydroxide solution and the electrode is measured as a cathode at 10 mA / cm 2 The overpotential relative to the standard hydrogen evolution electrode is 50mV, 350mA / cm 2 The overpotential is 178mV.

[0134] The electrodes prepared in each embodiment were subjected to 10 mA / cm 2 、350mA / cm 2 The overpotential of each embodiment at a current density of 15 A / cm2 relative to the standard hydrogen evolution electrode 2 The comparison of the enhanced life tests in current density and 30wt% potassium hydroxide is summarized in the table below.

[0135] It can be seen from the table that the overpotential of the present invention is low, and compared with the existing hydrogen evolution active cathode, its service life is longer, and it has the advantage of industrial application.

[0136] Table 1. Comparison of overpotential and enhanced life test of each embodiment and comparative example

[0137]

[0138] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the above implementation is only to illustrate the technical concept and features of the present invention, and its purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and it cannot be used to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing an iron-based noble metal catalytic electrode for electrolysis of water for hydrogen evolution, characterized in that: The following steps are involved: S2. Pre-treat the iron-based materials. Remove oxides and oil stains from the surface of iron-based materials, and perform pickling and etching; S2. Prepare a plating solution containing precious metals, Deionized water is used, the electrolyte includes potassium ions, sulfate ions, sulfite ions, and at least two of the following: platinum ions, iridium ions, ruthenium ions, and palladium ions, and the pH value is adjusted to 1-4; S3. Using the above-mentioned plating solution as an electrolyte, the above-mentioned pretreated iron-based material as a cathode, and a DSA electrode or a carbon-based electrode as an anode for electrodeposition; The parameters are as follows: the temperature of the plating solution is 20-80°C, the current density is 0.1-100mA / cm 2 The power-on time is 40-4000s, and the ratio of power-on to power-off time is 1:0-1:

100.

2. The method for preparing an iron-based noble metal catalytic electrode for hydrogen evolution by electrolysis of water according to claim 1, characterized in that: The iron-based material is common carbon steel or stainless steel in mesh, plate, felt or foam form.

3. The method for preparing an iron-based noble metal catalytic electrode for hydrogen evolution by electrolysis of water according to claim 1, characterized in that: During the pretreatment of the iron-based material, grinding, water washing, alkali washing, water washing, acid washing, etching and water washing are sequentially performed. Grinding the substrate with sandpaper or sandblasting can effectively remove dirt such as oxides on the surface of the substrate, and then alkali washing is performed after water washing. Ultrasonic cleaning is performed in a solution of potassium hydroxide or sodium hydroxide with a concentration of 1-5 mol / L for 1-30 minutes to remove oil stains on the surface of the substrate; after water washing, it is placed in 10-30% hydrochloric acid for acid washing and etching for a time of 2-30 minutes.

4. The method for preparing an iron-based noble metal catalytic electrode for hydrogen evolution by electrolysis of water according to claim 1, characterized in that: The plating solution contains potassium sulfate K2SO4, potassium sulfite K2SO3, and at least two of the following: chloroplatinic acid H2PtCl6, chloroiridic acid H2IrCl6, ruthenium trichloride RuCl3, and palladium chloride PdCl2.

5. The method for preparing an iron-based noble metal catalytic electrode for hydrogen evolution by electrolysis of water according to claim 1, characterized in that: The concentration of potassium sulfate K2SO4 is 1-300g / L, the concentration of potassium sulfite K2SO3 is 0.1-500g / L, the concentration of chloroplatinic acid H2PtCl6 calculated as platinum metal is 100-10000mg / L, the concentration of chloroiridic acid H2IrCl6 calculated as iridium metal is 100-12000mg / L, the concentration of ruthenium trichloride RuCl3 calculated as ruthenium metal is 100-2500mg / L, and the concentration of palladium chloride PdCl2 calculated as palladium metal is 100-4000mg / L.

6. The method for preparing an iron-based noble metal catalytic electrode for hydrogen evolution by electrolysis of water according to claim 1, characterized in that: In the plating solution preparation steps: potassium sulfate K2SO4 and potassium sulfite K2SO3 are dissolved in deionized water, stirred and dissolved, and then chloroplatinic acid H2PtCl6, chloroiridic acid H2IrCl6, and ruthenium trichloride RuCl are added. 3、 Two or more precursors of palladium chloride PdCl2, when stirred.

7. The method for preparing an iron-based noble metal catalytic electrode for hydrogen evolution by electrolysis of water according to claim 1, characterized in that: During electrodeposition, a stirring bar is added for stirring.

8. An iron-based noble metal catalytic electrode for hydrogen evolution by electrolysis of water, characterized in that: A method for preparing an iron-based noble metal catalytic electrode for electrolyzing water to produce hydrogen according to any one of claims 1 to 7.

9. Use of the iron-based noble metal catalytic electrode for hydrogen evolution by electrolysis of water as claimed in claim 8 as a catalyst for hydrogen evolution by electrolysis of water.

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