Preparation method and application of fluorine-doped transition metal oxide hydrogen evolution electrocatalyst

Abstract

The application discloses a preparation method and application of a fluorine-doped transition metal oxide hydrogen evolution electrocatalyst. 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3‑δ‑0.5α F α The BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3‑δ‑0.5α F α The F element in the electrocatalyst has higher electronegativity, is easier to take electrons of oxygen sites, activates lattice oxygen, promotes the formation of oxygen vacancies in the catalyst, increases active sites for hydrogen evolution, improves the catalytic activity of the catalyst, and the BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.925‑δ F 0.15 The overpotential is reduced by 71 mV under 10 mA / cm 2 The BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3‑δ ​

Description

Technical Field

[0001] This invention belongs to the field of electrocatalytic materials technology, specifically relating to a method for preparing and applying a fluorine-doped transition metal oxide hydrogen evolution electrocatalyst. Background Technology

[0002] Currently, hydrogen, as the energy carrier with the highest energy density, is attracting much attention among various new energy raw materials. Hydrogen energy not only boasts high energy density and is clean with zero pollution, but also has a wide range of sources, showing great promise in the field of new energy development. Currently, a major source of hydrogen is the cracking of fossil fuels such as petroleum. Its main drawbacks include the scarcity and limited availability of raw materials, high energy consumption in the production process, and low purity of the produced hydrogen. The biggest drawback is that hydrogen obtained through fossil fuel cracking still contains impurities such as sulfur (S) and phosphorus (P), requiring further desulfurization through complex processes. This not only increases production costs but also, incomplete desulfurization can easily poison catalysts such as phosphorus (Pt) in hydrogen energy production equipment. The most ideal way to produce hydrogen is through water electrolysis. On the one hand, the raw materials are simple and readily available, allowing for large-scale application and conversion of scattered energy sources such as solar and wind power into hydrogen for storage. On the other hand, the produced hydrogen is pure, requiring no further desulfurization, and the process is simple.

[0003] Currently, catalysts used for hydrogen evolution reactions (HERs) are mainly noble metals and their alloys, such as Pt and Pt alloys. However, these noble metal-based catalysts are scarce, expensive, and prone to poisoning, making large-scale application difficult in practice. In recent years, many researchers have focused on developing catalysts that do not contain noble metals. Among them, transition metal oxides, with their advantages of low cost and excellent performance, are considered to have great potential to compete with noble metals and become the preferred commercial catalysts for next-generation HERs. Summary of the Invention

[0004] In order to overcome the shortcomings of the existing technology, the purpose of this invention is to provide a method for preparing and applying a fluorine-doped transition metal oxide hydrogen evolution electrocatalyst.

[0005] This invention first provides an electrocatalyst for hydrogen evolution reaction by using fluorine doping to regulate and activate the lattice oxygen activity of transition metal oxides.

[0006] Another object of the present invention is to provide a method for preparing the above-mentioned hydrogen evolution electrocatalyst.

[0007] Another object of the present invention is to provide a hydrogen evolution electrode prepared from the above-mentioned hydrogen evolution electrocatalyst.

[0008] The objective of this invention is achieved by at least one of the following technical solutions:

[0009] A fluorine-doped transition metal oxide hydrogen evolution electrocatalyst with the chemical formula BaCo0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ-0.5α F α , where δ is the oxygen defect stoichiometry, with a value range of 0 < δ < 2, and α is the F doping amount, with a value range of 0.01 ≤ α ≤ 0.5.

[0010] Preferably, the value of α is in the range of 0.1≤α≤0.3.

[0011] The preparation method of the above-mentioned fluorine-doped transition metal oxide hydrogen evolution electrocatalyst includes the following steps:

[0012] (1) Barium oxide, cobalt oxide, iron oxide, zirconium oxide, yttrium oxide and yttrium fluoride powders are mixed in stoichiometric ratio and anhydrous ethanol is added to obtain a mixed solution. Then the mixed solution is ball-milled.

[0013] (2) Heat the above ball-milled mixed solution until the anhydrous ethanol is completely evaporated to obtain a mixed powder;

[0014] (3) The above mixed powder is ground and then calcined at high temperature;

[0015] (4) The calcined powder was ball-milled to obtain a fluorine-doped transition metal oxide hydrogen evolution electrocatalyst.

[0016] Preferably, the volume ratio of liquid to solid in the mixed solution in step (1) is 2:1 to 3:1;

[0017] Preferably, the ball milling time in step (1) is 5-15 hours;

[0018] Preferably, the rotational speed of the ball mill in step (1) is 800-1500 rpm;

[0019] Preferably, the heating in step (2) is performed under an infrared lamp; the heating temperature is 60-80℃.

[0020] Preferably, the calcination temperature in step (3) is 1000-1200℃;

[0021] Preferably, the calcination time in step (3) is 8-12 hours.

[0022] Preferably, the ball milling time in step (4) is 18-30 hours;

[0023] Preferably, the rotation speed of the ball mill in step (4) is 800-1500 rpm.

[0024] A hydrogen evolution electrode comprising the aforementioned fluorine-doped transition metal oxide hydrogen evolution electrocatalyst (catalytically active material).

[0025] A method for preparing a hydrogen evolution electrode includes the following steps:

[0026] (a) The above-mentioned fluorine-doped transition metal oxide hydrogen evolution electrocatalyst was dispersed in a mixed solution of isopropanol, water and perfluorosulfonic acid resin, and ultrasonically treated to obtain a catalyst suspension.

[0027] (b) The catalyst suspension obtained in step (a) is coated onto the surface of carbon paper and dried at room temperature to obtain a hydrogen evolution electrode.

[0028] Preferably, the concentration of the fluorine-doped transition metal oxide hydrogen evolution electrocatalyst in the catalyst suspension in step (a) is 5 to 20 mg / mL; more preferably, it is 10 mg / mL.

[0029] Preferably, the volume percentages of isopropanol, water, and perfluorosulfonic acid resin in the mixed solution described in step (a) are 10–80%, 10–80%, and 5–20%, respectively, calculated as 5 wt% dispersion.

[0030] Preferably, the ultrasonic treatment time in step (a) is 1 to 5 hours;

[0031] Preferably, the catalyst suspension in step (b) has a single-sided loading of 1–5 mg / cm² on the carbon paper surface. 2 ;

[0032] Preferably, the carbon paper surface described in step (b) is coated on both sides;

[0033] Preferably, the drying time at room temperature in step (b) is 6 to 36 hours.

[0034] A hydrogen evolution electrode is prepared by the above-described preparation method.

[0035] Application of the above-mentioned fluorine-doped transition metal oxide hydrogen evolution electrocatalyst, or the above-mentioned hydrogen evolution electrode, or the hydrogen evolution electrode prepared by the above-mentioned preparation method, in hydrogen evolution reactions.

[0036] The principle of this invention is: BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ-0.5α F α The fluorine element in BaCo has higher electronegativity, making it easier to abstract electrons from oxygen sites, thereby activating lattice oxygen and promoting BaCo... 0.4 Fe 0.4 Zr 0.1 Y 0.1O 3-δ-0.5α F α The formation of oxygen vacancies in the material increases the active sites for hydrogen evolution, thereby improving the catalytic activity of the catalyst.

[0037] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0038] (1) The BaCo provided by this invention 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ-0.5α F α The electrocatalyst is synthesized by a solid-phase method, which is simple to prepare and suitable for large-scale production.

[0039] (2) The carbon paper current collector used in this invention can be prepared into electrodes of any shape and size, and has strong applicability in practical applications.

[0040] (3) The F-doping strategy proposed in this invention to regulate the electrocatalytic activity of transition metal oxides is also applicable to other transition metal oxides. Various transition metal compound catalysts can be easily prepared according to requirements, and it has universality.

[0041] (4) The BaCo provided by this invention 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ-0.5α F α The catalyst exhibits highly efficient hydrogen evolution performance. BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.925-δ F 0.15 At 10mA / cm 2 Overpotential ratio BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ It decreased by 71mV. Attached Figure Description

[0042] Figure 1 The linear sweep voltammetry curves obtained in the comparative example and Example 1 are shown.

[0043] Figure 2 The X-ray diffraction patterns are for the electrocatalysts obtained in the comparative example and Example 1.

[0044] Figure 3 XPS O1s spectra of the electrocatalysts obtained in the comparative example and Example 1.

[0045] Figure 4 The linear sweep voltammetry curves obtained in the comparative example and Example 2 are shown.

[0046] Figure 5 The linear sweep voltammetry curves obtained in the comparative example and Example 3 are shown. Detailed Implementation

[0047] The specific implementation of the present invention will be further described below with reference to the accompanying drawings and examples, but the implementation and protection of the present invention are not limited thereto. It should be noted that any processes not specifically described in detail below are those that can be implemented or understood by those skilled in the art by referring to the prior art. Reagents or instruments whose manufacturers are not specified are considered to be conventional products that can be purchased commercially.

[0048] Comparative example:

[0049] This comparative example provides a hydrogen evolution electrocatalyst BaCo. 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ The preparation method includes the following steps:

[0050] 1. Barium oxide, cobalt oxide, iron oxide, zirconium oxide, and yttrium oxide powders were mixed in stoichiometric ratios, and anhydrous ethanol was added to obtain a mixed solution with a liquid-to-solid volume ratio of 2:1. The mixed solution was then ball-milled for 10 hours at a speed of 1200 rpm.

[0051] 2. Place the ball-milled mixture under an infrared lamp and heat it to 70°C until the anhydrous ethanol is completely evaporated, yielding a mixed powder.

[0052] 3. After grinding the above mixed powder, place it in a muffle furnace for high-temperature calcination at a temperature of 1200℃ for 10 hours.

[0053] 4. The calcined powder was then ball-milled for 24 hours at a speed of 1200 rpm to obtain BaCo. 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ Electrocatalyst.

[0054] The X-ray diffraction pattern of the electrocatalyst obtained in the comparative example is as follows: Figure 2 XPS O1s graph as follows Figure 3 .

[0055] In addition, this comparative example provides a hydrogen evolution electrode, the preparation method of which includes the following steps:

[0056] 1. The catalytically active material BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ The catalyst was dispersed in a mixed solution of isopropanol, ultrapure water, and perfluorosulfonic acid resin. The concentration of the catalytic active material was 10 mg / mL, and the volume percentages of isopropanol, ultrapure water, and perfluorosulfonic acid resin (calculated as a 5 wt% dispersion) were 45%, 45%, and 10%, respectively. The mixed solution was then sonicated for 2 hours to obtain a catalyst suspension.

[0057] 2. The obtained catalyst suspension was coated onto the surface of carbon paper (double-sided coating), with a single-sided loading of 2 mg / cm³. 2 The hydrogen evolution electrode was obtained by drying at room temperature for 24 hours.

[0058] The hydrogen evolution catalytic activity of the obtained hydrogen evolution electrode was tested in this comparative example. Test conditions: A standard three-electrode system was used as the test system, with the obtained catalyst material as the working electrode, saturated Ag / AgCl as the reference electrode, and a graphite rod as the counter electrode. 1 mol L⁻¹ -1 KOH solution was used as the electrolyte, and the testing instrument was a Shanghai Chenhua 660E electrochemical workstation. Linear sweep voltammetry curves were measured at room temperature (25℃). The obtained linear sweep voltammetry curves are shown below. Figure 1 As shown.

[0059] Example 1:

[0060] This embodiment provides a hydrogen evolution electrocatalyst BaCo. 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.95-δ F 0.1 The preparation method includes the following steps:

[0061] 1. Barium oxide, cobalt oxide, iron oxide, zirconium oxide, yttrium oxide, and yttrium fluoride powders were mixed in stoichiometric ratios, and anhydrous ethanol was added to obtain a mixed solution with a liquid-to-solid volume ratio of 2:1. The mixed solution was then ball-milled for 10 hours at a speed of 1200 rpm.

[0062] 2. Place the ball-milled mixture under an infrared lamp and heat it to 70°C until the anhydrous ethanol is completely evaporated, yielding a mixed powder.

[0063] 3. After grinding the above mixed powder, place it in a muffle furnace for high-temperature calcination at a temperature of 1200℃ for 10 hours.

[0064] 4. The calcined powder was then ball-milled for 24 hours at a speed of 1200 rpm to obtain BaCo. 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.95-δ F 0.1 Electrocatalyst.

[0065] The X-ray diffraction pattern of the electrocatalyst obtained in Example 1 is as follows: Figure 2 XPS O1s graph as follows Figure 3 .

[0066] Furthermore, this embodiment provides a hydrogen evolution electrode, the preparation method of which includes the following steps:

[0067] 1. The catalytically active material BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.95-δ F 0.1 The catalyst was dispersed in a mixed solution of isopropanol, ultrapure water, and perfluorosulfonic acid resin. The concentration of the catalytic active material was 10 mg / mL, and the volume percentages of isopropanol, ultrapure water, and perfluorosulfonic acid resin (calculated as a 5 wt% dispersion) were 45%, 45%, and 10%, respectively. The mixed solution was then sonicated for 2 hours to obtain a catalyst suspension.

[0068] 2. The obtained catalyst suspension was coated onto the surface of carbon paper (double-sided coating), with a single-sided loading of 2 mg / cm³. 2 The hydrogen evolution electrode was obtained by drying at room temperature for 24 hours.

[0069] This embodiment tests the hydrogen evolution catalytic activity of the obtained hydrogen evolution electrode. Test conditions: A standard three-electrode system was used as the test system, with the obtained catalyst material as the working electrode, saturated Ag / AgCl as the reference electrode, and a graphite rod as the counter electrode. 1 mol L⁻¹ -1 KOH solution was used as the electrolyte, and the testing instrument was a Shanghai Chenhua 660E electrochemical workstation. Linear sweep voltammetry curves were measured at room temperature (25℃). The obtained linear sweep voltammetry curves are shown below. Figure 1 As shown.

[0070] Example 2:

[0071] This embodiment provides a hydrogen evolution electrocatalyst BaCo. 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.925-δ F 0.15The preparation method includes the following steps:

[0072] 1. Barium oxide, cobalt oxide, iron oxide, zirconium oxide, yttrium oxide, and yttrium fluoride powders were mixed in stoichiometric ratios, and anhydrous ethanol was added to obtain a mixed solution with a liquid-to-solid volume ratio of 2:1. The mixed solution was then ball-milled for 12 hours at a speed of 1000 rpm.

[0073] 2. Place the ball-milled mixture under an infrared lamp and heat it to 70°C until the anhydrous ethanol is completely evaporated, yielding a mixed powder.

[0074] 3. After grinding the above mixed powder, place it in a muffle furnace for high-temperature calcination at 1100℃ for 12 hours.

[0075] 4. The calcined powder was then ball-milled for 30 hours at a speed of 1000 rpm to obtain BaCo. 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.925-δ F 0.15 Electrocatalyst.

[0076] Furthermore, this embodiment provides a hydrogen evolution electrode, the preparation method of which includes the following steps:

[0077] 1. The catalytically active material BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.925-δ F 0.15 The catalyst was dispersed in a mixed solution of isopropanol, ultrapure water, and perfluorosulfonic acid resin. The concentration of the catalytic active material was 10 mg / mL, and the volume percentages of isopropanol, ultrapure water, and perfluorosulfonic acid resin (calculated as a 5 wt% dispersion) were 45%, 45%, and 10%, respectively. The mixed solution was then sonicated for 2 hours to obtain a catalyst suspension.

[0078] 2. The obtained catalyst suspension was coated onto the surface of carbon paper (double-sided coating), with a single-sided loading of 2 mg / cm³. 2 The hydrogen evolution electrode was obtained by drying at room temperature for 24 hours.

[0079] This embodiment tests the hydrogen evolution catalytic activity of the obtained hydrogen evolution electrode. Test conditions: A standard three-electrode system was used as the test system, with the obtained catalyst material as the working electrode, saturated Ag / AgCl as the reference electrode, and a graphite rod as the counter electrode. 1 mol L⁻¹ -1KOH solution was used as the electrolyte, and the testing instrument was a Shanghai Chenhua 660E electrochemical workstation. Linear sweep voltammetry curves were measured at room temperature (25℃). The obtained linear sweep voltammetry curves are shown below. Figure 4 As shown.

[0080] Example 3:

[0081] This embodiment provides a hydrogen evolution electrocatalyst BaCo. 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.85-δ F 0.3 The preparation method includes the following steps:

[0082] 1. Barium oxide, cobalt oxide, iron oxide, zirconium oxide, yttrium oxide, and yttrium fluoride powders were mixed in stoichiometric ratios, and anhydrous ethanol was added to obtain a mixed solution with a liquid-to-solid volume ratio of 2:1. The mixed solution was then ball-milled for 12 hours at a speed of 1200 rpm.

[0083] 2. Place the ball-milled mixture under an infrared lamp and heat it to 70°C until the anhydrous ethanol is completely evaporated, yielding a mixed powder.

[0084] 3. After grinding the above mixed powder, place it in a muffle furnace for high-temperature calcination at a temperature of 1200℃ for 8 hours.

[0085] 4. The calcined powder was then ball-milled for 20 hours at a speed of 1500 rpm to obtain BaCo. 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.85-δ F 0.3 Electrocatalyst.

[0086] Furthermore, this embodiment provides a hydrogen evolution electrode, the preparation method of which includes the following steps:

[0087] 1. The catalytically active material BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.85-δ F 0.3 The catalyst was dispersed in a mixed solution of isopropanol, ultrapure water, and perfluorosulfonic acid resin. The concentration of the catalytic active material was 10 mg / mL, and the volume percentages of isopropanol, ultrapure water, and perfluorosulfonic acid resin (calculated as a 5 wt% dispersion) were 45%, 45%, and 10%, respectively. The mixed solution was then sonicated for 2 hours to obtain a catalyst suspension.

[0088] 2. The obtained catalyst suspension was coated onto the surface of carbon paper (double-sided coating), with a single-sided loading of 2 mg / cm³. 2 The hydrogen evolution electrode was obtained by drying at room temperature for 24 hours.

[0089] This embodiment tests the hydrogen evolution catalytic activity of the obtained hydrogen evolution electrode. Test conditions: A standard three-electrode system was used as the test system, with the obtained catalyst material as the working electrode, saturated Ag / AgCl as the reference electrode, and a graphite rod as the counter electrode. 1 mol L⁻¹ -1 KOH solution was used as the electrolyte, and the testing instrument was a Shanghai Chenhua 660E electrochemical workstation. Linear sweep voltammetry curves were measured at room temperature (25℃). The obtained linear sweep voltammetry curves are shown below. Figure 5 As shown.

[0090] Data Analysis:

[0091] The X-ray diffraction patterns of the electrocatalysts obtained in the comparative examples and Example 1 are as follows: Figure 2 XPS O1s graph as follows Figure 3 .

[0092] like Figure 2 As shown, the BaCo obtained in Example 1 and the comparative example 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ Compared to electrocatalysts, the BaCo obtained in Example 1... 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.95-δ F 0.1 The X-ray diffraction pattern of the electrocatalyst shows a significant shift towards higher angles, indicating that BaCo... 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.95-δ F 0.1 Electrocatalysts have smaller crystal lattices. Furthermore, such as... Figure 3 As shown, the BaCo obtained in Example 1 and the comparative example 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ Compared to electrocatalysts, the BaCo obtained in Example 1... 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.95-δ F 0.1The lower lattice oxygen signal in the O1s XPS spectrum of the electrocatalyst indicates that BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 2.95-δ F 0.1 The lattice oxygen in the electrocatalyst is activated because F has a higher electronegativity and more easily abstracts electrons from oxygen sites, thereby activating the lattice oxygen and promoting BaCo. 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ-0.5α F α The formation of oxygen vacancies in materials.

[0093] The linear sweep voltammetric curves of Examples 1-3 and the comparative examples are as follows: Figure 1 , Figure 4 , Figure 5 Overpotentials are shown in Table 1.

[0094] As shown in Table 1, the electrocatalysts obtained in the comparative examples, Example 1, Example 2, and Example 3 at 10 mA / cm 2 The overpotentials at current densities were 320mV, 275mV, 249mV, and 300mV, respectively, at 100mA / cm². 2 The overpotentials at the current densities were 452 mV, 351 mV, 330 mV, and 377 mV, respectively. Compared with the comparative examples, the BaCo obtained in Examples 1, 2, and 3... 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ-0.5α F α The electrocatalyst exhibits a lower overpotential, at 10 mA / cm². 2 The overpotential decreased by 45mV, 71mV and 20mV at current densities, respectively, at 100mA / cm 2 The overpotential at the current density decreased by 101mV, 122mV and 75mV, respectively.

[0095] Table 1. Electrocatalysts obtained in the comparative examples and embodiments at 10 mA / cm² 2 and 100mA / cm 2 Overpotential at current density

[0096] <![CDATA[10mA / cm 2 Overpotential <![CDATA[100mA / cm 2 Overpotential Comparative Example 320mV 452mV Example 1 275mV 351mV Example 2 249mV 330mV Example 3 300mV 377mV

[0097] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. The application of a fluorine-doped transition metal oxide hydrogen evolution electrocatalyst in the hydrogen evolution reaction, characterized in that, The electrocatalyst has the chemical formula BaCo. 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ-0.5α F α Where δ is the oxygen defect stoichiometry, α ranges from 0.1 to 0.3, and α is the F doping amount, ranging from 0.01 to 0.5; the preparation method of the electrocatalyst includes the following steps: (1) Barium oxide, cobalt oxide, iron oxide, zirconium oxide, yttrium oxide and yttrium fluoride powders are mixed in stoichiometric ratio and anhydrous ethanol is added to obtain a mixed solution. Then the mixed solution is ball-milled. (2) Heat the above ball-milled mixed solution until the anhydrous ethanol is completely evaporated to obtain a mixed powder; (3) Grind the above mixed powder and then calcine it at high temperature; (4) The calcined powder was ball-milled to obtain a fluorine-doped transition metal oxide hydrogen evolution electrocatalyst.

2. The application of the fluorine-doped transition metal oxide hydrogen evolution electrocatalyst according to claim 1 in the hydrogen evolution reaction, characterized in that, The volume ratio of liquid to solid in the mixed solution described in step (1) is 2:1 to 3:1; The ball milling time mentioned in step (1) is 5-15 hours; The ball mill speed mentioned in step (1) is 800-1500 rpm; The heating in step (2) is performed under an infrared lamp; the heating temperature is 60-80℃.

3. The application of the fluorine-doped transition metal oxide hydrogen evolution electrocatalyst according to claim 1 in the hydrogen evolution reaction, characterized in that, The calcination temperature mentioned in step (3) is 1000-1200℃; The calcination time mentioned in step (3) is 8-12 hours.

4. The application of the fluorine-doped transition metal oxide hydrogen evolution electrocatalyst according to claim 1 in the hydrogen evolution reaction, characterized in that, The ball milling time mentioned in step (4) is 18-30 hours; The ball milling speed in step (4) is 800-1500 rpm.

5. An application of a hydrogen evolution electrode in a hydrogen evolution reaction, characterized in that, The hydrogen evolution electrode comprises the hydrogen evolution electrocatalyst as described in any one of claims 1-2.

6. The application of the hydrogen evolution electrode according to claim 5 in the hydrogen evolution reaction, characterized in that, The preparation of the hydrogen evolution electrode includes the following steps: (a) Disperse the fluorine-doped transition metal oxide hydrogen evolution electrocatalyst according to any one of claims 1-2 in a mixed solution of isopropanol, water and perfluorosulfonic acid resin, and sonicate to obtain a catalyst suspension. (b) The catalyst suspension obtained in step (a) is coated on the surface of carbon paper and dried at room temperature to obtain a hydrogen evolution electrode.

7. The application of the hydrogen evolution electrode according to claim 6 in the hydrogen evolution reaction, characterized in that, The concentration of the fluorine-doped transition metal oxide hydrogen evolution electrocatalyst in the catalyst suspension in step (a) is 5–20 mg / mL; The volume percentages of isopropanol, water, and perfluorosulfonic acid resin in the mixed solution described in step (a) are 10–80%, 10–80%, and 5–20%, respectively, calculated as a 5 wt% dispersion. The duration of the ultrasonic treatment in step (a) is 1 to 5 hours; The catalyst suspension described in step (b) has a single-sided loading of 1–5 mg / cm² on the carbon paper surface. 2 ; The carbon paper surface described in step (b) is coated on both sides; The drying time at room temperature in step (b) is 6 to 36 hours.

Images