High-performance transition metal-noble metal oxide cluster heterostructure oxygen evolution reaction electrocatalyst as well as preparation method and application thereof

Abstract

The invention discloses a high-performance transition metal-noble metal oxide cluster heterostructure oxygen evolution reaction electrocatalyst as well as a preparation method and application thereof, and belongs to the technical field of electrochemical catalysis. The preparation method comprises the following steps: mixing a noble metal oxide with a transition metal carbonyl compound, and then carrying out heat treatment at 100-400 DEG C in an inert atmosphere, thereby obtaining the catalyst, wherein the noble metal oxide comprises one, two or a solid solution material of iridium dioxide or ruthenium dioxide. The preparation method provided by the invention is simple and easy to control and easy for large-scale production, and meanwhile, the prepared cluster heterostructure oxygen evolution reaction electrocatalyst has excellent catalytic activity and stability, is relatively low in cost and can be applied to the field of electrochemical energy conversion, such as an electrocatalyst for hydrogen production by water electrolysis of a proton exchange membrane.

Description

Technical Field

[0001] The present invention relates to the field of electrochemical catalysis technology, and in particular to a high-performance transition metal-noble metal oxide cluster heterostructure oxygen evolution reaction electrocatalyst, a preparation method and an application thereof. Background Art

[0002] The information disclosed in the background of the invention is only intended to enhance the understanding of the overall background of the invention and should not be necessarily regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Proton exchange membrane water electrolysis (PEMWE) is a key hydrogen production technology supporting the global energy transition. Compared with traditional alkaline electrolyzers, PEMWE has achieved a revolutionary breakthrough with perfluorosulfonic acid proton membrane: the current density is increased to 6A / cm 2 (15 times that of alkaline technology), dynamic response reaches millisecond level, equipment volume is reduced by 80%, and it perfectly adapts to the fluctuation characteristics of wind and photovoltaic power. However, the strong oxidation and strong acid working environment produced by the oxygen evolution reaction at the anode end poses a great challenge to the stability of the electrocatalyst. At present, the commonly used oxygen evolution reaction electrocatalysts are mainly concentrated in iridium, ruthenium and other precious metal materials. However, the content of elements such as iridium and ruthenium in the earth's crust is extremely low, resulting in high cost of hydrogen production, and there is an urgent need to reduce the catalyst precious metals to reduce costs. At present, the traditional modification strategies of oxygen evolution catalytic materials are mainly concentrated through heterogeneous atom doping, alloying, and construction of heterogeneous load-type interfaces. The above strategies can effectively improve the catalytic activity, but it is difficult to significantly improve the stability, and the catalyst still has the problem of rapid deactivation. Therefore, how to provide an oxygen evolution reaction electrocatalyst with both high catalytic activity and high stability and low cost is an urgent problem to be solved. Summary of the invention

[0004] In view of this, the present invention provides a high-performance transition metal-noble metal oxide cluster heterostructure oxygen evolution reaction electrocatalyst and a preparation method and application thereof. The oxygen evolution reaction electrocatalyst provided by the present invention has a large number of heterogeneous cluster interfaces that regulate the redox characteristics of metal sites and active oxygen, and the interface multi-site synergistically catalyzes a multi-step proton coupled electron transfer (PCET) process, effectively optimizes the water oxidation reaction path, greatly improves the catalytic activity of the oxygen evolution reaction, and significantly reduces the kinetic process of dissolution of noble metal oxides at high potentials.

[0005] In a first aspect, the present invention provides a method for preparing a high-performance transition metal-noble metal oxide cluster heterostructure oxygen evolution reaction electrocatalyst, comprising the following steps:

[0006] The noble metal oxide is mixed with a transition metal carbonyl compound, and then heat-treated in an inert atmosphere at 100 to 400° C. to obtain the product; wherein the noble metal oxide comprises one, two or a solid solution material of iridium dioxide or ruthenium dioxide.

[0007] In a second aspect, the present invention provides a high-performance transition metal-noble metal oxide cluster heterostructure oxygen evolution reaction electrocatalyst obtained by the above preparation method; the size of the noble metal oxide cluster is 1 to 3 nm, and the size of the transition metal oxide cluster is 0.5 to 2 nm.

[0008] In a third aspect, the present invention provides the application of the above-mentioned high-performance transition metal-noble metal oxide cluster heterostructure oxygen evolution reaction electrocatalyst in the field of electrochemical energy conversion.

[0009] Compared with the prior art, the present invention has achieved the following beneficial effects:

[0010] (1) The preparation method of the present invention utilizes relatively low-cost transition metals and noble metal oxides to form cluster heterostructures, which helps to reduce costs. At the same time, the preparation method is simple and easy to control, and is easy to mass produce.

[0011] (2) The present invention can obtain a high-density transition metal-noble metal oxide cluster heterostructure. The high-density heterogeneous cluster interface can not only maximize the number of interfacial active sites, but more importantly, it can optimize the adsorption behavior of catalytic sites and key oxygen evolution reaction intermediates, break the inherent linear adsorption relationship of oxygen intermediate species, and significantly improve the activity.

[0012] (3) In the oxygen evolution reaction electrocatalyst of the present invention, the strongly coupled heterogeneous cluster interaction effectively regulates the redox characteristics of the active sites, significantly reduces the dissolution kinetics of the noble metal sites, optimizes the reaction path of water oxidation, avoids the participation of lattice oxygen, and maintains the stability of the crystal structure.

[0013] (4) In the oxygen evolution reaction electrocatalyst of the present invention, the transition metal nanoclusters can serve as Lewis acid sites, which can promote the enrichment of interfacial water molecules on the catalyst surface, and act as proton acceptors to significantly accelerate the proton-coupled electron transfer process. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The drawings constituting part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their description are used to explain the present invention and do not constitute an improper limitation of the present invention. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0015] Figure 1 is MoO of Example 1 of the present inventionx -IrO 2 X-ray diffraction pattern of the oxygen evolution reaction electrocatalyst of the double oxide clusters;

[0016] Figure 2 is MoO of Example 1 of the present invention x -IrO 2 High-resolution transmission electron microscopy image of the oxygen evolution reaction electrocatalyst of the double oxide cluster;

[0017] Figure 3 is MoO of Example 1 of the present invention x -IrO 2 Double oxide cluster oxygen evolution reaction electrocatalyst and IrO of comparative example 1 2 Comparison of Ir 4f X-ray photoelectron spectra of oxygen evolution reaction electrocatalysts;

[0018] Figure 4 is MoO of Example 1 of the present invention x -IrO 2 Double oxide cluster oxygen evolution reaction electrocatalyst and IrO of comparative example 1 2 Linear sweep voltammetry comparison curve (a) and Tafel comparison curve (b) of oxygen evolution reaction electrocatalysts;

[0019] Figure 5 is MoO of Example 1 of the present invention x -IrO 2 Double oxide cluster oxygen evolution reaction electrocatalyst and IrO of comparative example 1 2 Multi-step chronopotentiometry comparison of oxygen evolution reaction electrocatalysts;

[0020] Figure 6 is MoO of Example 1 of the present invention x -IrO 2 Chronopotentiometry of the oxygen evolution reaction electrocatalysts of dual oxide clusters (@10 mA / cm 2 )curve;

[0021] Figure 7 is MoO of Example 1 of the present invention x -IrO 2 Chronopotentiometry of the oxygen evolution reaction electrocatalysts of dual oxide clusters (@100mA / cm 2 )curve;

[0022] Figure 8 is MoO of Example 2 of the present invention x -RuO 2 Double oxide cluster oxygen evolution reaction electrocatalyst and RuO of comparative example 2 2 Comparative linear sweep voltammetry curves of oxygen evolution reaction electrocatalysts. DETAILED DESCRIPTION

[0023] It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0024] The present invention provides a method for preparing a high-performance transition metal-noble metal oxide cluster heterostructure oxygen evolution reaction electrocatalyst, comprising the following steps:

[0025] The noble metal oxide is mixed with a transition metal carbonyl compound, and then heat-treated in an inert atmosphere at 100 to 400° C. to obtain the product; wherein the noble metal oxide comprises one, two or a solid solution material of iridium dioxide or ruthenium dioxide.

[0026] The failure mechanism of precious metal oxides such as ruthenium dioxide and iridium dioxide under acidic oxygen evolution reaction conditions is mainly attributed to the following reasons: ① At a relatively high oxidation potential (>1.8V), the metal is oxidized into soluble high-valent metal ions, causing a large amount of active atoms to dissolve and fail; ② The electrophilic lattice oxygen participates in the water oxidation process, thereby generating a large number of oxygen defects, further causing the collapse of the crystal structure. This situation is particularly obvious in ruthenium-based catalytic systems. The electrocatalyst obtained by the above-mentioned preparation method of the present invention has a large number of heterogeneous cluster interfaces to regulate the redox characteristics of metal sites and active oxygen, and the interface multi-site synergistic catalysis of the multi-step proton electron coupling transfer (PCET) process effectively optimizes the water oxidation reaction path, greatly improves the catalytic activity of the oxygen evolution reaction, and significantly reduces the kinetic process of the dissolution of precious metal oxides at high potentials.

[0027] In the above-mentioned preparation method of the present invention, the noble metal oxide and the transition metal carbonyl compound are mixed and heat-treated, wherein the transition metal carbonyl compound loses CO molecules during the pyrolysis process and releases metal atoms (such as Mo, W, Cr, etc., similar to chemical vapor deposition). The noble metal oxide serves as a stable substrate, provides nucleation sites, induces the heterogeneous growth of the transition metal oxide on its surface, and inhibits the migration and agglomeration of the transition metal oxide, thereby forming a clear, high-density, strongly coupled heterogeneous cluster interface.

[0028] In the present invention, the transition metal carbonyl compound is selected from Mo(CO) 6 、W(CO) 6 、Cr(CO) 6 、V(CO) 6 、Ni(CO) 4 , Mn 2 (CO) 10 , Fe 3 (CO) 12 、Re 2(CO) 10 or Co 4 (CO) 12 In one or more specific embodiments of the present invention, the transition metal carbonyl compound is selected from Mo(CO) 6 、W(CO) 6 or Cr(CO) 6 Any one of .

[0029] In the present invention, the molar ratio of the noble metal oxide to the transition metal carbonyl compound is (0.2-5):1, more preferably (0.5-2):1.

[0030] After the step of mixing the noble metal oxide and the transition metal carbonyl compound, the present invention further comprises the step of grinding the mixture of the two, wherein the grinding methods include but are not limited to manual grinding and mechanical grinding, and preferably, manual grinding is used for a grinding time of 0.5 to 4 hours.

[0031] In the present invention, the inert atmosphere includes one or more of argon, helium or nitrogen. In one or more embodiments of the present invention, the inert atmosphere is selected from argon.

[0032] In the present invention, the heat treatment time is 0.5 to 5 hours, more preferably 1 to 3 hours. The heat treatment temperature is more preferably 150 to 300°C, further preferably 180 to 250°C.

[0033] In the present invention, the noble metal oxide is not limited by the preparation method, and the specific preparation methods include high temperature pyrolysis, sol-gel method, hydrothermal method or chemical precipitation method, etc., preferably high temperature pyrolysis. Further, the preparation method of the noble metal oxide is: iridium salt or ruthenium salt is mixed with sodium nitrate in a solvent, and after evaporating the solvent, calcined in an air atmosphere, and then acid-washed and water-washed in sequence. The present invention does not impose any special restrictions on the reaction parameters and solvents in the preparation process, and the reaction parameters and solvents commonly used in the art can be used.

[0034] The present invention also provides a high-performance transition metal-noble metal oxide cluster heterostructure oxygen evolution reaction electrocatalyst obtained by the above preparation method; the size of the noble metal oxide cluster is 1 to 3 nm, and the size of the transition metal oxide cluster is 0.5 to 2 nm.

[0035] The electrocatalyst of the present invention has a high-density heterogeneous cluster interface, which maximizes the number of active sites on the interface. At the same time, it can also optimize the adsorption behavior of the catalytic site and the key oxygen evolution reaction intermediate, breaking the inherent linear adsorption relationship of oxygen intermediate species and significantly improving the activity. The strongly coupled heterogeneous cluster interaction effectively regulates the redox characteristics of the active site, significantly reduces the dissolution kinetics of the noble metal site, and optimizes the reaction path of water oxidation, avoiding the participation of lattice oxygen and maintaining the stability of the crystal structure. Transition metal nanoclusters can act as Lewis acid sites, promote the enrichment of interfacial water molecules on the catalyst surface, and act as proton receptors to significantly accelerate the proton coupling-transfer process.

[0036] The present invention also provides the application of the above-mentioned high-performance transition metal-noble metal oxide cluster heterostructure oxygen evolution reaction electrocatalyst in the field of electrochemical energy conversion, including but not limited to proton exchange membrane water electrolysis hydrogen production, carbon dioxide reduction, NO x Restore, etc.

[0037] The technical solution of the present invention is further described below in conjunction with specific examples. The present invention has no particular limitation on the source of the reagents used in the following examples, and commercially available products known to those skilled in the art can be used.

[0038] Example 1

[0039] This embodiment provides a MoO x -IrO 2 The double oxide cluster electrocatalyst, the preparation method specifically comprises:

[0040] (1) 20 mg IrCl 3 Hydrate with 1g NaNO 3 The mixture was dispersed in a mixed solvent of ethanol and water in a volume ratio of 3:1, subjected to ultrasonic treatment for 1 h, and dried in a water bath at 60° C. to obtain a mixed solid.

[0041] (2) The mixed solid obtained in step (1) was heated to 350° C. in an air atmosphere, kept at this temperature for 2 h, and then naturally cooled to room temperature.

[0042] (3) The above product was washed with hydrochloric acid, water, and ethanol in sequence to obtain a porous IrO 2 Nanocluster materials.

[0043] (4) Remove 20 mg IrO 2 With 20mg Mo(CO) 6 (molar ratio of 1.18:1) were uniformly mixed, ground for 0.5 h, placed in a tube furnace under Ar atmosphere at 200 ° C for 2 h, and then naturally cooled to room temperature to obtain the MoO x -IrO 2Double oxide clusters as electrocatalysts for oxygen evolution reaction.

[0044] In this example, the obtained MoO x -IrO 2 The double oxide cluster oxygen evolution reaction electrocatalyst was characterized by XRD, such as Figure 1 As shown. x -IrO 2 The only detected catalyst is IrO 2 diffraction peaks, but no MoO x The relevant diffraction peaks indicate that MoO x In porous IrO 2 The nanoparticles are evenly dispersed. Figure 2 As shown, MoO x and IrO 2 The size of the clusters is about 2 nm, and a high-density heterogeneous cluster interface is formed. Figure 3 X-ray photoelectron spectroscopy showed that MoO x with IrO 2 There is a strong interfacial electron transfer between them.

[0045] Example 2

[0046] This embodiment provides a MoO x -RuO 2 The double oxide cluster electrocatalyst, the preparation method specifically comprises:

[0047] (1) 20 mg RuCl 3 Hydrate with 0.8 g NaNO 3 The mixture was dispersed in a mixed solvent of ethanol and water in a volume ratio of 3:1, subjected to ultrasonic treatment for 1 h, and dried in a water bath at 60° C. to obtain a mixed solid.

[0048] (2) The mixed solid obtained in step (1) is heated to 450° C. in an air atmosphere, kept at this temperature for 2 h, and then naturally cooled to room temperature.

[0049] (3) The above product was washed with hydrochloric acid, water, and ethanol in sequence to obtain a porous RuO 2 Nanocluster materials.

[0050] (4) Take out 20 mg RuO 2 With 20mg Mo(CO) 6 (molar ratio of 1.98:1) were uniformly mixed, ground for 0.5 h, placed in a tube furnace under Ar atmosphere at 200 ° C for 2 h, and then naturally cooled to room temperature to obtain the MoO x -RuO 2 Double oxide clusters as electrocatalysts for oxygen evolution reaction.

[0051] Example 3

[0052] This embodiment provides a WO x -IrO 2 The double oxide cluster electrocatalyst, the preparation method specifically comprises:

[0053] (1) 20 mg IrCl 3 Hydrate with 1g NaNO 3 The mixture was dispersed in a mixed solvent of ethanol and water in a volume ratio of 3:1, subjected to ultrasonic treatment for 1 h, and dried in a water bath at 60° C. to obtain a mixed solid.

[0054] (2) The mixed solid obtained in step (1) was heated to 350° C. in an air atmosphere, kept at this temperature for 2 h, and then naturally cooled to room temperature.

[0055] (3) The above product was washed with hydrochloric acid, water, and ethanol in sequence to obtain a porous IrO 2 Nanocluster materials.

[0056] (4) Remove 20 mg IrO 2 With 30mg W(CO) 6 (molar ratio of 1.05:1) were uniformly mixed, ground for 1 hour, placed in a tube furnace under Ar atmosphere at 180 ° C for 2 hours, and then naturally cooled to room temperature to obtain the WO x -IrO 2 Double oxide clusters as electrocatalysts for oxygen evolution reaction.

[0057] Example 4

[0058] This embodiment provides a CrO x -IrO 2 The double oxide cluster electrocatalyst, the preparation method specifically comprises:

[0059] (1) 20 mg IrCl 3 Hydrate with 1g NaNO 3 The mixture was dispersed in a mixed solvent of ethanol and water in a volume ratio of 3:1, subjected to ultrasonic treatment for 1 h, and dried in a water bath at 60° C. to obtain a mixed solid.

[0060] (2) The mixed solid obtained in step (1) was heated to 350° C. in an air atmosphere, kept at this temperature for 2 h, and then naturally cooled to room temperature.

[0061] (3) The above product was washed with hydrochloric acid, water, and ethanol in sequence to obtain a porous IrO 2 Nanocluster materials.

[0062] (4) Remove 20 mg IrO 2With 15mg Cr(CO) 6 (molar ratio of 1.3:1) were uniformly mixed, ground for 1 hour, placed in a tube furnace at 250 ° C for 2 hours under Ar atmosphere, and then naturally cooled to room temperature to obtain the CrO x -IrO 2 Double oxide clusters as electrocatalysts for oxygen evolution reaction.

[0063] Example 5

[0064] This embodiment provides a MoO x -RuIrO x The double oxide cluster electrocatalyst, the preparation method specifically comprises:

[0065] (1) 10 mg RuCl 3 、10mgIrCl 3 Hydrate with 1g NaNO 3 The mixture was dispersed in a mixed solvent of ethanol and water in a volume ratio of 3:1, subjected to ultrasonic treatment for 1 h, and dried in a water bath at 60° C. to obtain a mixed solid.

[0066] (2) The mixed solid obtained in step (1) was heated to 350° C. in an air atmosphere, kept at this temperature for 4 h, and then naturally cooled to room temperature.

[0067] (3) The above product was washed with hydrochloric acid, water, and ethanol in sequence to obtain a porous RuIrO x Nanocluster materials.

[0068] (4) Take out 20 mg RuIrO x With 15mg Mo(CO) 6 (molar ratio of 1.6:1) were uniformly mixed, ground for 1 hour, placed in a tube furnace under Ar atmosphere at 200 ° C for 2 hours, and then naturally cooled to room temperature to obtain the MoO x -RuIrO x Double oxide clusters as electrocatalysts for oxygen evolution reaction.

[0069] Comparative Example 1

[0070] This comparative example uses the porous IrO 2 Nanocluster materials as electrocatalysts for oxygen evolution reaction.

[0071] Comparative Example 2

[0072] This comparative example uses the porous IrO 2 Nanocluster materials as electrocatalysts for oxygen evolution reaction.

[0073] Comparative Example 3

[0074] This comparative example is different from Example 1 in that: in step (4), Mo(CO) 6 Precursor replaced with Na 2 MoO 4 ·2H 2 O, resulting in large size, low interface density and weakly interacting supported MoO x / IrO 2 Oxygen evolution reaction electrocatalyst.

[0075] Comparative Example 4

[0076] The difference between this comparative example and Example 1 is that the heat treatment temperature in step (4) is 800°C, and the Mo-IrO 2 Oxygen evolution reaction electrocatalyst.

[0077] Test example

[0078] The electrochemical oxygen evolution reaction test was carried out on the oxygen evolution reaction electrocatalysts of Examples 1 to 2 and Comparative Examples 1 to 4.

[0079] The specific steps are as follows:

[0080] Before conducting the electrochemical oxygen evolution reaction test, the glassy carbon electrode was continuously polished with aluminum oxide powder with a particle size of 50nm, and then cleaned with ethanol and water to obtain a clean surface. Take 5mg of the oxygen evolution reaction electrocatalyst prepared in the above embodiments and comparative examples, add 490mL of isopropanol and 10μL of a mixed solution of 5wt% Nafion, and ultrasonically disperse for 1h to obtain a uniform slurry. Take 10μL of the slurry and drop it on the surface of the glassy carbon electrode with a diameter of 5mm. After the slurry is dried, a loading of 0.5mg / cm 2 The working electrode is a platinum electrode, and the counter electrode is Hg / Hg 2 SO 4 The electrode was used as a reference electrode, and 0.5 mol / L sulfuric acid solution was used as the electrolyte. A rotating disc motor was used, the working electrode speed was 1600 rpm, and the linear polarization curve of the oxygen evolution reaction was obtained at a scanning speed of 5 mV / s.

[0081] In Example 1, MoO x -IrO 2 Double oxide cluster electrocatalyst at 10 mA / cm 2 The overpotential at the working current density is 207mV, and the Tafel slope is 64mV / dec. Figure 4 The working current density in the three-electrode electrolytic cell was recorded using an electrochemical workstation at 10, 50, 100, 200 and 500 mA / cm 2When the working potential changes after continuous operation for 100s, Figure 5 As shown. x -IrO 2 The catalyst showed excellent catalytic stability at different current densities. The long-term stability of the catalyst was further evaluated using chronopotentiometry (CP). Figure 6 and Figure 7 Display, MoO x -IrO 2 Catalyst at 10mA / cm 2 and 100mA / cm 2 It can operate stably for 600h and 500h at different current densities, with decay rates of only 0.07mV / h and 0.21mV / h respectively.

[0082] IrO of Comparative Example 1 2 Oxygen evolution reaction electrocatalyst at 10mA / cm 2 The overpotential at the working current density is 271 mV, and the Tafel slope is 72 mV / dec, which is significantly higher than that of MoO in Example 1. x -IrO 2 The stability test shows that when the potential is greater than 1.7V, its catalytic performance decreases greatly. Figure 5 shown.

[0083] MoO of Example 2 x -RuO 2 Double oxide clusters electrocatalysts for oxygen evolution reaction at 10 mA / cm 2 The overpotential at the working current density is 197mV. Figure 8 As shown. Comparative Example 2 RuO 2 Oxygen evolution reaction electrocatalyst at 10mA / cm 2 The overpotential at the working current density is 221 mV, which is higher than that of MoO x -RuO 2 .

[0084] Comparative Example 3 Supported MoO x / IrO 2 Oxygen evolution reaction electrocatalyst at 10mA / cm 2 The overpotential at the working current density is 317 mV, and the Tafel slope is 83 mV / dec, which is significantly higher than that of MoO in Example 1. x -IrO 2 .

[0085] Mo-IrO without heterogeneous interface structure of Comparative Example 4 2 Oxygen evolution reaction electrocatalyst at 10mA / cm 2The overpotential at the working current density is 355 mV, and the Tafel slope is 96 mV / dec, which is significantly higher than that of MoO in Example 1. x -IrO 2 .

[0086] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a high-performance transition metal-noble metal oxide cluster heterostructure oxygen evolution reaction electrocatalyst, characterized in that: The steps include: The noble metal oxide is mixed with a transition metal carbonyl compound, and then heat-treated in an inert atmosphere at 100 to 400° C. to obtain the product; wherein the noble metal oxide comprises one, two or a solid solution material of iridium dioxide or ruthenium dioxide.

2. The preparation method according to claim 1, characterized in that The transition metal carbonyl compound is selected from Mo(CO)6, W(CO)6, Cr(CO)6, V(CO)6, Ni(CO)4, Mn2(CO) 10 、Fe3(CO) 12 、Re2(CO) 10 or Co4(CO) 12 One or more of .

3. The preparation method according to claim 2, characterized in that: The transition metal carbonyl compound is selected from any one of Mo(CO)6, W(CO)6 or Cr(CO)6.

4. The preparation method according to claim 1, characterized in that: The molar ratio of the noble metal oxide to the transition metal carbonyl compound is (0.2-5):

1.

5. The preparation method according to claim 1, characterized in that: The inert atmosphere includes one or more of argon, helium or nitrogen.

6. The preparation method according to claim 1, characterized in that: The heat treatment time is 0.5 to 5 hours.

7. The preparation method according to claim 1, characterized in that: The preparation method of the noble metal oxide is a sol-gel method, a hydrothermal method, a chemical precipitation method or a high-temperature pyrolysis method.

8. The preparation method according to claim 7, characterized in that: The preparation method of the noble metal oxide is as follows: iridium salt or ruthenium salt and sodium nitrate are mixed in a solvent, the solvent is evaporated and then calcined in an air atmosphere, and then acid-washed and water-washed in sequence to obtain the noble metal oxide.

9. The high-performance transition metal-noble metal oxide cluster heterostructure oxygen evolution reaction electrocatalyst obtained by the preparation method according to any one of claims 1 to 8, characterized in that: The size of the noble metal oxide cluster is 1-3 nm, and the size of the transition metal oxide cluster is 0.5-2 nm.

10. Application of the high-performance transition metal-noble metal oxide cluster heterostructure oxygen evolution reaction electrocatalyst as claimed in claim 9 in the field of electrochemical energy conversion.

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