Acidic electrolytic water anode oxygen evolution electrocatalytic material, preparation method and application thereof

Abstract

The application discloses an anodic oxygen evolution electrocatalytic material for acidic electrolytic water and a preparation method and application thereof. The catalytic material comprises a carrier and iridium dioxide loaded on the carrier, the carrier is selected from Nb2O5, Ta2O5, ZrO2 or TiO2, and the carrier is modified by plasma-assisted ball milling and has oxygen-rich defects. The carrier and milling balls are loaded into a ball milling tank, and the carrier is modified by plasma-assisted ball milling; iridium trichloride and the modified carrier are weighed, and a mixed solution is formed by adding water; the mixed solution is subjected to hydrothermal reaction at 180 DEG C-200 DEG C for 12-24 hours, and then washed and centrifuged after cooling; and the centrifuged product is dried to obtain the catalytic material. The carrier is modified by plasma-assisted ball milling, and the oxygen defects are increased; the defects on the carrier can promote the interaction between the support and the carrier, enhance the binding force therebetween, improve the stability of the catalyst, help prevent the aggregation and peeling of the support, and thus prolong the service life of the catalyst.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrogen production materials by electrolysis of water, in particular to an anode oxygen evolution electrocatalytic material for acidic water electrolysis and a preparation method and application thereof. BACKGROUND

[0002] As a clean and efficient secondary energy source, hydrogen energy has become a dominant means for large-scale development, storage, and consumption of renewable energy. Among various hydrogen production technologies, proton exchange membrane (PEM) water electrolysis is considered a promising green hydrogen production technology due to its high efficiency, small space occupation, and high gas separation purity. However, the market share of this technology is relatively small, mainly due to the high cost of PEM membrane electrode key material catalysts.

[0003] In acidic environments, the benchmark catalyst is still the use of noble metals such as Ir and Ru. Although Ru exhibits good catalytic performance in water electrolysis, due to its stability problems, especially in the OER electrocatalytic process, it is easily oxidized to RuO4 and dissolved under high voltage, affecting its practicality. In contrast, Ir is relatively stable in acidic environments and has good oxidation resistance, capable of withstanding high voltage and strong oxidation conditions, thereby reducing the risk of catalyst deactivation. However, the high cost and limited resources of Ir limit its widespread application. Therefore, we are committed to exploring new catalysts to overcome the limitations of Ir, reduce Ir content while maintaining high catalytic activity, reduce costs, and promote the better adaptation of acidic water electrolysis technology to sustainable energy needs.

[0004] Under this background, loading the catalyst on a carrier can reduce the amount of noble metal. Anchoring active substances on carbon-based matrices is a common method. However, typical carbon-based materials are easily oxidized in acidic media and exhibit undesirable electrochemical stability. SUMMARY

[0005] The technical problem to be solved by the present application is to provide an anode oxygen evolution electrocatalytic material for acidic water electrolysis and a preparation method and application thereof, to at least achieve the purpose of improving the stability of the catalyst.

[0006] To solve the above technical problems, according to one aspect of the present application, an anode oxygen evolution electrocatalytic material for acidic water electrolysis is provided, which comprises a carrier and iridium dioxide loaded on the carrier, the carrier is selected from Nb2O5, Ta2O5, ZrO2 or TiO2, and the carrier has oxygen-rich defects after being modified by plasma-assisted ball milling.

[0007] According to another aspect of the present application, a preparation method of the above-mentioned anode oxygen evolution electrocatalytic material for acidic water electrolysis is provided, comprising:

[0008] Step one, the carrier and the grinding ball are loaded into the ball mill tank, and the carrier is modified by plasma assisted ball milling;

[0009] Step two, the modified carrier and iridium trichloride are weighed, and water is added to form a mixed solution;

[0010] Step three, the mixed solution is hydrothermally reacted at 180-200°C for 12-24 hours, and then washed and centrifuged after cooling;

[0011] Step four, the centrifuged product is dried to obtain the catalytic material.

[0012] Further, in step one, the mass ratio of the carrier to the grinding ball is 1: (50-100).

[0013] Further, in step one, the plasma voltage is 10-11 kV.

[0014] Further, in step one, the plasma assisted ball milling time is 2-6 hours.

[0015] Further, in step two, the mass ratio of the carrier to iridium trichloride is 1: (0.5-1.5).

[0016] Further, in step three, the centrifuged product is washed with water and ethanol alternately for 3 times after cooling.

[0017] Further, in step four, the centrifuged product is dried at 60-80°C.

[0018] According to another aspect of the present application, the acid electrolyzed water anode oxygen evolution electrocatalytic material is provided for use in anodic oxygen evolution reaction in an acidic environment.

[0019] According to still another aspect of the present application, an anode material is provided, comprising the acid electrolyzed water anode oxygen evolution electrocatalytic material as described above, which is drop-coated on carbon paper.

[0020] By constructing a metal oxide support interaction (SOSI), the metal cations of the oxide catalyst are closely combined with the oxide support to form a binary oxide nanostructure. At the same time, the defects on the oxide support can promote the interaction between the supported material and the support, enhance their binding force, improve the stability of the catalyst, help to prevent the aggregation and peeling of the supported material, and prolong the service life of the catalyst. By adjusting the geometric and electronic properties of the metal, SOSI can effectively control the catalytic activity and selectivity. The repositioning interface of the electrons on the support will adjust the electronic properties of the active sites, and unique structural deformation and different atomic coordination environments will occur at the interface, thereby changing the adsorption behavior of the reaction intermediates and the energy barrier of the reaction sub-steps.

[0021] Based on this, the overall concept of the present application is to modify the support by plasma-assisted ball milling to increase oxygen defects, and then load iridium dioxide on the defect-rich niobium pentoxide, or defect-rich tantalum pentoxide, or defect-rich zirconium dioxide, or defect-rich titanium dioxide by hydrothermal method to form a metal oxide support interaction to prepare an electrocatalyst for anodic oxygen evolution in an acidic environment.

[0022] Compared with the prior art, the present application has the beneficial technical effects that:

[0023] 1. By plasma-assisted ball milling technology, supports (Nb2O 5-x , Ta2O 5-x , ZrO 2-x , TiO 2-x ) with different oxygen vacancy structures can be synthesized.

[0024] 2. The catalytic material prepared by the present application has excellent acid electrolytic water catalytic anodic oxygen evolution performance, the defects on the support can promote the interaction (SOSI) between the support and the supported material, enhance the binding force between them, improve the stability of the catalyst, help to prevent the aggregation and peeling of the supported material, and thus prolong the service life of the catalyst.

[0025] 3. The electronic structure of IrO2 is successfully adjusted by the present application, and the structure is stabilized by enhanced oxide support interaction, further improving the stability of the electrocatalyst.

[0026] 4. Specifically, the IrO2 / Nb2O 5-x catalyst achieves a current density overpotential of only 225 mV and 277 mV at 10 mA / cm 2 and 50 mA / cm 2 in 0.5 M H2SO4, and has a durability of more than 200 hours. When used in a PEM electrolytic cell, it can be stably operated at a current density of 500 mA / cm 2 for 200 hours, and the Ir content is only 0.2852 mg, proving its practical application prospects.

[0027] 5. The preparation process of the present application is simple, the electrode components and types are adjustable, and it has good application prospects. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 is the scanning electron microscope picture of the IrO2 / Nb2O 5-x catalyst obtained in Example 1.

[0029] Figure 2 is the scanning electron microscope picture of the IrO2 / Nb2O 5-xX-ray diffraction pattern of the catalyst.

[0030] Figure 3 IrO2 / Nb2O5 catalyst obtained from Example 1 5-x Electron paramagnetic resonance spectrum of the catalyst.

[0031] Figure 4 IrO2 / Nb2O5 catalyst obtained from Example 1 5-x Linear voltammetry plot of the catalyst for oxygen evolution performance test (0.5 mol / L H2SO4 solution).

[0032] Figure 5 IrO2 / Nb2O5 catalyst obtained from Example 1 5-x Stability plot of the catalyst for oxygen evolution performance test.

[0033] Figure 6 IrO2 / Nb2O5 catalyst obtained from Example 1 5-x Linear voltammetry plot of the catalyst for PEM cell test.

[0034] Figure 7 IrO2 / Nb2O5 catalyst obtained from Example 1 5-x Stability plot of the catalyst for PEM cell test.

[0035] Figure 8 IrO2 / Ta2O5 catalyst obtained from Example 2 5-x Linear voltammetry plot of the catalyst for oxygen evolution performance test.

[0036] Figure 9 IrO2 / Ta2O5 catalyst obtained from Example 2 5-x Stability plot of the catalyst for oxygen evolution performance test.

[0037] Figure 10 IrO2 / ZrO2 catalyst obtained from Example 3 2-x Linear voltammetry plot of the catalyst for oxygen evolution performance test.

[0038] Figure 11 IrO2 / ZrO2 catalyst obtained from Example 3 2-x Stability plot of the catalyst for oxygen evolution performance test.

[0039] Figure 12 IrO2 / TiO2 catalyst obtained from Example 4 2-x Stability plot of the catalyst for oxygen evolution performance test.

[0040] Figure 13 IrO2 / TiO2 catalyst obtained from Example 4 2-x Stability plot of the catalyst for oxygen evolution performance test.

[0041] Figure 14 Linear voltammogram of the IrO2 / Nb2O5catalyst obtained in Example 5. 5-x Linear voltammogram of the IrO2 / Nb2O5catalyst obtained in Example 5.

[0042] Figure 15 Linear voltammogram of the IrO2 / Nb2O5catalyst obtained in Example 5. 5-x Linear voltammogram of the IrO2 / Nb2O5catalyst obtained in Example 5.

[0043] Figure 16 Linear voltammogram of the IrO2 / Nb2O5catalyst obtained in Example 5.

[0044] Figure 17 Linear voltammogram of the IrO2 / Nb2O5catalyst obtained in Example 5.

[0045] Figure 18 Linear voltammogram of the IrO2 / Nb2O5catalyst obtained in Example 5. DETAILED DESCRIPTION

[0046] The technical solutions claimed in the present application are further illustrated below by some examples. However, the examples and comparative examples are used to explain the embodiments of the present application and do not exceed the scope of the subject matter of the present application, and the protection scope of the present application is not limited by the examples. Unless otherwise specified, the materials and reagents used in the present application can be obtained from commercial products in the art.

[0047] Example 1 (IrO2 / Nb2O5catalyst) 5-x

[0048] 2g of niobium pentoxide and 100g of grinding balls were loaded into a ball mill tank, a vacuum pump and a vacuum air valve were connected by a hose, the ball mill tank was evacuated, and then oxygen was filled. The gas needs to be washed for more than 2 times to improve the purity of the gas in the tank.

[0049] The ball mill tank was installed and fixed on the rack of the ball mill, the positive line of the high-voltage power supply was connected with the metal electrode, and the ground wire was connected with the bolt of the front cover plate. Turn on the ball mill control power supply, and the ball mill starts to vibrate. After the ball mill vibrates stably, turn on the plasma power supply to realize plasma-assisted ball milling, the plasma voltage is 11kV, and the plasma-assisted ball milling time is 2h.

[0050] The niobium pentoxide powder after plasma-assisted ball milling was collected, 0.015g of niobium pentoxide and 0.015g of iridium trichloride were weighed and added into 20ml of deionized water, stirred for 20min to obtain a mixed solution.

[0051] The above mixed solution was placed in a polytetrafluoroethylene hydrothermal kettle at 180℃ for 12h of hydrothermal treatment, and after cooling, it was washed and centrifuged with water and ethanol alternately for 3 times.​

[0052] The centrifuged product was dried at 80 °C to obtain iridium dioxide / niobium pentoxide (IrO2 / Nb2O3). 5-x The catalyst is drop-coated onto carbon paper to obtain the anode material.

[0053] The IrO2 / Nb2O prepared in Example 1 5-x Scanning electron microscope images of the catalyst are as follows: Figure 1 As shown, Figure 1 It can be seen that the prepared IrO2 / Nb2O 5-x The catalyst morphology consists of small particles uniformly loaded on a niobium pentoxide support. The support provides a large surface area for the metal loading, which can effectively improve the utilization rate of the precious metal, thereby enhancing the electrocatalytic activity.

[0054] The IrO2 / Nb2O prepared in Example 1 5-x The X-ray diffraction pattern of the catalyst is as follows Figure 2 As shown, by Figure 2 It can be seen that IrO2 / Nb2O 5-x The characteristic peaks of the electrocatalyst correspond to the characteristic peaks of IrO2 and Nb2O5.

[0055] The IrO2 / Nb2O prepared in Example 1 5-x The electron paramagnetic resonance image of the catalyst is as follows Figure 3 As shown, by Figure 3 It can be seen that IrO2 / Nb2O 5-x The catalyst is rich in oxygen vacancies.

[0056] The IrO2 / Nb2O prepared in Example 1 5-x The linear voltammetric curves for testing the oxygen evolution performance of the catalyst are shown below. Figure 4 As shown, by Figure 4 It can be seen that the prepared IrO2 / Nb2O 5-x The catalyst only requires 225mV to reach 10mA / cm 2 Current density.

[0057] The IrO2 / Nb2O prepared in Example 1 5-x Catalyst at 10 mA / cm 2 and 50mA / cm 2 The stability test curve is as follows Figure 5 As shown, by Figure 5 It can be seen that the prepared IrO2 / Nb2O 5-x The catalyst can stably drive the oxygen evolution reaction in an acidic environment for a long period of time.

[0058] To determine IrO2 / Nb2O 5-xThe industrial application potential of Nafion 117 membrane and IrO2 / Nb2O in acidic electrolytes. 5-x Using commercially available Pt / C as the cathode, a 1*1 cm² anode was constructed. 2 The proton exchange membrane electrolysis (PEMWE) unit has a catalyst mass loading of 1 mg / cm³. 2 The linear voltammetric curve in the PEM electrolytic cell is as follows: Figure 6 As shown, by Figure 6 It can be seen that IrO2 / Nb2O 5-x ||Pt / C reaches 500 mA / cm 2 The required battery voltage is 1.79 V.

[0059] The IrO2 / Nb2O prepared in Example 1 5-x ||Pt / C catalyst in PEM electrolyzer 500mA / cm 2 The stability test curve is as follows Figure 7 As shown, by Figure 7 It is evident that significant stability was observed within 200 hours, with no obvious degradation, making it a promising acidic OER electrocatalyst for practical PEMWE applications.

[0060] Example 2 (IrO2 / Ta2O) 5-x )

[0061] Place 2g of tantalum pentoxide and 100g of grinding balls into a grinding jar. Connect a vacuum pump to a vacuum valve via a hose to evacuate the grinding jar, then fill it with oxygen. Repeat the gas purging process at least twice to improve the purity of the gas inside the jar.

[0062] Install and secure the grinding jar onto the ball mill frame. Connect the positive wire of the high-voltage power supply to the metal electrode, and connect the ground wire to the bolt on the front cover plate. Turn on the ball mill control power, and the ball mill will begin to vibrate. After the ball mill vibration stabilizes, turn on the plasma power supply to achieve plasma-assisted ball milling. The plasma voltage is 11kV, and the plasma-assisted ball milling time is 2 hours.

[0063] Collect tantalum pentoxide after plasma-assisted ball milling, weigh 0.015 g of tantalum pentoxide and 0.015 g of iridium trichloride, add them to 20 ml of deionized water, stir for 20 min, and obtain a mixed solution.

[0064] The above mixed solution was placed in a polytetrafluoroethylene hydrothermal reactor and hydrothermated at 180°C for 12 hours. After cooling, it was washed and centrifuged three times alternately with water and ethanol.

[0065] The centrifuged product was dried at 80 °C to obtain iridium dioxide / tantalum pentoxide (IrO2 / Ta2O). 5-x The catalyst is drop-coated onto carbon paper to obtain the anode material.

[0066] The IrO2 / Ta2O prepared in Example 2 5-x The linear voltammetric curves for testing the oxygen evolution performance of the catalyst are shown below. Figure 8 As shown, by Figure 8 It can be seen that the prepared IrO2 / Ta2O 5-x Catalyst at 10 mA / cm 2 The overpotential at the current density is 245mV.

[0067] The IrO2 / Ta2O prepared in Example 2 5-x Catalyst at 10 mA / cm 2 The stability test curve is as follows Figure 9 As shown, by Figure 9 It can be seen that the prepared IrO2 / Ta2O 5-x Catalyst at 10 mA / cm 2 It can maintain stability for 100 hours at the current density.

[0068] Example 3 (IrO2 / ZrO) 2-x )

[0069] Place 2g of zirconium dioxide and 100g of grinding balls into the grinding jar. Connect the vacuum pump and vacuum valve through a hose to evacuate the grinding jar, then fill it with oxygen. Repeat the gas purging process at least twice to improve the purity of the gas inside the jar.

[0070] Install and secure the grinding jar onto the ball mill frame. Connect the positive wire of the high-voltage power supply to the metal electrode, and connect the ground wire to the bolt on the front cover plate. Turn on the ball mill control power, and the ball mill will begin to vibrate. After the ball mill vibration stabilizes, turn on the plasma power supply to achieve plasma-assisted ball milling. The plasma voltage is 11kV, and the plasma-assisted ball milling time is 2 hours.

[0071] Collect the zirconium dioxide after plasma-assisted ball milling, weigh 0.015 g of zirconium dioxide and 0.015 g of iridium trichloride, add them to 20 ml of deionized water, stir for 20 min, and obtain a mixed solution.

[0072] The above mixed solution was placed in a polytetrafluoroethylene hydrothermal reactor and hydrothermated at 180°C for 12 hours. After cooling, it was washed and centrifuged three times alternately with water and ethanol.

[0073] The centrifuged product was dried at 80 °C to obtain iridium dioxide / zirconium dioxide (IrO2 / ZrO2). 2-x The catalyst is drop-coated onto carbon paper to obtain the anode material.

[0074] The IrO2 / ZrO prepared in Example 3 2-x The linear voltammetric curves for testing the oxygen evolution performance of the catalyst are shown below. Figure 10 As shown, byFigure 10 It can be seen that the prepared IrO2 / ZrO 2-x Catalyst at 10 mA / cm 2 The overpotential at the current density is 248mV.

[0075] The IrO2 / ZrO prepared in Example 3 2-x Catalyst at 10 mA / cm 2 The stability test curve is as follows Figure 11 As shown, by Figure 11 It can be seen that the prepared IrO2 / ZrO 2-x Catalyst at 10 mA / cm 2 It can maintain stability for 100 hours at the current density.

[0076] Example 4 (IrO2 / TiO) 2-x )

[0077] Place 2g of titanium dioxide and 100g of grinding balls into the grinding jar. Connect the vacuum pump and vacuum valve through a hose to evacuate the grinding jar, then fill it with oxygen. Repeat the gas purging process at least twice to improve the purity of the gas inside the jar.

[0078] Install and secure the grinding jar onto the ball mill frame. Connect the positive wire of the high-voltage power supply to the metal electrode, and connect the ground wire to the bolt on the front cover plate. Turn on the ball mill control power, and the ball mill will begin to vibrate. After the ball mill vibration stabilizes, turn on the plasma power supply to achieve plasma-assisted ball milling. The plasma voltage is 11kV, and the plasma-assisted ball milling time is 2 hours.

[0079] Collect the titanium dioxide after plasma-assisted ball milling, weigh 0.015 g of titanium dioxide and 0.015 g of iridium trichloride, add them to 20 ml of deionized water, stir for 20 min, and obtain a mixed solution.

[0080] The above solution was placed in a polytetrafluoroethylene hydrothermal reactor and hydrothermally heated at 180°C for 12 hours. After cooling, it was washed and centrifuged three times alternately with water and ethanol.

[0081] The centrifuged product was dried at 80 °C to obtain iridium dioxide / titanium dioxide (IrO2 / TiO2). 2-x The catalyst is drop-coated onto carbon paper to obtain the anode material.

[0082] The IrO2 / TiO2 prepared in Example 4 2-x The linear voltammetric curves for testing the oxygen evolution performance of the catalyst are shown below. Figure 12 As shown, by Figure 12 It can be seen that the prepared IrO2 / TiO 2-x Catalyst at 10 mA / cm 2 The overpotential at the current density is 241mV.

[0083] The IrO2 / TiO2 prepared in Example 4 2-x Catalyst at 10 mA / cm 2 The stability test curve is as follows Figure 13 As shown, by Figure 13 It can be seen that the prepared IrO2 / TiO 2-x Catalyst at 10 mA / cm 2 It can maintain stability for 100 hours at the current density.

[0084] Example 5 (IrO2 / Nb2O) 5-x )

[0085] 2g of niobium pentoxide and 200g of grinding balls are placed into a grinding jar. A vacuum pump is connected to a vacuum valve via a hose to evacuate the grinding jar, followed by the introduction of oxygen. The gas purging process needs to be repeated at least twice to improve the purity of the gas inside the jar.

[0086] Install and secure the grinding jar onto the ball mill frame. Connect the positive wire of the high-voltage power supply to the metal electrode, and connect the ground wire to the bolt on the front cover plate. Turn on the ball mill control power, and the ball mill will begin to vibrate. After the ball mill vibration stabilizes, turn on the plasma power supply to achieve plasma-assisted ball milling. The plasma voltage is 10kV, and the plasma-assisted ball milling time is 6 hours.

[0087] Collect niobium pentoxide powder after plasma-assisted ball milling, weigh 0.030 g of niobium pentoxide and 0.015 g of iridium trichloride, add them to 20 ml of deionized water, stir for 20 min to obtain a mixed solution.

[0088] The above mixed solution was placed in a polytetrafluoroethylene hydrothermal reactor and hydrothermally heated at 200°C for 18 hours. After cooling, it was washed and centrifuged three times alternately with water and ethanol.

[0089] The centrifuged product was dried at 60 °C to obtain iridium dioxide / niobium pentoxide (IrO2 / Nb2O3). 5-x The catalyst is drop-coated onto carbon paper to obtain the anode material.

[0090] The IrO2 / Nb2O prepared in Example 5 5-x The linear voltammetric curves for testing the oxygen evolution performance of the catalyst are shown below. Figure 14 As shown, by Figure 14 It can be seen that the prepared IrO2 / Nb2O 5-x Catalyst at 10 mA / cm 2 The overpotential at the current density is 250mV.

[0091] Example 6 (IrO2 / Nb2O) 5-x )

[0092] 2g of niobium pentoxide and 150g of grinding balls are placed into the grinding jar. A vacuum pump is connected to the vacuum valve via a hose to evacuate the grinding jar, followed by filling it with oxygen. The gas purging process needs to be repeated at least twice to improve the purity of the gas inside the jar.

[0093] Install and secure the grinding jar onto the ball mill frame. Connect the positive wire of the high-voltage power supply to the metal electrode, and connect the ground wire to the bolt on the front cover plate. Turn on the ball mill control power, and the ball mill will begin to vibrate. After the ball mill vibration stabilizes, turn on the plasma power supply to achieve plasma-assisted ball milling. The plasma voltage is 11kV, and the plasma-assisted ball milling time is 4 hours.

[0094] Collect niobium pentoxide powder after plasma-assisted ball milling, weigh 0.010 g of niobium pentoxide and 0.015 g of iridium trichloride, add them to 20 ml of deionized water, stir for 20 min, and obtain a mixed solution.

[0095] The above mixed solution was placed in a polytetrafluoroethylene hydrothermal reactor and hydrothermally heated at 190°C for 24 hours. After cooling, it was washed and centrifuged three times alternately with water and ethanol.

[0096] The centrifuged product was dried at 70 °C to obtain iridium dioxide / niobium pentoxide (IrO2 / Nb2O3). 5-x The catalyst is drop-coated onto carbon paper to obtain the anode material.

[0097] The IrO2 / Nb2O prepared in Example 6 5-x The linear voltammetric curves for testing the oxygen evolution performance of the catalyst are shown below. Figure 15 As shown, by Figure 15 It can be seen that the prepared IrO2 / Nb2O 5-x Catalyst at 10 mA / cm 2 The overpotential at the current density is 229mV.

[0098] Comparative Example 1 (Commercial IrO2 catalyst)

[0099] Weigh 0.005 g of commercial iridium dioxide and add it to 150 μL of ethanol, 100 μL of water and 11 μL of Nafion. Sonicate for 40 min. Drop the solution onto carbon paper to obtain the anode material.

[0100] The linear voltammetric curves for oxygen evolution performance testing of the commercial IrO2 catalyst provided in Comparative Example 1 are shown below. Figure 16 As shown, by Figure 16 It can be seen that the prepared IrO2 catalyst has a performance of 10 mA / cm². 2 The overpotential at the current density was 399 mV, indicating that the performance of commercial IrO2 catalysts is far inferior to that of catalysts prepared by plasma-assisted ball milling.

[0101] Comparative Example 2 (Unmodified IrO2 / Nb2O5 catalyst)

[0102] Weigh 0.015g of unmodified niobium pentoxide and 0.015g of iridium trichloride and add them to 20ml of deionized water. Stir for 20min to obtain a mixed solution.

[0103] The above mixed solution was placed in a polytetrafluoroethylene hydrothermal reactor and hydrothermated at 180°C for 12 hours. After cooling, it was washed and centrifuged three times alternately with water and ethanol.

[0104] The centrifuged product was dried at 80°C to obtain an iridium dioxide / niobium pentoxide (IrO2 / Nb2O5) catalyst, which was then drop-coated onto carbon paper to obtain the anode material.

[0105] The linear voltammetric curves for oxygen evolution performance testing of the IrO2 / Nb2O5 catalyst prepared in Comparative Example 2 are shown below. Figure 17 As shown, by Figure 17 It can be seen that the prepared IrO2 / Nb2O5 catalyst at 10 mA / cm 2 The overpotential at the current density is 259mV.

[0106] The IrO2 / Nb2O5 catalyst prepared in Comparative Example 2 was tested at 10 mA / cm². 2 The stability test curve is as follows Figure 18 As shown, by Figure 18 It can be seen that the prepared IrO2 / Nb2O5 catalyst at 10 mA / cm 2 It only maintains stability for 15 hours at the current density.

[0107] The above experiments demonstrate that the presence of oxygen vacancies in the support enhances the interaction between the support and the loaded material, forming strong metal oxide support interaction (SOSI), thereby improving the catalyst's stability. The SOSI effect induces charge transfer from Nb₂O₃... 5-x The IrO2 is transferred to IrO2, thereby inhibiting the formation of Ir peroxides. Furthermore, IrO2 / Nb2O is used in the PEM electrolyzer. 5-x As an anode, it exhibits excellent overall water electrolysis activity and stability under an ultra-low Ir loading of 0.2852 mg.

Claims

1. A method for preparing an acidic water electrolysis anode oxygen evolution electrocatalyst material, characterized in that, include: Step 1: Load the carrier and grinding balls into the ball mill jar, evacuate the ball mill jar and fill it with oxygen, and use plasma-assisted ball milling to modify the carrier to obtain a modified carrier with oxygen-rich defects; the carrier is selected from Nb2O5, Ta2O5, ZrO2 or TiO2. Step 2: Weigh iridium trichloride and the modified carrier obtained in Step 1, and add water to form a mixed solution; Step 3: The mixed solution is subjected to hydrothermal reaction at 180℃-200℃ for 12-24 hours, and then washed and centrifuged after cooling. Step four: After centrifugation and drying, the catalytic material is obtained.

2. The preparation method of the acidic water electrolysis anode oxygen evolution electrocatalytic material according to claim 1, characterized in that: In step one, the mass ratio of the carrier to the grinding ball is 1:(50-100).

3. The preparation method of the acidic water electrolysis anode oxygen evolution electrocatalytic material according to claim 2, characterized in that: In step one, the plasma voltage is 10kV-11kV.

4. The preparation method of the acidic water electrolysis anode oxygen evolution electrocatalytic material according to claim 3, characterized in that: In step one, the plasma-assisted ball milling time should be 2 to 6 hours.

5. The method for preparing the acidic water electrolysis anode oxygen evolution electrocatalytic material according to claim 1 or 4, characterized in that: In step two, the mass ratio of the carrier to iridium trichloride is 1:(0.5-1.5).

6. The method for preparing the acidic water electrolysis anode oxygen evolution electrocatalytic material according to claim 5, characterized in that: In step three, after cooling, the product is washed and centrifuged three times alternately with water and ethanol.

7. The preparation method of the acidic water electrolysis anode oxygen evolution electrocatalytic material according to claim 6, characterized in that: In step four, the centrifuged product is dried at 60°C to 80°C.

8. The acidic water electrolysis anode oxygen evolution electrocatalyst material obtained by the preparation method of the acidic water electrolysis anode oxygen evolution electrocatalyst material according to any one of claims 1-7.

9. The application of the acidic water electrolysis anodic oxygen evolution electrocatalyst material as described in claim 8 for carrying out the anodic oxygen evolution reaction in an acidic environment.

10. An anode material, characterized in that: The method includes the acidic water electrolysis anode oxygen evolution electrocatalyst material as described in claim 8, wherein the acidic water electrolysis anode oxygen evolution electrocatalyst material is drop-coated onto carbon paper.

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