W-doped Co3O4 loaded Ru monatomic catalyst for acidic OER and preparation method of W-doped Co3O4 loaded Ru monatomic catalyst

Abstract

The invention relates to the technical field of electrocatalytic materials, in particular to a W-doped Co3O4 loaded Ru monatomic catalyst for acidic OER and a preparation method of the W-doped Co3O4 loaded Ru monatomic catalyst. Comprising the following steps: firstly, dissolving 2-methylimidazole in ultrapure water, dissolving Co (NO3) 2.6 H2O in ultrapure water in another beaker, pouring a Co (NO3) 2.6 H2O solution into a 2-methylimidazole solution, stirring until the Co (NO3) 2.6 H2O solution is completely dissolved, dipping carbon cloth in the solution, collecting the washed carbon cloth, and drying; dissolving Na2WO4. 2H2O in ultrapure water and an ethanol solution, putting the carbon cloth into the solution, carrying out a hydrothermal reaction, collecting the washed carbon cloth, drying, putting the carbon cloth into a RuCl3 aqueous solution, carrying out ion exchange, and finally calcining in air. The electronic structure and the surface property of the catalyst are regulated and controlled, lattice oxygen is prevented from participating in the reaction, and peroxidation of Ru in OER is prevented, so that the stability is improved. The overpotential of the synthesized RuCoWOx / CC under the current density of 10mA cm <-2 > is 198mV, and the RuCoWOx / CC can stably run for 200h under the current density.

Description

Technical Field

[0001] The present invention relates to the technical field of catalytic materials, and in particular to a W-doped Co3O4-loaded Ru single-atom catalyst for acidic OER and a preparation method thereof. Background Art

[0002] The overuse of non-renewable fossil fuels such as coal, oil, and natural gas has not only led to energy depletion but also caused serious environmental problems such as global warming and air pollution. Hydrogen is a renewable, clean energy source with advantages such as abundant resources, high calorific value, and zero pollution and emissions. Currently, the vast majority of hydrogen is produced through the methane steam reforming process, which releases CO2 greenhouse gases and is environmentally unfriendly. The electrolysis of water to produce hydrogen, however, offers a simple process and zero carbon emissions, making it a promising alternative to methane steam reforming as the next-generation clean method for producing hydrogen fuel. Water electrolysis involves two half-reactions: the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). The performance of water electrolysis depends primarily on the overpotentials of the HER and OER. Lower overpotentials and faster reaction kinetics favor electrocatalytic water splitting. The overpotential of water electrolysis primarily stems from the anodic portion of the OER (a complex four-electron elementary reaction). Developing efficient and inexpensive OER catalysts is a key technology for water electrolysis.

[0003] Existing water electrolysis hydrogen production technologies mainly include three types: alkaline water electrolysis (AWE), solid oxide water electrolysis (SOEC) and proton exchange membrane water electrolysis (PEMWE). Currently, SOEC is in the experimental research stage, and the process of AWE is relatively mature. However, the electrolyte it uses is corrosive and has large ohmic losses; the operating pressure is low. In contrast, PEMWE hydrogen production technology has the advantages of low ohmic losses, high current density, high hydrogen production purity, compact system design and fast system response. At present, PEM anodes are mainly based on Ir-based catalysts. However, compared with Ir (240-250 yuan / g), Ru (19.5-20.5 yuan / g) is not only more abundant in earth reserves and cheaper in price, but also has a much higher theoretical catalytic activity than Ir. Ru is used as an acidic OER catalyst. For example, CN202411678190 discloses a "double transition metal-doped RuO2 acidic OER electrocatalyst" in which ruthenium salt, Zr salt, Mo salt, and ethanol are added to water, the resulting mixed solution is subjected to a hydrothermal reaction, and the product is washed, dried, and then annealed. However, the RuO2 catalyst provided by this solution has the following key problems: low Ru atom utilization, easy oxidation at high potential, resulting in poor stability. Moreover, the Ru content of the Ru-based catalyst is too high, and the material cost remains high.

[0004] Recently, single-atom catalysts have demonstrated high catalytic activity and up to 100% atomic utilization in the oxygen evolution reaction (OER) due to their abundant unsaturated coordination active sites and unique quantum size effects. Therefore, loading Ru in the form of single atoms on specific supports to construct a low-cost, highly active, and highly stable Ru single-atom catalyst, thereby avoiding the participation of lattice oxygen in the OER reaction, is expected to be an effective approach to addressing the above-mentioned issues.

[0005] Based on the above ideas, a method for preparing Ru single-atom catalyst RuTiCeO was disclosed in CN202410577120. x 》When loading precious metal Ru, RuCl3 was used as the precious metal source and the bimetallic oxide support TiCeO was synthesized by sol-gel method. x In air atmosphere, Ru NPs are re-decomposed and dispersed on the support by temperature driving, thus forming single atoms. However, the catalyst is actually used in the catalysis of chlorobenzene. x The weak metal-support interaction in RuTiCeO may not be able to maintain structural stability under the harsh conditions of acidic OER and cannot be applied to water decomposition. x The preparation process is relatively complicated and requires evaporation and calcination to obtain TiCeO x The Ru colloidal solution was then prepared by oil bath reflux, and finally mixed and calcined to obtain RuTiCeO x . Summary of the Invention

[0006] The purpose of the present invention is to provide a W-doped Co3O4-loaded Ru single-atom catalyst for acidic OER and a preparation method thereof, so as to solve the problems existing in the prior art of low Ru atom utilization, easy oxidation at high potential, resulting in poor stability and high material cost.

[0007] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is:

[0008] A W-doped Co3O4-loaded Ru single-atom catalyst for acidic OER and a preparation method thereof, comprising the following steps:

[0009] Step 1. Preparation of Co MOF / CC: Add a certain amount of 2-methylimidazole to the aqueous solution and stir evenly; similarly, add a certain amount of Co(NO3)2·6H2O to the aqueous solution and stir evenly. Then quickly pour the Co(NO3)2·6H2O aqueous solution into the 2-methylimidazole aqueous solution and continue stirring until it is completely dissolved. Next, place the carbon cloth vertically into the mixed solution, and then transfer the solution and carbon cloth to an oven for ion exchange. After naturally cooling to room temperature, collect the carbon cloth, wash it with anhydrous ethanol and ultrasonicate it several times, collect the washed carbon cloth, and then air dry it;

[0010] Step 2: Preparation of Co W LDH / CC: Dissolve a certain amount of Na₂WO₄·2H₂O in a mixture of ultrapure water and ethanol, stir thoroughly, and then transfer the mixture to a polytetrafluoroethylene reactor. Place the carbon cloth from Step 1 in the mixture and transfer both to an oven for a hydrothermal reaction. After cooling naturally to room temperature, collect the carbon cloth, wash it several times with ultrapure water and anhydrous ethanol, and then dry it in air.

[0011] Step 3: Preparation of Co W LDH / CC loaded with Ru: Place Co W LDH / CC in an aqueous solution of RuCl 3 for a certain period of time to undergo ion exchange reaction, and then dry;

[0012] Step 4: RuCoWO x Preparation of Co W LDH / CC: The Ru-loaded Co W LDH / CC sample was calcined in air for a certain time to obtain the final product.

[0013] Furthermore, in the above step 1, the amounts of 2-methylimidazole, Co(NO3)2·6H2O and water used are 35.62 mmol; 4.48 mmol; 100 mL.

[0014] Furthermore, in the above step 1, the stirring time is 30 minutes twice.

[0015] Furthermore, in the above step 1, the oven temperature is 50° C. and the immersion time is 5 h.

[0016] Furthermore, in the above step 1, the product was washed with anhydrous ethanol and ultrasonicated 3 times, and dried at 60° C. for 12 h.

[0017] Furthermore, in the above step 2, the amount of water and ethanol mixed solution is 30 mL of aqueous solution, the amount of ethanol solution is 10 mL, the stirring time is 10 min, the conditions of the hydrothermal reaction are 80 ° C for 90 min, washed with ultrapure water and anhydrous ethanol 3 times, and dried at 60 ° C for 12 h.

[0018] Furthermore, in the above step 3, the concentration of the RuCl3 aqueous solution was 10 mg / mL, the immersion time was 2 min, and the solution was dried at 60°C for 12 h.

[0019] Furthermore, in the above step 4, the calcination temperature is 300° C., the calcination time is 3 h, and the calcination rate is 2° C. / min.

[0020] The above preparation method prepares a W-doped Co3O4-loaded Ru single-atom catalyst for acidic OER.

[0021] Compared with the prior art, the present invention has the following advantages:

[0022] 1. The present invention discloses a W-doped Co₃O₄-loaded Ru single-atom catalyst for acidic OER. The corrosion-resistant element W is introduced into Co₃O₄ via a hydrothermal method to form a heterogeneous interface between Co₃O₄ and CoWO₄, thereby regulating its electronic structure and surface properties. Furthermore, the introduction of Ru can change the local structure of electrons, thereby promoting electron transfer between interfaces, preventing lattice oxygen from participating in the OER process, reducing the oxidation state of Ru, and thus enhancing the intrinsic activity of the catalyst. The catalyst of the present invention exhibits significant OER activity and stability.

[0023] 2. The present invention discloses a W-doped Co3O4-loaded Ru single-atom catalyst for acidic OER and its preparation method. Ruthenium salt and transition metal salt are selected as raw materials. The size of catalyst particles is precisely controlled by impregnation, hydrothermal and ion exchange methods to ensure that W is doped in Co3O4 and Ru exists in single-atom form. At the same time, the low-temperature annealing process in air can convert it into metal oxide, improve its thermal stability and durability, and realize RuCoWO x Controllable preparation of / CC materials. At the same time, the RuCoWO prepared by the present invention x / CC uses impregnation, hydrothermal and ion exchange methods, and the operation steps are relatively simple, which can effectively reduce production costs.

[0024] 3. The catalyst prepared by the present invention loads Ru in the form of single atoms on a W-doped Co3O4 carrier through an impregnation method, constructing a low-cost, highly active and highly stable Ru single-atom catalyst. By dispersing Ru atoms in isolated form on the carrier, each atom is exposed on the surface to participate in the reaction, which can provide more active sites and maximize the utilization of Ru atoms, thereby reducing the amount of precious metal ruthenium used and lowering the production cost of the catalyst. At the same time, the strong metal-carrier interaction can enhance the overall electrocatalytic performance, providing an efficient, economical and environmentally friendly solution. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1RuCoWO prepared in Example 1 x / CC, RuCoO prepared in Comparative Example 1 x / CC and XRD patterns of RuO2 / CC materials prepared in comparative example 2;

[0026] Figure 2 RuCoWO prepared in Example 1 x / XPS spectrum of CC materials;

[0027] Figure 3 RuCoWO prepared in Example 1 x / SEM images of CC materials;

[0028] Figure 4 RuCoWO prepared in Example 1 x / TEM images of CC materials;

[0029] Figure 5 RuCoWO prepared in Example 1 x / Spherical aberration electron microscope image of CC material;

[0030] Figure 6 RuCoWO prepared in Example 1 x / CC, RuCoO prepared in Comparative Example 1 x LSV curves of acidic OER of RuO2 / CC, RuO2 / CC prepared in comparative example 2, and commercial RuO2 (C-RuO2) materials prepared in comparative example 3;

[0031] Figure 7 RuCoWO prepared in Example 1 x / CC, RuCoO prepared in Comparative Example 1 x Tafel slope plots of acidic OER of RuO2 / CC, RuO2 / CC prepared in comparative example 2, and commercial RuO2 (C-RuO2) materials prepared in comparative example 3;

[0032] Figure 8 RuCoWO prepared in Example 1 x / CC, RuCoO prepared in Comparative Example 1 x EIS impedance diagrams of acidic OER of RuO2 / CC, RuO2 / CC prepared in comparative example 2, and commercial RuO2 (C-RuO2) materials prepared in comparative example 3;

[0033] Figure 9 RuCoWO prepared in Example 1 x / CC, RuCoO prepared in Comparative Example 1 x / CC, RuO2 / CC prepared in comparative example 2 and commercial RuO2 (C-RuO2) materials prepared in comparative example 3 have double layer capacitance values ​​C dl Fitting graph;

[0034] Figure 10 RuCoWO prepared in Example 1 x / CC, RuCoO prepared in Comparative Example 1 x / CC, RuO2 / CC prepared in comparative example 2 and commercial RuO2 (C-RuO2) prepared in comparative example 3 at 10 mA cm -2 Stability test diagram under current density. DETAILED DESCRIPTION

[0035] In order to make the objectives, technical solutions and advantages of the present invention more clear, the present invention will be further described in detail below through embodiments and drawings.

[0036] Example 1, a method for preparing a W-doped Co3O4-supported Ru single-atom catalyst for acidic OER, comprising the following steps:

[0037] Step 1, Preparation of Co MOF / CC: Add 2.925g 2-methylimidazole to 100mL aqueous solution and stir for 30min to form solution A. Similarly, add 1.305g Co(NO3)2·6H2O to 100mL aqueous solution and stir to form solution B. Then, pour solution B into solution A and continue stirring for 30min until it is completely dissolved. Next, add a 2×5cm -2 The carbon cloth was placed vertically into the mixed solution, and then the solution and the carbon cloth were transferred to an oven together and immersed at 50°C for 5 hours. After naturally cooling to room temperature, the carbon cloth was collected, washed with anhydrous ethanol and ultrasonicated 3 times, and the washed carbon cloth was collected and then dried in air at 60°C for 12 hours.

[0038] Step 2, Preparation of Co W LDH / CC: Dissolve 200 mg of Na2WO4·2H2O in 30 mL of ultrapure water and 10 mL of ethanol, stir evenly, then transfer the mixed solution to a high-pressure reactor, then place the carbon cloth in step 1 into it, and transfer them together to an oven for hydrothermal reaction at a reaction temperature of 80°C for 90 min; after naturally cooling to room temperature, collect the carbon cloth, wash it three times with ultrapure water and anhydrous ethanol respectively, and then dry it in air at 60°C for 12 h.

[0039] Step 3. Preparation of Co W LDH / CC loaded with Ru: Co W LDH / CC was placed in a 10 mg / mL RuCl 3 aqueous solution for 2 min to undergo ion exchange reaction, and then dried in air at 60 °C for 12 h.

[0040] Step 4: RuCoWO xPreparation of / CC: The CoW LDH / CC loaded Ru sample was calcined in air at an annealing temperature of 300°C, a holding time of 3 h, and a heating rate of 2°C / min to obtain the final product.

[0041] To prove that RuCoWO x / CC and other samples were tested by XRD. Figure 1 As shown, the prepared material RuCoWO x / CC diffraction peaks are in good agreement with the standard cards of CoWO4 (PDF#15-0867) and Co3O4 (PDF#42-1467). x / CC is composed of a composite phase of CoWO4 and Co3O4, but no metallic Ru or oxidized RuO is observed. x The diffraction peaks of the species indicate that the Ru species may be loaded on the carrier in a highly dispersed form. x The diffraction peaks of / CC correspond to the standard card of Co3O4, and the diffraction peaks of RuO2 / CC correspond to the standard card of RuO2 (PDF#88-0322).

[0042] Figure 2 RuCoWO x / CC XPS spectrum. In Figure a, the two spin-orbit split peaks and two oscillation satellite peaks of the Co 2p spectrum are clearly distinguishable. The peaks at 782.65 and 797.27 eV are assigned to Co 2+ species, while the peaks at 780.69 and 795.64 eV were identified as Co 3+ species, among which Co 2+ / Co 3+ =0.97, indicating that Co 3+ Dominant. In Figure b, W 2p 5 / 2 The peak value is located at 37.35eV, W 2p 7 / 2 The peak is located at 35.22 eV. Figure c shows the XPS Ru 3d and C1s spectra, where the peak at 284.80 eV corresponds to C=C (deconvoluted into C=C and CO bands) and the Ru 3d generated due to the partial overlap of the C1s and Ru 3d peak signals. 3 / 2 For RuCoWO x / CC's Ru 3d 5 / 2 spectrum, can be deconvoluted to 281.37 eV (Ru 4+ ) and 282.59eV (satellite peak). In Figure d, there are three peaks in the O1s XPS spectrum, which can be attributed to lattice oxygen (O L ), vacancy oxygen (O V ) and adsorbed oxygen (O ad). These results prove that RuCoWO x / CC was successfully synthesized.

[0043] To demonstrate that the obtained RuCoWO x / CC microstructure, SEM test. The test results are as follows Figure 3 As shown, SEM testing showed that it is a cicada wing-like lamellar structure uniformly grown on carbon fiber.

[0044] Figure 4 Shown is the prepared RuCoWO x / CC transmission electron microscopy images, observing RuCoWO x From the interplanar spacing of / CC, it can be found that d = 0.258nm is the (220) crystal plane of Co3O4, while the surrounding d = 0.246nm and d = 0.568nm are the (120) and (010) crystal planes of CoWO4, respectively. It can be judged that W is successfully doped into the Co3O4 lattice, Co3O4 and CoWO4 form a heterogeneous interface, and Ru, Co, W, and O elements are evenly distributed in the catalyst.

[0045] Figure 5 Shown is the prepared RuCoWO x Spherical aberration electron microscopy image of / CC. Some bright spots related to Ru atoms are marked with circles in the image. These bright spots are clearly visible, confirming the existence of single Ru atoms.

[0046] The preparation of Comparative Example 1 is the same as that of Example 1, except that Na2WO4·2H2O in step 2 is replaced by an equimolar amount of Co(NO3)2·6H2O.

[0047] Preparation of Comparative Example 2:

[0048] Step 1: Preparation of carbon cloth impregnated with Ru: Pure carbon cloth was immersed in a RuCl3 aqueous solution with a concentration of 10 mg / mL for 2 min, and then dried in air at 60 °C;

[0049] Step 2: Preparation of RuO2 / CC: The sample from step 1 was calcined in air at an annealing temperature of 300°C, a holding time of 3 h, and a heating rate of 2°C / min to obtain the final product.

[0050] Comparative Example 3 is commercial RuO2 (C-RuO2).

[0051] The RuCoWO prepared in Example 1 was used x / CC, RuCoO prepared in Comparative Example 1 x / CC, the RuO2 / CC acidic OER electrocatalyst prepared in Comparative Example 2 and the commercial RuO2 electrode prepared in Comparative Example 3 were prepared. The specific method was carried out as follows:

[0052] 1) Pretreatment of the carbon cloth substrate: A carbon cloth with an area of ​​10*10 cm was placed in a polytetrafluoroethylene reactor containing 17.5 mL of concentrated HNO3 and 52.5 mL of concentrated H2SO4. The reactor was transferred to a blast oven and subjected to a hydrothermal reaction at 110°C for 10 h. After the reactor cooled to room temperature, the carbon cloth was removed with tweezers, washed several times with deionized water and anhydrous ethanol, and then dried in a 60°C oven overnight to obtain a carbon cloth substrate.

[0053] 2) Preparation of working electrode: Example 1, Comparative Example 1 and Comparative Example 2 are self-supporting electrodes, which can be directly cut into 1*0.5cm size. For Comparative Example 3, 8mg of catalyst needs to be weighed first, the powder is placed in a 5mL sample bottle, 650μL ultrapure water, 300μL anhydrous ethanol and 50μL of 5wt% Nafion solution are added, and then placed in an ultrasonic machine for 1h to form a uniform suspension. Finally, the suspension is measured with a pipette and evenly applied on the carbon cloth to make the catalyst loading 1mgcm -2 , and dried naturally to obtain a commercial RuO2 electrode.

[0054] RuCoWO x / CC electrode, RuCoO x The application of RuO2 / CC electrode, RuO2 / CC and commercial RuO2 (C-RuO2) electrode for electrocatalytic water splitting (OER) is as follows:

[0055] 1) Prepare 0.5 M H2SO4 acidic solution: Weigh 27.2 mL of 98% concentrated sulfuric acid, dissolve in 500 mL of ultrapure water, and stir until uniform. After cooling, transfer to a 1000 mL volumetric flask and dilute to 1000 mL.

[0056] 2) Prepare the working electrode: Use an electrode clamp to clamp the edge of the carbon paper of the electrode so that the area of ​​the electrode immersed in the 0.5M H2SO4 solution is 0.5*0.5cm;

[0057] 3) Electrocatalytic oxygen evolution reaction: All electrochemical tests were carried out in a three-electrode system at room temperature. During the reaction, a graphite rod was used as the counter electrode, a saturated calomel electrode was used as the reference electrode, and RuCoWO x / CC electrode, RuCoO x / CC electrode, RuO2 / CC and commercial RuO2 (C-RuO2) electrodes were used as working electrodes, and 0.5 M H2SO4 was used as the electrolyte for all electrochemical tests.

[0058] Figure 6 The RuCoWO prepared in Example 1 is shown x / CC electrode, Comparative Example 1 Preparation of RuCoO x / CC electrode, RuO2 / CC prepared in comparative example 2, and commercial RuO2 electrode prepared in comparative example 3 show the OER polarization curves. x / CC showed the best OER activity at 10 mA cm -2 Only 198mV overpotential is required, which is much lower than that of RuCoO x / CC (224mV), RuO2 / CC (226mV) and C-RuO2 (247mV).

[0059] Figure 7 Their Tafel curve fitting diagram is shown, from which it can be seen that RuCoWO x The Tafel slope of the / CC catalyst is 63.77 mV dec -1 , lower than RuCoO x / CC(131.80mV dec -1 )、RuO2 / CC(84.13mV dec -1 ) and commercial RuO2 (103.80mV dec -1 ), indicating that RuCoWO x / CC has a faster OER process. Combined with the above test results, it can be seen that RuCoWO x / CC has the best electrocatalytic performance, and Example 1 is the best example.

[0060] Figure 8 Their EIS impedance graphs are shown. It can be seen that RuCoWO x / CC has the smallest semicircle diameter, charge transfer resistance (R ct ) is the smallest, the charge transfer rate is the fastest, and the reaction kinetics is faster.

[0061] Figure 9 RuCoWO x / CC、RuCoO x The double layer capacitance values ​​C of RuO2 / CC, RuO2 / CC and C-RuO2 dl Fitting diagram, data results show that RuCoWO x / CC has the largest C dl value, reaching 49.74mF cm -2 , which is 2.4 times that of commercial RuO2. It is known that ECSA = C dl / C s , where C s 0.035mF cm -2 , then C dl The value is linearly proportional to ECSA, indicating that RuCoWOx / CC has a larger electrochemical reaction active area.

[0062] Figure 10 It is RuCoWO x / CC、RuCoO x / CC, RuO2 / CC and C-RuO2 at 10 mA cm -2 The stability test curve under current density shows that commercial RuO2 loses its activity rapidly within the first 20 hours, and homemade RuO2 / CC also loses its activity within 25 hours. x / CC ran stably for about 75 hours and then gradually lost its activity, while RuCoWO x / CC showed excellent stability within 200h, and the decay rate was only 0.37mV / h.

[0063] The technical effects of the present invention have been tested and the specific contents are as follows:

[0064] The present invention is known by XRD detection: RuCoWO x / CC is a composite phase structure of CoWO4 and Co3O4, but no metallic Ru or oxidized RuO is observed. x The diffraction peaks of the species indicate that the Ru species may be loaded on the carrier in a highly dispersed form.

[0065] The present invention was tested by scanning electron microscopy, transmission electron microscopy and spherical aberration electron microscopy, and it can be seen that the catalyst RuCoWO x / CC has a lamellar structure, which verifies that it is a heterostructure of CoWO4 and Co3O4, and Ru exists in the form of single atoms.

[0066] RuCoWO x The LSV curve of / CC shows that: at 10mA cm -2 Its overpotential is only 198 mV at a current density of 1.5 %.

[0067] RuCoWO x / CC stability test curve shows that: at 10mA cm -2 It can operate stably for 200 hours at the current density with a decay rate of only 0.37mV / h.

[0068] The above description is an explanation of the specific implementation of the present invention, rather than a limitation of the present invention. Those skilled in the relevant technical field can also make various equivalent technical solutions without departing from the scope of the present invention, so all equivalent technical solutions should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a W-doped Co3O4-supported Ru single-atom catalyst for acidic OER, characterized by: The following steps are involved: Step 1, preparation of Co MOF / CC: First, add a certain amount of 2-methylimidazole to the aqueous solution and stir evenly; similarly, add a certain amount of Co(NO3)2·6H2O to the aqueous solution and stir evenly; then quickly pour the Co(NO3)2·6H2O aqueous solution into the 2-methylimidazole aqueous solution and continue stirring until it is completely dissolved; then vertically place the carbon cloth into the mixed solution, and then transfer the solution and carbon cloth to an oven for impregnation; finally, after naturally cooling to room temperature, collect the carbon cloth, wash it with anhydrous ethanol and ultrasonicate it several times, collect the washed carbon cloth, and dry it; Step 2, Preparation of Co W LDH / CC: First, a certain amount of Na2WO4·2H2O was dissolved in a mixed solution of ultrapure water and ethanol and stirred evenly; then the mixed solution was transferred to a high-pressure reactor, followed by the carbon cloth prepared in step 1, and then transferred together to an oven for hydrothermal reaction; finally, after cooling naturally to room temperature, the carbon cloth was collected and washed several times with deionized water and anhydrous ethanol, respectively, and then dried; Step 3: Preparation of Co W LDH / CC loaded with Ru: The carbon loaded with Co W LDH / CC was placed in an aqueous solution of RuCl3 for a certain period of time to undergo ion exchange reaction, and then dried; Step 4: RuCoWO x Preparation of / CC: CoW LDH / CC loaded with Ru carbon cloth was calcined in air for a certain time to obtain the final product.

2. The method for preparing a W-doped Co3O4-supported Ru single-atom catalyst for acidic OER according to claim 1, characterized in that: In the step 1, the amount of 2-methylimidazole, Co(NO3)2·6H2O and aqueous solution is 35.62 mmol; 4.48mmol; 100mL.

3. The method for preparing a W-doped Co3O4-supported Ru single-atom catalyst for acidic OER according to claim 2, characterized in that: In the above step 1, the stirring time is 30 min twice.

4. The method for preparing a W-doped Co3O4-supported Ru single-atom catalyst for acidic OER according to claim 3, characterized in that: In the above step 1, the oven temperature is 50° C. and the immersion time is 5 h.

5. The method for preparing a W-doped Co3O4-supported Ru single-atom catalyst for acidic OER according to claim 4, characterized in that: In the above step 1, the product was washed with anhydrous ethanol and ultrasonicated three times, and dried at 60°C for 12 h.

6. The method for preparing a W-doped Co3O4-supported Ru single-atom catalyst for acidic OER according to claim 5, characterized in that: In the above step 2, in the mixed solution of water and ethanol, the amount of aqueous solution is 30 mL, the amount of ethanol solution is 10 mL, the stirring time is 10 min, the hydrothermal reaction conditions are 80°C, the heat preservation is 90 min, and the mixture is washed with deionized water and anhydrous ethanol three times, and dried at 60°C for 12 h.

7. The method for preparing a W-doped Co3O4-supported Ru single-atom catalyst for acidic OER according to claim 6, characterized in that: In the above step 3, the concentration of RuCl3 aqueous solution is 10 mg / mL, the drying time is 2 min, and the drying is carried out at 60°C for 12 h.

8. The method for preparing a W-doped Co3O4-supported Ru single-atom catalyst for acidic OER according to claim 6, characterized in that: In the above step 4, the calcination temperature is 300° C., the calcination time is 3 h, and the calcination rate is 2° C. / min.

9. A W-doped Co3O4-loaded Ru single-atom catalyst for acidic OER prepared by the preparation method according to claim 1.

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