A dual electrode material for hydrogen production by electrolysis of water in an acidic environment and a preparation method thereof
By loading ruthenium dioxide or cerium dioxide onto carbon spheres to form a bifunctional electrocatalyst, the problem of poor stability of Ru-based materials in acidic environments was solved, achieving efficient water electrolysis for hydrogen production and reducing costs.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- TAIYUAN UNIVERSITY OF TECHNOLOGY
- Filing Date
- 2023-03-29
- Publication Date
- 2026-04-24
AI Technical Summary
In existing PEM water electrolysis hydrogen production technology, Ru-based materials have poor stability in acidic environments, especially during the OER electrocatalysis process, where they are easily oxidized to RuO4 and dissolved, affecting their practicality. In addition, the high cost of the catalyst limits its large-scale application.
Ruthenium dioxide or cerium dioxide was prepared on carbon spheres using hydrothermal and annealing methods, or ruthenium dioxide/cerium dioxide heterojunctions were prepared on carbon spheres to form bifunctional electrocatalysts, which were then drop-coated onto carbon paper to prepare dual-electrode materials.
It improves the stability and activity of the catalyst, reduces the amount of precious metals used, and achieves efficient water electrolysis for hydrogen production under acidic conditions. It has good structural stability and high oxygen/hydrogen evolution catalytic activity.
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Figure CN116288503B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of materials technology for hydrogen production by water electrolysis, specifically to a dual-electrode material for hydrogen production by water electrolysis under acidic conditions and its preparation method. Background Technology
[0002] Hydrogen energy, as a clean and efficient secondary energy source, is a primary means of large-scale development, storage, and utilization of renewable energy. The hydrogen energy industry can drive the transformation and upgrading of my country's energy and equipment manufacturing industries. Water electrolysis for hydrogen production is the main method for large-scale hydrogen production from renewable energy sources and is an important foundation for the development of the entire hydrogen energy industry.
[0003] Among numerous hydrogen production technologies, proton exchange membrane (PEM) water electrolysis is a promising green hydrogen production technology due to its high efficiency, small footprint, high gas separation purity, and good compatibility with wind and solar power. However, PEM water electrolysis currently only accounts for a very small market share, mainly because the catalyst, a key material for PEM membrane electrodes, is too expensive.
[0004] Ru, belonging to the Pt group of noble metals, has attracted considerable attention in water electrolysis due to its outstanding catalytic performance, wide pH adaptability, and low cost among noble metals. However, Ru-based materials suffer from severe stability issues, particularly in OER electrocatalysis. High voltage causes RuO2 to become highly unstable, easily oxidizing to RuO4 and dissolving, significantly impacting its practicality. Previous studies have shown that metal doping is an effective strategy for improving the electrocatalytic activity of transition metal oxides. The incorporation of heteroatoms can effectively increase conductivity and alter electronic structure, and the synergistic effect of different metal sites in multi-metal oxides can significantly improve catalyst activity and stability. Interfacial modification optimization of catalysts is another approach to enhance the activity and stability of Ru-based catalysts. Loading Ru-based materials onto highly conductive supports improves the utilization rate of noble metal atoms, allowing for reduced noble metal usage while maintaining catalytic activity and saving costs. Therefore, developing low-cost, high-efficiency, and acid-stable electrocatalytic materials is the core issue for breaking through the large-scale application of PEM water electrolysis technology. The key to solving this problem is how to construct a long-range catalytically stable Ru-based catalyst that combines high catalytic activity and high atom utilization. Summary of the Invention
[0005] This invention overcomes the shortcomings of the prior art and provides a bifunctional electrocatalyst for hydrogen production by water electrolysis under acidic conditions.
[0006] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: a bifunctional electrocatalyst for hydrogen production by water electrolysis under acidic conditions, wherein ruthenium dioxide is supported on carbon spheres, or cerium dioxide is supported on carbon spheres, or a ruthenium dioxide / cerium dioxide heterojunction is supported on carbon spheres to obtain a bifunctional electrocatalyst for oxygen evolution at the anode and hydrogen evolution at the cathode.
[0007] The present invention also provides a dual-electrode material for hydrogen production by water electrolysis under acidic conditions, which is prepared by using the bifunctional electrocatalyst as described above, i.e., the bifunctional electrocatalyst is drop-coated onto carbon paper to obtain the dual-electrode material.
[0008] In addition, the present invention also provides a method for preparing the above-mentioned dual-electrode material for hydrogen production by water electrolysis under acidic conditions, comprising the following steps:
[0009] 1) Add ruthenium chloride (RuCl3·xH2O), cerium nitrate (Ce(NO3)3·6H2O), and glucose to water and stir to dissolve;
[0010] 2) Place the above solution in a polytetrafluoroethylene hydrothermal reactor and hydrothermally heat it at 180°C for 10 hours. After cooling, wash and centrifuge three times alternately with water and ethanol.
[0011] 3) The centrifuged product was annealed at 400°C in air for 2 hours to obtain a bifunctional electrocatalyst with ruthenium dioxide / cerium dioxide heterojunction supported on carbon spheres. The bifunctional electrocatalyst was then drop-coated onto carbon paper to obtain a dual-electrode material.
[0012] Furthermore, the molar ratio of ruthenium chloride and cerium nitrate in step 1) is 1:1.
[0013] Furthermore, in step 2), the annealing temperature rise rate is 5°C / min.
[0014] Furthermore, the concentration of glucose in step 1) is 5 mol / L.
[0015] Compared with the prior art, the present invention has the following beneficial effects:
[0016] The catalytic material prepared by this invention has good water electrolysis catalytic performance. Under acidic electrolysis conditions, it exhibits good structural stability and high oxygen / hydrogen evolution catalytic activity. Its preparation process is simple, and the electrode components and types are adjustable, showing good application prospects. Attached Figure Description
[0017] Figure 1 This is a scanning electron microscope image of the RuO2 / CeO2@C catalyst obtained in Example 1 of the present invention.
[0018] Figure 2The image shows the X-ray diffraction pattern of the RuO2 / CeO2@C catalyst obtained in Example 1 of this invention.
[0019] Figure 3 The image shows the Raman spectrum of the RuO2 / CeO2@C catalyst obtained in Example 1 of this invention.
[0020] Figure 4 The graph shows the linear voltammetric curve (0.5 M sulfuric acid) for testing the oxygen evolution performance of the RuO2 / CeO2@C catalyst obtained in Example 1 of this invention.
[0021] Figure 5 The stability curve of the oxygen evolution performance test of the RuO2 / CeO2@C catalyst obtained in Example 1 of this invention is shown.
[0022] Figure 6 The linear voltammetric curve for testing the hydrogen evolution performance of the RuO2 / CeO2@C catalyst obtained in Example 1 of this invention is shown.
[0023] Figure 7 The graph shows the stability curve of the hydrogen evolution performance test of the RuO2 / CeO2@C catalyst obtained in Example 1 of this invention.
[0024] Figure 8 The linear voltammetric curve is shown for the full hydrolysis performance test of the RuO2 / CeO2@C catalyst obtained in Example 1 of this invention.
[0025] Figure 9 The graph shows the stability of the RuO2 / CeO2@C catalyst obtained in Example 1 of this invention during the full hydrolysis performance test.
[0026] Figure 10 Linear voltammetric curve of oxygen evolution performance test of RuO2@C catalyst prepared in Example 2 of this invention.
[0027] Figure 11 Linear voltammetric curves for oxygen evolution performance testing of the IrO2 / CeO2@C catalyst prepared in Example 3 of this invention.
[0028] Figure 12 Linear voltammetric curves for oxygen evolution performance testing of the RuO2 / CrO2@C catalyst prepared in Example 4 of this invention.
[0029] Figure 13 Linear voltammetric curves for oxygen evolution performance testing of the RuO2 / MnO2@C catalyst prepared in Example 5 of this invention.
[0030] Figure 14 Linear voltammetric curves for oxygen evolution performance testing of the RuO2 / MoO3@C catalyst prepared in Example 6 of this invention.
[0031] Figure 15 Linear voltammetric curves for oxygen evolution performance testing of the RuO2 / Co3O4@C catalyst prepared in Example 7 of this invention. Detailed Implementation
[0032] The present invention will be further described below with reference to specific embodiments. Example 1
[0033] A method for preparing a dual-electrode material for hydrogen production via acidic water electrolysis includes the following steps:
[0034] (1) Add 0.0519g of ruthenium chloride (RuCl3·xH2O), 0.1085g of cerium nitrate (Ce(NO3)3·6H2O) and 1.8g of glucose to 20mL of water and stir to dissolve;
[0035] (2) Place the above solution in a polytetrafluoroethylene hydrothermal reactor and hydrothermally heat it at 180°C for 10 hours. After natural cooling, wash and centrifuge it three times alternately with water and ethanol.
[0036] (3) The centrifuged product was annealed at 400℃ with a heating rate of 5℃ / min in air atmosphere for 2h to obtain RuO2 / CeO2@C catalyst with ruthenium dioxide / cerium dioxide heterojunction supported on carbon spheres. The catalyst was then drop-coated onto carbon paper to obtain the electrode.
[0037] The scanning electron microscope image of the RuO2 / CeO2@C catalyst prepared in Example 1 is shown below. Figure 1 As shown, Figure 1 It can be seen that the prepared RuO2 / CeO2@C catalyst has the morphology of small particles uniformly loaded on nanospheres. The nanospheres provide a large specific surface area for the metal loading, which can effectively improve the utilization rate of atoms, thereby improving the electrocatalytic activity.
[0038] The X-ray diffraction pattern of the RuO2 / CeO2@C catalyst prepared in Example 1 is shown below. Figure 2 As shown, by Figure 2 It can be seen that the characteristic peaks of the RuO2 / CeO2@C electrocatalyst correspond to the characteristic peaks of RuO2 and CeO2.
[0039] The Raman spectrum of the RuO2 / CeO2@C catalyst prepared in Example 1 is as follows: Figure 3 As shown, by Figure 3 It can be seen that the Raman peak of RuO2 / CeO2@C includes the E of RuO2. g Peak, F of CeO2 2g Peaks and carbon I G and I D peak.
[0040] The linear voltammetric curve for testing the oxygen evolution performance of the RuO2 / CeO2@C catalyst prepared in Example 1 is shown below. Figure 4 As shown, by Figure 4 It can be seen that the prepared RuO2 / CeO2@C catalyst only requires 170mV to reach 10mA / cm 2 Current density.
[0041] The RuO2 / CeO2@C catalyst prepared in Example 1 operates at 10 mA / cm². 2 The stability test curve is as follows Figure 5 As shown, by Figure 5 It can be seen that the prepared RuO2 / CeO2@C catalyst can stably drive the oxygen evolution reaction in an acidic environment for a long time.
[0042] The linear voltammetric curve for testing the hydrogen evolution performance of the RuO2 / CeO2@C catalyst prepared in Example 1 is shown below. Figure 6 As shown, by Figure 6 It can be seen that the prepared RuO2 / CeO2@C catalyst only requires 120mV to reach -10mA / cm 2 Current density.
[0043] The RuO2 / CeO2@C catalyst prepared in Example 1 operates at -10 mA / cm². 2 The stability test curve is as follows Figure 7 As shown, by Figure 7 It can be seen that the prepared RuO2 / CeO2@C catalyst can stably drive the hydrogen evolution reaction in an acidic environment for a long time.
[0044] The linear voltammetric curve of the RuO2 / CeO2@C catalyst prepared in Example 1 is shown below. Figure 8 As shown, by Figure 8 It can be seen that the prepared RuO2 / CeO2@C catalyst achieves a total hydrolysis efficiency of 10 mA / cm². 2 The required current density is only 1.54V.
[0045] The RuO2 / CeO2@C catalyst prepared in Example 1 operates at 10 mA / cm². 2 The total hydrolysis stability test curve is as follows: Figure 9 As shown, by Figure 9 It can be seen that the prepared RuO2 / CeO2@C catalyst can stably drive the water electrolysis reaction for a long time as both an anode and cathode under acidic conditions. Example 2
[0046] A method for preparing a bifunctional electrocatalytic material for hydrogen production by acidic water electrolysis includes the following steps:
[0047] (1) Add 0.0519g of ruthenium chloride (RuCl3·xH2O) and 1.8g of glucose to 20mL of water and stir to dissolve;
[0048] (2) Place the above solution in a polytetrafluoroethylene hydrothermal reactor and hydrothermally heat it at 180°C for 10 hours. After natural cooling, wash and centrifuge it three times alternately with water and ethanol.
[0049] (3) The centrifuged product was annealed at 400℃ (heating rate of 5℃ / min) in air atmosphere for 2h to obtain a catalyst with ruthenium dioxide supported on carbon spheres. The catalyst was then drop-coated onto carbon paper to obtain an electrode.
[0050] The linear voltammetric curve for testing the oxygen evolution performance of the RuO2@C catalyst prepared in Example 2 is shown below. Figure 10 As shown, by Figure 10 It can be seen that the prepared RuO2@C catalyst has a performance of 10 mA / cm². 2 The overpotential at the current density is 290mV. Example 3
[0051] A method for preparing a bifunctional electrocatalytic material for hydrogen production by acidic water electrolysis includes the following steps:
[0052] (1) Add 0.05g iridium chloride (IrCl3·xH2O), 0.1085g cerium nitrate (Ce(NO3)3·6H2O) and 1.8g glucose to 20mL of water and stir to dissolve;
[0053] (2) Place the above solution in a polytetrafluoroethylene hydrothermal reactor and hydrothermally heat it at 180°C for 10 hours. After natural cooling, wash and centrifuge it three times alternately with water and ethanol.
[0054] (3) The centrifuged product was annealed at 400℃ (heating rate of 5℃ / min) in air atmosphere for 2h to obtain a catalyst supported on carbon spheres by iridium dioxide / cerium dioxide. The catalyst was then drop-coated onto carbon paper to obtain an electrode.
[0055] The linear voltammetric curve for testing the oxygen evolution performance of the IrO2 / CeO2@C catalyst prepared in Example 3 is shown below. Figure 11 As shown, by Figure 11 It can be seen that the prepared IrO2 / CeO2@C catalyst has a performance of 10 mA / cm². 2 The overpotential at the current density is 250mV. Example 4
[0056] A method for preparing a bifunctional electrocatalytic material for hydrogen production by acidic water electrolysis includes the following steps:
[0057] (1) Add 0.0519g of ruthenium chloride (RuCl3·xH2O), 0.1g of chromium nitrate (Cr(NO3)3·9H2O) and 1.8g of glucose to 20mL of water and stir to dissolve;
[0058] (2) Place the above solution in a polytetrafluoroethylene hydrothermal reactor and hydrothermally heat it at 180°C for 10 hours. After natural cooling, wash and centrifuge it three times alternately with water and ethanol.
[0059] (3) The centrifuged product was annealed at 400℃ (heating rate of 5℃ / min) in air atmosphere for 2h to obtain a catalyst supported on carbon spheres by ruthenium dioxide / chromium dioxide. The catalyst was then drop-coated onto carbon paper to obtain an electrode.
[0060] The linear voltammetric curves for testing the oxygen evolution performance of the RuO2 / CrO2@C catalyst prepared in Example 4 are shown below. Figure 12 As shown, by Figure 12 It can be seen that the prepared RuO2 / CrO2@C catalyst has a performance of 10 mA / cm². 2 The overpotential at the current density is 220mV. Example 5
[0061] A method for preparing a bifunctional electrocatalytic material for hydrogen production by acidic water electrolysis includes the following steps:
[0062] (1) Add 0.0519g of ruthenium chloride (RuCl3·xH2O), 0.1g of manganese dichloride (MnCl2·H2O) and 1.8g of glucose to 20mL of water and stir to dissolve;
[0063] (2) Place the above solution in a polytetrafluoroethylene hydrothermal reactor and hydrothermally heat it at 180°C for 10 hours. After natural cooling, wash and centrifuge it three times alternately with water and ethanol.
[0064] (3) The centrifuged product was annealed at 400℃ (heating rate of 5℃ / min) in air atmosphere for 2h to obtain a catalyst supported on carbon spheres by ruthenium dioxide / manganese dioxide. The catalyst was then drop-coated onto carbon paper to obtain an electrode.
[0065] The linear voltammetric curve for testing the oxygen evolution performance of the RuO2 / MnO2@C catalyst prepared in Example 5 is shown below. Figure 13 As shown, by Figure 13 It can be seen that the prepared RuO2 / MnO2@C catalyst has a performance of 10 mA / cm². 2 The overpotential at the current density is 300mV. Example 6
[0066] A method for preparing a bifunctional electrocatalytic material for hydrogen production by acidic water electrolysis includes the following steps:
[0067] (1) Add 0.0519g of ruthenium chloride (RuCl3·xH2O) and 0.3089g of ammonium molybdate ((NH4)6Mo7O) 24 Add 4H₂O and 1.8g of glucose to 20mL of water and stir to dissolve;
[0068] (2) Place the above solution in a polytetrafluoroethylene hydrothermal reactor and hydrothermally heat it at 180°C for 10 hours. After natural cooling, wash and centrifuge it three times alternately with water and ethanol.
[0069] (3) The centrifuged product was annealed at 400℃ (heating rate of 5℃ / min) in air atmosphere for 2h to obtain a catalyst supported on carbon spheres by ruthenium dioxide / molybdenum trioxide. The catalyst was then drop-coated onto carbon paper to obtain an electrode.
[0070] The linear voltammetric curves for testing the oxygen evolution performance of the RuO2 / MoO3@C catalyst prepared in Example 6 are shown below. Figure 14 As shown, by Figure 14 It can be seen that the prepared RuO2 / MoO3@C catalyst did not reach 10 mA / cm. 2 Current density. Example 7
[0071] A method for preparing a bifunctional electrocatalytic material for hydrogen production by acidic water electrolysis includes the following steps:
[0072] (1) Add 0.0519g of ruthenium chloride (RuCl3·xH2O), 0.0595g of cobalt dichloride (CoCl2·6H2O) and 1.8g of glucose to 20mL of water and stir to dissolve;
[0073] (2) Place the above solution in a polytetrafluoroethylene hydrothermal reactor and hydrothermally heat it at 180°C for 10 hours. After natural cooling, wash and centrifuge it three times alternately with water and ethanol.
[0074] (3) The centrifuged product was annealed at 400℃ (heating rate of 5℃ / min) in air atmosphere for 2h to obtain a catalyst supported on carbon spheres by ruthenium dioxide / cobalt oxide. The catalyst was then drop-coated onto carbon paper to obtain an electrode.
[0075] The linear voltammetric curve for testing the oxygen evolution performance of the RuO2 / Co3O4@C catalyst prepared in Example 7 is shown below. Figure 15 As shown, by Figure 15 It can be seen that the prepared RuO2 / Co3O4@C catalyst has a performance of 10 mA / cm². 2 The overpotential at the current density is 270mV.
[0076] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the embodiments of the present invention have been described in detail, those skilled in the art should understand that modifications or equivalent substitutions to the technical solutions of the present invention do not depart from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of protection of the claims of the present invention.
Claims
1. A method for preparing a dual-electrode material for hydrogen production by water electrolysis under acidic conditions, characterized in that, Includes the following steps: 1) Add ruthenium chloride, cerium nitrate, and glucose to water and stir to dissolve; 2) Place the solution in a polytetrafluoroethylene hydrothermal reactor and hydrothermally heat it at 180°C for 10 hours. After cooling, wash and centrifuge it three times alternately with water and ethanol. 3) The centrifuged product was annealed at 400°C in air for 2 hours to obtain a bifunctional electrocatalyst with ruthenium dioxide / cerium dioxide heterojunction supported on carbon spheres. The bifunctional electrocatalyst was then drop-coated onto carbon paper to obtain a dual-electrode material.
2. The method for preparing a dual-electrode material for hydrogen production by water electrolysis under acidic conditions according to claim 1, characterized in that, The molar ratio of ruthenium chloride and cerium nitrate in step 1) is 1:
1.
3. The method for preparing a dual-electrode material for hydrogen production by water electrolysis under acidic conditions according to claim 1, characterized in that, Step 3) The annealing temperature rise rate is 5℃ / min.
4. The method for preparing a dual-electrode material for hydrogen production by water electrolysis under acidic conditions according to claim 1, characterized in that, Step 1) The concentration of glucose is 5 mol / L.
5. A dual-electrode material for hydrogen production by water electrolysis under acidic conditions, obtained by the preparation method according to any one of claims 1-4.