Ru-Mn2O3 / MnO2 composite material serving as acidic OER electrocatalyst and preparation method of Ru-Mn2O3 / MnO2 composite material

Abstract

The invention discloses a Ru-Mn2O3 / MnO2 composite material used as an acidic OER electrocatalyst and a preparation method of the Ru-Mn2O3 / MnO2 composite material. The preparation method of the composite material comprises the following steps: calcining prepared MnO2 nano powder as a reaction precursor by using an ultrafast sintering technology to obtain a Mn2O3 / MnO2 composite material; and preparing a uniformly dispersed aqueous solution from the MnO2 and ruthenium chloride hydrate, and obtaining Ru-Mn2O3 / MnO2 by utilizing the principle of electrochemical replacement reaction. The preparation method disclosed by the invention has the advantages of low raw material cost, mild reaction conditions, high reaction rate, energy conservation, environment friendliness and the like; according to the preparation method disclosed by the invention, the Mn2O3 / MnO2 composite material is prepared by regulating and controlling the ultra-fast sintering reaction temperature; the Ru-Mn2O3 / MnO2 composite material prepared by the invention is used as an OER electrocatalyst, has low overpotential in an oxygen evolution reaction under an acidic condition, and shows a good acidic electrocatalytic oxygen production application prospect.

Description

Technical Field

[0001] The present invention belongs to the field of new energy technology, and in particular relates to a Ru-Mn2O3 / MnO2 composite material as an acidic OER electrocatalyst and a preparation method thereof. Background Art

[0002] Proton exchange membrane (PEM) technology for water splitting hydrogen production offers several advantages. This acidic electrolysis process can adapt to intermittent power supply conditions, produces high-purity hydrogen, improves hydrogen production efficiency, eliminates the need for caustic soda treatment, and can be quickly started and stopped to match the volatility of renewable energy.

[0003] However, compared with the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER) requires a slow four-electron transfer step, so a higher overpotential is required to achieve the desired hydrogen yield. In order to improve energy conversion efficiency and reduce the cost of hydrogen production, it is urgent to develop low-cost OER catalysts with excellent catalytic activity and stability. Among them, the acidic reaction medium has more stringent requirements on catalyst activity and corrosion resistance. Although RuO2 exhibits excellent oxygen evolution catalytic activity and Ru is relatively cheap in the precious metal family, it still faces serious challenges of activity decay and insufficient stability, which restricts the application prospects of this type of catalyst in large-scale commercial water electrolysis for hydrogen production. In acidic OER, chemically stable transition metal oxides are used as supports, and monodispersed Ru atoms anchored by metal MO-Ru bonding have lower overpotentials and better cycling stability than commercial RuO2. The advantages of monodisperse Ru atoms are: (1) each metal atom can be fully utilized as an active center, maximizing the atomic utilization rate; (2) the unique low coordination / defect structure and special electronic structure give it unique activity; (3) the active sites are evenly dispersed on the support surface, maximizing the exposure of the active sites and avoiding agglomeration; (4) the metal-support interaction can regulate the charge transfer between the metal atoms and the support, thereby significantly affecting the reaction activity of the catalyst.

[0004] Ideal support materials should not only have high chemical stability to ensure no structural damage or dissolution under electrocatalytic conditions, but also possess a high specific surface area and an open atomic structure to achieve highly uniform dispersion of dopant atoms, and have strong chemical bonding to immobilize and stabilize the dopant atoms. Furthermore, in acidic OER reaction systems, support materials should also possess certain OER catalytic activity and conductivity to fully exploit the synergistic catalytic effect between single atoms and the support. Manganese-based oxides have a variety of valence states and crystal structures. Among them, α-MnO2 and β-MnO2 with tunnel structures exhibit considerable electrocatalytic performance in acidic OER, and they can anchor Ru atoms through electrochemical redox reactions.

[0005] Most current studies of manganese-based oxides as supports for monodisperse Ru atoms have limited their composition, which, to a certain extent, restricts the electronic coupling effect between the single-atom active center and the support. Based on the flexible and adjustable ratio of Mn and O in manganese-based oxides, the construction of multi-component allotropic manganese-based oxides as support materials is expected to optimize the electronic interaction between Ru atoms and the manganese-based oxide support, thereby enhancing the activity and stability of the electrocatalyst. Summary of the Invention

[0006] The purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a Ru-Mn2O3 / MnO2 composite material as an acidic OER electrocatalyst and a preparation method thereof. The allotrope Mn2O3 / MnO2 has a rich heterogeneous structure that can accelerate the electron transmission rate through the built-in electric field generated by the interface, thereby optimizing the charge interaction between monodispersed Ru atoms and manganese-based oxide carriers, thereby achieving improved OER performance under acidic conditions.

[0007] The purpose of the present invention is achieved through the following technical solutions.

[0008] Ru-MnO as an acidic OER electrocatalyst x Materials, the Ru-MnO x The material has a nanorod morphology with a diameter of ~250 nm and a length of ~3 μm. x The material is a Ru-Mn2O3 / MnO2 composite material, or any one of Ru-MnO2 or Ru- Mn2O3, wherein the position of the diffraction peak of the Ru-Mn2O3 / MnO2 composite material is completely consistent with the position of the diffraction peak of the standard card of β-MnO2 and Mn2O3, and there is no RuO2 diffraction peak and other impurity peaks; wherein the position of the diffraction peak of Ru-MnO2 is completely consistent with the position of the diffraction peak of the standard card of β-MnO2; the position of the diffraction peak of Ru- Mn2O3 is completely consistent with the position of the diffraction peak of the standard card of Mn2O3. And the Ru-MnO x There are no RuO2 diffraction peaks or other impurity peaks in the diffraction peaks of the material. The Ru element exists in the manganese-based oxide in a monodisperse form and does not form RuO2.

[0009] The present invention also provides the above-mentioned Ru-MnO as an acidic OER electrocatalyst x The method for preparing the material comprises the following steps: Step (1): MnSO4·H2O, (NH4)2S2O8 and Na2SO4·10H2O are mixed into a uniform aqueous solution, reacted in a high-pressure reactor at 140°C for 12 hours, cooled, centrifuged, washed and dried to obtain MnO2 nanopowder.

[0010] Step (2): Place the MnO2 nanopowder described in step (1) in the center of a 5*13 cm*cm graphite paper and fold it into three along the short side of the graphite paper. Fix the folded graphite paper on the heating element of the ultra-fast sintering furnace to ensure that the sample is placed in the center position between the two heating elements. In the long pulse heating mode, set the heating temperature to 500℃~650℃, the heating time (including the heating and holding stages) to 10 minutes, and the heating rate to 1℃ / ms. β-MnO2, β-MnO2 / Mn2O3 or Mn2O3 nanorod powders are obtained at different heating temperatures.

[0011] Step (3): The nanorod powder obtained in step (2) is dispersed with RuCl3 in water to form a stable suspension, reacted in a water bath at 35°C for 12 hours, centrifuged, washed and dried to obtain a series of Ru-MnO2, Ru-Mn2O3 / MnO2 or Ru-Mn2O3 nanorods.

[0012] The molar ratio of MnSO4·H2O, (NH4)2S2O8 and Na2SO4·10H2O in step (1) is 1:1:3.

[0013] Preferably, the heating temperature in step (2) is 580-620° C., and step (2) obtains β-MnO2 / Mn2O3 nanorod powder; then step (3) is completed to obtain the Ru-Mn2O3 / MnO2 composite material.

[0014] Step (3) RuCl3 and MnO x The molar ratio is 1:10.

[0015] The present invention also provides the use of the above-mentioned Ru-Mn2O3 / MnO2 composite material as an electrode material in an acidic OER working electrode.

[0016] The application method is as follows: the Ru-Mn2O3 / MnO2 composite material and a 5wt% Nafion aqueous solution are dispersed in a mixed solution of ultrapure water and ethanol, the slurry obtained by ultrasonic treatment is evenly applied to the surface of carbon paper, and then dried under infrared light to obtain a working electrode for acidic OER electrocatalytic reaction.

[0017] The ratio of the amount of the Ru-Mn2O3 / MnO2 composite material to the amount of the Nafion aqueous solution is 0.33 mg / μL.

[0018] The volume ratio of ultrapure water to ethanol is 37:60.

[0019] The volume ratio of Nafion aqueous solution to ethanol is 1:20.

[0020] The loading amount of the composite material is 1~3.3 mg / cm 2 between.

[0021] The present invention also provides an electrolytic cell for acidic OER electrocatalytic reaction, which adopts the above-mentioned working electrode, the counter electrode is a platinum sheet, the reference electrode is Ag / AgCl, and the electrolyte is an H2SO4 aqueous solution with a pH=0.

[0022] Beneficial effects of the present invention: The preparation method is simple and efficient: The disclosed method for preparing the Ru-Mn2O3 / MnO2 composite material utilizes ultrafast sintering technology and an electrochemical replacement reaction. This method offers mild reaction conditions, a fast reaction rate, low raw material costs, and is energy-efficient and environmentally friendly. Furthermore, by regulating the ultrafast sintering temperature, pure MnO2, Mn2O3, and M2O3 / MnO2 composite materials can be flexibly prepared to meet diverse needs.

[0023] Excellent electrocatalytic performance: The Ru-Mn2O3 / MnO2 composite material prepared by the present invention can be used as an excellent acidic oxygen evolution ion electrocatalyst. Under acidic conditions, the oxygen evolution reaction has a low overpotential and good stability, showing good application prospects in acidic electrocatalytic oxygen production.

[0024] Unique heterostructure advantages: The Ru-Mn2O3 / MnO2 allotrope composite material in the present invention has rich heterogeneous interface structures. These interfaces can generate built-in electric fields, accelerate the transmission rate of electrons, optimize the charge interaction between monodisperse Ru atoms and manganese-based oxide carriers, and thus improve the overall catalytic activity. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is the SEM image of Ru-MnO2 prepared in Example 1 of the present invention.

[0026] Figure 2 This is the XRD pattern of Ru-MnO2 prepared in Example 1 of the present invention.

[0027] Figure 3 This is the linear voltammetric scan curve when Ru-MnO2 prepared in Example 1 of the present invention is used as the working electrode material for the OER electrocatalytic reaction.

[0028] Figure 4 This is the SEM image of Ru-Mn2O3 / MnO2 prepared in Example 2 of the present invention.

[0029] Figure 5 This is the XRD pattern of Ru-Mn2O3 / MnO2 prepared in Example 2 of the present invention.

[0030] Figure 6This is the linear voltammetric scan curve when Ru-Mn2O3 / MnO2 prepared in Example 2 of the present invention is used as the working electrode material for the OER electrocatalytic reaction.

[0031] Figure 7 This is the SEM image of Ru-Mn2O3 prepared in Example 3 of the present invention.

[0032] Figure 8 This is the XRD pattern of Ru-Mn2O3 prepared in Example 3 of the present invention.

[0033] Figure 9 This is the linear voltammetric scan curve when Ru-Mn2O3 prepared in Example 3 of the present invention is used as the working electrode material for the OER electrocatalytic reaction. DETAILED DESCRIPTION

[0034] To make the above-mentioned objects and advantages of the present invention clear and easy to understand, the technical solutions in the embodiments of the present invention will be described in detail below with reference to the accompanying drawings in the embodiments of the present invention, but the present invention is not limited to the specific embodiments. The materials mentioned above are all commercially available unless otherwise specified.

[0035] Example 1

[0036] The preparation of Ru-MnO2 material is as follows: (1) Weigh 2 mmol of MnSO4·H2O, 2 mmol of (NH4)2S2O8 and 6 mmol of Na2SO4·10H2O and dissolve them in 70 mL of deionized water. React in a high-pressure reactor at 140°C for 12 h. Cool, centrifuge, wash and dry to obtain MnO2 nanopowder.

[0037] (2) Weigh 30 mg of MnO2 nanopowder and place it in the center of a 5*13 cm*cm graphite paper. Fold the paper into three folds along the short side of the graphite paper. Fix the folded graphite paper on the heating element of the ultra-fast sintering furnace to ensure that the sample is placed in the center between the two heating elements. In the long pulse heating mode, set the heating temperature to 500℃ and the heating time (including the heating and holding stages) to 10 minutes. The heating rate is 1℃ / ms to obtain calcined β-MnO2 nanorods.

[0038] (3) Weigh 24 mg of calcined β-MnO2 and ultrasonically disperse it in 20 mL of deionized water to form a stable suspension. Transfer it to a 50 mL single-necked glass flask and stir it in a 35°C water bath until the temperature stabilizes. Then use a pipette to draw 2 mL of 0.01 M RuCl3 aqueous solution and slowly add it dropwise to the above suspension. The reaction time is 12 h. Centrifuge, wash and dry to obtain Ru-MnO2 nanorods.

[0039] The inventors found through repeated experiments that by adjusting the heating temperature in the ultrafast sintering furnace in step (2), the composition of the nanorods obtained after calcination treatment was different. When the heating temperature was between 500°C and 580°C, pure β-MnO2 nanorods after calcination treatment were obtained in step (2); when the heating temperature was above 580°C and below 620°C, β-MnO2 / Mn2O3 nanorod powder was obtained after step (2); and when the heating temperature was increased to 620°C to 650°C, pure Mn2O3 nanorod powder was obtained after step (2). These nanorod powders of different compositions obtained in step (2) were further subjected to step (3) as above to obtain Ru-MnO2 nanorods (such as in Example 1), Ru-Mn2O3 / MnO2 nanorods (such as in Example 2 below), and Ru-Mn2O3 nanorods (such as in Example 3 below).

[0040] The SEM image of Ru-MnO2 prepared in Example 1 is as follows Figure 1 As shown, its nanostructure is in the shape of nanorods, with a nanorod diameter of ~250 nm and a nanorod length of ~3 μm. Figure 2 Corresponding to its XRD pattern and compared with the standard card JCPDS#NO.72-1984, the position of the diffraction peak of the prepared Ru-MnO2 nanorods is completely consistent with the position of the diffraction peak of the standard card, and there is no RuO2 diffraction peak or other impurity peak, indicating that the prepared Ru-MnO2 nanorods have high purity, and the Ru element exists in MnO2 in a monodisperse form, and no RuO2 phase is formed.

[0041] The Ru-MnO2 material prepared in Example 1 was subjected to an OER performance test under acidic conditions. The test method is as follows: (1) Weigh 10 mg of Ru-MnO2 material and ultrasonically disperse it in 600 μL of ethanol, 370 μL of ultrapure water, and 30 μL of Nafion aqueous solution (5 wt%) to form a stable dispersed slurry.

[0042] (2) Use a pipette to draw 50 μL of slurry each time and evenly spread it on the surface of 1*1.5 cm*cm hydrophilic carbon paper. Dry it under infrared light. Repeat this step 5 times to ensure that the loading amount of active substance is 2.5 mg.

[0043] (3) A three-electrode electrochemical test system was used. The electrode sheet prepared above was used as the working electrode for the acidic OER electrocatalytic reaction. The counter electrode was a platinum sheet, the reference electrode was Ag / AgCl, and the electrolyte was a H2SO4 aqueous solution with a pH of 0. The test voltage range of the linear voltammetric scan curve was 1.0-1.6 V vs. RHE, and the scan rate was 5 mV s -1 .

[0044] The test results are as follows Figure 3 As shown in Figure 1, the Ru-MnO2 material prepared in Example 1 has a -2 The overpotential is 290 mV at a current density of 1.5 Å.

[0045] Example 2

[0046] The preparation of Ru-Mn2O3 / MnO2 composite material is as follows: (1) Weigh 2 mmol of MnSO4·H2O, 2 mmol of (NH4)2S2O8 and 6 mmol of Na2SO4·10H2O and dissolve them in 70 mL of deionized water. React in a high-pressure reactor at 140°C for 12 h. Cool, centrifuge, wash and dry to obtain MnO2 nanopowder.

[0047] (2) Weigh 30 mg of MnO2 nanopowder and place it in the center of a 5*13 cm*cm graphite paper. Fold the graphite paper into three folds along the short side of the graphite paper. Fix the folded graphite paper on the heating element of the ultra-fast sintering furnace to ensure that the sample is placed in the center between the two heating elements. In the long pulse heating mode, set the heating temperature to 600℃ and the heating time (including the heating and holding stages) to 10 minutes. The heating rate is 1℃ / ms to obtain β-MnO2 / Mn2O3 nanorod powder.

[0048] (3) Weigh 24 mg of Mn2O3 / MnO2 nanorod powder and ultrasonically disperse it in 20 mL of deionized water to form a stable suspension. Transfer it to a 50 mL single-necked glass flask and stir it in a 35°C water bath until the temperature stabilizes. Then use a pipette to draw 2 mL of 0.01 M ruthenium chloride hydrate aqueous solution and slowly add it dropwise to the above suspension. The reaction time is 12 h. Centrifuge, wash and dry to obtain Ru-Mn2O3 / MnO2 nanorods.

[0049] like Figure 4 As shown: After ultrafast sintering and calcination treatment, the morphology of the nanomaterial did not fragment, the diameter of the nanorods was ~250 nm, and the length of the nanorods was ~3 μm. Figure 5 Corresponding to the XRD pattern, compared with the standard cards JCPDS#NO.72-1984 and JCPDS#NO.71-0636, the positions of the diffraction peaks of the prepared Ru-Mn2O3 / MnO2 nanorods are completely consistent with the positions of the diffraction peaks of the standard cards, and there are no RuO2 diffraction peaks and other impurity peaks, indicating that the prepared Ru-Mn2O3 / MnO2 nanorods have high purity, and the Ru element exists in the manganese-based oxide in a monodisperse form, and no RuO2 is formed.

[0050] The Ru-Mn2O3 / MnO2 material prepared above was subjected to OER performance test under acidic conditions. The test method was the same as that in Example 1. The test results showed that: Figure 6 As shown in the figure, the Ru-Mn2O3 / MnO2 material of this example is -2 At a current density of 1.5 Å, the overpotential is 250 mV.

[0051] Example 3

[0052] The preparation of Ru-Mn2O3 material is as follows: (1) Weigh 2 mmol of MnSO4·H2O, 2 mmol of (NH4)2S2O8 and 6 mmol of Na2SO4·10H2O and dissolve them in 70 mL of deionized water. React in a high-pressure reactor at 140°C for 12 h. Cool, centrifuge, wash and dry to obtain MnO2 nanopowder.

[0053] (2) Weigh 30 mg of MnO2 nanopowder and place it in the center of a 5*13 cm*cm graphite paper. Fold the paper into three folds along the short side of the graphite paper. Fix the folded graphite paper on the heating element of the ultra-fast sintering furnace to ensure that the sample is placed in the center between the two heating elements. In the long pulse heating mode, set the heating temperature to 625℃ and the heating time (including the heating and holding stages) to 5 min, with a heating rate of 1 ms, to obtain calcined Mn2O3 nanorod powder.

[0054] (3) Weigh 24 mg of calcined Mn2O3 and ultrasonically disperse it in 20 mL of deionized water to form a stable suspension. Transfer it to a 50 mL single-necked glass flask and stir it in a 35°C water bath until the temperature stabilizes. Then use a pipette to draw 2 mL of 0.01M RuCl3 aqueous solution and slowly add it dropwise to the above suspension. The reaction time is 12 h. Centrifuge, wash and dry to obtain Ru-Mn2O3 nanorods.

[0055] like Figure 7 As shown: After ultrafast sintering and calcination treatment, the morphology of the nanomaterial did not fragment, the diameter of the nanorods was ~250 nm, and the length of the nanorods was ~3 μm. Figure 8 The corresponding XRD pattern is compared with the standard card JCPDS#NO.71-0636. The position of the diffraction peak of the prepared Ru-Mn2O3 nanorods is completely consistent with the position of the diffraction peak of the standard card, and there is no RuO2 diffraction peak or other impurity peak, indicating that the prepared Ru-Mn2O3 nanorods have high purity, and the Ru element exists in Mn2O3 in a monodisperse form, and no RuO2 phase is formed.

[0056] The Ru-Mn2O3 material prepared above was subjected to OER performance test under acidic conditions. The test method was the same as that in Example 1. The test results showed that: Figure 9 As shown in the figure, the Ru-Mn2O3 material of this example is -2 At a current density of 1.5 Å, the overpotential is 270 mV.

[0057] The inventors found in comparative studies that the Ru-Mn2O3 / MnO2 composite material prepared in the present invention has a lower overpotential and more stable cycle performance when applied to acidic OER electrocatalysis than Ru-Mn2O3 or Ru-MnO2, as shown in the test results of Examples 1, 2 and 3 above. In Example 2, the Ru-Mn2O3 / MnO2 composite material was tested for OER performance under acidic conditions. At 10 mA cm -2 At a current density of 1.5 Å, the overpotential is 250 mV, which is the lowest overpotential compared to the Ru-MnO2 of Example 1 and the Ru-Mn2O3 of Example 3. This is mainly due to the rich heterogeneous interface structures in the allotropic composite materials contained in the Ru-Mn2O3 / MnO2 composite material. These interfaces can generate built-in electric fields, accelerate the electron transport rate, optimize the charge interaction between the monodisperse Ru atoms and the manganese-based oxide support, and thus improve the overall catalytic activity.

[0058] The embodiments described above are merely descriptions of preferred implementations of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should fall within the scope of protection determined by the claims of the present invention.

Claims

1. Ru-MnO as an acidic OER electrocatalyst x Material, characterized by: The Ru-MnO x The material has a nanorod morphology; Wherein, the Ru-MnO x The material is a Ru-Mn2O3 / MnO2 composite material, and the position of its diffraction peak is completely consistent with the position of the standard card diffraction peak of β-MnO2 and Mn2O3; or the Ru-MnO x The material is Ru-MnO2, and the position of its diffraction peak is completely consistent with the position of the standard card diffraction peak of β-MnO2; or the Ru-MnO x The material is Ru-Mn2O3, and the position of its diffraction peak is completely consistent with the position of the diffraction peak of the standard card of Mn2O3; And the Ru-MnO x There are no RuO2 diffraction peaks or other impurity peaks in the diffraction peaks of the material. The Ru element exists in the manganese-based oxide in a monodisperse form and does not form RuO2.

2. Ru-MnO as an acidic OER electrocatalyst according to claim 1 x The method for preparing the material is characterized in that: The following steps are involved: Step (1), mixing MnSO4·H2O, (NH4)2S2O8 and Na2SO4·10H2O into a uniform aqueous solution, performing a hydrothermal reaction in a high-pressure reactor, cooling, centrifuging, washing and drying to obtain MnO2 nanopowder; Step (2), placing the MnO2 nanopowder described in step (1) in a folded graphite paper, fixing it on the heating element of the ultra-fast sintering furnace, and placing it in the center position between the two heating bodies. Under the long pulse heating mode, the heating temperature is set to 500°C to 650°C, and different heating temperatures are used to obtain β-MnO2, β-MnO2 / Mn2O3 or Mn2O3 nanorod powders; Step (3), dispersing the nanorod powder obtained in step (2) with RuCl3 in water to form a stable suspension, performing a water bath reaction, centrifuging, washing and drying to obtain Ru-MnO2, Ru-Mn2O3 / MnO2 or Ru-Mn2O3 nanorods.

3. Ru-MnO as an acidic OER electrocatalyst according to claim 2 x The method for preparing the material is characterized by: In step (1), the molar ratio of MnSO4·H2O, (NH4)2S2O8 and Na2SO4·10H2O is 1:1:3, the hydrothermal reaction temperature is 140°C, and the reaction time is 12 hours; in step (2), the long pulse heating is set to a heating time of 10 minutes, the heating time includes the heating and holding stages, and the heating rate is 1°C / ms.

4. Ru-MnO as an acidic OER electrocatalyst according to claim 2 x The method for preparing the material is characterized by: The heating temperature in step (2) is 580-620° C., and β-MnO2 / Mn2O3 nanorod powder is obtained in step (2); and Ru-Mn2O3 / MnO2 composite material is obtained after step (3) is completed.

5. Ru-MnO as an acidic OER electrocatalyst according to claim 2 x The method for preparing the material is characterized by: In step (3), the molar ratio of RuCl3 to Mn in the nanorod powder is 1:10, and the water bath reaction is carried out in a water bath at 35°C for 12 hours.

6. A working electrode for acidic OER electrocatalytic reaction, characterized by: The Ru-Mn2O3 / MnO2 composite material prepared by the preparation method according to any one of claims 2 to 5 or according to claim 1 is used as an electrode material in a working electrode of an acidic OER electrocatalytic reaction.

7. A working electrode for acidic OER electrocatalytic reaction according to claim 6, characterized in that: The Ru-Mn2O3 / MnO2 composite material and 5wt% Nafion aqueous solution were dispersed in a mixed solution of ultrapure water and ethanol. The slurry obtained by ultrasonic treatment was evenly applied to the surface of carbon paper and dried under infrared light to obtain a working electrode for acidic OER electrocatalytic reaction.

8. The working electrode for acidic OER electrocatalytic reaction according to claim 7, characterized in that: The ratio of the amount of the Ru-Mn2O3 / MnO2 composite material to the amount of the Nafion aqueous solution is 0.33 mg / μL; the volume ratio of ultrapure water to ethanol is 37:60; and the volume ratio of the Nafion aqueous solution to ethanol is 1:

20.

9. The working electrode for acidic OER electrocatalytic reaction according to claim 7, characterized in that: The loading amount of the Ru-Mn2O3 / MnO2 composite material on the carbon paper is 1-3.3 mg / cm 2 between.

10. An electrolytic cell for acidic OER electrocatalytic reaction, characterized in that: The working electrode according to any one of claims 6 to 9 is used, the counter electrode is a platinum sheet, the reference electrode is Ag / AgCl, and the electrolyte is an H2SO4 aqueous solution with a pH of 0.

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