Iridium-ruthenium diatom / sponge nickel composite material, preparation method thereof and application of iridium-ruthenium diatom / sponge nickel composite material in alkaline electro-catalytic hydrogen evolution
By preparing an iridium-ruthenium diatomic/sponge nickel composite material, the problem of insufficient electrode performance in water electrolysis for hydrogen production was solved, achieving efficient and stable alkaline electrocatalytic hydrogen evolution, which is suitable for the field of water electrolysis for hydrogen evolution.
Patent Information
- Application Number
- CN202511423003.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-30
- Publication Date
- 2026-01-20
AI Technical Summary
In existing water electrolysis hydrogen production technologies, conventional foamed nickel electrodes have insufficient performance under high current density, a limited number of catalytic sites, and iridium and ruthenium single atoms are easily dissolved under high oxidation/reduction potentials, leading to increased overpotential and shortened lifetime, making it difficult to achieve efficient and stable alkaline electrocatalytic hydrogen evolution.
An iridium-ruthenium diatomic/sponge nickel composite material was prepared by a hydrothermal method. After dissolving nickel acetate, chloroiridic acid and ruthenium trichloride, it was reacted with hydrazine hydrate to form a three-dimensional porous sponge nickel structure. The sponge nickel was loaded with iridium-ruthenium diatomic atoms, which synergistically catalyzed alkaline hydrogen evolution, provided active hydrogen species and facilitated rapid desorption.
This improves the hydrogen evolution performance of the electrocatalyst at high current densities, reduces overpotential, increases catalytic active sites, and enhances stability, making it suitable for large-area preparation.
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Figure CN121362982A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application relates to the technical field of electrolytic hydrogen production, in particular to an iridium-ruthenium diatomic / sponge nickel composite material, a preparation method thereof and application of the composite material in alkaline electrocatalytic hydrogen evolution. BACKGROUND
[0002] With the increase of global energy demand and environmental pollution problems, it is particularly important to develop clean and renewable energy. Hydrogen energy, as an ideal clean energy carrier, is considered an important part of the future energy system due to its high energy density, renewability and pollution-free characteristics. The electrolysis of water to produce hydrogen is one of the effective methods to obtain high-purity hydrogen at present, but its efficiency is limited by the slow kinetics of the anode oxygen evolution reaction (OER) and the cathode hydrogen evolution reaction (HER). Therefore, developing high-efficiency, stable and low-cost non-noble metal catalysts has become a hot research topic.
[0003] In recent years, electrochemical technologies represented by water electrolysis to produce hydrogen, CO2 electroreduction and fuel cells are considered as the core path to achieve the goal. However, the activity and selectivity data obtained in the laboratory with milliamperes of current density quickly fail when scaled up to industrial electrolyzers: the surface atoms of the catalyst are dissolved, reconstructed or even detached due to high oxidation / reduction potential and severe gas evolution, resulting in a sharp increase in overpotential and a rapid decrease in service life, which is the "current density gap" that restricts the technology landing. Therefore, it is particularly important to build an electrocatalytic system that can continuously operate at amperes of current density. Conventional foam nickel as an electrode electrocatalyst generally has poor performance at high current density, cannot obtain a 3D flexible sponge structure, and has limited number of catalytic sites and limited specific surface area, resulting in insufficient performance. In addition, the metal nickel site is beneficial to the dissociation of alkaline H2O, but the adsorption and desorption kinetics of active hydrogen after cracking is poor. However, iridium and ruthenium monatomic atoms have excellent hydrogen evolution kinetics. Therefore, there is an urgent need to develop a new iridium-ruthenium diatomic / sponge nickel composite material for water electrolysis hydrogen evolution electrocatalyst. The synergistic catalytic mechanism of the two is used to greatly improve the hydrogen evolution catalytic performance. SUMMARY
[0004] The purpose of the present application is to overcome the defects of the prior art, and to provide an iridium-ruthenium diatomic / sponge nickel composite material, a preparation method thereof and application of the composite material in alkaline electrocatalytic hydrogen evolution.
[0005] The iridium-ruthenium diatomic / sponge nickel composite material electrocatalyst is obtained by dissolving nickel acetate, hydrazine hydrate, chloroiridic acid and ruthenium trichloride aqueous solution in deionized water to configure a mixed solution and placing the mixed solution in a high-pressure reaction kettle for hydrothermal reaction.
[0006] To achieve the above-mentioned purpose, the following specific technical solutions are adopted in the present application.
[0007] The application provides a preparation method of a diatomic iridium ruthenium / sponge nickel composite water electrolysis hydrogen evolution electrocatalyst.
[0008] S1, a proper amount of nickel acetate is weighed, and deionized water is added and stirred to dissolve.
[0009] S2, after the solution is uniformly stirred, a hydrazine hydrate solution is measured and continuously stirred for several minutes.
[0010] S3, finally, the obtained solution is placed in a high-pressure reaction kettle for hydrothermal reaction.
[0011] S4, after the reaction is completed, a sample is taken out, washed with deionized water and dried to obtain the diatomic iridium ruthenium / sponge nickel composite material electrode.
[0012] Further, in step S3, the high-pressure reaction kettle is a polytetrafluoroethylene high-pressure reaction kettle, the hydrothermal reaction temperature is 150-220 DEG C, and the reaction time is 0.5-3 h.
[0013] Further, in step S4, the drying temperature of the oven is 60-80 DEG C, and the sample is dried until no moisture.
[0014] The diatomic iridium ruthenium / sponge nickel composite electrocatalyst provided by the application is prepared by the above preparation method. The diatomic iridium ruthenium / sponge nickel composite material comprises sponge nickel with a three-dimensional porous structure and diatomic iridium and ruthenium loaded at the lattice vacancies of the sponge nickel. The diatomic iridium ruthenium / sponge nickel composite material can synergistically catalyze alkaline hydrogen evolution, and the mechanism is that the nickel sites provide alkaline H2O cracking sites to obtain active hydrogen species, and further through the diatomic iridium and ruthenium, hydrogen protons are rapidly desorbed, so that more excellent alkaline electrocatalytic hydrogen evolution performance is obtained.
[0015] The application provides an application of the diatomic iridium ruthenium / sponge nickel composite water electrolysis hydrogen evolution electrocatalyst in water electrolysis hydrogen evolution. Further, the diatomic iridium ruthenium / sponge nickel composite material is used as a catalyst in an alkaline water electrolysis hydrogen evolution reaction with a large current of 400 mA-600 mA.
[0016] The application can achieve the following technical effects:
[0017] The iridium ruthenium diatomic / sponge nickel composite material prepared by the method has better basic electrocatalytic hydrogen evolution performance compared with the original sponge nickel electrocatalyst; the advantage is that the chloroiridic acid solution can cause part of the Ni atoms to be dissolved to generate Ni vacancies, thereby providing iridium ruthenium diatomic nucleation sites. By designing the iridium ruthenium diatomic / sponge nickel composite material, the basic hydrogen evolution can be synergistically catalyzed, the mechanism is that the nickel site provides a cracking site for basic H2O to obtain active hydrogen species, and further through the iridium ruthenium diatomic, the hydrogen proton is rapidly desorbed, thereby obtaining more excellent basic electrocatalytic hydrogen evolution performance. The preparation method provided by the application adopts a hydrothermal method, and the preparation method is simple, convenient, easy to control and easy to prepare in a large area. BRIEF DESCRIPTION OF DRAWINGS
[0018] Figure 1 is a flowchart of a preparation method of an iridium ruthenium diatomic / sponge nickel composite material electrolytic water hydrogen evolution electrocatalyst according to an embodiment of the application.
[0019] Figure 2 is an optical photograph of an iridium ruthenium diatomic / sponge nickel composite material electrocatalyst prepared according to an embodiment 1 of the application.
[0020] Figure 3 is a scanning electron microscope image of an iridium ruthenium diatomic / sponge nickel composite material prepared according to an embodiment 2 of the application.
[0021] Figure 4 is a scanning electron microscope image of an iridium ruthenium diatomic / sponge nickel composite material prepared according to an embodiment 3 of the application. DETAILED DESCRIPTION
[0022] Hereinafter, embodiments of the present application will be described with reference to the accompanying drawings. In the following description, the same modules are denoted by the same reference numerals. In the case of the same reference numerals, their names and functions are also the same. Therefore, detailed descriptions thereof will not be repeated.
[0023] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and do not constitute a limitation on the present application.
[0024] The embodiment of the present application provides a preparation method of a diatomic iridium ruthenium / sponge nickel composite material hydrogen evolution electrocatalyst, Figure 1 shows the flow of the preparation method, as Figure 1 shown, the preparation method comprises the following steps:
[0025] S1, weigh an appropriate amount of nickel acetate, add deionized water and stir to dissolve. After complete dissolution, add chloroiridic acid and ruthenium trichloride solution and continue stirring;
[0026] S2, after the solution is stirred uniformly, the hydrazine hydrate solution is measured and stirred for several minutes;
[0027] S3, finally, the obtained solution is placed in a high-pressure reaction kettle for hydrothermal reaction;
[0028] S4, after the reaction is completed, the sample is taken out, washed with deionized water and dried to obtain the diatomic iridium ruthenium / sponge nickel composite electrode.
[0029] The preparation method will be described below in combination with specific examples.
[0030] Example 1
[0031] 1.2g of nickel acetate is weighed and 2ml of chloroiridic acid, 1ml of ruthenium trichloride solution is dissolved in 60mL of deionized water, 6mL of hydrazine hydrate is added to the mixed solution after stirring uniformly, and stirred for 30 minutes until completely dissolved. The obtained solution is moved into a polytetrafluoroethylene high-pressure reaction kettle, the high-pressure reaction kettle is sealed, and hydrothermal reaction is carried out at 160℃ for 6 hours. After hydrothermal reaction, the sample surface is washed with deionized water for several times. The sample is dried in a 70℃ oven to obtain the target product of iridium ruthenium diatomic / sponge nickel composite material electrocatalyst. Figure 2 It is the optical photograph of the iridium ruthenium diatomic / sponge nickel composite material electrocatalyst prepared in Example 1.
[0032] Example 2
[0033] 1.2g of nickel acetate is weighed and 5ml of chloroiridic acid, 2ml of ruthenium trichloride solution is dissolved in 60mL of deionized water, 6mL of hydrazine hydrate is added to the mixed solution after stirring uniformly, and stirred for 30 minutes until completely dissolved. The obtained solution is moved into a polytetrafluoroethylene high-pressure reaction kettle, the high-pressure reaction kettle is sealed, and hydrothermal reaction is carried out at 150℃ for 10 hours. After hydrothermal reaction, the sample surface is washed with deionized water for several times. The sample is dried in a 70℃ oven to obtain the target product of iridium ruthenium diatomic / sponge nickel composite material electrocatalyst. Figure 3 It is the scanning electron microscope image of the iridium ruthenium diatomic / sponge nickel composite material electrocatalyst prepared in Example 2.
[0034] Example 3
[0035] 1.2g of nickel acetate is weighed and 8ml of chloroiridic acid, 5ml of ruthenium trichloride solution is dissolved in 60mL of deionized water, 6mL of hydrazine hydrate is added to the mixed solution after stirring uniformly, and stirred for 30 minutes until completely dissolved. The obtained solution is moved into a polytetrafluoroethylene high-pressure reaction kettle, the high-pressure reaction kettle is sealed, and hydrothermal reaction is carried out at 180℃ for 5 hours. After hydrothermal reaction, the sample surface is washed with deionized water for several times. The sample is dried in a 70℃ oven to obtain the target product of iridium ruthenium diatomic / sponge nickel composite material electrocatalyst. Figure 4A scanning electron microscope image of the iridium ruthenium diatomic / sponge nickel composite electrocatalyst prepared in Example 3.
[0036] Comparative Example 1
[0037] 1.2 g of nickel acetate was weighed into 60 mL of deionized water, and 6 mL of hydrazine hydrate was added after stirring to uniformity, and stirring was continued for 30 minutes. The resulting solution was moved into a polytetrafluoroethylene high-pressure reaction kettle, the high-pressure reaction kettle was sealed, and hydrothermal reaction was carried out at 160°C for 6 hours. After the hydrothermal reaction, the sample surface was washed with deionized water several times. The sample was dried in a 70°C oven to obtain the sponge nickel electrocatalyst target product.
[0038] The performance of the diatomic iridium ruthenium / sponge nickel composite electrocatalysts prepared in Examples 1-3 and the sponge nickel electrocatalyst prepared in Comparative Example 1 was tested as follows.
[0039] 0.5 cm 2 diatomic iridium ruthenium / sponge nickel composite electrocatalysts prepared in Examples 1-3 and 0.5 cm 2 sponge nickel prepared in Comparative Example 1 were directly used as working electrodes and were directly used as test electrodes in a three-electrode battery system for electrochemical testing, with a saturated calomel electrode (SCE), a carbon rod, and a 1M KOH solution being used as a reference electrode, a counter electrode, and an electrolyte, respectively.
[0040] The results of the performance testing are as follows:
[0041] The overpotential of the diatomic iridium ruthenium / sponge nickel composite electrocatalysts prepared in Examples 1-3 and the sponge nickel electrocatalyst prepared in Comparative Example 1 was 209 mV, 214 mV, 201 mV, and 357 mV, respectively, at a current density of 500 mA cm -1 (0.5 A cm -1 ). It can be seen that the diatomic iridium ruthenium / sponge nickel composite electrocatalysts prepared in the above examples have low overpotential at high current density and good electrocatalytic performance, and have more catalytic active sites and better stability characteristics compared to pure sponge nickel electrocatalysts. The advantage is that the chloroiridic acid solution will cause some Ni atoms to be dissolved to produce Ni vacancies, thereby providing iridium ruthenium diatomic nucleation sites. By designing iridium ruthenium diatomic / sponge nickel composites, the alkaline hydrogen evolution can be synergistically catalyzed. The nickel sites provide the cracking sites of alkaline H2O to obtain active hydrogen species, and further through the iridium ruthenium diatomic, the hydrogen protons are rapidly desorbed, thereby obtaining more excellent alkaline electrocatalytic hydrogen evolution performance. The preparation method provided by the present application uses a hydrothermal method, and the preparation method is simple, convenient, easy to control, easy to prepare in large areas, and can be applied in the field of water electrolysis hydrogen production.
[0042] In the description of the specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, different embodiments or examples described in the specification and the features of different embodiments or examples can be combined and combined by those skilled in the art without contradiction.
[0043] Although the embodiments of the present application have been shown and described above, it is understood that the above-described embodiments are exemplary and are not to be construed as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above-described embodiments within the scope of the present application.
[0044] The specific embodiments of the present application described above do not constitute a limitation on the scope of protection of the present application. Any various other corresponding changes and modifications made in accordance with the technical concept of the present application should be included in the scope of protection of the claims of the present application.
Claims
1. A method for producing an iridium-ruthenium diatomic / sponge nickel composite material, characterized by comprising the steps of: It comprises the following steps: S1, taking nickel acetate, adding deionized water to stir and dissolve, after complete dissolution, adding chloroiridic acid, ruthenium trichloride solution to continue stirring; S2, after the solution is stirred uniformly, taking hydrazine hydrate solution to continue stirring; S3, the solution obtained in step S2 is placed in a reaction kettle for hydrothermal reaction; S4, after the reaction is completed, the iridium ruthenium diatomic / sponge nickel composite material is obtained through post-treatment.
2. The method for producing an iridium-ruthenium diatomic / sponge nickel composite material according to claim 1, characterized by, In step S3, the polytetrafluoroethylene high-pressure reaction kettle is selected as the reaction kettle.
3. The method for preparing an iridium-ruthenium diatomic / sponge nickel composite material according to claim 1, characterized by, In step S3, the temperature of the hydrothermal reaction is 160-180 DEG C, and the time of the hydrothermal reaction is 6-10 h.
4. The method for preparing an iridium-ruthenium diatomic / sponge nickel composite material according to claim 1, characterized by, In step S4, the post-treatment specifically includes: taking out the product, rinsing with deionized water, and drying.
5. The method for preparing the iridium-ruthenium diatomic / sponge nickel composite material according to claim 1, characterized in that, In step S4, the drying is carried out in an oven, and the temperature is 60-80 DEG C.
6. The iridium ruthenium diatomic / sponge nickel composite material prepared by the preparation method according to any one of claims 1-5.
7. The iridium ruthenium diatomic / sponge nickel composite of claim 6, wherein, It comprises: Sponge nickel with a three-dimensional porous structure and diatomic iridium and ruthenium loaded at the lattice vacancies of the sponge nickel.
8. The iridium ruthenium diatomic / sponge nickel composite material according to claim 6 is applied in basic electrocatalytic hydrogen evolution.
9. The iridium ruthenium diatomic / sponge nickel composite material according to claim 6 is applied as a catalyst in the hydrogen evolution reaction of alkaline electrolytic water with a large current of 400 mA-600 mA.