Preparation method and application of porous high-activity iridium black catalyst
The porous iridium black catalyst was prepared through the synergistic mechanism of PVP template agent and zinc salt molten salt, which solved the problem of insufficient activity and stability of traditional iridium black catalyst, achieved efficient acidic oxygen evolution reaction, and promoted the application of proton exchange membrane water electrolysis to produce hydrogen.
Patent Information
- Application Number
- CN202510886307.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-30
- Publication Date
- 2025-10-17
AI Technical Summary
The existing iridium black catalyst has a low specific surface area, few active sites, poor stability, and a high preparation process cost and pollution. It is difficult to achieve high activity and stability in the acidic oxygen evolution reaction, which hinders the development of proton exchange membrane water electrolysis to produce hydrogen.
The PVP template-zinc salt molten salt synergistic mechanism was adopted to prepare a porous and highly active iridium black catalyst through heating, stirring, drying, calcination and other steps. PVPK15 was used as a soft template and cross-linking agent, and zinc nitrate molten salt formed a zinc oxide support layer to inhibit the sintering growth of iridium black and form a porous structure.
The prepared iridium black catalyst has a rich porous structure and a large specific surface area, which significantly increases the exposure of active sites, improves the catalytic activity and stability, realizes efficient electrolysis of water to produce hydrogen at high current density, and reduces preparation costs and pollution.
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Figure CN120797030A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the field of hydrogen production catalysts for water electrolysis, and particularly relates to a preparation method of porous high-activity iridium black and application thereof in an acid oxygen evolution reaction (OER). BACKGROUND
[0002] Proton exchange membrane water electrolysis (PEMWE) is highly valued for its advantages of compact design, simple structure, fast response speed, low ohmic loss, high voltage efficiency, and high gas purity. The oxygen evolution reaction (OER) is a complex process involving multi-step proton-coupled four-electron transfer, and its kinetic process is slow and has low conversion efficiency. Under the harsh conditions of high potential and strong acid environment, the long-term operation of the catalyst faces great challenges, so improving the activity and stability of the acid OER catalyst is of great significance to the prospect of PEMWE. However, so far, iridium is still one of the preferred elements for OER catalysts, but its low abundance on earth, extremely low annual output, and high cost seriously hinder the development of PEMWE. Therefore, reducing the dependence on iridium and improving the catalytic activity and stability of iridium are the keys to further promoting the large-scale application of PEMWE.
[0003] Since most OER occurs only on the surface and near-surface region of the catalyst, materials with higher specific surface area to volume ratio can expose more active sites, thereby improving catalytic activity. In addition, catalysts with highly open structures not only can adjust the electronic structure and effectively improve atomic utilization, but also can effectively improve mass transfer efficiency, thereby improving the activity and stability of the catalyst.
[0004] Traditional iridium black catalysts have problems of low specific surface area, few active sites, and poor stability, and the preparation process often involves high-temperature reduction or organic solvents, which is costly and polluting. Existing technologies cannot balance high activity, porous structure, and industrial feasibility. SUMMARY
[0005] To solve the above problems, one of the purposes of the present application is to provide a preparation method of a porous high-activity iridium black catalyst, which prepares the porous high-activity iridium black catalyst through a PVP template agent-zinc salt molten salt synergistic mechanism. Specifically, the technical scheme is as follows:
[0006] A preparation method of a porous high-activity iridium black catalyst, comprising the following steps:
[0007] S1: adding a soft template agent, chloroiridic acid, zinc nitrate, and zinc chloride into deionized water, and heating and stirring to form a uniform solution;
[0008] S2: drying the solution to form a precursor gel;
[0009] S3: calcining the precursor gel in an air atmosphere to obtain a crude catalyst;
[0010] S4: acid washing, filtering, washing and drying the crude catalyst to obtain a porous iridium black catalyst.
[0011] Preferably, the soft template agent is polyvinylpyrrolidone (PVP K15), and the mass ratio of the polyvinylpyrrolidone to chloroiridic acid is (8-12):(2.5-4.5).
[0012] Preferably, the mass ratio of the zinc nitrate to chloroiridic acid is (8-12):(2.5-4.5), and the mass ratio of the zinc chloride to chloroiridic acid is (0.5-2):(2.5-4.5); more preferably, the mass ratio of the zinc nitrate to chloroiridic acid is (8-10):(2.5-4.5), and the mass ratio of the zinc chloride to chloroiridic acid is (0.8-1.5):(2.5-4.5).
[0013] The temperature rising rate is 3-8℃ / min;
[0014] The calcination temperature is 400-500℃;
[0015] The calcination time is 1-3 hours.
[0016] More preferably, the calcination temperature is 420-480℃.
[0017] Preferably, the acid washing in step S4 uses a sulfuric acid solution with a concentration of 0.05-0.5mol / L, the acid washing temperature is 50-80℃, and the time is 1-2 hours.
[0018] Preferably, the washing end point in step S4 is that the conductivity of the filtrate is ≤1S / cm. 2 .
[0019] The second object of the present application is to provide an iridium black catalyst prepared by the above method, which has a rich porous structure and a large specific surface area, fully exposes active sites, greatly improves its intrinsic activity, and has the following characteristics:
[0020] The average particle size is 2-5nm;
[0021] The pore size distribution is 4-7nm;
[0022] The specific surface area is ≥250m 2 / g.
[0023] Preferably, the OER overpotential of the iridium black catalyst under a current density of 10mA / cm 2 is ≤310mV.
[0024] Preferably, the iridium black catalyst has an iridium loading of 0.8 mg / cm 2 at a current density of 1 A / cm 2 The electrolysis voltage is ≤ 1.65 V at a current density of 1 A / cm
[0025] A third object of the present application is to provide the use of the catalyst in the oxygen evolution reaction of the proton exchange membrane electrolysis of water.
[0026] It can effectively support nanostructures during the preparation of membrane electrodes, improve the utilization of noble metals, improve the mass transfer efficiency of reactants of membrane electrodes, and improve the activity and stability of catalysts under industrial high current density applications.
[0027] Compared with the prior art, the present application has the following beneficial effects:
[0028] (1) The preparation method of the catalyst provided by the present application uses PVPK15 as a soft template barrier agent and a crosslinking agent, and zinc nitrate molten salt generates a local inert environment, and zinc oxide formed in situ by decomposition and oxidation is removed as a support layer and a hard template barrier agent, effectively inhibiting the sintering and growth of iridium black, and forming a porous structure.
[0029] (2) Unlike traditional alcohol reduction or high-temperature hydrogen reduction, the preparation method is simple to operate, simple in equipment, high in safety, pollution-free, and suitable for scale-up production.
[0030] (3) The iridium black prepared by the method has a small particle size (average particle size of about 3 nm), a rich porous structure (5.514 nm), a large specific surface area (315.67 m2 / g), and good dispersibility. The overpotential is only 305 mV at a current density of 1 A / cm 2 at an iridium loading of 0.8 mg / cm 2 , realizing 1 A / cm 2 at 1.65 V, greatly improving the utilization of noble metals, and realizing efficient electrolysis of water to produce hydrogen. BRIEF DESCRIPTION OF DRAWINGS
[0031] Figure 1a SEM image of the porous high-activity Ir black prepared in Example 1;
[0032] Figure 1b SEM image of the irregular blocky Ir black prepared in Example 2;
[0033] Figure 1c SEM image of the nanoparticle Ir black prepared in Example 3;
[0034] Figure 2 TEM image of the porous high-activity Ir black prepared in Example 1 of the present application;
[0035] Figure 3N2 adsorption-desorption curve of the porous high-activity Ir black prepared in Example 1 of the present application;
[0036] Figure 4 XRD pattern of the porous high-activity Ir black prepared in Example 1 of the present application;
[0037] Figure 5 LSV test curve of the porous Ir black prepared in each example and comparative example;
[0038] Figure 6 Polarization curve of the porous high-activity Ir black prepared in Example 1 of the present application. DETAILED DESCRIPTION
[0039] In order to make the skilled in the art better understand the technical solutions of the present application, the preferred embodiments of the present application are described below in combination with specific examples, but it should not be understood as a limitation to the present application, but only as an example.
[0040] The test methods or test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are all obtained from conventional commercial channels or prepared by conventional methods unless otherwise specified.
[0041] Example 1:
[0042] First step, 8 g of PVP K15, 8 g of zinc nitrate, 1 g of zinc chloride, 2.85 g of chloroiridic acid were added to 300 mL of water, heated to 60℃, stirred for 30 minutes, and a clear gray-brown iridium precursor solution was obtained;
[0043] Second step, the precursor solution was dried at 90℃ for 8 hours to obtain an iridium precursor gel;
[0044] Third step, the gel was heated to 450℃ at 5℃ / min under air atmosphere, and calcined for 2 hours to obtain an iridium black crude product;
[0045] Fourth step, after the crude product was ground thoroughly, it was added into 0.1 mol / L sulfuric acid solution (50 times the mass), stirred at 60℃ for 1 hour; then hot filtration was performed, and washed with deionized water until the conductivity was ≤1 S / cm 2 . The filter cake was dried at 70℃ for 4 hours. Finally, a porous high-performance iridium black catalyst was obtained, the SEM pattern thereof is shown in Figure 1a , the N2 adsorption-desorption curve thereof is shown in Figure 3 , and the XRD pattern thereof is shown in Figure 4 .
[0046] It can be seen from the above detection spectra that the iridium black prepared by this method has a small particle size (average particle size is about 3nm), a rich porous structure (5.514nm) and a large specific surface area (315.67m2 / g), and good dispersibility.
[0047] Example 2
[0048] The difference between this embodiment and Example 1 is that the mass ratio of PVPK15 is different.
[0049] Step 1: Add 2 g of PVPK15, 8 g of zinc nitrate, 1 g of zinc chloride, and 2.85 g of chloroiridic acid to a three-necked flask containing 300 ml of deionized water, heat to 60°C, and stir for 30 minutes to obtain a clear gray-brown iridium precursor solution.
[0050] The second step is to dry the precursor solution at 90° C. for 8 hours to obtain an iridium precursor gel.
[0051] The third step is to heat the gel to 450°C at 5°C / min in an air atmosphere and calcine for 2 hours to obtain crude iridium black;
[0052] Step 4: After the crude product is fully ground, it is added into 0.1 mol / L sulfuric acid solution (50 times the mass), stirred at 60 ° C for 1 hour; then filtered while hot, and washed with deionized water until the conductivity is ≤1S / cm 2 The filter cake was dried at 70°C for 4 hours. Finally, the block iridium black catalyst ( Figure 1b ).
[0053] Example 3: Different from Example 1, the mass ratio of PVP K15 is different.
[0054] Step 1: Add 4g of PVPK15, 8g of zinc nitrate, 1g of zinc chloride, and 2.85g of chloroiridic acid to a three-necked flask containing 300ml of deionized water. Heat to 60°C and stir at 500 rpm for 30 minutes to obtain a clear, gray-brown iridium precursor solution.
[0055] Step 2: Place the precursor solution in a surface evaporating dish and dry at 90°C for 8 hours to obtain an iridium precursor gel. This gel is then calcined at 450°C in an air atmosphere at a heating rate of 5°C / min for 2 hours to obtain crude iridium black.
[0056] Step 3: Grind the crude product thoroughly, add it into 0.1 mol / L sulfuric acid solution, stir it at 60℃ for 1 hour, then filter it while hot and wash it with deionized water until the conductivity is ≤1S / cm 2 The filter cake was dried at 70°C for 4 hours. Finally, the nanoparticle iridium black catalyst ( Figure 1c ).
[0057] Example 4: Different from Example 1, the mass ratio of zinc chloride is different.
[0058] First step, add 2 g PVP K15, 8 g zinc nitrate, 0.5 g zinc chloride, 2.85 g chloroiridic acid into 300 mL water, heat to 60°C, stir for 30 minutes, to obtain a clear gray-brown iridium precursor solution;
[0059] Second step, dry the above precursor solution at 90°C for 8 hours to obtain an iridium precursor gel;
[0060] Third step, heat the gel to 450°C at a rate of 5°C / min under air atmosphere, calcine for 2 hours, and finally obtain an iridium black crude product;
[0061] Fourth step, after the crude product is fully ground, add it into 0.1 mol / L sulfuric acid solution (50 times mass), stir at 60°C for 1 hour; then hot suction filter, wash with deionized water until the conductivity is ≤1 S / cm 2 . Dry the filter cake at 70°C for 4 hours. Finally obtain an amorphous porous iridium black catalyst.
[0062] Example 5: Different from Example 1, the mass ratio of zinc chloride is different.
[0063] First step, add 2 g PVP K15, 8 g zinc nitrate, 2.0 g zinc chloride, 2.85 g chloroiridic acid into 300 mL water, heat to 60°C, stir for 30 minutes, to obtain a clear gray-brown iridium precursor solution;
[0064] Second step, dry the above precursor solution at 90°C for 8 hours to obtain an iridium precursor gel;
[0065] Third step, heat the gel to 450°C at a rate of 5°C / min under air atmosphere, calcine for 2 hours, and finally obtain an iridium black crude product;
[0066] Fourth step, after the crude product is fully ground, add it into 0.1 mol / L sulfuric acid solution (50 times mass), stir at 60°C for 1 hour; then hot suction filter, wash with deionized water until the conductivity is ≤1 S / cm 2 . Dry the filter cake at 70°C for 4 hours. Finally obtain an amorphous porous iridium black catalyst.
[0067] Example 6: Different from Example 1, the calcination temperature of the iridium black catalyst is different.
[0068] First step: Add 8g PVP K15, 8g zinc nitrate, 1g zinc chloride, 2.85g chloroiridic acid into a three-neck flask containing 300ml deionized water, heat to 60°C, stir for 30 minutes, get a clear gray-brown iridium precursor solution;
[0069] Second step: Dry the above precursor solution at 90°C for 8 hours to get an iridium precursor gel;
[0070] Third step: The gel is heated to 350°C at 5°C / min under air atmosphere, and the calcination time is 2 hours. Finally, the crude iridium black is obtained.
[0071] Fourth step: After the crude product is ground, it is added into 0.1 mol / L sulfuric acid solution (50 times the mass), stirred at 60°C for 1 hour; then hot suction filtration is performed, and washed with deionized water until the conductivity is ≤1 S / cm 2 . The filter cake is dried at 70°C for 4 hours. Finally, the iridium black catalyst containing a large amount of amorphous carbon is obtained.
[0072] Example 7: Different from example 1, the calcination temperature of the iridium black catalyst is different.
[0073] First step: Add 8g PVP K15, 8g zinc nitrate, 1g zinc chloride, 2.85g chloroiridic acid into a three-neck flask containing 300ml deionized water, heat to 60°C, stir for 30 minutes, get a clear gray-brown iridium precursor solution;
[0074] Second step: Dry the above precursor solution at 90°C for 8 hours to get an iridium precursor gel;
[0075] Third step: The gel is heated to 400°C at 5°C / min under air atmosphere, and the calcination time is 2 hours. Finally, the crude iridium black is obtained.
[0076] Fourth step: After the crude product is ground, it is added into 0.1 mol / L sulfuric acid solution (50 times the mass), stirred at 60°C for 1 hour; then hot suction filtration is performed, and washed with deionized water until the conductivity is ≤1 S / cm 2 . The filter cake is dried at 70°C for 4 hours. Finally, the iridium black catalyst containing a large amount of amorphous carbon is obtained.
[0077] Example 8: Different from example 1, the calcination temperature of the iridium black catalyst is different.
[0078] First step: Add 8g PVP K15, 8g zinc nitrate, 1g zinc chloride, 2.85g chloroiridic acid into a three-neck flask containing 300ml deionized water, heat to 60°C, stir for 30 minutes, get a clear gray-brown iridium precursor solution;
[0079] Second step, dry the precursor solution at 90°C for 8 hours to get the iridium precursor gel;
[0080] Third step, calcine the gel at 5°C / min to 500°C under air atmosphere for 2 hours to get the iridium black crude product;
[0081] Fourth step, after grinding the crude product, add 0.1 mol / L sulfuric acid solution (50 times mass) and stir at 60°C for 1 hour; then hot filtration, wash with deionized water until the conductivity is ≤1 S / cm 2 . Dry the filter cake at 70°C for 4 hours. Finally get the iridium black catalyst containing part of the iridium oxide phase.
[0082] Example 9: Different from example 1, the mass ratio of zinc nitrate is different.
[0083] First step: add 8g of PVP K15 and 5g of zinc nitrate, 1g of zinc chloride, 2.85g of chloroiridic acid into a three-necked flask containing 300ml of deionized water, heat to 60°C, stir for 30 minutes to get a clear gray-brown iridium precursor solution;
[0084] Second step, dry the precursor solution at 90°C for 8 hours to get the iridium precursor gel;
[0085] Third step, calcine the gel at 5°C / min to 450°C under air atmosphere for 2 hours to get the iridium black crude product;
[0086] Fourth step, after grinding the crude product, add 0.1 mol / L sulfuric acid solution (50 times mass) and stir at 60°C for 1 hour; then hot filtration, wash with deionized water until the conductivity is ≤1 S / cm 2 . Dry the filter cake at 70°C for 4 hours. Finally get the iridium black catalyst containing part of the iridium oxide phase.
[0087] Example 10: Different from example 1, the mass ratio of zinc nitrate is different.
[0088] First step, add 8g of PVP K15 and 12g of zinc nitrate, 1g of zinc chloride, 2.85g of chloroiridic acid into 300ml of water, heat to 60°C, stir for 30 minutes to get a clear gray-brown iridium precursor solution;
[0089] Second step, dry the precursor solution at 90°C for 8 hours to get the iridium precursor gel;
[0090] Third step, calcine the gel at 5°C / min to 450°C under air atmosphere for 2 hours to get the iridium black crude product;
[0091] Fourth step, after the crude product is fully ground, 0.1 mol / L sulfuric acid solution (50 times the mass) is added, and stirring is carried out at 60℃ for 1 hour; then hot filtration is carried out, and washing is carried out with deionized water until the conductivity is ≤1 S / cm 2 The filter cake is dried at 70℃ for 4 hours. Finally, an iridium black catalyst containing a partial iridium oxide phase is obtained.
[0092] In the present application, the polyethylene hydrophobic end of PVP K15 is the core, and the hydrophilic end pyrrolidone is chelated with Ir 4+ and Zn 2+ Chelation, decomposition at high temperature calcination, in-situ formed zinc oxide becomes a support layer and a barrier agent, effectively inhibiting the sintering and growth of iridium black, and at the same time forming a porous structure.
[0093] Comparative Example 1: An iridium black is prepared using a traditional ethylene glycol reduction method.
[0094] First step, 2.85g chloroiridic acid is added to 300mL ethylene glycol, and the temperature is raised to 180℃, and stirring is carried out for 3 hours to obtain an iridium black suspension;
[0095] Second step, after the above suspension is cooled to room temperature, filtration is carried out, and washing is carried out with deionized water until the conductivity is ≤1 S / cm 2 The filter cake is dried at 70℃ for 4 hours.
[0096] Third step, the filter cake is fully ground, and calcination is carried out under 5% H2 / Ar, the temperature raising rate is 5℃ / min, and the temperature is kept at 200℃ for 2 hours, and finally a traditional ethylene glycol method iridium black catalyst is obtained.
[0097] Performance test
[0098] 1. LSV curve test of iridium black catalyst
[0099] The catalytic performance of the iridium black catalysts prepared in each embodiment and the comparative example of the present application and a commercial Ir black (manufacturer: Suzhou Platinum Hydro New Energy Technology Co., Ltd., particle size: about 5nm; BET: 25.47m 2 g -1 ; model: IrHy1000) is tested, and the specific test steps are as follows:
[0100] Test conditions and steps:
[0101] A CS2350M double constant potential instrument is used, and in a three-electrode system, a 5mm glassy carbon electrode is used as a working electrode, a graphite rod is used as a counter electrode, and a mercury sulfate electrode is used as a reference electrode.
[0102] Preparation of Ink: Take 10 mg of sample, first add 2800 μL of ultrapure water, then add 200 μL of 5% Nafion. Ultrasonic dispersion. Take 8.4 μL of the well-dispersed sample and drop it on the black circle of the glassy carbon electrode, and use a needle to pick it up, so that the sample just completely covers the black circle, and is round without sharp corners, and the sample cannot exceed the black circle. After dropping, dry thoroughly at room temperature.
[0103] First, the electrochemical activation of the catalyst was tested by cyclic voltammetry (CV) method, using 0.5M H2SO4 solution as electrolyte. The parameters were set as follows: voltage range: -0.72~0.32V, scan speed: 50mV / s, number of circles: 10. After 5min of N2, the test was performed. After the test, linear sweep voltammetry (lsv) was used to test the OER, with a rotating disc speed of 1600rpm, a voltage range of 0.6~0.9V, a scan speed of 50mV / s, and 4 circles of testing, with the results of the 4th circle being taken.
[0104] The LSV test curve obtained by the test is shown in Figure 5 The test results show that the porous high-activity iridium black prepared in Example 1 has a 10mA / cm 2 overpotential of only 305mV, showing superior OER catalytic activity to commercial Ir black, especially with a mass specific activity increased by nearly 3 times.
[0105] 2. Polarization curve test of iridium black catalyst
[0106] The catalytic activity of Example 1 of the present application and the commercial iridium black as described above was tested, and the specific test method was as follows:
[0107] The prepared ink was uniformly dispersed on the Nafion 115 membrane by an ultrasonic spraying machine, with the anode being an iridium black catalyst and the cathode being a Pt / C catalyst. A 3x3 cm 2 membrane electrode was prepared. The 3x3 cm 2 standard electrolytic cell clamp was used to assemble it. Finally, a test electrolytic cell was obtained. (Note: the preparation method of the commercial Ir membrane electrode is consistent.)
[0108] The electrolytic cell was connected to the equipment, the water temperature was set to 65℃, and the program was set to measure the voltage under a constant current of 0.1~3A.
[0109] The polarization curve obtained is shown in Figure 6 In addition, the membrane electrode showed outstanding performance, with a 1A cm 2 @1.65V under an iridium loading of 0.8mg / cm 2 @1.65V, reaching the current requirements for catalysts (1A cm 2@1.75 V).
[0110] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art will appreciate that modifications can be made to the technical solutions described in the foregoing embodiments, or some of the technical features thereof can be replaced by equivalent features. Any modifications, equivalent replacements, improvements, and the like made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims
1. A method for preparing a porous high-activity iridium black catalyst, characterized in that: The following steps are involved: S1: Add the soft template, chloroiridic acid, zinc nitrate and zinc chloride into deionized water, heat and stir to form a homogeneous solution; S2: drying the solution to form a precursor gel; S3: calcining the precursor gel in an air atmosphere to obtain a crude catalyst; S4: acid-washing, filtering, washing and drying the crude catalyst to obtain a porous iridium black catalyst.
2. The method according to claim 1, characterized in that The soft template is polyvinyl pyrrolidone (PVP K15), and the mass ratio of polyvinyl pyrrolidone (PVP K15) to chloroiridic acid is (8-12): (2.5-4.5).
3. The method according to claim 1 or 2, characterized in that The mass ratio of the zinc nitrate to the chloroiridic acid is (8-12):(2.5-4.5), and the mass ratio of the zinc chloride to the chloroiridic acid is (0.5-2):(2.5-4.5).
4. The method according to claim 1, wherein The calcination conditions of step S3 are: Heating rate: 3-8℃ / min; Calcination temperature: 400-500℃; Calcination time: 1-3 hours.
5. The method according to claim 1, wherein The pickling in step S4 uses a sulfuric acid solution with a concentration of 0.05-0.5 mol / L, a pickling temperature of 50-80° C., and a pickling time of 1-2 hours.
6. The method according to claim 1, characterized in that The washing end point of step S4 is when the conductivity of the filtrate is ≤1S / cm 2 .
7. A porous high-activity iridium black catalyst, characterized in that Prepared by any method of claims 1-6, it has the following structural characteristics: Average particle size: 2-5nm; Pore size distribution: 4-7nm; Specific surface area: ≥250m 2 / g.
8. The catalyst according to claim 7, characterized in that At 10mA / cm 2 The OER overpotential at this current density is ≤310 mV.
9. The catalyst according to claim 7 or 8, characterized in that Its iridium loading is 0.8 mg / cm 2 When 1A / cm 2 The electrolysis voltage at the current density is ≤1.65V.
10. Use of the catalyst according to any one of claims 7 to 9 in oxygen evolution reaction by proton exchange membrane water electrolysis.