Use of a heteroatom-doped ruthenium dioxide catalyst in a hydrogen evolution reaction

Abstract

The application discloses application of a heteroatom-doped ruthenium dioxide catalyst in a hydrogen evolution reaction, wherein the heteroatom is one of transition metals or rare earth metals, and the transition metals or rare earth metals are doped into a ruthenium dioxide crystal lattice. The catalyst is used in an alkaline water electrolysis hydrogen evolution reaction, and excellent hydrogen evolution performance is exhibited.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalytic hydrogen production, specifically relating to the application of a heteroatom-doped ruthenium dioxide catalyst in the hydrogen evolution reaction. Background Technology

[0002] With the growing acceptance of green and sustainable development concepts, the development of green energy has become a mainstream research area in the energy sector. Hydrogen has attracted significant attention due to its high energy density and environmentally friendly, pollution-free characteristics. Among various industrial hydrogen production methods, water electrolysis offers a simple and rapid way to produce high-purity hydrogen, while also meeting green production requirements. For water electrolysis, a suitable catalyst can efficiently convert electrical energy into hydrogen energy. While phosphorus (Pt) is an ideal catalyst for water electrolysis, its limited availability and high cost necessitate ongoing research into novel Pt-free hydrogen evolution catalysts to reduce the cost of electrolysis. Currently, numerous transition metal catalysts, such as Fe, Co, and Ni-based catalysts, have been developed, but their relatively low activity and poor stability still fail to meet the demands of industrial production.

[0003] The Ru-H bond energy is similar to that of the Pt-H bond energy, but metallic Ru is cheaper than Pt. Therefore, the preparation of high-performance ruthenium-based hydrogen evolution catalysts using simple and rapid methods holds promise for further reducing the cost of hydrogen production through electrolysis. Ruthenium dioxide, as an oxygen evolution catalyst in water electrolysis, has seen numerous studies incorporating heteroatoms into its structure in current reports. Science 2023, 380 (6645), 609-616, Nat. Commun. 2024, 15 (1), 4974), to improve the stability of ruthenium dioxide catalysts under acidic conditions. However, there are relatively few reports on the use of ruthenium dioxide as a hydrogen evolution catalyst in alkaline solutions. Summary of the Invention

[0004] To achieve the above objectives, the present invention provides an application of heteroatom-doped ruthenium dioxide catalyst in the hydrogen evolution reaction. The heteroatom-doped ruthenium dioxide catalyst of the present invention exhibits excellent hydrogen evolution performance in alkaline solution.

[0005] Based on this, the present invention adopts the following technical solution: The application of a heteroatom-doped ruthenium dioxide catalyst in the hydrogen evolution reaction, wherein the heteroatom is one of a transition metal element or a rare earth element, and the transition metal element or rare earth element is doped into the ruthenium dioxide lattice.

[0006] According to an embodiment of the present invention, the heteroatom-doped ruthenium dioxide catalyst undergoes the hydrogen evolution reaction in an alkaline solution. Preferably, the alkaline solution is, for example, sodium hydroxide, potassium hydroxide, etc. Preferably, the concentration of the alkaline solution is 0.5-3M, for example, 0.5M, 1M, 2M, or 3M.

[0007] According to an embodiment of the present invention, the transition metal element is selected from at least one of chromium, manganese, cobalt, nickel, copper, and zinc.

[0008] According to an embodiment of the present invention, the rare earth element is selected from at least one of lanthanum, cerium, praseodymium, neodymium, sphagnum molybdenum, europium, erbium, and yttrium.

[0009] According to an embodiment of the present invention, transition metal elements or rare earth elements are doped into the ruthenium dioxide lattice in atomic form.

[0010] According to an embodiment of the present invention, in the heteroatom-doped ruthenium dioxide catalyst, the doping ratio of transition metal elements or rare earth elements is less than 1 wt%, for example, 0.01-0.9 wt%, and exemplary values ​​are 0.01 wt%, 0.1 wt%, 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt%, or 0.9 wt%.

[0011] According to an embodiment of the present invention, the preparation method of the heteroatom-doped ruthenium dioxide catalyst includes the following steps: (1) Dissolve ruthenium salt, rare earth salt or transition metal salt in water and heat to carry out hydrothermal reaction; (2) The product obtained in step (1) is heated and calcined to obtain the heteroatom-doped ruthenium dioxide catalyst.

[0012] According to an embodiment of the present invention, in step (1), the reaction temperature is 100~150 ℃ and the reaction time is 4~12 h.

[0013] According to an embodiment of the present invention, in step (1), the ruthenium salt is at least one of ruthenium bromide or ruthenium chloride; According to an embodiment of the present invention, in step (1), the rare earth salt is at least one of lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, tungsten nitrate, europium nitrate, erbium nitrate, and yttrium nitrate; According to an embodiment of the present invention, in step (1), the transition metal salt is at least one of the transition metal nitrates, acetates, and chlorides, for example, at least one of the nitrates, acetates, and chlorides of chromium, manganese, cobalt, nickel, copper, and zinc; According to an embodiment of the present invention, in step (1), the concentration of ruthenium ions in the ruthenium salt is 0.01~0.3 mol / L; for example, 0.01 mol / L, 0.05 mol / L, 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.25 mol / L or 0.3 mol / L.

[0014] According to an embodiment of the present invention, in step (1), the concentration of rare earth ions in the rare earth salt is 0.01~0.2 mol / L; for example, 0.01 mol / L, 0.02 mol / L, 0.05 mol / L, 0.1 mol / L, 0.15 mol / L or 0.2 mol / L.

[0015] According to an embodiment of the present invention, in step (1), the concentration of transition metal ions in the transition metal salt is 0.01~0.2 mol / L; for example, 0.01 mol / L, 0.02 mol / L, 0.05 mol / L, 0.1 mol / L, 0.15 mol / L or 0.2 mol / L.

[0016] According to an embodiment of the present invention, step (1) further includes a post-processing step: filtering the product after heating reaction to obtain a precipitate, drying the precipitate to obtain a solid product.

[0017] Preferably, the drying temperature is 60~100 ℃; According to an embodiment of the present invention, in step (2), the heating and roasting temperature is 200~500 ℃, for example 200 ℃, 300 ℃, 400 ℃ or 500 ℃, and the heating and roasting time is 20~60 min.

[0018] According to an embodiment of the present invention, in step (2), the calcination atmosphere is an inert atmosphere, which is nitrogen or argon.

[0019] The beneficial effects of this invention are: 1. This invention can prepare heteroatom-doped ruthenium dioxide catalysts in large quantities through a simple hydrothermal and calcination method, and the production cycle is short.

[0020] 2. By introducing heteroatoms into the catalyst, this invention improves the hydrogen evolution reaction activity of heteroatom-doped ruthenium dioxide catalysts, thus exhibiting activity comparable to commercial Pt / C catalysts.

[0021] 3. The catalyst of this invention exhibits excellent hydrogen evolution performance when used in alkaline water electrolysis hydrogen evolution reaction. Attached Figure Description

[0022] Figure 1 These are scanning electron microscope (SEM) images of the catalyst prepared in Example 1 at different magnifications; Figure 2 These are scanning electron microscope (SEM) images of the catalyst prepared in Example 2 at different magnifications; Figure 3 These are scanning electron microscope (SEM) images of the catalyst prepared in Example 3 at different magnifications; Figure 4 These are scanning electron microscope (SEM) images of the chemical agents prepared in Example 4 at different magnifications. Figure 5 The XRD patterns of the catalysts prepared in Examples 1-4 are shown below. Figure 6 The graphs show the hydrogen evolution performance of the catalysts prepared in Examples 1-4 in 1M KOH solution. Detailed Implementation

[0023] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0024] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0025] Example 1 1. Catalyst Preparation (1) Weigh 0.414g RuCl3 and 0.450g La(NO3)3 respectively, then add them to 40 ml of deionized water and stir well; (2) Pour the solution from step (1) into the reaction vessel and react at 120°C for 8 hours; (3) The precipitate obtained from the hydrothermal reaction in step (2) was washed with deionized water and dried at 60°C to obtain a powdered solid. (4) The dried powder solid from step (3) is placed in a tube furnace and calcined at 300°C in an argon atmosphere for 30 min. After cooling, the La-doped ruthenium dioxide hydrogen evolution catalyst is obtained. Figure 1 SEM images of the catalyst prepared by the above method at different magnifications; Figure 5 The phase characterization results of the catalyst prepared by the above method show that the main phase of the catalyst is RuO2.

[0026] After microwave digestion of the catalyst powder, the mass percentage of La in the catalyst was measured to be 0.02 wt% by inductively coupled plasma mass spectrometry (ICP-MS).

[0027] 2. Application Testing The hydrogen evolution performance of the La-doped ruthenium dioxide hydrogen evolution catalyst prepared in Example 1 under alkaline conditions was evaluated using a traditional three-electrode testing method. A 40% Pt / C catalyst from Johnson Matthey was also used for comparative testing. The specific testing procedure is as follows: Weigh 3 mg of La-doped ruthenium dioxide hydrogen evolution catalyst and add it to a solution containing 490 μL of ethanol and 10 μL of 5% perfluorosulfonic acid resin (Nafion). Sonicate for 30 min to prepare catalyst ink. Then, measure 30 μL of the catalyst ink and drop it onto a surface with an area of ​​0.5 × 0.5 cm². 2 The working electrode was prepared by drying the carbon paper at 60°C. A carbon rod was selected as the counter electrode, and mercury / mercury oxide with a salt bridge concentration of 1M KOH was used as the reference electrode. The hydrogen evolution performance was tested in 1M KOH solution.

[0028] Johnson Matthey's 40% Pt / C catalyst was tested using the same method.

[0029] Figure 6 The polarization curves of the catalyst were obtained using the above testing method. As can be seen from the figure, the catalyst prepared in Example 1 exhibits polarization at 10, 100, and 200 mA / cm². 2 The overpotentials at the current densities were 16.5, 55.5, and 84.6 mV, respectively, while the overpotentials corresponding to the commercial 40% Pt / C catalyst were 11.4, 60.3, and 93.4 mV, respectively.

[0030] Example 2 1. Catalyst Preparation (1) Weigh 0.207g RuCl3 and 0.5224g Sm(NO3)3 respectively, add them to 20 mL of deionized water, and stir well; (2) Pour the solution from step (1) into the reaction vessel and react at 100 °C for 12 h; (3) The precipitate obtained from the hydrothermal reaction in step (2) was washed with deionized water and dried at 60°C to obtain a powdered solid. (4) The dried powder solid from step (3) is placed in a tube furnace and calcined at 400°C in a nitrogen atmosphere for 20 min. After cooling, Sm-doped ruthenium dioxide hydrogen evolution catalyst is obtained.

[0031] Figure 2 SEM images of the catalyst prepared by the above method at different magnifications; Figure 5 The phase characterization results of the catalyst prepared by the above method show that the main phase of the catalyst is RuO2.

[0032] 2. Application Testing The testing method is the same as in Example 1. Figure 6 The test results show that the catalyst prepared in Example 2 performs well at 10, 100, and 200 mA / cm². 2 The overpotentials at the current densities are 18.9, 58.3, and 84.6 mV, respectively.

[0033] Example 3 1. Catalyst Preparation (1) Weigh 0.414g RuCl3 and 0.476g Cr(NO3)3 respectively, then add them to 40 ml of deionized water and stir well; (2) Pour the solution from step (1) into the reaction vessel and react at 120°C for 8 hours; (3) The precipitate obtained from the hydrothermal reaction in step (2) was washed with deionized water and dried at 60°C to obtain a powdered solid. (4) The dried powder solid from step (3) is placed in a tube furnace and calcined at 500°C in an argon atmosphere for 20 min. After cooling, Cr-doped ruthenium dioxide hydrogen evolution catalyst is obtained.

[0034] Figure 3 SEM images of the catalyst prepared by the above method at different magnifications; Figure 5 The phase characterization results of the catalyst prepared by the above method show that the main phase of the catalyst is RuO2.

[0035] 2. Application Testing The testing method is the same as in Example 1. Figure 6 The test results show that the catalyst prepared in Example 3 performs well at 10, 100, and 200 mA / cm². 2 The overpotentials at the current densities are 9.2, 34.7, and 62.3 mV, respectively.

[0036] Example 4 1. Catalyst Preparation (1) Weigh 0.207g RuCl3 and 0.2449g Co(NO3)3 respectively, add them to 10 mL of deionized water, and stir well; (2) Pour the solution from step (1) into the reaction vessel and react at 150 °C for 4 h; (3) The precipitate obtained from the hydrothermal reaction in step (2) was washed with deionized water and dried at 60°C to obtain a powdered solid. (4) The dried powder solid from step (3) is placed in a tube furnace and calcined at 200°C in a nitrogen atmosphere for 60 min. After cooling, a Co-doped ruthenium dioxide hydrogen evolution catalyst is obtained. Figure 4SEM images of the catalyst prepared by the above method at different magnifications; Figure 5 The phase characterization results of the catalyst prepared by the above method show that the main phase of the catalyst is RuO2.

[0037] 2. Application Testing The testing method is the same as in Example 1. Figure 6 The test results show that the catalyst prepared in Example 4 performs well at 10, 100, and 200 mA / cm². 2 The overpotentials at the current densities are 17.2, 61.5, and 92.3 mV, respectively.

[0038] The embodiments of the present invention have been described above by way of example. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. The application of a heteroatom-doped ruthenium dioxide catalyst in the hydrogen evolution reaction, characterized in that, The heteroatoms are one of the transition metal elements or rare earth elements, which are doped into the ruthenium dioxide lattice.

2. The application according to claim 1, characterized in that, The heteroatom-doped ruthenium dioxide catalyst undergoes a hydrogen evolution reaction in an alkaline solution.

3. The application according to claim 1, characterized in that, The transition metal element is selected from at least one of chromium, manganese, cobalt, nickel, copper, and zinc; The rare earth element is selected from at least one of lanthanum, cerium, praseodymium, neodymium, sulphine, europium, erbium, and yttrium.

4. The application according to claim 1, characterized in that, Transition metal elements or rare earth elements are doped into the ruthenium dioxide lattice in atomic form.

5. The application according to claim 1, characterized in that, In the heteroatom-doped ruthenium dioxide catalyst, the doping ratio of transition metal elements or rare earth elements is less than 1 wt%.

6. The application according to claim 1, characterized in that, The preparation method of the heteroatom-doped ruthenium dioxide catalyst includes the following steps: (1) Dissolve ruthenium salt, rare earth salt or transition metal salt in water and heat to carry out hydrothermal reaction; (2) The product obtained in step (1) is calcined to obtain the heteroatom-doped ruthenium dioxide catalyst.

7. The application according to claim 1, characterized in that, In step (1), the ruthenium salt is at least one of ruthenium bromide or ruthenium chloride; In step (1), the rare earth salt is at least one of lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, tungsten nitrate, europium nitrate, erbium nitrate, and yttrium nitrate; In step (1), the transition metal salt is at least one of the transition metal nitrate, acetate, and chloride salts.

8. The application according to claim 1, characterized in that, In step (1), the concentration of ruthenium ions in the ruthenium salt is 0.01~0.3 mol / L; In step (1), the concentration of rare earth ions in the rare earth salt is 0.01~0.2 mol / L; In step (1), the concentration of transition metal ions in the transition metal salt is 0.01~0.2 mol / L.

9. The application according to claim 1, characterized in that, In step (2), the heating and roasting temperature is 200~500℃ and the heating and roasting time is 20~60min.

10. The application according to claim 1, characterized in that, In step (2), the roasting atmosphere is an inert atmosphere, which is nitrogen or argon.

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