Ni-Nb-RuO2 solid solution catalyst for acidic oxygen evolution reaction and application of Ni-Nb-RuO2 solid solution catalyst
By preparing Ni-Nb-RuO2 solid solution catalysts, the problem of insufficient activity and stability of Ru-based catalysts in acidic oxygen evolution reaction was solved, achieving high efficiency and stable catalytic performance, which is suitable for use in proton exchange membrane water electrolysis devices.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- ANHUI UNIV
- Filing Date
- 2026-01-16
- Publication Date
- 2026-04-21
AI Technical Summary
Existing Ru-based catalysts suffer from problems such as activity-stability trade-offs, irreversible degradation due to lattice oxygen loss, and insufficient durability under high current in acidic oxygen evolution reactions.
A rutile Ni-Nb-RuO2 solid solution electrocatalyst was prepared by a two-step hydrothermal-annealing synthesis method using a Ni-Nb-RuO2 solid solution catalyst. By utilizing the RuO2-based solid solution doped with Ni and Nb elements, a stable two-dimensional nanosheet structure was formed, which improved the exposure of active sites.
It exhibits excellent catalytic activity and long-term stability in acidic media, and can operate stably at high current densities, significantly enhancing the commercial potential of the catalyst.
Smart Images
Figure CN121896676A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of acidic water electrolysis catalytic materials, specifically a Ni-Nb-RuO2 solid solution catalyst for acidic oxygen evolution reaction and its application. Background Technology
[0002] Proton exchange membrane electrolysis (PEMWE) is considered one of the most promising hydrogen generation technologies, with many unique advantages, including high current density, ultra-high purity pressurized hydrogen products, superior safety levels, and compact mass and volume characteristics. Generally, a PEMWE system consists of two half-cells separated by a proton exchange membrane. The oxygen evolution reaction (OER) occurs at the anode of PEMWE. Since OER involves a four-electron transfer process in acidic media, the reaction kinetics of OER are inherently slow. Furthermore, the combination of four-proton transfer to a proton-rich environment further reduces the reaction rate. In addition, the corrosiveness of strongly acidic electrolytes is very harsh on the anode catalyst, especially at the high oxidation potential during the OER reaction. Under acidic conditions, most excellent OER catalysts are mainly based on Ir and Ru-based oxides. In OER, Ru-based catalysts often exhibit higher intrinsic activity and lower cost than Ir-based catalysts, but their poor stability needs to be improved. Traditional RuO2 is prone to degradation in acidic OER processes through two pathways: over-oxidation to generate volatile RuO4 and irreversible demetallization caused by lattice oxygen loss, resulting in a significant activity-stability trade-off. Summary of the Invention
[0003] The purpose of this invention is to provide a Ni-Nb-RuO2 solid solution catalyst for the acidic oxygen evolution reaction and its application, thereby solving the technical problems of existing Ru-based catalysts in the background art, such as the activity-stability trade-off, irreversible degradation due to lattice oxygen loss, and insufficient durability under high current.
[0004] The above-mentioned technical objective of the present invention is achieved through the following technical solution: a Ni-Nb-RuO2 solid solution catalyst for acidic oxygen evolution reaction, wherein the electrocatalyst is a RuO2-based solid solution doped with Ni and Nb elements, and its crystal structure is rutile phase.
[0005] A method for preparing a Ni-Nb-RuO2 solid solution catalyst for the acidic oxygen evolution reaction includes the following steps: S1: C6H 12The solutions of O6•H2O, CO(NH2)2, NiCl2•6H2O, NbCl5, RuCl3 and deionized water are mixed and stirred evenly in a reaction vessel, and then subjected to hydrothermal reaction. The resulting product is centrifuged, washed and dried to obtain the reaction precursor. S2: Anneal the reaction precursor obtained in S1 in an air atmosphere to obtain the Ni-Nb-RuO2 solid solution electrocatalyst.
[0006] A further configuration of the present invention is: in S1, C6H 12 The ratio of O6•H2O, CO(NH2)2, NiCl2•6H2O, NbCl5, RuCl3 solution, and deionized water is 3-5 g : 0.6-1 g : 4-5 mg : 4-5 mg : 3-5 mL : 10-20 mL, wherein the concentration of RuCl3 solution is 0.01 g / mL. -1 .
[0007] A further setting of the present invention is: in S1, the reaction temperature of the hydrothermal reaction is 160-180 °C and the reaction time is 8-12 h.
[0008] A further setting of the present invention is: in S1, the centrifugation rate is 9000-11000 rpm and the centrifugation time is 3-5 minutes.
[0009] A further provision of the present invention is that, in S1, the washing is performed by sequentially centrifuging and washing with deionized water and anhydrous ethanol.
[0010] A further setting of the present invention is: in S1, the drying temperature is 60-80 °C and the time is 6-12 h.
[0011] A further setting of the present invention is: in S2, the annealing treatment temperature is 400-500 ℃ and the time is 10-12 h.
[0012] Application of a Ni-Nb-RuO2 solid solution catalyst for the acidic oxygen evolution reaction (OER), used as an anode electrocatalyst for the OER in a proton exchange membrane water electrolysis (PEMWE) device.
[0013] This invention employs a simple two-step synthesis method, using ruthenium trichloride, nickel chloride hexahydrate, and niobium pentachloride as metal sources, glucose as a structure directing agent and dispersant, urea as a pH adjuster for the reaction system, and water as a solvent. Through hydrothermal reaction, the metal precursors are uniformly dispersed and form a stable colloidal network to synthesize the reaction precursors. Then, the precursors are subjected to high-temperature annealing in an air atmosphere to promote the successful doping of metal ions into the RuO2 lattice, ultimately synthesizing a highly efficient and stable rutile phase Ni-Nb-RuO2 solid solution electrocatalyst.
[0014] The rutile phase Ni-Nb-RuO2 solid solution material synthesized in this invention is used as an anode electrocatalyst for the acidic oxygen evolution reaction (OER) in a proton exchange membrane water electrolysis (PEMWE) device. Through the synergistic effect of the Ni-Nb dual active sites, it exhibits excellent catalytic activity and long-term stability.
[0015] In summary, the present invention has the following beneficial effects: 1. This invention uses a simple hydrothermal-annealing two-step synthesis method to prepare rutile phase Ni-Nb-RuO2 solid solution electrocatalysts, with glucose as a structure directing agent and urea as a pH adjuster. The process is simple and controllable, with significant cost advantages and good reproducibility, making it suitable for large-scale industrial production. 2. The Ni-Nb-RuO2 solid solution electrocatalyst prepared in this invention exhibits excellent catalytic activity. In a 0.5 mol / L sulfuric acid electrolyte solution, an overpotential of only 157 mV is required to reach 10 mA / cm². 2 Industrial-related catalytic current density; 3. The Ni-Nb-RuO2 solid solution electrocatalyst prepared by this invention exhibits superior stability, and can withstand 100 mA / cm² in a 0.5 mol / L sulfuric acid electrolyte solution. 2 It can operate stably for 200 hours at high current density, and achieves 250 mA / cm² in a single proton exchange membrane electrolysis (PEMWE) cell. 2 It can still operate stably for 200 hours under current density; 4. The Ni-Nb-RuO2 solid solution electrocatalyst prepared by this invention is an atomically uniformly dispersed two-dimensional nanosheet structure with a surface rich in wrinkles, which significantly improves the exposure of active sites. 5. When the rutile phase Ni-Nb-RuO2 solid solution material prepared in this invention is used as an anode catalyst in a proton exchange membrane water electrolysis device, it exhibits catalytic activity and long-term stability far exceeding those of commercial RuO2 and single-doped Ru-based catalysts, providing key support for the commercialization of PEMWE technology. Attached Figure Description
[0016] Figure 1 This is a scanning electron microscope image of the rutile phase Ni-Nb-RuO2 solid solution obtained in Example 1.
[0017] Figure 2 This is a transmission electron microscope image of the rutile phase Ni-Nb-RuO2 solid solution obtained in Example 1.
[0018] Figure 3 This is a high-resolution transmission electron microscope image of the rutile phase Ni-Nb-RuO2 solid solution obtained in Example 1.
[0019] Figure 4 The image shows the X-ray diffraction pattern of the rutile phase Ni-Nb-RuO2 solid solution obtained in Example 1.
[0020] Figure 5 The polarization curves of the materials obtained in Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 in 0.5 M H2SO4 solution are shown.
[0021] Figure 6 The rutile Ni-Nb-RuO2 solid solution electrocatalyst obtained in Example 1 was reacted in 0.5 M H2SO4 solution at 100 mA cm⁻¹ -2 Voltage versus time curve at constant current density.
[0022] Figure 7 After assembling a proton exchange membrane water electrolysis (PEMWE) single cell using the rutile Ni-Nb-RuO2 solid solution electrocatalyst obtained in Example 1 as the anode, the cell was tested at 0.25 A cm⁻¹. -2 The curve of battery voltage versus time at constant current density. Detailed Implementation
[0023] The present invention will be further described below with reference to the accompanying drawings in the embodiments of the present invention.
[0024] Example 1: In this example, a Ni-Nb-RuO2 solid solution electrocatalyst was prepared according to the following steps: Step 1: Add 3 g of C6H to a polytetrafluoroethylene-lined reactor. 12 O6•H2O (AR), 0.6 g CO (NH2) 2 (AR), 4.3×10 -3 g NiCl2•6H2O (AR), 4.89×10 -3 g NbCl5 (AR), 3 mL RuCl3 solution (0.01 g mL) -1 ) and 10 mL of deionized water, stir the mixture evenly, and then perform hydrothermal reaction at 160℃ for 8 h. After the reaction is completed, cool to room temperature, and centrifuge the product (centrifugation speed is 10000 rpm, centrifugation time is 4 min), wash it 3 times with deionized water and anhydrous ethanol respectively, and then dry it in an oven at 60℃ for 12 h to obtain the reaction precursor. Step 2: The reaction precursor obtained in Step 1 is annealed in an air atmosphere at 400 °C for 12 h. After naturally cooling to room temperature, a rutile phase Ni-Nb-RuO2 solid solution electrocatalyst is obtained.
[0025] The scanning electron microscope (SEM) and transmission electron microscope (TEM) images of the rutile Ni-Nb-RuO2 solid solution electrocatalyst prepared in this embodiment are shown below. Figure 1 , Figure 2 As shown; by Figure 1-2 As can be seen, the product obtained in this embodiment exhibits a uniform two-dimensional nanosheet morphology with a surface rich in wrinkled structures.
[0026] The high-resolution transmission electron microscope (TEM) image and X-ray diffraction pattern of the rutile Ni-Nb-RuO2 solid solution prepared in this embodiment are shown below. Figure 3 , Figure 4 As shown; by Figure 3 It can be observed that the lattice spacings of the products obtained in this embodiment are 0.319 nm, 0.256 nm, and 0.226 nm, respectively, and these lattice fringes correspond exactly to... Figure 4 The (110), (101) and (200) crystal planes of the material further prove that Ni and Nb successfully substituted Ru sites to form a single-phase rutile Ni-Nb-RuO2 solid solution structure.
[0027] The electrochemical performance of the Ni-Nb-RuO2 solid solution electrocatalyst obtained in this embodiment was tested using a three-electrode system. Two mg of catalyst was added to a mixed solvent containing 15 µL of Nafion D-520 dispersion aqueous solution (5%, Thermos Scientific), 375 µL of water, and 125 µL of anhydrous ethanol. The mixture was then dispersed by sonication under oscillation for at least 30 minutes to produce a uniform black ink. A 3 mm diameter glassy carbon electrode was polished with alumina powder slurry, rinsed with ultrapure water and ethanol, and allowed to air dry at room temperature to obtain a clean mirror surface. 5 µL of the prepared dispersion ink was then drop-coated onto the electrode surface and allowed to air dry before being used as the working electrode in the test. The reference electrode was a Hg / Hg₂SO₄ electrode, the counter electrode was a Pt wire electrode, and the electrolyte solution was an oxygen-saturated 0.5 mol / L sulfuric acid solution. Polarization curves were tested on the Ni-Nb-RuO₂ solid solution electrocatalyst. The electrocatalytic performance was represented by the overpotential at an oxygen evolution current density of 10 mA / cm², with a smaller overpotential indicating better performance. The overpotential was set at 100 mA / cm². 2 The oxygen evolution current was used to perform constant current testing on the Ni-Nb-RuO2 solid solution electrocatalyst. As time progressed, the corresponding overpotential increased. The magnitude of the overpotential increase represents the stability, and the smaller the potential increase, the better the stability.
[0028] The polarization curve of the rutile Ni-Nb-RuO2 solid solution electrocatalyst obtained in this embodiment in 0.5 M H2SO4 solution is shown below. Figure 5 As shown, the scan rate is 10 mV / s. -1 The sample (RuO2) of Comparative Example 3 was used as the standard catalyst; Figure 5As can be seen, the rutile Ni-Nb-RuO2 solid solution electrocatalyst prepared in this embodiment can provide 10 mA cm⁻¹ at an overpotential of only 157 mV. -2 The industrial-relevant current density showed a significant improvement in catalytic activity compared to the sample in Comparative Example 3 (RuO2 overpotential of 295 mV); further, a high current density (100 mA / cm²) was achieved on carbon paper. 2 Stability testing, such as Figure 6 The catalyst obtained in this embodiment, as shown, has a strength of 100 mA / cm² in acidic media. 2 After a 200-hour stability test under high current, the catalytic activity remained almost unchanged.
[0029] To further demonstrate the industrial application potential of the solid solution catalyst obtained in this embodiment, such as Figure 7 As shown, it was used as an anode catalyst to assemble a proton exchange membrane electrolysis (PEMWE) single cell, and its durability was tested under an ultra-high current of 0.25 A / cm². The results showed that the voltage did not decrease significantly after 200 h of stable operation, demonstrating long-term stability that meets the requirements of industrial applications, and providing key data support for its commercial promotion.
[0030] Example 2: In this example, a Ni-Nb-RuO2 solid solution electrocatalyst was prepared according to the following steps: Step 1: Add 3 g of C6H to a polytetrafluoroethylene-lined reactor. 12 O6•H2O (AR), 0.6 g CO (NH2) 2 (AR), 4.3×10 -3 g NiCl2•6H2O (AR), 4.89×10 -3 g NbCl5 (AR), 3 mL RuCl3 solution (0.01 g mL) -1 ) and 10 mL of deionized water, stir the mixture evenly, and then perform hydrothermal reaction at 160℃ for 8 h. After the reaction is completed, cool to room temperature, and centrifuge the product (centrifugation speed is 10000 rpm, centrifugation time is 4 min), wash it 3 times with deionized water and anhydrous ethanol respectively, and then dry it in an oven at 60℃ for 12 h to obtain the reaction precursor. Step 2: The reaction precursor obtained in Step 1 is annealed in an air atmosphere at 400℃ for 10 h. After naturally cooling to room temperature, a rutile phase Ni-Nb-RuO2 solid solution electrocatalyst is obtained.
[0031] Characterization showed that the product obtained in this embodiment exhibits a uniform rutile phase solid solution structure with consistent size.
[0032] The electrochemical performance of the Ni-Nb-RuO2 solid solution electrocatalyst obtained in this example was tested using the same method as in Example 1. The results showed that the rutile Ni-Nb-RuO2 solid solution electrocatalyst prepared in this example could provide 10 mA cm⁻¹ at an overpotential of only 164 mV. -2 The current density.
[0033] Example 3: In this example, a Ni-Nb-RuO2 solid solution electrocatalyst was prepared according to the following steps: Step 1: Add 5 g of C6H to a polytetrafluoroethylene-lined reactor. 12 O6•H2O (AR), 1 g CO (NH2) 2 (AR), 5×10 -3 g NiCl2•6H2O (AR), 5×10 -3 g NbCl5 (AR), 5 mL RuCl3 solution (0.01 g mL) -1 ) and 20 mL of deionized water, stir the mixture evenly, and then perform hydrothermal reaction at 160℃ for 8 h. After the reaction is completed, cool to room temperature, and centrifuge the product (centrifugation speed is 10000 rpm, centrifugation time is 4 min), wash it 3 times with deionized water and anhydrous ethanol respectively, and then dry it in an oven at 60℃ for 12 h to obtain the reaction precursor. Step 2: The reaction precursor obtained in Step 1 is annealed in an air atmosphere at 400℃ for 12 h. After naturally cooling to room temperature, a rutile phase Ni-Nb-RuO2 solid solution electrocatalyst is obtained.
[0034] Characterization showed that the product obtained in this embodiment exhibits a uniform rutile phase solid solution structure with consistent size.
[0035] The electrochemical performance of the Ni-Nb-RuO2 solid solution electrocatalyst obtained in this example was tested using the same method as in Example 1. The results showed that the rutile Ni-Nb-RuO2 solid solution electrocatalyst prepared in this example could provide 10 mA cm⁻¹ at an overpotential of 168 mV. -2 The current density.
[0036] Example 4: In this example, a Ni-Nb-RuO2 solid solution electrocatalyst was prepared according to the following steps: Step 1: Add 3 g of C6H into a polytetrafluoroethylene-lined reactor. 12 O6•H2O (AR), 0.6 g CO (NH2) 2 (AR), 4.3×10 -3 g NiCl2•6H2O (AR), 4.89×10 -3 g NbCl5 (AR), 3 mL RuCl3 solution (0.01 g mL)-1 ) and 10 mL of deionized water, stir the mixture evenly, and then perform hydrothermal reaction at 180℃ for 8 h. After the reaction is completed, cool to room temperature, and centrifuge the product (centrifugation speed is 10000 rpm, centrifugation time is 4 min), wash it 3 times with deionized water and anhydrous ethanol respectively, and then dry it in an oven at 60℃ for 12 h to obtain the reaction precursor. Step 2: The reaction precursor obtained in Step 1 is annealed in an air atmosphere at 400℃ for 12 h. After naturally cooling to room temperature, a rutile phase Ni-Nb-RuO2 solid solution electrocatalyst is obtained.
[0037] Characterization showed that the product obtained in this embodiment exhibits a uniform rutile phase solid solution structure with consistent size.
[0038] The electrochemical performance of the Ni-Nb-RuO2 solid solution electrocatalyst obtained in this example was tested using the same method as in Example 1. The results showed that the rutile Ni-Nb-RuO2 solid solution electrocatalyst prepared in this example could provide 10 mA cm⁻¹ at an overpotential of 169 mV. -2 The current density.
[0039] Example 5: In this example, a Ni-Nb-RuO2 solid solution electrocatalyst was prepared according to the following steps: Step 1: Add 4 g of C6H into a polytetrafluoroethylene-lined reactor. 12 O6•H2O (AR), 0.8 g CO (NH2) 2 (AR), 4×10 -3 g NiCl2•6H2O (AR), 4×10 -3 g NbCl5 (AR), 4 mL RuCl3 solution (0.01 g mL) -1 ) and 15 mL of deionized water, stir the mixture evenly, and then perform hydrothermal reaction at 160℃ for 8 h. After the reaction is completed, cool to room temperature, and centrifuge the product (centrifugation speed is 10000 rpm, centrifugation time is 4 min), wash it 3 times with deionized water and anhydrous ethanol respectively, and then dry it in an oven at 60℃ for 12 h to obtain the reaction precursor. Step 2: The reaction precursor obtained in Step 1 is annealed in an air atmosphere at 400℃ for 12 h. After naturally cooling to room temperature, a rutile phase Ni-Nb-RuO2 solid solution electrocatalyst is obtained.
[0040] Characterization showed that the product obtained in this embodiment exhibits a uniform rutile phase solid solution structure with consistent size.
[0041] The electrochemical performance of the Ni-Nb-RuO2 solid solution electrocatalyst obtained in this example was tested using the same method as in Example 1. The results showed that the rutile Ni-Nb-RuO2 solid solution electrocatalyst prepared in this example could provide 10 mA cm⁻¹ at an overpotential of 189 mV. -2 The current density.
[0042] Example 6: In this example, a Ni-Nb-RuO2 solid solution electrocatalyst was prepared according to the following steps: Step 1: Add 3 g of C6H to a polytetrafluoroethylene-lined reactor. 12 O6•H2O (AR), 0.6 g CO (NH2) 2 (AR), 4.3×10 -3 g NiCl2•6H2O (AR), 4.89×10 -3 g NbCl5 (AR), 3 mL RuCl3 solution (0.01 g mL) -1 ) and 10 mL of deionized water, stir the mixture evenly, and then perform hydrothermal reaction at 160℃ for 12 h. After the reaction is completed, cool to room temperature, and centrifuge the product (centrifugation speed is 10000 rpm, centrifugation time is 4 min), wash it 3 times with deionized water and anhydrous ethanol respectively, and then dry it in an oven at 60℃ for 12 h to obtain the reaction precursor. Step 2: The reaction precursor obtained in Step 1 is annealed in an air atmosphere at 400℃ for 12 h. After naturally cooling to room temperature, a rutile phase Ni-Nb-RuO2 solid solution electrocatalyst is obtained.
[0043] Characterization showed that the product obtained in this embodiment exhibits a uniform rutile phase solid solution structure with consistent size.
[0044] The electrochemical performance of the Ni-Nb-RuO2 solid solution electrocatalyst obtained in this example was tested using the same method as in Example 1. The results showed that the rutile Ni-Nb-RuO2 solid solution electrocatalyst prepared in this example could provide 10 mA cm⁻¹ at an overpotential of 186 mV. -2 The current density.
[0045] Example 7: In this example, a Ni-Nb-RuO2 solid solution electrocatalyst was prepared according to the following steps: Step 1: Add 3 g of C6H to a polytetrafluoroethylene-lined reactor. 12 O6•H2O (AR), 0.6 g CO (NH2) 2 (AR), 4.3×10 -3 g NiCl2•6H2O (AR), 4.89×10 -3g NbCl5 (AR), 3 mL RuCl3 solution (0.01 g mL) -1 ) and 10 mL of deionized water, stir the mixture evenly, and then perform hydrothermal reaction at 160℃ for 8 h. After the reaction is completed, cool to room temperature, and centrifuge the product (centrifugation speed is 10000 rpm, centrifugation time is 4 min), wash it 3 times with deionized water and anhydrous ethanol respectively, and then dry it in an oven at 60℃ for 12 h to obtain the reaction precursor. Step 2: The reaction precursor obtained in Step 1 is annealed in an air atmosphere at 500℃ for 12 h. After naturally cooling to room temperature, a rutile phase Ni-Nb-RuO2 solid solution electrocatalyst is obtained.
[0046] Characterization showed that the product obtained in this embodiment exhibits a uniform rutile phase solid solution structure with consistent size.
[0047] The electrochemical performance of the Ni-Nb-RuO2 solid solution electrocatalyst obtained in this example was tested using the same method as in Example 1. The results show that the rutile Ni-Nb-RuO2 solid solution electrocatalyst prepared in this example can provide 10 mA cm⁻¹ at an overpotential of 190 mV. -2 The current density.
[0048] To better illustrate the performance of the catalyst electrode prepared in this invention, comparative samples 1, 2, and 3 were prepared in this embodiment, and their test results were compared with those of the highly efficient and stable Ni-Nb-RuO2 solid solution electrocatalyst of this invention. The preparation methods of each comparative sample are as follows: Comparative Example 1: The Ni-RuO2 electrocatalyst in this comparative example was prepared according to the following steps: Step 1: Add 3 g of C6H to a polytetrafluoroethylene-lined reactor. 12 O6•H2O (AR), 0.6 g CO (NH2) 2 (AR), 4.3×10 -3 g NiCl2•6H2O (AR), 3 mL RuCl3 solution (0.01 g mL) -1 ) and 10 mL of deionized water, stir the mixture evenly, and then perform hydrothermal reaction at 160℃ for 8 h. After the reaction is completed, cool to room temperature, and centrifuge the product (centrifugation speed is 10000 rpm, centrifugation time is 4 min), wash it 3 times with deionized water and anhydrous ethanol respectively, and then dry it in an oven at 60℃ for 12 h to obtain the reaction precursor. Step 2: The reaction precursor obtained in Step 1 is annealed in an air atmosphere at 400℃ for 12 h. After naturally cooling to room temperature, the Ni-RuO2 electrocatalyst is obtained.
[0049] Characterization revealed that the product obtained in this comparative example exhibits a rutile phase.
[0050] The Ni-RuO2 electrocatalyst obtained in this comparative example was tested for electrochemical performance using the same method as in Example 1. The results showed that the Ni-RuO2 electrocatalyst prepared in this comparative example provided 10 mA cm⁻¹ electrochemical performance. -2 The required current density requires an overpotential of 227 mV.
[0051] Comparative Example 2: The Nb-RuO2 electrocatalyst in this comparative example was prepared according to the following steps: Step 1: Add 3 g of C6H to a polytetrafluoroethylene-lined reactor. 12 O6•H2O (AR), 0.6 g CO (NH2) 2 (AR), 4.89×10 -3 g NbCl5 (AR), 3 mL RuCl3 solution (0.01 g mL) -1 ) and 10 mL of deionized water, stir the mixture evenly, and then perform hydrothermal reaction at 160℃ for 8 h. After the reaction is completed, cool to room temperature, and centrifuge the product (centrifugation speed is 10000 rpm, centrifugation time is 4 min), wash it 3 times with deionized water and anhydrous ethanol respectively, and then dry it in an oven at 60℃ for 12 h to obtain the reaction precursor. Step 2: The reaction precursor obtained in Step 1 is annealed in an air atmosphere at 400℃ for 12 h. After naturally cooling to room temperature, the Nb-RuO2 electrocatalyst is obtained.
[0052] Characterization revealed that the product obtained in this comparative example exhibits a rutile phase.
[0053] The Nb-RuO2 electrocatalyst obtained in this comparative example was tested for electrochemical performance using the same method as in Example 1. The results showed that the Nb-RuO2 electrocatalyst prepared in this comparative example provided 10 mA cm⁻¹. -2 The required current density requires an overpotential of 256 mV.
[0054] Comparative Example 3: This comparative example prepared a RuO2 electrocatalyst in the rutile phase according to the following steps: Step 1: Add 3 g of C6H to a polytetrafluoroethylene-lined reactor. 12 O6•H2O (AR), 0.6 g CO(NH2)2 (AR), 3 mL RuCl3 solution (0.01 g mL) -1) and 10 mL of deionized water, stir the mixture evenly, and then perform hydrothermal reaction at 160℃ for 8 h. After the reaction is completed, cool to room temperature, and centrifuge the product (centrifugation speed is 10000 rpm, centrifugation time is 4 min), wash it 3 times with deionized water and anhydrous ethanol respectively, and then dry it in an oven at 60℃ for 12 h to obtain the reaction precursor. Step 2: The reaction precursor obtained in Step 1 is annealed in an air atmosphere at 400℃ for 12 h. After naturally cooling to room temperature, the rutile phase RuO2 electrocatalyst is obtained.
[0055] Characterization revealed that the product obtained in this comparative example exhibits a rutile phase.
[0056] The electrochemical performance of the RuO2 electrocatalyst obtained in this comparative example was tested using the same method as in Example 1. The results showed that the rutile phase RuO2 electrocatalyst prepared in this comparative example provided 10 mA cm⁻¹. -2 The required current density requires an overpotential of 295 mV.
[0057] The above description is only a preferred embodiment of the present invention. Therefore, all equivalent changes or modifications made to the structure, features and principles described in the claims of this patent application are included in the scope of this patent application.
Claims
1. A Ni-Nb-RuO2 solid solution catalyst for acidic oxygen evolution reaction, characterized in that, The electrocatalyst is a RuO2-based solid solution doped with Ni and Nb elements, and its crystal structure is rutile phase.
2. A method for preparing a Ni-Nb-RuO2 solid solution catalyst for acidic oxygen evolution reaction as described in claim 1, characterized in that, Includes the following steps: S1: C6H 12 After O6•H2O, CO(NH2)2, NiCl2•6H2O, NbCl5, RuCl3 solution and deionized water are mixed and stirred evenly in a reaction vessel, a hydrothermal reaction is carried out. The resulting product is centrifuged, washed and dried to obtain the reaction precursor. S2: Anneal the reaction precursor obtained in S1 in an air atmosphere to obtain the Ni-Nb-RuO2 solid solution electrocatalyst.
3. The method for preparing the Ni-Nb-RuO2 solid solution catalyst for acidic oxygen evolution reaction according to claim 2, characterized in that, In S1, C6H 12 The ratio of O6•H2O, CO(NH2)2, NiCl2•6H2O, NbCl5, RuCl3 solution, and deionized water is 3-5 g : 0.6-1 g : 4-5 mg : 4-5 mg : 3-5 mL : 10-20 mL, wherein the concentration of RuCl3 solution is 0.01 g / mL. -1 .
4. The method for preparing the Ni-Nb-RuO2 solid solution catalyst for acidic oxygen evolution reaction according to claim 2, characterized in that, In S1, the hydrothermal reaction temperature is 160-180 ℃ and the reaction time is 8-12 h.
5. The method for preparing the Ni-Nb-RuO2 solid solution catalyst for acidic oxygen evolution reaction according to claim 2, characterized in that, In S1, the centrifugation rate is 9000-11000 rpm, and the centrifugation time is 3-5 minutes.
6. The method for preparing the Ni-Nb-RuO2 solid solution catalyst for acidic oxygen evolution reaction according to claim 2, characterized in that, In S1, the washing process involves sequentially centrifuging and washing with deionized water and anhydrous ethanol.
7. The method for preparing the Ni-Nb-RuO2 solid solution catalyst for acidic oxygen evolution reaction according to claim 2, characterized in that, In S1, the drying temperature is 60-80 ℃ and the time is 6-12 h.
8. The method for preparing the Ni-Nb-RuO2 solid solution catalyst for acidic oxygen evolution reaction according to claim 2, characterized in that, In S2, the annealing treatment is carried out at a temperature of 400-500 ℃ for 10-12 h.
9. The application of the Ni-Nb-RuO2 solid solution catalyst as described in claim 1 for the acidic oxygen evolution reaction, characterized in that: Used as an anode electrocatalyst for catalyzing the acidic oxygen evolution reaction (OER) in a proton exchange membrane water electrolysis (PEMWE) device.