Preparation method and application of zirconium dioxide supported iridium oxide nanocluster oxygen evolution electrocatalyst

Abstract

The application discloses a preparation method and application of a zirconium dioxide loaded iridium oxide nanocluster oxygen evolution electrocatalyst. A mixed solution of zirconium salt, amide solvent and organic acid is prepared, and the mixed solution is kept at 120 DEG C for 24 hours; after cooling, the white product is separated, washed and dried. Then, the product and iridium salt are dispersed in a mixed solution of tetrahydrofuran and water, and sodium nitrate and potassium nitrate aqueous solution are added under stirring; after stirring, rotary evaporation is carried out at 60 DEG C, and the greenish powder obtained after drying is vacuum dried at 60 DEG C for 12 hours; the greenish powder is kept in a muffle furnace at 450 DEG C for 30 minutes, and then cooled in air; the greenish powder is washed with deionized water and anhydrous ethanol for multiple times, and finally vacuum dried at 60 DEG C for 12 hours. The zirconium dioxide loaded iridium oxide material based on oxygen overflow stable tetragonal zirconia can be specially applied to an electrocatalyst for an oxygen evolution reaction in an acidic electrolyte, has excellent oxygen evolution reaction activity, follows a lattice oxygen mechanism in the reaction process, and can realize an oxygen overflow effect from tetragonal zirconia to iridium oxide nanoclusters to stabilize the catalyst.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalyst technology, and relates to a method for preparing an oxygen evolution electrocatalyst based on tetragonal zirconia supported on iridium oxide nanoclusters with oxygen overflow stabilization. It also relates to its application in the preparation of an electrocatalyst for oxygen evolution reaction in acidic electrolytes, as well as its application in proton exchange membrane water electrolysis oxygen absorption electrode. It also has potential application value in other fields such as energy development and environmental protection. Background Technology

[0002] Proton exchange membrane (PEM) water electrolysis plays a crucial role in converting renewable energy into green hydrogen due to its high current density and fast response. However, commercial anode electrocatalysts based on iridium-based materials have significantly hampered the further application of this technology due to the low natural abundance and high cost of iridium. Therefore, reducing the iridium loading is essential for the large-scale implementation of PEM water electrolysis.

[0003] Previous studies have shown that adjusting the oxygen evolution reaction pathway can effectively mediate the trade-off between reactivity and stability; the lattice oxygen oxidation mechanism can directly form *OO. 2- The intermediate *OOH, which is the intermediate in the oxygen evolution oxidation mechanism, is formed without forming an adsorbed oxygen oxidation intermediate, thus breaking the linear relationship between the oxygen-containing intermediate and the oxidation overpotential. However, the participation of lattice oxygen can also generate soluble high-valence metal oxides, leading to poor collapse stability of the catalyst structure. Therefore, most currently developed oxygen evolution electrocatalysts are tuned to follow the adsorbed oxygen oxidation mechanism to meet the requirements of PEM electrolyzers, which inevitably sacrifices activity. The oxygen overflow mechanism, on the other hand, allows the oxygen intermediate adsorbed on the inert support to overflow to the iridium site, thereby stabilizing the catalyst structure and synergistically enhancing both activity and stability. Summary of the Invention

[0004] This invention addresses the aforementioned problems by providing a method for preparing and applying an oxygen evolution electrocatalyst based on tetragonal zirconium dioxide supported on iridium oxide nanoclusters with oxygen overflow stability. This provides a novel design approach for noble metal-based supported materials, enabling economical, efficient, and sustainable development of proton exchange membrane water electrolysis. The catalyst preparation method is simple, low-cost, and allows for large-scale synthesis, exhibiting high efficiency and stable oxygen evolution, and possesses the potential for large-scale industrial applications.

[0005] To achieve the above objectives, the specific technical solution adopted by the present invention is as follows:

[0006] In a first aspect, the present invention provides a method for preparing an oxygen evolution electrocatalyst supported on zirconium dioxide and iridium oxide nanoclusters, comprising the following steps:

[0007] A. Preparation of Zirconia Support

[0008] A mixed solution of zirconium salt, amide solvent and organic acid was prepared and kept at 120°C for 24 hours. Then it was cooled to room temperature. After centrifugation, the white product was washed multiple times with N,N-dimethylformamide and anhydrous ethanol and dried in a vacuum oven at 60°C for 12 hours to obtain a white powder.

[0009] B. Iridium oxide nanoclusters supported

[0010] After the iridium salt was dispersed in a mixed solvent of tetrahydrofuran and water, the white powder was added. After stirring for 24 hours, a mixed solution of sodium nitrate and potassium nitrate was added and stirred for 30-40 minutes. The solvent was removed by rotary evaporation at 60°C, and the product was dried in a vacuum oven at 60°C for 12 hours. The resulting light green powder was placed in a muffle furnace at 450°C and kept warm for 30-40 minutes. Then it was directly removed and cooled in air. The product was washed multiple times with deionized water and anhydrous ethanol, and finally dried in a vacuum oven at 60°C for 12 hours to obtain the electrocatalyst.

[0011] Preferably, the preferred process conditions for each of the above steps are as follows:

[0012] (1) Step A

[0013] The zirconium salt is selected from any one or more combinations of zirconium nitrate, zirconium tetrachloride, and zirconium oxynitrate; the amide is selected from any one or more combinations of N,N'-dimethylformamide, N,N'-dimethylacetamide, and N,N'-dimethylacrylamide; and the organic acid is selected from any one or more combinations of benzoic acid, formic acid, and terephthalic acid.

[0014] Furthermore, in a specific embodiment of the present invention, the organic acid is selected from a mixture of terephthalic acid and benzoic acid, and the molar ratio of terephthalic acid to benzoic acid is 0.09 to 0.1:1; the mass-volume ratio between zirconium salt and amide is 13 to 13.5 g / L, and the molar ratio between zirconium salt and terephthalic acid is 1 to 1.1:1.

[0015] (2) Step B

[0016] The volume ratio of tetrahydrofuran to water is 1:1; the concentration of iridium salt in the mixed solvent is 1 g / L; the mass ratio of white powder to iridium salt is 0.4–1.1:1; the mass ratio of sodium nitrate to potassium nitrate is 6:4; and the mass ratio of the mixture of iridium salt and sodium nitrate to potassium nitrate is 3:100.

[0017] In a second aspect, the present invention provides a zirconium dioxide-supported iridium oxide nanoclusters oxygen evolution electrocatalyst (IrO). x / t-ZrO2), which is prepared by the above method.

[0018] Transmission electron microscopy analysis revealed that the electrocatalyst consisted of porous nanostructured nanoparticles with a size of approximately 1.33 nm and an iridium loading of 0.1 mg / cm³. 2 Since the atomic number Z of iridium is greater than that of zirconium, the distribution of iridium can be directly determined by comparing Z. It can be seen that iridium oxide is a nanocluster loaded on tetragonal zirconium dioxide.

[0019] X-ray diffraction analysis results show that the characteristic diffraction peaks at angles of 30.2°, 50.2°, and 60.2° correspond to the (101), (112), and (211) crystal planes of tetragonal zirconium dioxide crystals. After loading iridium oxide, the peak intensity near 35° is enhanced, which corresponds to the (101) crystal plane of iridium dioxide crystals.

[0020] Applying different voltages to the material revealed that the Ir-O bonds shortened, indicating that the iridium coordination structure rearranged via a lattice oxygen mechanism. During the oxygen evolution reaction, the coordination number of Zr-O also decreased, indicating an oxygen overflow process. However, the oxygen vacancies were quickly filled, thus preventing structural collapse that could have been caused by oxygen vacancies.

[0021] The material of this invention can be applied to the electrocatalytic oxygen evolution reaction under acidic electrolyte conditions and to proton exchange membrane electrolyzers under pure water conditions.

[0022] Electrochemical performance testing: using IrO coated with x A glassy carbon electrode was used as the working electrode for the / t-ZrO2 catalyst, with a silver-silver chloride electrode as the reference electrode and a platinum mesh electrode as the counter electrode. The electrolyte solution was 0.5 M HClO4. Electrochemical tests were conducted at room temperature and pressure. The results showed that the mass activity of the catalyst at 1.55 V and 1.60 V was 609.1 A g. Ir -1 and 1457.4Ag Ir -1 And far exceeding the commercial iridium black material in Comparative Example 3 (46.7 Ag, respectively). Ir -1 and 110.7Ag Ir -1 This indicates that metallic iridium in IrO x / t-ZrO2 has high utilization efficiency.

[0023] It was prepared as an anode electrode material for a proton exchange membrane electrolyzer. Full-cell tests were conducted in an acidic water electrolyzer using a proton exchange membrane to simulate an industrial water electrolysis environment. The results showed that the Ir loading was only 0.1 mg·cm³. -2 The assembled proton exchange membrane electrolyzer can achieve 3.1 A·cm⁻¹ at a voltage of 1.9 V. -2The current density, and at 1 A·cm -2 It can operate stably for 1600 hours at a current density with a decay rate of only 6.25 μV·h. -1 .

[0024] Therefore, in a third aspect, the present invention provides the application of the above-mentioned zirconium dioxide-supported iridium oxide nanoclusters oxygen evolution electrocatalyst in the preparation of an acidic electrolytic oxygen evolution electrode.

[0025] In a fourth aspect, the present invention provides an acidic electrochemical oxygen evolution anode electrode, comprising an anode support and a catalyst material supported thereon, wherein the catalyst material is a zirconium dioxide-supported iridium oxide nanoclusters oxygen evolution electrocatalyst prepared by any of the methods described above.

[0026] In a fifth aspect, the present invention provides a method for electrolyzing water, using the above-described electrolytic oxygen anode electrode as the anode.

[0027] Preferably, the electrolyte is a 0.5M HClO4 solution or deionized water.

[0028] Compared with the prior art, the beneficial effects of the present invention are:

[0029] (1) To date, most developed acidic oxygen evolution electrocatalysts following the lattice oxygen pathway have failed to maintain the harsh environment under actual proton exchange membrane water electrolysis conditions. This invention provides new insights into the lattice oxygen pathway for oxygen spillage stabilization for the first time and successfully constructs a novel low-iridium anode electrocatalyst that can operate continuously in a proton exchange membrane electrolyzer.

[0030] (2) IrO prepared using the present invention x / t-ZrO2 electrocatalyst as anode material (0.1mg) Ir ·cm -2 The assembled PEM electrolyzer achieved 3.1 A·cm⁻¹ at a cell voltage of 1.90 V. -2 The current density is 1.0 A·cm. -2 After running for 1600 hours, no significant degradation was observed (6.25 μV / h). The results indicate that IrO... x / t-ZrO2 reaches 3.1 A·cm -2 The voltage and noble metal loading required for the current density are superior to those of state-of-the-art PEM anode electrocatalysts.

[0031] (3) The catalyst material prepared by the present invention is simple and low in cost, can be synthesized in large quantities, and has the potential for large-scale industrial application due to its high efficiency and stable oxygen evolution. Attached Figure Description

[0032] Figure 1IrO prepared in Example 1 x X-ray diffraction patterns of t-ZrO2 and the t-ZrO2 material prepared in Example 2.

[0033] Figure 2 IrO prepared in Example 1 x Transmission electron microscopy image of / t-ZrO2 material.

[0034] Figure 3 IrO prepared in Example 1 x Aberration-corrected high-angle annular dark-field scanning transmission microscope image of / t-ZrO2 material.

[0035] Figure 4 IrO prepared for Example 1, Comparative Example 1, and Comparative Example 2 x The in-situ X-ray absorption fine structure near-edge spectrum and magnified image of the iridium L3 edge of / t-ZrO2 material, along with its R-space spectrum, are shown. Comparative Example 1 shows the iridium L3 edge of / t-ZrO2 after applying a voltage of 1.5V. x / t-ZrO2 material, Comparative Example 2 is IrO after applying a voltage of 1.7V. x / t-ZrO2 material.

[0036] Figure 5 IrO prepared for Example 1, Comparative Example 1, and Comparative Example 2 x The in-situ X-ray absorption fine structure near-edge spectrum and magnified image of the zirconium K-edge of / t-ZrO2 material, and its R-space spectrum, are shown. Comparative Example 1 shows the IrO2 material after applying a voltage of 1.5V. x / t-ZrO2 material, Comparative Example 2 is IrO after applying a voltage of 1.7V. x / t-ZrO2 material.

[0037] Figure 6 The figures show the linear sweep voltammetry curves of the materials in Examples 1, 2, 3, and Comparative Example 3 in the three-electrode test system, where Example 1 is IrO with an iridium content of 20 wt%. x / t-ZrO2 material, Example 2 is IrO with iridium content of 30wt%. x / t-ZrO2 material, Example 3 is IrO with iridium content of 50wt%. x / t-ZrO2 material, Comparative Example 3 is commercial iridium black material.

[0038] Figure 7 IrO prepared in Example 1 x The mass activity of / t-ZrO2 material and Comparative Example 3 material was compared at relative standard hydrogen electrode voltages of 1.55V and 1.6V, where Comparative Example 3 was iridium black material.

[0039] Figure 8 IrO prepared in Example 1 x Current density-voltage curve of / t-ZrO2 material as anode catalyst in proton exchange membrane water electrolysis device.

[0040] Figure 9 IrO prepared in Example 1 x / t-ZrO2 material was used as an anode catalyst in a proton exchange membrane water electrolysis device at 1A·cm -2 Constant current curve at current density. Detailed Implementation

[0041] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the described embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0042] The “range” disclosed in this document takes the form of a lower limit and an upper limit. It can be one or more lower limits and one or more upper limits, respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this way are inclusive and composable; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 100–140 and 500–900 are listed for a specific parameter, it is also expected that ranges of 100–140 and 500–900 are also included. Furthermore, if the minimum range values ​​are listed as 1 and 2, and if the maximum ranges are listed as 3, 4, and 5, then the following ranges are all expected: 1–2, 1–4, 1–5, 2–3, 2–4, and 2–5.

[0043] In this invention, unless otherwise specified, the numerical range "a~b" represents an abbreviation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0~5" means that all real numbers between "0~5" have been listed in this document, and "0~5" is simply an abbreviation of these numerical combinations.

[0044] In this invention, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0045] I. Preparation of Catalyst Materials

[0046] Example 1: Preparation of an oxygen evolution electrocatalyst based on tetragonal zirconium dioxide supported on oxygen overflow

[0047] (1) Dissolve cobalt chloride hexahydrate in deionized water to prepare a 2 mol / L cobalt chloride hexahydrate aqueous solution, which is called solution A;

[0048] (2) At the same time, weigh a certain amount of potassium ferricyanide reagent. The weight of the weighed reagent is in a molar ratio of 2:1 to the amount of cobalt chloride hexahydrate used in solution A. This reagent is used as reagent B.

[0049] (3) Slowly add reagent B to solution A under light-protected and stirred conditions. After the reaction is complete, place the electrode support substrate into the mixed suspension. The substrate size is 10 cm. 2 / 30mL of mixed suspension was allowed to stand and age for 6 hours at 60℃ in the dark without any interference.

[0050] (4) The electrode support substrate after the reaction is repeatedly rinsed with deionized water and ethanol, and then naturally air-dried and oxidized in the air environment to obtain the catalyst precursor (traditional bimetallic Prussian blue analogue) grown on the electrode support substrate.

[0051] (5) The catalyst precursor was continuously treated with oxygen plasma for 30 minutes in the chamber of the radio frequency plasma enhanced chemical vapor deposition (RF-PECVD) system, while maintaining the chamber pressure at 50 Pa and the radio frequency plasma discharge power at 200 W, to obtain the oxygen evolution electrocatalyst supported on zirconium dioxide iridium oxide nanoclusters.

[0052] Example 2

[0053] Repeat the steps of Example 1, except that iridium trichloride powder is not added in step (4).

[0054] Example 3

[0055] Repeat the steps of Example 1, except that in step (4), the mass of the white powder is 24.2 mg.

[0056] Example 4

[0057] The operation steps of Example 1 were repeated, except that in step (4), the mass of the white powder was 48.3 mg.

[0058] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

[0059] Comparative Example 1

[0060] Repeat the steps of Example 1, except that a voltage of 1.5V is applied to the synthesized catalyst material.

[0061] Comparative Example 2

[0062] Repeat the steps of Example 1, except that a voltage of 1.7V is applied to the synthesized catalyst material.

[0063] Comparative Example 3

[0064] Commercially available iridium black was used as the anode catalyst for water electrolysis, and the electrocatalytic oxygen evolution performance test conditions were the same as in Example 1.

[0065] II. Performance Characterization Test

[0066] Figure 1 The oxygen evolution electrocatalyst IrO supported on tetragonal zirconium dioxide with oxygen overflow stability prepared in Example 1 x X-ray diffraction patterns of / t-ZrO2 and tetragonal zirconium dioxide prepared in Example 4. Figure 1 It can be seen that the characteristic diffraction peaks at angles of 30.2°, 50.2°, and 60.2° correspond to the (101), (112), and (211) crystal planes of tetragonal zirconium dioxide crystal. After loading iridium oxide, the peak intensity near 35° is enhanced, which corresponds to the (101) crystal plane of iridium dioxide crystal.

[0067] Figure 2 The oxygen evolution electrocatalyst IrO supported on tetragonal zirconium dioxide with oxygen overflow stability prepared in Example 1 x Transmission electron micrograph of / t-ZrO2. Figure 2 It is evident that the catalyst has a porous structure.

[0068] Figure 3 The oxygen evolution electrocatalyst IrO supported on tetragonal zirconium dioxide with oxygen overflow stability prepared in Example 1 x Aberration-corrected high-angle annular dark-field scanning transmission microscopy image of / t-ZrO2. Figure 3 It can be seen that the observed d-interval of 0.298 nm corresponds to the (101) crystal plane of tetragonal zirconium dioxide. Since the atomic number Z of iridium is greater than that of zirconium, the distribution of iridium can be directly determined by Z comparison, and it can be seen that iridium oxide is a nanocluster loaded on tetragonal zirconium dioxide.

[0069] Figure 4 IrO prepared for Example 1, Comparative Example 1, and Comparative Example 2 x The in-situ X-ray absorption fine structure near-edge spectrum and magnified image of the iridium L3 edge of / t-ZrO2 material, along with its R-space spectrum, are shown. Comparative Example 1 shows the iridium L3 edge of / t-ZrO2 after applying a voltage of 1.5V. x / t-ZrO2 material, Comparative Example 2 is IrO after applying a voltage of 1.7V. x / t-ZrO2 material.

[0070] Upon application of voltage, the white line peak intensifies and undergoes a positive shift, indicating a rapid increase in the valence state of iridium. This is attributed to more electrons moving from iridium to nearby adsorbed oxygen, which then promotes the oxidation reaction via the lattice oxygen mechanism. However, with further increases in voltage, the white line peak shows almost no change, suggesting that the valence state of iridium is stable during the oxygen evolution reaction. This finding indicates that the catalyst structure can avoid collapse caused by oxygen vacancies due to oxygen overflowing from the support to the infrared sites. The Ir-O bond also shortens upon application of voltage, indicating that the coordination structure of iridium rearranges via the lattice oxygen mechanism for the reaction. During the oxygen evolution reaction, oxygen vacancies can be rapidly filled, thus avoiding structural collapse that could be caused by oxygen vacancies.

[0071] Figure 5 IrO prepared for Example 1, Comparative Example 1, and Comparative Example 2 x The in-situ X-ray absorption fine structure near-edge spectrum and magnified image of the zirconium K-edge of / t-ZrO2 material, and its R-space spectrum, are shown. Comparative Example 1 shows the IrO2 material after applying a voltage of 1.5V. x / t-ZrO2 material, Comparative Example 2 is IrO after applying a voltage of 1.7V. x / t-ZrO2 material. When the applied potential increases, the white line peak undergoes a negative shift, and the decrease in the valence state of zirconium indicates that oxygen intermediates on the zirconium surface have overflowed onto the iridium. During the oxygen evolution reaction, the coordination number of Zr-O also decreases, indicating the occurrence of oxygen overflow.

[0072] III. Electrochemical Performance Testing

[0073] IrO x All electrochemical hydrogen evolution performance tests of the / t-ZrO2 catalyst were conducted in a three-electrode system, using a platinum mesh as the counter electrode, Ag / AgCl as the reference electrode, and an IrO2-coated electrode. x A glassy carbon electrode with / t-ZrO2 catalyst was used as the working electrode. In Example 1, 2.5 mg of catalyst powder was added to 960 μL of isopropanol, followed by the addition of 40 μL of 5 wt% [a specific catalyst]. The catalyst slurry was ultrasonically cleaned for 30 minutes at 30 degrees Celsius to ensure uniform dispersion. Then, 5 μL of the slurry was dispensed using a microsyringe and dropped onto a glassy carbon electrode. The electrode was then placed in a ventilated area for 15 minutes and allowed to air dry naturally. An electrochemical workstation (Chenhua CHI 760E) was used, with 0.5 M HClO4 as the electrolyte solution, and electrochemical tests were conducted at room temperature and pressure.

[0074] Figure 6 The linear sweep voltammetry curves are shown for the materials in Examples 1, 2, 3, and Comparative Example 3 in the three-electrode test system. Figure 6As can be seen, with the increase of iridium loading, the performance of Experimental Examples 2 and 3 is not much different from that of Experimental Example 1. Example 1 can achieve 10 mA·cm at an overpotential of 288 mV. -2 The current density is superior to that of commercial iridium black in Comparative Example 3.

[0075] Figure 7 IrO prepared in Example 1 x A comparison of the mass activity of / t-ZrO2 material and Comparative Example 3 material, where Comparative Example 3 is a commercially available iridium black material. Figure 7 As can be seen, the mass activities of the catalyst in Example 1 at 1.55V and 1.60V are 609.1 A·g, respectively. Ir -1 and 1457.4A·g Ir -1 And far exceeding the commercial iridium black material of Comparative Example 3 (46.7 A·g, respectively) Ir -1 and 110.7A·g Ir -1 This indicates that metallic iridium in IrO x / t-ZrO2 has high utilization efficiency.

[0076] IV. Industrial Electrolysis of Water Simulation

[0077] IrO was tested using a proton exchange membrane electrolyzer system. x Electrocatalytic performance of / t-ZrO2. IrO is used as the anode catalyst. x / t-ZrO2 catalyst, the cathode catalyst used is commercial 40% Pt / C. Weigh 5 mg of the powdered catalyst from Example 1 and add it to 47 μL of 5 wt% of the catalyst. An anode catalyst slurry was prepared in isopropanol and deionized water. Then, 10 mg of commercial 40% Pt / C was weighed and added to a mixture containing 27 μL of 5 wt% [amount missing]. A cathode catalyst slurry was prepared in isopropanol and deionized water solutions. Both were ultrasonicated in a low-temperature water bath for at least 30 minutes to obtain a homogeneous catalyst slurry. The anode and cathode catalyst slurries were then sprayed onto polytetrafluoroethylene (PTFE) films, dried, and then transferred onto both sides of a Nafion 115 / 212 proton exchange membrane using a hot press. After removing the PTFE films, the cathode and anode electrode materials for the proton exchange membrane electrolyzer were obtained. The iridium metal loading at the anode was 0.1 mg·cm⁻¹. -2 Finally, carbon paper and titanium felt were loaded and assembled into a proton exchange membrane electrolyzer for testing. The electrolyte solution was deionized water, the test temperature was 80℃, and the flow rate was 30 mL / min. -1 .

[0078] Figure 8IrO prepared in Example 1 x Current density-voltage curves of / t-ZrO2 material as an anode catalyst in a proton exchange membrane water electrolysis device. Figure 7 It is evident that the assembled proton exchange membrane electrolyzer can achieve 3.1 A·cm⁻¹ at a voltage of 1.9 V. -2 The current density indicates that IrO x / t-ZrO2 materials exhibit high catalytic activity under high current density in proton exchange membrane electrolyzers.

[0079] Figure 9 IrO prepared in Example 1 x / t-ZrO2 material was used as an anode catalyst in a proton exchange membrane water electrolysis device at 1A·cm -2 A constant current curve at current density. (From...) Figure 8 It can be seen that the assembled proton exchange membrane electrolyzer operates at 1 A·cm⁻¹. -2 After 1600 hours of continuous operation at the current density, the decay rate was only 6.25 μV / h, indicating that the catalyst has significant potential in practical applications of proton exchange membrane hydrogen production.

[0080] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the embodiments described. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of the present invention, and these equivalent modifications or substitutions are all included within the scope defined by the claims of this application.

Claims

1. A method for preparing a zirconium dioxide-supported iridium oxide nanoclusters oxygen evolution electrocatalyst, characterized in that, Includes the following steps: A. Preparation of Zirconia Support A mixed solution of zirconium salt, amide solvent and organic acid was prepared and kept at 120°C for 24 hours. Then it was cooled to room temperature. After centrifugation, the white product was washed multiple times with N,N-dimethylformamide and anhydrous ethanol and dried in a vacuum oven at 60°C for 12 hours to obtain a white powder. Zirconium salts are selected from any one or more combinations of zirconium nitrate, zirconium tetrachloride, and zirconium oxynitrate. The amide is selected from any one or more combinations of N,N'-dimethylformamide, N,N'-dimethylacetamide, and N,N'-dimethylacrylamide; The organic acid is selected from a mixture of terephthalic acid and benzoic acid, with a molar ratio of terephthalic acid to benzoic acid of 0.09~0.1:1; The mass-to-volume ratio of zirconium salt to amide is 13~13.5 g / L, and the molar ratio of zirconium salt to terephthalic acid is 1~1.1 :

1. B. Iridium oxide nanoclusters supported The iridium salt was dispersed in a mixed solvent of tetrahydrofuran and water, and then the white powder was added. After stirring for 24 hours, a mixed solution of sodium nitrate and potassium nitrate was added, and the mixture was stirred for 30-40 minutes. The solvent was removed by rotary evaporation at 60°C, and the product was dried in a vacuum oven at 60°C for 12 hours. The resulting pale green powder was placed in a muffle furnace at 450°C and kept at that temperature for 30-40 minutes. Then, it was directly removed and cooled in air. The product was washed multiple times with deionized water and anhydrous ethanol, and finally dried in a vacuum oven at 60°C for 12 hours to obtain the electrocatalyst. The volume ratio of tetrahydrofuran to water is 1:1, and the concentration of iridium salt in the mixed solvent is 1 g / L; The mass ratio of the white powder to the iridium salt is 0.4~1.1 : 1; The mass ratio of sodium nitrate to potassium nitrate is 6:4, and the mass ratio of iridium salt and the mixture of sodium nitrate and potassium nitrate is 3:

100.

2. A zirconium dioxide-supported iridium oxide nanoclusters oxygen evolution electrocatalyst, characterized in that, The oxygen evolution electrocatalyst supported on zirconium dioxide and iridium oxide nanoclusters as described in claim 1 was prepared.

3. The zirconium dioxide-supported iridium oxide nanoclusters oxygen evolution electrocatalyst according to claim 2, characterized in that, The electrocatalyst consists of porous nanostructured nanoparticles with a size of 1.33 nm and an iridium loading of 0.1 mg / cm³. 2 .

4. The application of the zirconium dioxide-supported iridium oxide nanoclusters oxygen evolution electrocatalyst described in claim 2 in the preparation of an acidic electrochemical oxygen evolution electrode.

5. An acidic electrolytic oxygen anode electrode, characterized in that, The catalyst includes an anode support and a catalyst material supported thereon, wherein the catalyst material is a zirconium dioxide-supported iridium oxide nanocluster oxygen evolution electrocatalyst prepared by the method for preparing zirconium dioxide-supported iridium oxide nanocluster oxygen evolution electrocatalyst according to claim 1.

6. A method for electrolyzing water, characterized in that: The acidic electrolytic oxygen anode electrode as described in claim 5 is used as the anode.

7. The method for electrolyzing water according to claim 6, characterized in that: in, The electrolyte is 0.5 M HClO4 solution or deionized water.

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