A ruthenium-tungsten oxide material, a preparation method and application thereof

Abstract

The application relates to a ruthenium-tungsten oxide material and a preparation method and application thereof, and the preparation method comprises the following steps: (1) uniformly stirring water, glucose, urea, ruthenium chloride and cetyltrimethylammonium bromide to obtain solution A, and the solution is transparent, and then the solution is prepared; (2) adding tungsten chloride into ethanol and stirring to obtain solution B; (3) slowly adding solution B into solution A and uniformly stirring; (4) standing the mixed solution obtained above; (5) transferring the mixed solution obtained above into a drying box and drying; (6) calcining the dried product under an air atmosphere, annealing and cooling to room temperature to obtain the target product, i.e. the ruthenium-tungsten oxide material. Compared with the prior art, the application has the advantages of good chemical stability, excellent anti-physical structure deterioration and high tolerance to impurity ions.

Description

Technical Field

[0001] This invention relates to the field of composite materials technology, and in particular to a ruthenium tungsten oxide material, its preparation method, and its applications. Background Technology

[0002] Coal chemical waste salt is a hazardous waste with complex composition, high toxicity, and difficulty in degradation. It mainly originates from the evaporation and crystallization process of production side reactions or wastewater "zero discharge," during which toxic and harmful substances are highly concentrated. Taking the coal chemical industry as an example, the massive amount of waste salt generated annually, if landfilled as hazardous waste, would incur billions of yuan in disposal costs, leading to inventory buildup and potential environmental risks for enterprises. Therefore, promoting the resource utilization of waste salt is imperative. Against this backdrop, using the mainstream ion-exchange membrane chlor-alkali electrolysis process to convert sodium chloride in waste salt into chlor-alkali products is considered a high-value resource utilization path. However, this technology faces a core challenge in treating coal chemical waste salt: the heavy metals and organic toxic substances enriched in the waste salt severely poison the precious metal anode coating and ion exchange membrane of the electrolyzer, causing a sharp decline in chlorine evolution reaction efficiency, an increase in side reactions, and an increase in cell voltage, ultimately leading to electrode deactivation and membrane fouling, making it difficult to maintain the stability and economic viability of the entire process.

[0003] Size-stabilized anodes (DSA) are widely used in fields involving chlorine evolution reactions, such as the chlor-alkali industry using ion-exchange membranes, and their active layers are typically based on RuO2. However, traditional RuO2-based catalysts face significant challenges in practical operation, especially in complex industrial electrolytes, where they are susceptible to impurity ions (such as Ca2+). 2+ Mg 2+ SO4 2- The effects of pH fluctuations (such as those caused by the presence of substances like CaO and Cr) lead to the loss of active components, coating peeling, and rapid decline in catalytic activity, resulting in "contamination" and "poisoning" problems. This severely limits the lifespan of the electrode and the continuity of production. This is because in acidic or fluctuating media, Ru active sites in pure RuO2 or simply doped RuO2 are prone to dissolution or the formation of soluble ruthenium chloride, leading to permanent loss of active centers. During electrolysis, changes in internal stress between the substrate and the active coating, and between coating particles, as well as the crystallization of impurities in the pores, can easily cause microcracks, pulverization, or even large-area peeling of the coating, resulting in physical deactivation. 2+ Mg 2+ Impurity ions readily adsorb onto the catalyst surface or form hydroxide / carbonate precipitates in the pores, blocking active sites; while SO4 2- Anions may compete with active sites for adsorption, thus inhibiting the chlorine evolution reaction.

[0004] Patent application CN121063519A discloses a platinum-zinc alloy-supported nitrogen-doped porous multi-level carbon material and its preparation and application. This invention uses rod-shaped hierarchical porous carbon nanomaterials as a carrier, with platinum-zinc alloy particles and zinc single atoms co-loaded on the carrier surface. The material is prepared through the following steps: zinc acetate and hexadecyltrimethylammonium bromide are added to DMF, ultrasonically treated, and then added to a polyacrylonitrile solution with stirring; the resulting spinning precursor solution is electrospun; the obtained nanofibers are added to a zinc acetate dihydrate solution, followed by a dimethylimidazole solution, and subjected to a hydrothermal reaction; the resulting product is then immersed in a chloroplatinic acid methanol solution and subsequently freeze-dried; carbonization is carried out under an inert atmosphere, followed by annealing and cooling to obtain the target product. This invention exhibits good catalytic performance in redox reactions and chlorine evolution reactions. However, the preparation process of this material is complex, the size of the platinum-zinc alloy is difficult to control, and platinum is expensive. Furthermore, its catalytic activity in the chlorine evolution reaction remains insufficient.

[0005] Therefore, developing low-cost, highly active, and durable ruthenium-tungsten oxide catalysts has become a key research focus in the chlor-alkali industry. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing ruthenium tungsten oxide materials and their applications, which have significantly enhanced chemical stability and resistance to component loss, as well as high tolerance to impurity ions.

[0007] The objective of this invention can be achieved through the following technical solutions: In a first aspect, the present invention provides a method for preparing a ruthenium-tungsten oxide catalyst, comprising the following steps: S1. Mix water, glucose, urea, ruthenium chloride and hexadecyltrimethylammonium bromide until they become transparent to obtain solution A; S2. Add tungsten chloride to ethanol and stir to obtain solution B; S3. Add solution B to solution A, stir evenly, let stand, dry, then calcine in air atmosphere, then anneal and cool to room temperature to obtain ruthenium tungsten oxide catalyst.

[0008] Furthermore, in S1, the mass ratio of glucose, urea, ruthenium chloride and hexadecyltrimethylammonium bromide is (18~22):(8~12):1:(8~12), and for example, it can be 20:10:1:10, etc.

[0009] Furthermore, in S2, the mass ratio of tungsten chloride to ethanol is 1:(8~10), for example, it can be 1:9.

[0010] Furthermore, in S3, the amounts of solution B and solution A added satisfy the following condition: the molar ratio of ruthenium chloride to tungsten chloride is (1~2):1.

[0011] Furthermore, in S3, the settling conditions are: in an air environment, settling at 25°C for 2~6 hours.

[0012] Furthermore, in S3, the drying process specifically involves maintaining the temperature at 70~90℃ for 8~12 hours.

[0013] Furthermore, in S3, the calcination process is as follows: heat to 400~700℃ and hold for 6~12 hours.

[0014] Furthermore, in S3, the heating rate during the calcination process is 0.5~2℃ / min.

[0015] In a second aspect, the present invention provides a ruthenium tungsten oxide material, which is prepared by the preparation method described in the first aspect above.

[0016] In a third aspect, the present invention provides an application of ruthenium-tungsten oxide material as a catalyst for chlorine evolution reaction at the anode of a chlor-alkali electrolytic cell in coal chemical waste salt.

[0017] This invention introduces tungsten to form a stable heterojunction material of ruthenium-tungsten oxide. Due to tungsten's strong oxygen bonding ability, lattice stability is enhanced, and the "anchoring effect" effectively inhibits the dissolution and loss of ruthenium active sites. It can also modulate the electronic structure of ruthenium sites, making the catalyst surface more responsive to Cl... - The adsorption is moderate, but the adsorption of impurity ions is weak. Tungsten oxide, as a structural stabilizer, can refine grains, enhance coating density, and improve adhesion to the titanium substrate. This composite structure possesses higher mechanical strength and toughness, effectively resisting physical stress caused by bubble erosion, temperature changes, and impurity crystallization. This significantly improves its resistance to chemical corrosion in electrolytes with fluctuating composition and effectively reduces the occupation of active sites by impurity ions, thus exhibiting excellent resistance to poisoning and contamination. Therefore, the ruthenium-tungsten oxide catalyst system provides a new approach for the development of catalysts for the chlorine evolution reaction.

[0018] Compared with the prior art, the present invention has the following beneficial effects: (1) Significantly enhanced chemical stability and resistance to component loss WO3 and RuO2 form a stable heterojunction structure. The high oxidation state and strong oxygen bonding ability of tungsten significantly enhance the stability of the entire oxide lattice. This "anchoring effect" effectively inhibits the dissolution and loss of ruthenium active sites, thus exhibiting excellent resistance to chemical corrosion and contamination.

[0019] (2) Excellent resistance to physical structural degradation and coating peeling The unique microstructure formed by RuO2-WO3 composite oxide has higher mechanical strength and toughness, and can effectively resist physical stress caused by bubble erosion, temperature changes and impurity crystallization, thus exhibiting extremely strong resistance to physical structural contamination and extending the mechanical life of the electrode.

[0020] (3) High tolerance to impurity ions (anti-poisoning ability) The RuO2-WO3 catalyst surface exhibits unique electronic properties, showing moderate adsorption strength for chloride ions but weak adsorption capacity for impurity ions. Due to the adjustment of the d-band center of the ruthenium u sites by tungsten, the catalyst surface demonstrates high selectivity for chloride ions, reducing the occupation of active sites by impurity ions and exhibiting excellent resistance to poisoning and contamination. Attached Figure Description

[0021] Figure 1 This is a scanning electron microscope image of the RuO2-WO3 material prepared in Example 1 of this invention; Figure 2 The diagram shows the electrocatalytic performance of the RuO2-WO3 material prepared in Example 1 of this invention in a chlor-alkali electrolyzer for chlorine evolution. Detailed Implementation

[0022] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the specification of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application.

[0024] As used herein, the terms "and / or," "or / and," and "and / or" encompass any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected using at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that, in this application, the technical solution undoubtedly includes solutions connected by "logical AND," and also undoubtedly includes solutions connected by "logical OR."

[0025] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0026] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0027] This document only specifically discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0028] Unless otherwise specified, the temperature parameters in this application may be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows temperature fluctuations within the precision range controlled by the instrument, such as ±5°C, ±4°C, ±3°C, ±2°C, or ±1°C.

[0029] In this document, the term "suitable" as used in phrases such as "suitable combination," "suitable method," and "any suitable method" refers to the ability to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.

[0030] In this application, terms such as "further," "even further," and "particularly" are used to describe purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0031] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0032] In the description of the application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0033] Unless otherwise specified, all preparations and tests described herein took place at 25°C.

[0034] The terms “comprising,” “including,” “containing,” “having,” “comprising,” or other variations thereof are intended to cover non-closed inclusion, and no distinction is made between these terms. The term “comprising” means that other steps and ingredients may be added without affecting the final result. The compositions and methods / processes of the present invention comprise, consist of, and substantially consist of the essential elements and limitations described herein, as well as any additional or optional ingredients, components, steps, or limitations described herein. No distinction is made between the terms “efficacy,” “performance,” “effect,” and “potency” herein.

[0035] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions. Unless otherwise specified, all technical features and optional technical features of this application can be combined to form new technical solutions.

[0036] Unless otherwise specified, all steps of this application may be performed sequentially or randomly, but sequentially is preferred.

[0037] Example 1 (1) Weigh 400 mg of glucose, 200 mg of urea, 20 mg of ruthenium chloride and 200 mg of cetyltrimethylammonium bromide, add them to water and stir until a clear solution is obtained, to obtain solution A; add 38.2 mg of tungsten chloride to ethanol and stir until a clear solution is obtained, to obtain solution B. Mix solutions A and B, stir thoroughly and let stand to obtain a mixed solution.

[0038] (2) Drying: Take the mixed solution obtained in step (1) and place it in a circulating air drying oven. Heat the oven to 80 °C for 10 h. Remove water and ethanol solvent from the mixed solution to obtain solid powder.

[0039] (3) Oxide formation process: The dried solid powder obtained in step (2) is placed in a crucible, then placed in a muffle furnace, heated to 500 ℃ at a heating rate of 1 ℃ / min under air atmosphere, held for 8 h, and then naturally cooled to room temperature to obtain RuO2-WO3 material, i.e., the target product. (e.g.) Figure 1 (As shown) (4) Chlorine evolution performance test of chlor-alkali electrolytic cell: RuO2-WO3 was used as the anode material of chlor-alkali electrolytic cell, the reference electrode was a calomel electrode with saturated potassium chloride solution, a polytetrafluoroethylene tube salt bridge, the experimental electrolyte was 5 M NaCl solution, and the experimental current density was 2 kA / m under constant DC input. 2The experimental temperature was 25±2 ℃. After 10 minutes of electrolysis, the instantaneous lowest potential value was recorded within 20 seconds; this was taken as the chlorine evolution potential of the electrode. The portion of the chlorine evolution potential exceeding the theoretical voltage value of the chlorine evolution reaction was considered the overpotential. The closer the overpotential was to 0 V, the better the catalyst performance, the lower the actual voltage required to reach the relative current density, the lower the energy consumption, and the higher the catalytic activity. A value of 10 mA cm⁻¹ was typically chosen. -2 The performance of a catalyst is judged based on the current density at a given point and the corresponding conditions. For example... Figure 2 As shown, the electrode sheet in this embodiment reaches 10 mA cm⁻¹. -2 The overpotential of the current density is 80 mV, which is significantly better than that of commercial DSA (130 mV), demonstrating better catalytic performance for chlorine evolution reaction.

[0040] Example 2 (1) Weigh 400 mg of glucose, 200 mg of urea, 20 mg of ruthenium chloride and 10 mg of cetyltrimethylammonium bromide, add them to water and stir until a clear solution is obtained, to obtain solution A; add 38.2 mg of tungsten chloride to ethanol and stir until a clear solution is obtained, to obtain solution B. Mix solutions A and B, stir thoroughly and let stand to obtain a mixed solution.

[0041] (2) Drying reaction: Take the mixed solution obtained in step (1) and place it in a circulating air drying oven. Heat the oven to 80 °C for 8 h. Remove water and ethanol solvent from the mixed solution to obtain solid powder.

[0042] (3) Oxide formation process: The dried solid powder obtained in step (2) is placed in a crucible and then placed in a muffle furnace. It is heated to 400 °C at a heating rate of 1 °C / min in an air atmosphere, held for 8 h, and then naturally cooled to room temperature to obtain RuO2-WO3 material, i.e. the target product.

[0043] (4) Chlorine evolution performance test of chlor-alkali electrolytic cell: RuO2-WO3 was used as the anode material of chlor-alkali electrolytic cell, the reference electrode was a calomel electrode with saturated potassium chloride solution, a polytetrafluoroethylene tube salt bridge, the experimental electrolyte was 5 M NaCl solution, and the experimental current density was 2 kA / m under constant DC input. 2 The experimental temperature was 25±2 ℃. After 10 minutes of electrolysis, the instantaneous lowest potential value was recorded within 20 seconds; this was taken as the chlorine evolution potential of the electrode. The portion of the chlorine evolution potential exceeding the theoretical voltage value of the chlorine evolution reaction was considered the overpotential. The closer the overpotential was to 0 V, the better the catalyst performance, the lower the actual voltage required to reach the relative current density, the lower the energy consumption, and the higher the catalytic activity. A value of 10 mA cm⁻¹ was typically chosen. -2The catalyst performance is judged under the corresponding current density at a given location. In this embodiment, the electrode plate reaches 10 mA cm⁻¹. -2 The overpotential of the current density is 100 mV, which is significantly better than that of commercial DSA (130 mV), demonstrating better catalytic performance for chlorine evolution reaction.

[0044] Example 3 (1) Weigh 400 mg of glucose, 200 mg of urea, 20 mg of ruthenium chloride and 200 mg of cetyltrimethylammonium bromide, add them to water and stir until a clear solution is obtained, to obtain solution A; add 38.2 mg of tungsten chloride to ethanol and stir until a clear solution is obtained, to obtain solution B. Mix solutions A and B, stir thoroughly and let stand.

[0045] (2) Drying reaction: Take the mixed solution obtained in step (1) and place it in a circulating air drying oven. The temperature in the drying oven is raised to 80 °C for 10 h. Remove the water and ethanol solvent from the mixed solution to obtain solid powder.

[0046] (3) Oxide formation process: The dried solid powder obtained in step (2) is placed in a crucible and then placed in a muffle furnace. It is heated to 600 °C at a heating rate of 1 °C / min in an air atmosphere, held for 8 h, and then naturally cooled to room temperature to obtain RuO2-WO3 material, i.e. the target product.

[0047] (4) Chlorine evolution performance test of chlor-alkali electrolytic cell: RuO2-WO3 was used as the anode material of chlor-alkali electrolytic cell, the reference electrode was a calomel electrode with saturated potassium chloride solution, a polytetrafluoroethylene tube salt bridge, the experimental electrolyte was 5 M NaCl solution, and the experimental current density was 2 kA / m under constant DC input. 2 The experimental temperature was 25±2 ℃. After 10 minutes of electrolysis, the instantaneous lowest potential value was recorded within 20 seconds; this was taken as the chlorine evolution potential of the electrode. The portion of the chlorine evolution potential exceeding the theoretical voltage value of the chlorine evolution reaction was considered the overpotential. The closer the overpotential was to 0 V, the better the catalyst performance, the lower the actual voltage required to reach the relative current density, the lower the energy consumption, and the higher the catalytic activity. A value of 10 mA cm⁻¹ was typically chosen. -2 The catalyst performance is judged under the corresponding current density at a given location. In this embodiment, the electrode plate reaches 10 mA cm⁻¹. -2 The overpotential of the current density is 105 mV, which is significantly better than that of commercial DSA (130 mV), demonstrating better catalytic performance for chlorine evolution reaction.

[0048] Example 4 (1) Weigh 400 mg of glucose, 200 mg of urea, 20 mg of ruthenium chloride and 200 mg of cetyltrimethylammonium bromide, add them to water and stir until a clear solution is obtained, to obtain solution A; add 38.2 mg of tungsten chloride to ethanol and stir until a clear solution is obtained, to obtain solution B. Mix solutions A and B, stir thoroughly and let stand.

[0049] (2) Drying reaction: Take the mixed solution obtained in step (1) and place it in a circulating air drying oven. The temperature in the drying oven is raised to 80 °C for 10 h. Remove water and ethanol solvent from the mixed solution to obtain solid powder.

[0050] (3) Oxide formation process: The dried solid powder obtained in step (2) is placed in a crucible and then placed in a muffle furnace. It is heated to 700 °C at a heating rate of 1 °C / min in an air atmosphere, held for 8 h, and then naturally cooled to room temperature to obtain RuO2-WO3 material, i.e. the target product.

[0051] (4) Chlorine evolution performance test of chlor-alkali electrolytic cell: RuO2-WO3 was used as the anode material of chlor-alkali electrolytic cell, the reference electrode was a calomel electrode with saturated potassium chloride solution, a polytetrafluoroethylene tube salt bridge, the experimental electrolyte was 5 M NaCl solution, and the experimental current density was 2 kA / m under constant DC input. 2 The experimental temperature was 25±2 ℃. After 10 minutes of electrolysis, the instantaneous lowest potential value was recorded within 20 seconds; this was taken as the chlorine evolution potential of the electrode. The portion of the chlorine evolution potential exceeding the theoretical voltage value of the chlorine evolution reaction was considered the overpotential. The closer the overpotential was to 0 V, the better the catalyst performance, the lower the actual voltage required to reach the relative current density, the lower the energy consumption, and the higher the catalytic activity. A value of 10 mA cm⁻¹ was typically chosen. -2 The catalyst performance is judged under the corresponding current density at a given location. In this embodiment, the electrode plate reaches 10 mA cm⁻¹. -2 The overpotential of the current density is 110 mV, which is significantly better than that of commercial DSA (130 mV), demonstrating better catalytic performance for chlorine evolution reaction.

[0052] Comparative Example 1 Compared with Example 1, most of the results are the same, except that the amount of tungsten chloride added is different, in which the amount of tungsten chloride added is adjusted to 12.7 mg.

[0053] (1) Weigh out glucose, urea, ruthenium chloride and hexadecyltrimethylammonium bromide, add them to water and stir until a clear solution is obtained, to obtain solution A; add tungsten chloride to ethanol and stir until a clear solution is obtained, to obtain solution B. Mix solutions A and B, stir thoroughly and let stand to obtain a mixed solution.

[0054] (2) Drying reaction: Take the mixed solution obtained in step (1) and place it in a circulating air drying oven. The temperature in the drying oven is raised to 80 °C for 10 h. Remove water and ethanol solvent from the mixed solution to obtain solid powder.

[0055] (3) Oxide formation process: The dried solid powder obtained in step (2) is placed in a crucible and then placed in a muffle furnace. It is heated to 500 °C at a heating rate of 1 °C / min in an air atmosphere, held for 8 h, and then naturally cooled to room temperature to obtain RuO2-WO3 material, i.e. the target product.

[0056] (4) Chlorine evolution performance test of chlor-alkali electrolytic cell: RuO2-WO3 was used as the anode material of chlor-alkali electrolytic cell, the reference electrode was a calomel electrode with saturated potassium chloride solution, a polytetrafluoroethylene tube salt bridge, the experimental electrolyte was 5 M NaCl solution, and the experimental current density was 2 kA / m under constant DC input. 2 The experimental temperature was 25±2 ℃. After 10 minutes of electrolysis, the instantaneous lowest potential value was recorded within 20 seconds; this was taken as the chlorine evolution potential of the electrode. The portion of the chlorine evolution potential exceeding the theoretical voltage value of the chlorine evolution reaction was considered the overpotential. The closer the overpotential was to 0 V, the better the catalyst performance, the lower the actual voltage required to reach the relative current density, the lower the energy consumption, and the higher the catalytic activity. A value of 10 mA cm⁻¹ was typically chosen. -2 The catalyst performance was evaluated under the corresponding current density at a given location. The comparative electrode achieved a current density of 10 mA cm⁻¹. -2 The overpotential of the current density is 180 mV, which is significantly worse than that of commercial DSA (130 mV), and it exhibits general catalytic performance for chlorine evolution reaction.

[0057] Comparative Example 2 The majority of the results were the same as in Example 1, except for the amount of tungsten chloride added, which was 9.6 mg.

[0058] (1) Weigh out glucose, urea, ruthenium chloride and hexadecyltrimethylammonium bromide, add them to water and stir until a clear solution is obtained, to obtain solution A; add tungsten chloride to ethanol and stir until a clear solution is obtained, to obtain solution B. Mix solutions A and B, stir thoroughly and let stand.

[0059] (2) Drying reaction: Take the mixed solution obtained in step (1) and place it in a circulating air drying oven. The temperature in the drying oven is raised to 80 °C for 10 h. Remove water and ethanol solvent from the mixed solution to obtain solid powder.

[0060] (3) Oxide formation process: The dried solid powder obtained in step (2) is placed in a crucible and then placed in a muffle furnace. It is heated to 500 °C at a heating rate of 1 °C / min in an air atmosphere, held for 8 h, and then naturally cooled to room temperature to obtain RuO2-WO3 material, i.e. the target product.

[0061] (4) Chlorine evolution performance test of chlor-alkali electrolytic cell: RuO2-WO3 was used as the anode material of chlor-alkali electrolytic cell, the reference electrode was a calomel electrode with saturated potassium chloride solution, a polytetrafluoroethylene tube salt bridge, the experimental electrolyte was 5 M NaCl solution, and the experimental current density was 2 kA / m under constant DC input. 2 The experimental temperature was 25±2 ℃. After 10 minutes of electrolysis, the instantaneous lowest potential value was recorded within 20 seconds; this was taken as the chlorine evolution potential of the electrode. The portion of the chlorine evolution potential exceeding the theoretical voltage value of the chlorine evolution reaction was considered the overpotential. The closer the overpotential was to 0 V, the better the catalyst performance, the lower the actual voltage required to reach the relative current density, the lower the energy consumption, and the higher the catalytic activity. A value of 10 mA cm⁻¹ was typically chosen. -2 The catalyst performance was evaluated under the corresponding current density at a given location. The comparative electrode achieved a current density of 10 mA cm⁻¹. -2 The overpotential of the current density is 250 mV, which is significantly worse than that of commercial DSA (130 mV), and it exhibits general catalytic performance for chlorine evolution reaction.

[0062] Comparative Example 3 The majority of the results were the same as in Example 1, except for the order and amount of tungsten chloride added, in which the amount of tungsten chloride added was 7.6 mg.

[0063] (1) Weigh out glucose, urea, ruthenium chloride and hexadecyltrimethylammonium bromide, add them to water and stir until a clear solution is obtained, to obtain solution A; add tungsten chloride to ethanol and stir until a clear solution is obtained, to obtain solution B. Mix solutions A and B, stir thoroughly and let stand.

[0064] (2) Drying reaction: Take the mixed solution obtained in step (1) and place it in a circulating air drying oven. The temperature in the drying oven is raised to 80 °C for 10 h. Remove water and ethanol solvent from the mixed solution to obtain solid powder.

[0065] (3) Oxide formation process: The dried solid powder obtained in step (2) is placed in a crucible and then placed in a muffle furnace. It is heated to 500 °C at a heating rate of 1 °C / min in an air atmosphere, held for 8 h, and then naturally cooled to room temperature to obtain RuO2-WO3 material, i.e. the target product.

[0066] (4) Chlorine evolution performance test of chlor-alkali electrolytic cell: RuO2-WO3 was used as the anode material of chlor-alkali electrolytic cell, the reference electrode was a calomel electrode with saturated potassium chloride solution, a polytetrafluoroethylene tube salt bridge, the experimental electrolyte was 5 M NaCl solution, and the experimental current density was 2 kA / m under constant DC input. 2 The experimental temperature was 25±2 ℃. After 10 minutes of electrolysis, the instantaneous lowest potential value was recorded within 20 seconds; this was taken as the chlorine evolution potential of the electrode. The portion of the chlorine evolution potential exceeding the theoretical voltage value of the chlorine evolution reaction was considered the overpotential. The closer the overpotential was to 0 V, the better the catalyst performance, the lower the actual voltage required to reach the relative current density, the lower the energy consumption, and the higher the catalytic activity. A value of 10 mA cm⁻¹ was typically chosen. -2 The catalyst performance was evaluated under the corresponding current density at a given location. The comparative electrode achieved a current density of 10 mA cm⁻¹. -2 The overpotential of the current density is 280 mV, which is significantly worse than that of commercial DSA (130 mV), and it exhibits general catalytic performance for chlorine evolution reaction.

[0067] Comparative Example 4 It is largely the same as Example 1, except that tungsten chloride is not added.

[0068] (1) Weigh out glucose, urea, ruthenium chloride and hexadecyltrimethylammonium bromide, add them to water, stir until a clear solution is formed, stir thoroughly and let stand.

[0069] (2) Drying reaction: Take the mixed solution obtained in step (1) and place it in a circulating air drying oven. The temperature in the drying oven is raised to 80 °C for 10 h. Remove water and ethanol solvent from the mixed solution to obtain solid powder.

[0070] (3) Oxide formation process: The dried solid powder obtained in step (2) is placed in a crucible and then placed in a muffle furnace. It is heated to 500 °C at a heating rate of 1 °C / min in an air atmosphere, held for 8 h, and then naturally cooled to room temperature to obtain RuO2 material, i.e. the target product.

[0071] (4) Chlorine evolution performance test of chlor-alkali electrolytic cell: RuO2 was used as the anode material of chlor-alkali electrolytic cell, the reference electrode was a calomel electrode with saturated potassium chloride solution, a polytetrafluoroethylene tube salt bridge was used, the experimental electrolyte was 5 M NaCl solution, and the experimental current density was 2 kA / m under constant DC input. 2The experimental temperature was 25±2 ℃. After 10 minutes of electrolysis, the instantaneous lowest potential value was recorded within 20 seconds; this was taken as the chlorine evolution potential of the electrode. The portion of the chlorine evolution potential exceeding the theoretical voltage value of the chlorine evolution reaction was considered the overpotential. The closer the overpotential was to 0 V, the better the catalyst performance, the lower the actual voltage required to reach the relative current density, the lower the energy consumption, and the higher the catalytic activity. A value of 10 mA cm⁻¹ was typically chosen. -2 The performance of a catalyst is determined by the current density at a given point under the corresponding conditions. Figure 2 The figure shows the electrocatalytic performance of the chlorine evolution in the chlor-alkali electrolyzer. As can be seen from the figure, the electrode of this comparative example achieves 10 mA cm⁻¹. -2 The overpotential at the current density was 320 mV, significantly inferior to that of commercial DSA (130 mV) and RuO2-WO3 in Example 1 (80 mV), exhibiting typical catalytic performance for the chlorine evolution reaction. This indicates that the addition of tungsten can regulate the electron density of Ru sites on the RuO2 surface, inhibiting excessive oxidation and dissolution of Ru and stabilizing lattice oxygen. Simultaneously, WO3 possesses excellent electrochemical conductivity, forming a highly efficient charge transport channel after recombination with RuO2, accelerating the electron transfer process.

[0072] Comparative Example 5 It is largely the same as Example 1, except that urea is replaced with an equimolar amount of dicyandiamide.

[0073] (1) Weigh 400 mg of glucose, 280 mg of dicyandiamide, 20 mg of ruthenium chloride and 200 mg of cetyltrimethylammonium bromide, add them to water and stir until a clear solution is obtained, to obtain solution A; add 38.2 mg of tungsten chloride to ethanol and stir until a clear solution is obtained, to obtain solution B. Mix solutions A and B, stir thoroughly and let stand to obtain a mixed solution.

[0074] (2) Drying: Take the mixed solution obtained in step (1) and place it in a circulating air drying oven. Heat the oven to 80 °C for 10 h. Remove water and ethanol solvent from the mixed solution to obtain solid powder.

[0075] (3) Oxide formation process: The dried solid powder obtained in step (2) is placed in a crucible and then placed in a muffle furnace. It is heated to 500 °C at a heating rate of 1 °C / min in an air atmosphere, held for 8 h, and then naturally cooled to room temperature to obtain RuO2-WO3 material, i.e. the target product.

[0076] (4) Chlorine evolution performance test of chlor-alkali electrolytic cell: RuO2-WO3 was used as the anode material of chlor-alkali electrolytic cell, the reference electrode was a calomel electrode with saturated potassium chloride solution, a polytetrafluoroethylene tube salt bridge, the experimental electrolyte was 5 M NaCl solution, and the experimental current density was 2 kA / m under constant DC input. 2 The experimental temperature was 25±2 ℃. After 10 minutes of electrolysis, the instantaneous lowest potential value was recorded within 20 seconds; this was taken as the chlorine evolution potential of the electrode. The portion of the chlorine evolution potential exceeding the theoretical voltage value of the chlorine evolution reaction was considered the overpotential. The closer the overpotential was to 0 V, the better the catalyst performance, the lower the actual voltage required to reach the relative current density, the lower the energy consumption, and the higher the catalytic activity. A value of 10 mA cm⁻¹ was typically chosen. -2 The catalyst performance was evaluated under the corresponding current density at a given location. The comparative electrode achieved a current density of 10 mA cm⁻¹. -2 The overpotential of the current density is 240 mV, which is significantly worse than that of commercial DSA (130 mV), and it exhibits general catalytic performance for chlorine evolution reaction.

[0077] Comparative Example 6: It is largely the same as Example 1, except that the addition of urea is omitted.

[0078] (1) Weigh 400 mg of glucose, 20 mg of ruthenium chloride and 200 mg of cetyltrimethylammonium bromide, add them to water and stir until a clear solution is obtained, to obtain solution A; add 38.2 mg of tungsten chloride to ethanol and stir until a clear solution is obtained, to obtain solution B. Mix solutions A and B, stir thoroughly and let stand to obtain a mixed solution.

[0079] (2) Drying: Take the mixed solution obtained in step (1) and place it in a circulating air drying oven. Heat the oven to 80 °C for 10 h. Remove water and ethanol solvent from the mixed solution to obtain solid powder.

[0080] (3) Oxide formation process: The dried solid powder obtained in step (2) is placed in a crucible and then placed in a muffle furnace. It is heated to 500 °C at a heating rate of 1 °C / min in an air atmosphere, held for 8 h, and then naturally cooled to room temperature to obtain RuO2-WO3 material, i.e. the target product.

[0081] (4) Chlorine evolution performance test of chlor-alkali electrolytic cell: RuO2-WO3 was used as the anode material of chlor-alkali electrolytic cell, the reference electrode was a calomel electrode with saturated potassium chloride solution, a polytetrafluoroethylene tube salt bridge, the experimental electrolyte was 5 M NaCl solution, and the experimental current density was 2 kA / m under constant DC input. 2The experimental temperature was 25±2 ℃. After 10 minutes of electrolysis, the instantaneous lowest potential value was recorded within 20 seconds; this was taken as the chlorine evolution potential of the electrode. The portion of the chlorine evolution potential exceeding the theoretical voltage value of the chlorine evolution reaction was considered the overpotential. The closer the overpotential was to 0 V, the better the catalyst performance, the lower the actual voltage required to reach the relative current density, the lower the energy consumption, and the higher the catalytic activity. A value of 10 mA cm⁻¹ was typically chosen. -2 The catalyst performance was evaluated under the corresponding current density at a given location. The comparative electrode achieved a current density of 10 mA cm⁻¹. -2 The overpotential of the current density is 310 mV, which is significantly worse than that of commercial DSA (130 mV), and it exhibits general catalytic performance for chlorine evolution reaction.

[0082] Comparative Example 7: It is largely the same as Example 1, except that the addition of glucose is omitted.

[0083] (1) Weigh 200 mg of urea, 20 mg of ruthenium chloride and 200 mg of cetyltrimethylammonium bromide, add them to water and stir until a clear solution is obtained, to obtain solution A; add 38.2 mg of tungsten chloride to ethanol and stir until a clear solution is obtained, to obtain solution B. Mix solutions A and B, stir thoroughly and let stand to obtain a mixed solution.

[0084] (2) Drying: Take the mixed solution obtained in step (1) and place it in a circulating air drying oven. Heat the oven to 80 °C for 10 h. Remove water and ethanol solvent from the mixed solution to obtain solid powder.

[0085] (3) Oxide formation process: The dried solid powder obtained in step (2) is placed in a crucible and then placed in a muffle furnace. It is heated to 500 °C at a heating rate of 1 °C / min in an air atmosphere, held for 8 h, and then naturally cooled to room temperature to obtain RuO2-WO3 material, i.e. the target product.

[0086] (4) Chlorine evolution performance test of chlor-alkali electrolytic cell: RuO2-WO3 was used as the anode material of chlor-alkali electrolytic cell, the reference electrode was a calomel electrode with saturated potassium chloride solution, a polytetrafluoroethylene tube salt bridge, the experimental electrolyte was 5 M NaCl solution, and the experimental current density was 2 kA / m under constant DC input. 2 The experimental temperature was 25±2 ℃. After 10 minutes of electrolysis, the instantaneous lowest potential value was recorded within 20 seconds; this was taken as the chlorine evolution potential of the electrode. The portion of the chlorine evolution potential exceeding the theoretical voltage value of the chlorine evolution reaction was considered the overpotential. The closer the overpotential was to 0 V, the better the catalyst performance, the lower the actual voltage required to reach the relative current density, the lower the energy consumption, and the higher the catalytic activity. A value of 10 mA cm⁻¹ was typically chosen. -2The catalyst performance was evaluated under the corresponding current density at a given location. The comparative electrode achieved a current density of 10 mA cm⁻¹. -2 The overpotential of the current density is 290 mV, which is significantly worse than that of commercial DSA (130 mV), and it exhibits general catalytic performance for chlorine evolution reaction.

[0087] The chlorine evolution performance test results of the chlor-alkali electrolyzers in the examples and comparative examples are shown in Table 1 below: Table 1 As shown in the table above, ruthenium-tungsten oxide materials were prepared by adjusting the amount of tungsten oxide and the calcination temperature. Examples 1-4 exhibited better chlorine evolution performance compared to Comparative Examples 1-7. The introduction of tungsten effectively controlled the d-band center of Ru, enhancing its resistance to Cl. - The adsorption strength of RuO2 is reduced, while the adsorption of intermediate *Cl is weakened, thus avoiding poisoning of active sites. Appropriate tungsten doping can optimize the adsorption energy distribution on the RuO2 surface, but high tungsten doping will cover the active sites of RuO2, reducing the effective active area and leading to a decrease in the catalytic effect of the chlorine evolution reaction. Glucose is chosen as the carbon template for pyrolysis because it can react with Ru... 3+ W 6+ The formation of stable chelate complexes ensures uniform mixing of the two metal ions, preventing aggregation and guaranteeing full exposure of active sites. Using urea as the nitrogen source, which releases gases such as NH3 and N2 during pyrolysis, allows the material to form a rich porous structure, significantly increasing its specific surface area and mass transfer efficiency. In contrast, other nitrogen sources result in more violent pyrolysis processes compared to urea, which can easily lead to material structural collapse and make them less stable than urea.

[0088] In the above embodiments, the range of process conditions involved can be arbitrarily adjusted within the following limits according to actual needs (i.e., arbitrarily adjusted to its endpoint value or any intermediate point value): The amount of tungsten chloride added was 19.1–39.2 mg; The specific process of heating and carbonization involves controlling the heating rate to be 0.5~2. o C / min, heating to 400-700 o At temperature C, keep warm for 6–12 hours to complete the carbonization process.

[0089] The foregoing has shown and described the basic process, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a ruthenium-tungsten oxide catalyst, characterized in that, Includes the following steps: S1. Mix water, glucose, urea, ruthenium chloride and hexadecyltrimethylammonium bromide until they become transparent to obtain solution A; S2. Add tungsten chloride to ethanol and stir to obtain solution B; S3. Add solution B to solution A, stir evenly, let stand, dry, then calcine in air atmosphere, then anneal and cool to room temperature to obtain ruthenium tungsten oxide catalyst.

2. The method for preparing a ruthenium-tungsten oxide catalyst according to claim 1, characterized in that, In S1, the mass ratio of glucose, urea, ruthenium chloride and hexadecyltrimethylammonium bromide is (18~22):(8~12):1:(8~12).

3. The method for preparing a ruthenium-tungsten oxide catalyst according to claim 1, characterized in that, In S2, the mass ratio of tungsten chloride to ethanol is 1:(8~10).

4. The method for preparing a ruthenium-tungsten oxide catalyst according to claim 1, characterized in that, In S3, the amounts of solution B and solution A added satisfy the following condition: the molar ratio of ruthenium chloride to tungsten chloride is (1~2):

1.

5. The method for preparing a ruthenium-tungsten oxide catalyst according to claim 1, characterized in that, In S3, the standing conditions are: in an air environment, stand at 25℃ for 2~6 hours.

6. The method for preparing a ruthenium-tungsten oxide catalyst according to claim 1, characterized in that, In S3, the drying process specifically involves maintaining the temperature at 70~90℃ for 8~12 hours.

7. The method for preparing a ruthenium-tungsten oxide catalyst according to claim 1, characterized in that, In S3, the calcination process is as follows: heat up to 400~700℃ and hold for 6~12 hours.

8. The method for preparing a ruthenium-tungsten oxide catalyst according to claim 7, characterized in that, In S3, the heating rate during the calcination process is 0.5~2℃ / min.

9. A ruthenium-tungsten oxide material, characterized in that, It is prepared by the preparation method described in any one of claims 1-8.

10. The application of the ruthenium-tungsten oxide material as described in claim 9 as a catalyst for the chlorine evolution reaction at the anode of a chlor-alkali electrolytic cell in coal chemical waste salt.

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