Cobalt-based nanosheet anchored noble metal oxide cluster catalyst as well as preparation method and application thereof

Abstract

The invention discloses a cobalt-based nanosheet anchored noble metal oxide cluster catalyst and a preparation method and application thereof, and relates to the technical field of catalysts.The preparation method comprises the steps that after a cobalt acetate solution, a metal salt solution, ammonium metavanadate and acetylene black are fully mixed to be uniform, stirring is conducted at the temperature of 50-100 DEG C, and a sample is filtered and collected; performing vacuum drying on the sample, and performing pyrolysis in an air atmosphere to obtain a catalyst; the invention also provides application of the catalyst in the field of energy catalysis. The preparation method has the beneficial effects that the catalyst has a definite structure and relatively high electric / ionic conductivity, catalytic activity and stability. Meanwhile, the catalyst is simple in preparation method and low in cost, can be synthesized on a large scale, has high potential industrial application value in the field of energy catalysis, and can be used for electrocatalytic water decomposition, oxygen reduction reaction, carbon dioxide reduction reaction and various organic catalytic reactions.

Description

Technical Field

[0001] The invention relates to the technical field of catalysts, and in particular to a cobalt-based nanosheet-anchored noble metal oxide cluster catalyst and a preparation method and application thereof. Background Art

[0002] Ruthenium dioxide (RuO 2 As a highly catalytically active material, RuO exhibits excellent catalytic performance in many organic reactions and electrocatalytic reactions. Its unique electronic structure and excellent conductivity make it 2 In the electrocatalytic water splitting reaction, especially in the oxygen evolution reaction (OER), RuO shows extremely high catalytic activity. 2 Although they have excellent catalytic performance, their high cost and scarce resources severely limit their feasibility in large-scale commercial applications. Therefore, the development of efficient and low-cost electrocatalysts is crucial to promote the development of the electrocatalytic field.

[0003] In order to solve the problem of precious metal scarcity and high price and reduce the amount of precious metals used, RuO 2 Making clusters and loading them on a carrier with high specific surface area and excellent conductivity has become an effective strategy. This strategy can not only significantly reduce RuO 2 The amount of RuO 2 The interactions between clusters further regulate the electronic structure of the catalyst and optimize its catalytic performance for the electrocatalytic water splitting reaction. Summary of the invention

[0004] The purpose of the present invention is to solve at least one of the technical problems existing in the prior art and to provide a cobalt-based nanosheet-anchored noble metal oxide cluster catalyst and a preparation method and application thereof.

[0005] Cobalt vanadate (CoV 2 O 6 ) nanosheets, as a two-dimensional material, provide abundant active sites for electrocatalytic reactions due to their unique layered structure and high specific surface area. 2 O 6 The nanosheets also have good chemical stability and corrosion resistance, and can work stably for a long time in alkaline electrolytes. 2 Cluster loading on CoV 2 O 6 Nanosheets are expected to combine the advantages of both to prepare efficient and low-cost electrocatalytic water splitting catalysts. In addition, the Co in cobalt vanadate is conjugated with multivalent vanadium, palladium, and platinum, and the additional active sites are expected to be combined with RuO 2 、PdO、PtO 2The electronic structure of the clusters produces a synergistic effect, further enhancing the catalytic performance of the catalyst for oxygen evolution reaction (OER). Therefore, the present invention uses cobalt vanadate nanosheets to anchor precious metal oxides (ruthenium dioxide, PdO, PtO 2 ) clusters, which are expected to be used to prepare efficient and low-cost electrocatalytic water splitting catalysts, providing a new solution for the industrial application of electrocatalytic water splitting technology, and are of great significance for promoting the development of the field of energy catalysis.

[0006] The technical solution of the present invention is as follows: The first aspect of the present invention provides a method for preparing a cobalt-based nanosheet-anchored noble metal oxide cluster catalyst, comprising the following steps: After the cobalt acetate solution, the metal salt solution, ammonium metavanadate and acetylene black are fully mixed, the mixture is stirred at a temperature of 50° C. to 100° C., and the sample is collected by filtration; wherein the metal species involved in the metal salt solution include at least one of Ru, Pd and Pt; The sample is vacuum dried and then pyrolyzed in an air atmosphere to obtain a cobalt-based nanosheet-anchored noble metal oxide cluster catalyst.

[0007] Optionally, the volume ratio of the cobalt acetate solution to the metal salt solution is 3:1-20:1, and the mass ratio of the ammonium metavanadate to acetylene black is 1:1-10:1.

[0008] Optionally, the salt type involved in the metal salt solution is at least one of metal acetate, metal chloride and vanadate.

[0009] Optionally, the concentration of the metal salt solution is 0.06 mol / L to 0.4 mol / L, and the concentration of the cobalt acetate solution is 0.05 mol / L to 0.07 mol / L.

[0010] Optionally, the vacuum drying is performed at a temperature of 50° C. to 100° C. for 12 to 24 hours.

[0011] Optionally, the specific steps of pyrolysis in air atmosphere include: The vacuum-dried sample is heated to 300°C~500°C at a heating rate of 5°C / min~20°C / min in a tube furnace atmosphere, kept at the constant temperature for 5 h~15 h, and then naturally cooled to room temperature to obtain a cobalt-based nanosheet-anchored precious metal oxide cluster catalyst.

[0012] The second aspect of the present invention provides a cobalt-based nanosheet-anchored noble metal oxide cluster catalyst, which is obtained by the above-mentioned preparation method.

[0013] Among them, noble metal oxides include RuO 2 、PdO、PtO2 .

[0014] The catalyst includes RuO 2 @CoV 2 O 6 、PdO@CoV 2 O 6 , PtO 2 @CoV 2 O 6 .

[0015] Optionally, the cobalt-based nanosheets are cobalt vanadate nanosheets, the noble metal oxides loaded on the cobalt vanadate nanosheets are in the form of nanoclusters, and the loading amount of the noble metal is 0.8 wt% to 5.1 wt%.

[0016] Optionally, the catalyst is an ultra-thin nanosheet with a thickness of 1 nm to 3 nm, and the average particle size of the loaded noble metal oxide nanoclusters is 0.7 nm to 1.5 nm.

[0017] The second aspect of the present invention provides the application of the above-mentioned catalyst in the field of energy catalysis, including application in water decomposition reaction, oxygen reduction reaction, carbon dioxide reduction reaction and organic catalytic reaction.

[0018] The catalyst prepared by the present invention (RuO 2 @CoV 2 O 6 、PdO@CoV 2 O 6 , PtO 2 @CoV 2 O 6 ) can be used as anode catalyst for electrocatalytic OER reaction, RuO 2 @CoV 2 O 6 Up to 10 mA·cm on glassy carbon electrode -2 The overpotential of the current density is only 167 mV, reaching 100 mA cm on the glassy carbon electrode and carbon cloth. -2 The overpotentials for the current densities only require 230 and 201 mV, respectively.

[0019] The present invention has at least one of the following beneficial effects: The present invention synthesized the noble metal oxide (RuO) anchored on the cobalt vanadate nanosheets through a simple one-pot synthesis + calcination method. 2 、PdO、PtO 2 ) Nanocluster catalyst RuO 2 @CoV 2 O 6 、PdO@CoV 2 O6 , PtO 2 @CoV 2 O 6 The material morphology is a nanosheet with a thickness of about 2 nm. 2 、PdO、PtO 2 The size of the cluster is about 1 nm, and the loading amount of ruthenium, palladium and platinum metals is 0.8wt%~5.1wt%. The catalyst has a clear structure, high electrical / ionic conductivity, catalytic activity and stability. At the same time, the preparation method used in the present invention is simple and low in cost, only about 32 yuan per gram (only RuO 2 1 / 46 of the original value).

[0020] The catalyst RuO prepared by the present invention 2 @CoV 2 O 6 、PdO@CoV 2 O 6 , PtO 2 @CoV 2 O 6 Excellent electrochemical stability at 500 mA / cm 2 The sample can maintain good stability for 45 hours at a current density of 1.0 M and exhibit excellent OER catalytic performance. In a classic three-electrode system with 1.0 M KOH as electrolyte, the sample can drive 10 mA cm at an overpotential of only 167 mV on the glassy carbon electrode. -2 The current density of 100 mA cm-2 can be driven with an overpotential of only 230 and 201 mV on the glassy carbon electrode and carbon cloth support electrode. -2 Therefore, the cobalt vanadate nanosheet anchored noble metal oxide cluster catalyst prepared by the present invention has a high potential application value in the field of energy catalysis and can be used in other processes such as ORR, CO 2 RR and various organic catalytic reactions. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 is RuO in Example 1 of the present invention 2 @CoV 2 O 6 X-ray powder diffraction pattern of .

[0022] Figure 2 is RuO in Example 1 of the present invention 2 @CoV 2 O 6 Atomic force microscopy image.

[0023] Figure 3 is RuO in Example 1 of the present invention 2 @CoV2 O 6 Transmission electron microscopy image.

[0024] Figure 4 is RuO in Example 1 of the present invention 2 @CoV 2 O 6 Spherical aberration-corrected transmission electron micrograph.

[0025] Figure 5 is RuO in Example 1 of the present invention 2 @CoV 2 O 6 Linear sweep voltammetry curves of OER on glassy carbon.

[0026] Figure 6 is RuO in Example 1 of the present invention 2 @CoV 2 O 6 Linear sweep voltammetry curves of OER on carbon cloth.

[0027] Figure 7 is RuO in Example 1 of the present invention 2 @CoV 2 O 6 Tafel curve diagram.

[0028] Figure 8 is RuO in Example 1 of the present invention 2 @CoV 2 O 6 At 500 mA·cm -2 Diagram of constant voltage electrolysis under current density.

[0029] Fig. 9 is RuO in Example 1 of the present invention 2 @CoV 2 O 6 Electrochemical impedance spectroscopy.

[0030] Fig.10 is RuO in Example 1 of the present invention 2 @CoV 2 O 6 Electrochemical specific surface area diagram.

[0031] Fig.11 is RuO in Example 1 of the present invention 2 @CoV 2 O 6 Electrochemical specific surface area conversion chart.

[0032] Fig.12 PdO@CoV in Example 2 of the present invention 2 O 6X-ray powder diffraction pattern of .

[0033] Fig.13 PdO@CoV in Example 2 of the present invention 2 O 6 Linear sweep voltammetry curves of OER on glassy carbon.

[0034] Fig.14 PdO@CoV in Example 2 of the present invention 2 O 6 At 500 mA·cm -2 Diagram of constant voltage electrolysis under current density.

[0035] Fig.15 is PtO in Example 3 of the present invention 2 @CoV 2 O 6 X-ray powder diffraction pattern of .

[0036] Fig.16 is PtO in Example 3 of the present invention 2 @CoV 2 O 6 Linear sweep voltammetry curves of OER on glassy carbon.

[0037] Fig.17 is PtO in Example 3 of the present invention 2 @CoV 2 O 6 Figure 1. Constant current electrolysis at 0.78 V.

[0038] Fig.18 is RuO in Example 4 of the present invention 2 @CoV 2 O 6 -1. RuO 2 @CoV 2 O 6 -2 and RuO 2 @CoV 2 O 6 -4's X-ray powder diffraction pattern.

[0039] Fig.19 is RuO in Example 4 of the present invention 2 @CoV 2 O 6 -1 Transmission electron micrograph.

[0040] Fig. 20 is RuO in Example 4 of the present invention 2 @CoV 2 O 6 -2 Transmission electron micrograph.

[0041] Fig.21 is RuO in Example 4 of the present invention 2 @CoV 2 O 6 -4 Transmission electron microscopy image.

[0042] Fig. 22 is RuO in Example 4 of the present invention 2 @CoV 2 O 6 -1~ RuO 2 @CoV 2 O 6 -4 OER linear sweep voltammetry curve on glassy carbon. DETAILED DESCRIPTION

[0043] In order to make the technical problems, technical solutions and beneficial effects solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0044] Example 1 Catalyst RuO 2 @CoV 2 O 6 The preparation method comprises the following steps: Prepare 19 mL of 0.06 mol / L cobalt acetate solution, 1 mL of 0.2 mol / L ruthenium chloride solution, 50 mL of 0.05 mol / L ammonium metavanadate solution, and 40 mg of acetylene black; The cobalt acetate solution, ruthenium chloride solution, ammonium metavanadate solution and acetylene black were mixed, and after the acetylene black was fully dissolved, the mixture was stirred at 80° C. for 5 hours, and the sample was collected by filtration.

[0045] The sample was then washed with water and alcohol and centrifuged and dried in a vacuum oven at 60°C for 12 hours.

[0046] Finally, the dried sample was heated to 500°C in a tube furnace at a heating rate of 10°C / min, kept at this temperature for 15 h, and then naturally cooled to room temperature to obtain the product RuO 2 @CoV 2 O 6 .

[0047] ProductRuO 2 @CoV 2 O 6 The X-ray diffraction pattern of Figure 1 ,Depend on Figure 1 It can be seen that the catalyst prepared in this example contains both cobalt vanadate and ruthenium dioxide phases, which proves that the product RuO 2@CoV 2 O 6 The synthesis was successful; see the atomic force microscope image Figure 2 ,Depend on Figure 2 It can be seen that the catalyst prepared by the present invention is an ultra-thin nanosheet with a thickness of 1 nm to 3 nm; the transmission electron microscopy image is shown in Figure 3 ,Depend on Figure 3 It can be seen that the catalyst prepared by the present invention has a lamellar structure, and the ruthenium dioxide clusters are evenly anchored on the cobalt vanadate nanosheets; the spherical aberration corrected transmission electron microscopy image is shown in Figure 4 ,Depend on Figure 4 It can be seen that the average particle size of the catalyst-loaded ruthenium dioxide clusters prepared by the present invention is 0.7 nm to 1.5 nm, which is a very small particle size and is an ultrafine ruthenium dioxide cluster.

[0048] The product RuO prepared in Example 1 2 @CoV 2 O 6 Perform performance testing, the test methods and results are as follows: (1) RuO 2 @CoV 2 O 6 Electrocatalytic OER performance test Example 1 obtained RuO 2 @CoV 2 O 6 The electrocatalytic OER performance test was carried out on a CHI760E electrochemical workstation at room temperature using a classic three-electrode system. The electrolyte was 1.0 M KOH solution. Hg / HgO and Pt sheets were used as reference electrodes and counter electrodes. 4 mg RuO 2 @CoV 2 O 6 , add 150 uL isopropanol and 10 uL Nafion, and after ultrasonication for 20 minutes, drop the sample on the glassy carbon electrode and carbon cloth as the working electrode.

[0049] Figure 5 , Figure 6 The linear sweep voltammetry curve shown was obtained at a scan rate of 5 mV / s. Figure 5 and Figure 6 It can be seen that RuO 2 @CoV 2 O 6 Driven at 10 mA·cm on a glassy carbon electrode -2 The overpotential required for the current density is 167 mV, and the current density is 100 mA cm on the glassy carbon electrode and carbon cloth. -2 The overpotentials required for the current densities are 230 and 201 mV, respectively. Figure 7 The Tafel curve shown is from Figure 5 , Figure 6 Calculation shows that RuO 2 @CoV 2 O 6 The Tafel slope on the glassy carbon electrode is 56.4 mV·dec -1 ( Figure 7 RuO 2 @CoV 2 O 6 -GCE), RuO 2 @CoV 2 O 6 The Tafel slope on the carbon cloth electrode is 54.4 mV·dec -1 ( Figure 7 RuO 2 @CoV 2 O 6 -CC). Figure 8 Shown at 500 mA·cm -2 RuO at current density 2 @CoV 2 O 6 After 95 hours of electrolysis, the performance decreased by only 9.7%, indicating that RuO 2 @CoV 2 O 6 The stability is very good.

[0050] (2) RuO 2 @CoV 2 O 6 Electrochemical Impedance Spectroscopy Test Electrochemical impedance spectroscopy (EIS) measurements were performed in the frequency range of 0.01 Hz to 100 kHz.

[0051] Electrochemical impedance spectroscopy Fig. 9 ,Depend on Fig. 9 It can be seen that RuO 2 @CoV 2 O 6 The charge transfer resistance of the catalyst is about 15 Ω, which indicates that RuO 2 @CoV 2 O 6 Has a faster reaction rate.

[0052] (3) RuO 2 @CoV 2 O 6 Electrochemical surface area test Cyclic voltammetry (CV) measurements were performed to investigate the electrochemical double layer capacitance (C dlCVs were performed in the non-Faradaic range (0.9–1.0 V vs RHE) with a scan rate of 20 mV s -1 , 40 mV s -1 , 60 mVs -1 , 80 mV s -1 and 100 mV s -1 A linear plot was obtained by plotting the current density versus scan rate at 0.95 V vs RHE. dl It is half the slope of the linear graph and is used to represent the ECSA.

[0053] Electrochemical specific surface area diagram Fig.10 and Fig.11 ,Depend on Fig.10 and Fig.11 It can be seen that RuO 2 @CoV 2 O 6 C dl The value is 23.99 mF cm -2 , with a larger electrochemical surface area and double-layer capacitance, indicating that the catalyst has more active sites and better performance.

[0054] Example 2 Catalyst PdO@CoV 2 O 6 The preparation method comprises the following steps: The “ruthenium chloride solution” was changed to “palladium chloride solution”, and the rest was the same as in Example 1.

[0055] Fig.12 The X-ray diffraction pattern of the catalyst prepared in Example 2 is Fig.12 It can be seen that cobalt vanadate and palladium oxide phases exist in the catalyst at the same time, proving that the catalyst PdO@CoV 2 O 6 The synthesis was successful.

[0056] Fig.13 The OER performance of the catalyst prepared in Example 2, PdO@CoV obtained in Example 2 2 O 6 The electrocatalytic OER performance test conditions are consistent with those in Example 1. Fig.13 It can be seen that PdO@CoV 2 O 6 Driven at 10 mA·cm on a glassy carbon electrode -2 The overpotential required for the current density is 305 mV.

[0057] Fig.14 The stability test of the catalyst prepared in Example 2 is as follows: Fig.14Shown at 500 mA·cm -2 PdO@CoV at current density 2 O 6 After 45 hours of electrolysis, the performance decreased by only 9.3%, indicating that PdO@CoV 2 O 6 The stability is very good.

[0058] Example 3 Catalyst PtO 2 @CoV 2 O 6 The preparation method comprises the following steps: The “ruthenium chloride solution” was changed to “platinum chloride solution”, and the rest was the same as in Example 1.

[0059] Fig.15 The X-ray diffraction pattern of the catalyst prepared in Example 3 is Fig.15 It can be seen that cobalt vanadate and platinum oxide phases exist in the catalyst at the same time, proving that the catalyst PtO 2 @CoV 2 O 6 The synthesis was successful.

[0060] Fig.16 The OER performance of the catalyst prepared in Example 3. The PtO 2 @CoV 2 O 6 The electrocatalytic OER performance test conditions are consistent with those in Example 1. Fig.16 It can be seen that PtO 2 @CoV 2 O 6 Driven at 10 mA·cm on a glassy carbon electrode -2 The overpotential required for the current density is 290 mV.

[0061] Fig.17 The stability test of the catalyst prepared in Example 3 is as follows: Fig.17 PtO at 0.78 V 2 @CoV 2 O 6 After 40 hours of electrolysis, the performance decreased by only 10.2%, indicating that PtO 2 @CoV 2 O 6 The stability is very good.

[0062] Example 4 The only difference from Example 1 is that the concentrations of the ruthenium chloride solution and the cobalt acetate solution are changed, and the rest are the same as Example 1.

[0063] In Example 1, the concentration of the cobalt acetate solution is 0.060 mol / L, the concentration of the ruthenium chloride solution is 0.20 mol / L, and the (main sample) RuO 2 @CoV 2 O 6 -3; The ruthenium chloride solution and the cobalt acetate solution of each sample in this embodiment are as follows: (1) The concentration of cobalt acetate solution was changed to 0.067 mol / L, and the concentration of ruthenium chloride solution was changed to 0.067 mol / L to prepare RuO 2 @CoV 2 O 6 -1; (2) The concentration of cobalt acetate solution was changed to 0.062 mol / L, and the concentration of ruthenium chloride solution was changed to 0.15 mol / L to prepare RuO 2 @CoV 2 O 6 -2; (3) The concentration of cobalt acetate solution was changed to 0.058 mol / L, and the concentration of ruthenium chloride solution was changed to 0.23 mol / L to prepare RuO 2 @CoV 2 O 6 -4.

[0064] Fig.18 This is the X-ray diffraction pattern of the catalyst prepared in Example 4, wherein: Fig.18 "(Main sample) RuO 2 @CoV 2 O 6 -3" is the catalyst prepared in Example 1, Fig.18 It can be seen that compared with the "(main sample) RuO prepared in Example 1 2 @CoV 2 O 6 -3”, RuO prepared in Example 4 2 @CoV 2 O 6 -1. RuO 2 @CoV 2 O 6 -2 and RuO 2 @CoV 2 O 6 -4 catalysts both have cobalt vanadate and ruthenium dioxide phases, proving that the catalysts RuO 2 @CoV 2 O 6 The synthesis was successful.

[0065] Figure 19~Figure 21 The RuO prepared in Example 4 is2 @CoV 2 O 6 -1. RuO 2 @CoV 2 O 6 -2 and RuO 2 @CoV 2 O 6 -4 catalyst transmission electron microscopy image, by Figure 19~Figure 21 It can be seen that RuO 2 @CoV 2 O 6 -1. RuO 2 @CoV 2 O 6 -2 and RuO 2 @CoV 2 O 6 The ruthenium dioxide clusters of the -4 catalyst are evenly anchored on the cobalt vanadate nanosheets.

[0066] Fig. 22 The OER performance of the catalyst prepared in Example 4. The RuO 2 @CoV 2 O 6 The electrocatalytic OER performance test conditions are consistent with those in Example 1. Fig. 22 It can be seen that the RuO prepared in Example 4 2 @CoV 2 O 6 -1. RuO 2 @CoV 2 O 6 -2 and RuO 2 @CoV 2 O 6 -4 catalysts all have certain catalytic performance, among which "(main sample) RuO 2 @CoV 2 O 6 -3" driven at 10 mA·cm on a glassy carbon electrode -2 The overpotential required for the current density was 167 mV, which showed the best performance. This indicated that increasing or decreasing the concentration of ruthenium chloride solution and cobalt acetate solution would lead to a decrease in catalyst performance.

[0067] The present invention uses cobalt vanadate as a carrier, and can prepare ultra-thin (2nm) and loaded with an average particle size (1.0 nm) ultra-fine RuO 2 、PdO、PtO 2 Composite RuO clusters with long-term electrochemical stability 2 @CoV 2 O6 、PdO@CoV 2 O 6 , PtO 2 @CoV 2 O 6 The cobalt vanadate nanosheets anchor RuO 2 、PdO、PtO 2 The catalyst preparation method of the cluster is simple and low-cost, suitable for large-scale synthesis, and has high potential industrial application value in the field of energy catalysis. It can be used for electrocatalytic water decomposition reaction, oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO 2 RR) and various organocatalytic reactions.

[0068] Taking electrocatalytic water splitting as an example, since hydrogen has a high energy density and is clean and environmentally friendly, the electrocatalytic water splitting hydrogen production technology has broad application prospects. Water splitting includes two half reactions: hydrogen evolution reaction (HER) on the cathode and oxygen evolution reaction (OER) on the anode. Both require the introduction of catalysts to reduce the reaction overpotential in the electrocatalytic reaction and improve the reaction efficiency. Some precious metals and their oxides are currently recognized as excellent water electrolysis catalysts. However, due to the scarcity of resources and high cost of such catalysts, their commercial application is greatly limited. RuO 2 @CoV 2 O 6 、PdO@CoV 2 O 6 , PtO 2 @CoV 2 O 6 It has excellent OER electrocatalytic performance, which is better than the current commercial catalyst RuO 2 .

[0069] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for preparing a cobalt-based nanosheet-anchored noble metal oxide cluster catalyst, characterized in that: The following steps are involved: After the cobalt acetate solution, the metal salt solution, ammonium metavanadate and acetylene black are fully mixed, the mixture is stirred at a temperature of 50° C. to 100° C., and the sample is collected by filtration; wherein the metal species involved in the metal salt solution include at least one of Ru, Pd and Pt; The sample is vacuum dried and then pyrolyzed in an air atmosphere to obtain a cobalt-based nanosheet-anchored noble metal oxide cluster catalyst.

2. The preparation method according to claim 1, characterized in that: The volume ratio of the cobalt acetate solution to the metal salt solution is 3:1-20:1, and the mass ratio of the ammonium metavanadate to acetylene black is 1:1-10:

1.

3. The preparation method according to claim 1, characterized in that: The salt type involved in the metal salt solution is at least one of metal acetate, metal chloride and vanadate.

4. The preparation method according to claim 1, characterized in that: The concentration of the metal salt solution is 0.06 mol / L to 0.4 mol / L, and the concentration of the cobalt acetate solution is 0.05 mol / L to 0.07 mol / L.

5. The preparation method according to claim 1, characterized in that: The vacuum drying temperature is 50° C. to 100° C., and the vacuum drying time is 12 to 24 hours.

6. The preparation method according to claim 1, characterized in that: The specific steps of pyrolysis under air atmosphere include: The vacuum-dried sample is heated to 300°C~500°C at a heating rate of 5°C / min~20°C / min in a tube furnace atmosphere, kept at the constant temperature for 5 h~15 h, and then naturally cooled to room temperature to obtain a cobalt-based nanosheet-anchored precious metal oxide cluster catalyst.

7. A cobalt-based nanosheet-anchored noble metal oxide cluster catalyst, characterized in that: The method is obtained by any one of claims 1 to 6.

8. The catalyst according to claim 7, characterized in that The cobalt-based nanosheets are cobalt vanadate nanosheets. The noble metal oxides loaded on the cobalt vanadate nanosheets exist in the form of nanoclusters, and the loading amount of the noble metal is 0.8 wt% to 5.1 wt%.

9. The catalyst according to claim 8, characterized in that The catalyst is an ultra-thin nanosheet with a thickness of 1 nm to 3 nm, and the average particle size of the loaded noble metal oxide nanoclusters is 0.7 nm to 1.5 nm.

10. Use of the catalyst according to any one of claims 7 to 9 in the field of energy catalysis, characterized in that: Including applications in water decomposition reactions, oxygen reduction reactions, carbon dioxide reduction reactions and organic catalytic reactions.

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