Vanadium-modified ferronickel catalytic material, preparation method thereof and application of vanadium-modified ferronickel catalytic material in electrolytic hydrogen production test
By synthesizing vanadium-modified nickel-iron electrocatalytic materials on commercial nickel-iron foam, the problems of high cost, long time consumption and environmental unfriendliness in the existing technology have been solved, and a highly efficient and stable electrolytic hydrogen production process has been realized.
Patent Information
- Application Number
- CN202511197738.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-26
- Publication Date
- 2025-12-05
AI Technical Summary
Existing electrochemical catalytic material preparation processes suffer from high costs, time-consuming preparation procedures, environmental unfriendliness, and catalyst instability and easy detachment.
Vanadium-modified nickel-iron electrocatalysts were synthesized on commercial nickel-iron foam using electrochemical corrosion and annealing. The catalyst performance was tested by linear sweep voltammetry using the vanadium-modified nickel-iron catalyst as the anode, Hg/HgO as the reference electrode, and a platinum sheet as the cathode in a 1M KOH electrolyte. The catalyst was then annealed in a muffle furnace.
This improved the OER activity of the catalytic material, reduced the overpotential, and enabled a more efficient electrolytic hydrogen production process.
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the field of electrochemical hydrogen production, and particularly relates to a vanadium-modified nickel-iron catalytic material, a preparation method thereof, and application of the vanadium-modified nickel-iron catalytic material in electrolytic hydrogen production testing. BACKGROUND
[0002] Electrocatalytic water splitting for hydrogen production can effectively reduce carbon dioxide emissions, thereby promoting the source carbon neutralization strategy. At present, although many researchers are committed to developing high-activity and stable electrocatalysts, noble metal materials are still considered to be the best catalysts for electrochemical water splitting. Therefore, it is highly desirable to develop efficient, non-noble metal electrocatalysts and fundamentally improve the reaction efficiency.
[0003] In alkaline water splitting, nickel-based compounds are developed due to their high OER activity. Generally, the OER activity can be improved by adjusting the Fe content, amorphization, and forming a metal oxide core-shell structure. The Fe doping in the nickel compound with spinel hydroxide and oxyhydroxide structures changes the electronic structure of the active center. Randomly arranged atoms enhance the diffusion of examples through the catalyst layer. The metal core enhances the charge transfer of the transition metal oxyhydroxide, which is the real active site of OER.
[0004] Recently, many researchers have found that adsorbed species, such as anionic compounds (e.g., SeO4 2- , VO4 3- ), carboxylic acid ligands, and adsorbed species not only change the electronic structure of intermediates, but also change the binding strength of intermediates. Adsorbed species are generated by pre-catalyst elements through continuous-adsorption oxidation.
[0005] In this study, we successfully synthesized vanadium-modified nickel-iron electrocatalytic materials on commercial nickel-iron foam through electrochemical corrosion and annealing. The doping of vanadium improves the OER activity of the commercial nickel-iron foam. SUMMARY
[0006] The technical problems solved by the application are:
[0007] The existing electrochemical catalytic material preparation process has the problems of high cost, long preparation process time, environmental unfriendliness, and unstable and easy-to-fall-off catalysts.
[0008] The technical scheme adopted by the application is:
[0009] First, the application provides a vanadium-modified nickel-iron self-supporting catalytic material.
[0010] The catalytic material is tested for performance by linear sweep voltammetry using 1M KOH as electrolyte, a treated vanadium-modified nickel-iron catalytic material as anode, Hg / HgO as reference electrode and platinum sheet as cathode in a standard three-electrode configuration.
[0011] Secondly, the present application provides a preparation method of the aforementioned nickel-iron catalytic material, comprising the following steps:
[0012] After the metal substrate is treated by electrochemical corrosion in the treatment solution, it is annealed in a muffle furnace at a temperature of 200-400℃. The treated material is used as working electrode to test performance in a three-electrode system.
[0013] According to some preferred embodiments, the optimal annealing temperature of the vanadium-modified nickel-iron catalytic material is 200℃.
[0014] According to some preferred embodiments, the metal substrate is selected from foamed nickel-iron.
[0015] According to some preferred embodiments, the ratio of sodium metavanadate to sodium chloride in the treatment solution is 0.8M / 3M.
[0016] According to some preferred embodiments, the scan rate of cyclic voltammetry is 10mV / s and the number of cycles is 3.
[0017] In the present application, the vanadium-modified nickel-iron catalytic material is prepared by electrochemical corrosion and annealing method using the strong corrosive property of sodium metavanadate and sodium chloride.
[0018] Thirdly, the vanadium-modified nickel-iron catalytic material provided by the present application has the following advantages: the vanadium-modified catalytic material provided by the present application has a lower overpotential compared with other samples. BRIEF DESCRIPTION OF DRAWINGS
[0019] Figure 1 The LSV test graph of each test sample;
[0020] Figure 2 The overpotential graph of oxygen evolution reaction of each test sample; DETAILED DESCRIPTION
[0021] In order to make the purpose, technical scheme and advantages of the embodiments of the present application more clear, the technical scheme in the embodiments of the present application will be described clearly and completely below. The specific conditions are not specified in the embodiments, and are carried out according to conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be purchased on the market.
[0022] Example 1
[0023] The embodiment provides a vanadium-modified nickel-iron catalytic material, and a preparation method thereof, which comprises the following steps: placing untreated nickel-iron foam into a mixed solution composed of 0.8M NaVO3 and 3M NaCl at 50°C, taking the nickel-iron foam as an anode, taking Hg / HgO as a reference electrode, and taking a platinum sheet as a counter electrode. The nickel-iron foam is treated by using a cyclic voltammetry method in a voltage window range of 0-1V (V vs. Hg / HgO), a scanning speed is 10mV / s, and the number of cycles is 3. The electrode after corrosion is placed in a muffle furnace to be annealed at 200°C for 2h, and is recorded as NV-NFF-200.
[0024] The specific proportion of each parameter in Example 1 is shown in Table 1.
[0025] Table 1 shows the details of each parameter in the experiment.
[0026]
[0027] Comparative Example 1
[0028] The difference between the comparative example and Example 1 is that only a 3M NaCl aqueous solution is used to treat commercial nickel-iron foam, the nickel-iron foam is treated by using a cyclic voltammetry method at 50°C, a scanning speed is 10mV / s, and the number of cycles is 3. The electrode after corrosion is placed in a muffle furnace to be annealed at 200°C for 2h, and is recorded as N-NFF-200. The specific proportion of each parameter in Comparative Example 1 is shown in Table 2.
[0029] Table 2 shows the details of each parameter in the experiment.
[0030]
[0031] Comparative Example 2
[0032] The difference between the comparative example and Example 1 is that only a 3M NaCl aqueous solution is used to treat commercial nickel-iron foam, the nickel-iron foam is treated by using a cyclic voltammetry method at 50°C, a scanning speed is 10mV / s, and the number of cycles is 3. The electrode after corrosion is placed in a muffle furnace to be annealed at 200°C for 2h, and is recorded as N-NFF-200. The specific proportion of each parameter in Comparative Example 1 is shown in Table 2.
[0033] Table 3 shows the details of each parameter in the experiment.
[0034]
[0035] Comparative Example 3
[0036] The comparative example is different from example 1 in that only a commercial nickel-iron foam is treated with an aqueous solution of 3M NaCl, and the nickel-iron foam is treated at 50°C using cyclic voltammetry with a scan rate of 10 mV / s and 3 cycles, and is denoted as N-NFF. The specific parameter ratios in comparative example 3 are shown in Table 4.
[0037] Table 4: Details of parameters in experiments
[0038]
[0039] Comparative example 4
[0040] The untreated nickel-iron foam is placed in a mixed solution composed of 0.8M NaVO3 and 3M NaCl at 50°C, with the nickel-iron foam as the anode, Hg / HgO as the reference electrode, and a platinum sheet as the counter electrode. The nickel-iron foam is treated using cyclic voltammetry in a voltage window of 0-1V (V vs. Hg / HgO) with a scan rate of 10 mV / s and 3 cycles, and is denoted as NV-NFF. The specific parameter ratios in example 1 are shown in Table 5.
[0041] Table 5: Details of parameters in experiments
[0042]
[0043] LSV test
[0044] Taking the NV-NFF-200 catalyst in example 1 as an example, performance testing is carried out.
[0045] The testing process is as follows: in 1M KOH, a standard three-electrode system is used, with a platinum sheet (10mm*10mm*0.1mm) as the counter electrode, Hg / HgO as the reference electrode, and NV-NFF-200 as the anode, CV activation is carried out, and after the CV activation is completed, the performance of the catalyst is tested using linear sweep voltammetry, with a voltage range of 1-0 (V vs. Hg / HgO) and a scan rate of 5mV / s. The test results are shown in Table 6, and through comparison, it can be found that the sample treated by sodium metavanadate and sodium chloride and annealed at a temperature of 200°C exhibits excellent performance at each current density.
[0046] Table 6: Comparison of overpotential
[0047]
[0048]
[0049] The above merely provides the preferred embodiments of the present application, and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the principles and technical scope of the present application shall fall into the scope of the present application.
Claims
1. A vanadium-modified nickel-iron catalytic material, characterized in that, The catalytic material is obtained by electrochemical corrosion and annealing of sodium metavanadate and sodium chloride.
2. The nickel-iron catalytic material of claim 1, wherein, The performance of the vanadium modified nickel-iron catalyst is different at different annealing temperatures.
3. A process for the production of a ferronickel catalytic material as claimed in claim 1 or 2, characterized in that, The method comprises the following steps: annealing a commercial nickel-iron foam metal electrode in a treatment liquid after electrochemical CV corrosion at high temperature for 2 hours; and testing the electrochemical performance of the annealed metal substrate as a working electrode in a standard three-electrode system; the treatment liquid is a mixed solution of NaCl and NaVO3.
4. The process for the preparation of vanadium-modified nickel-iron metal catalyst according to claim 3, characterized in that, The size of the metal substrate is about 15 mm in length, 10 mm in width and 15 mm in height.
5. The process for preparing a vanadium-modified nickel-iron catalytic material according to claim 3, characterized in that, Three-electrode system: the treated metal substrate is an anode, Hg / HgO is a reference electrode, a platinum plate is a counter electrode, and 1M potassium hydroxide is an electrolyte.
6. The process for the preparation of vanadium-modified nickel-iron catalytic material according to claim 3, characterized in that, Electrochemical corrosion: the commercial nickel-iron foam is placed in a treatment liquid, and is scanned 4 times at a voltage window of 0-1V by cyclic voltammetry at a scanning speed of 10 mV / s.
7. The process for the preparation of a vanadium-modified nickel-iron catalytic material according to any one of claims 3 to 5, characterized in that, The addition ratio of sodium metavanadate to sodium chloride is 0.8M:3M.
8. The process for the preparation of vanadium-modified nickel-iron catalytic material according to any one of claims 3 to 5, characterized in that, The electrochemical corrosion is carried out in a treatment liquid at 50°C.
9. The process for the preparation of vanadium-modified nickel-iron catalytic material according to any one of claims 3 to 5, characterized in that, Annealing is carried out at 200°C and 400°C.