Titanium-doped ruthenium dioxide, and preparation method and application thereof
The preparation of titanium-doped ruthenium dioxide by a solvothermal method solves the stability and activity problems of pure-phase ruthenium dioxide during electrochemical service, achieving efficient and low-cost improvement of electrocatalytic performance, which is suitable for industrial applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NANTONG UNIV
- Filing Date
- 2026-03-30
- Publication Date
- 2026-06-16
Smart Images
Figure CN122214948A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of electrochemical energy materials, specifically relating to a titanium-doped ruthenium dioxide, its preparation method, and its application. Background Technology
[0002] Ruthenium dioxide, as a classic transition metal oxide functional material, possesses excellent electronic conductivity, outstanding electrochemical activity, and excellent chemical stability. It has broad application prospects in fields such as electrocatalysis, electrochemical energy storage, and chlor-alkali industry electrodes, and has become one of the core research objects in the energy and chemical industries.
[0003] However, pure-phase ruthenium dioxide still has significant technical drawbacks in practical applications, severely limiting its industrial promotion and application. Firstly, during long-term electrochemical service, pure-phase ruthenium dioxide is prone to crystal structure collapse and particle agglomeration, leading to a rapid loss of active sites and a significant decrease in electrochemical cycle stability, failing to meet the requirements for long-term stable service. Secondly, pure-phase ruthenium dioxide has a small specific surface area and insufficient exposure of active sites, making it difficult to further improve catalytic activity and energy storage capacity, thus failing to meet the performance requirements of high-end electrochemical devices.
[0004] To overcome the inherent defects of pure-phase ruthenium dioxide, existing technologies often employ elemental doping modification to optimize the overall electrochemical performance of ruthenium dioxide by controlling the electronic structure, surface morphology, and pore structure. However, conventional preparation methods all have significant limitations: wet chemical synthesis requires high-temperature and high-pressure environments and relies on high-pressure reactors to complete the reaction, resulting in high equipment costs, high operational risks, long reaction cycles, and poor product uniformity; while thin film preparation technologies such as physical vapor deposition and chemical vapor deposition can produce high-purity products, the processes are highly dependent on high-vacuum equipment, plasma generators, and other precision instruments, leading to high production costs and low capacity, making large-scale industrial production impossible. Summary of the Invention
[0005] To address the shortcomings of existing technologies, this invention aims to overcome the deficiencies of current processes and provide a titanium-doped ruthenium dioxide material, its preparation method, and its electrochemical applications. The preparation method disclosed in this invention eliminates the need for stringent process conditions such as high-pressure reactions and high-vacuum environments, requiring no specialized high-precision equipment. The operation is simple and controllable, and process parameters are easily adjustable, significantly reducing equipment investment costs, shortening the preparation cycle, and improving production efficiency. Simultaneously, by precisely controlling the molar ratio of titanium to ruthenium, the material's crystal structure and surface active site distribution are optimized, resulting in a titanium-doped ruthenium dioxide material with significantly superior electrochemical activity compared to products prepared by conventional processes, resulting in a substantial improvement in overall electrochemical performance.
[0006] To address the aforementioned technical problems, a first aspect of the present invention provides a method for preparing titanium-doped ruthenium dioxide, comprising the following steps: S1. Weigh ruthenium trichloride and tetrabutyl titanate and dissolve them in an alcohol solvent. Mix them evenly by ultrasonication to obtain a precursor solution. S2. Transfer the precursor solution to the reaction vessel and place it in an oil bath for reaction. After the reaction is completed and cooled to room temperature, perform multiple washing and centrifugation purification processes to obtain the purified sample. S3. Disperse the conductive carrier in an ethanol solution, add the purified sample, mix thoroughly by ultrasonication, centrifuge again to collect the precipitate, and dry the precipitate to obtain a powder sample. S4. The powdered sample is placed in a muffle furnace and calcined to obtain titanium-doped ruthenium dioxide.
[0007] The preparation method of this invention successfully synthesizes titanium-doped ruthenium dioxide without requiring demanding equipment such as high pressure and high vacuum. By loading the purified sample onto a carbon support, particle agglomeration can be avoided, increasing its specific surface area and thus exposing more active sites. Simultaneously, the excellent conductivity of carbon materials accelerates charge transfer between active sites and the external circuit, improving the reaction rate. Furthermore, by utilizing the difference in electronegativity between titanium and ruthenium, electron transfer is modulated, optimizing the adsorption energy of oxygen evolution reaction (OER) intermediates, lowering the reaction energy barrier, and enhancing catalytic activity. The introduction of titanium induces a change in the reaction mechanism, thereby improving catalytic stability.
[0008] Preferably, the mass ratio of ruthenium trichloride to tetrabutyl titanate in step S1 is 1:(0.07~3.24).
[0009] Preferably, the alcohol solvent in step S1 is ethylene glycol, and the concentration of ruthenium trichloride in ethylene glycol after dissolution is 1.3 mg / mL.
[0010] Preferably, the reaction temperature in step S2 is 160~200℃, and the reaction time is 1~10h; more preferably, the reaction temperature in step S2 is 180℃, and the reaction time is 5h. The washing solvent is acetone, and the centrifugation time is 2~5min, the rotation speed is 10000~12000rpm, and the process is repeated at least twice.
[0011] Preferably, the conductive carrier in step S3 is one of carbon black, carbon nanotubes, or porous carbon. The preferred mass ratio of ruthenium trichloride to the conductive carrier is 1:0.96.
[0012] Preferably, the drying temperature in step S3 is 60~80℃ and the drying time is 6~24h.
[0013] Preferably, in step S4, the calcination temperature is 350℃, the heating rate is 10℃ / min, and the calcination time is 2h.
[0014] A second aspect of the present invention is to provide titanium-doped ruthenium dioxide prepared by the preparation method described in the first aspect of the present invention.
[0015] The titanium-doped ruthenium dioxide prepared by this invention has excellent electrocatalytic OER activity.
[0016] A third aspect of the present invention is to provide the application of titanium-doped ruthenium dioxide as a catalyst, as described in the second aspect of the present invention, in the electrolysis of water to produce hydrogen.
[0017] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention uses ruthenium trichloride and tetrabutyl titanate as reaction raw materials, replacing the expensive organic titanium source in the traditional process. The raw materials are readily available, inexpensive, and have a stable supply. Moreover, no flammable or explosive reagents are used throughout the process, making it green, environmentally friendly, and highly safe. The resulting titanium-doped ruthenium dioxide exhibits a loose and porous microstructure, which can significantly increase the number of exposed active sites and endow the material with excellent electrocatalytic oxygen evolution reaction activity.
[0018] (2) The present invention uses a solvothermal method to synthesize materials, which does not require high-pressure reaction devices, high-vacuum systems, plasma generators and other precision equipment. The process steps are simple, the reaction conditions are mild, safe and easy to control, and the preparation time is short. The amount of reagents used in the reaction process is small, the amount of waste emissions is low, which is environmentally friendly. It can significantly reduce production input and time costs, and is suitable for industrial mass production.
[0019] (3) The titanium-doped ruthenium dioxide prepared by the present invention, based on the difference in electronegativity between titanium and ruthenium, regulates the internal electron transfer and arrangement of the material, effectively reduces the reaction energy barrier of oxygen evolution reaction, and significantly improves catalytic activity; at the same time, titanium doping can induce the optimization of catalytic reaction mechanism, further enhancing the electrochemical stability and service life of the material.
[0020] (4) This invention further optimizes the crystal structure and pore morphology of the material by precisely controlling key process parameters such as the mass ratio of ruthenium trichloride to tetrabutyl titanate, reaction temperature, reaction time, and calcination temperature, resulting in an electrochemical performance of the product that far exceeds that of products produced by traditional simple processes. When this titanium-doped ruthenium dioxide was used as an oxygen evolution catalyst in a water electrolysis hydrogen production system, it exhibited excellent oxygen evolution catalytic performance at 10 mA·cm⁻¹. -2 At current density, the overpotential is as low as 234mV, while also exhibiting good long-term operational stability. Attached Figure Description
[0021] Figure 1 The images shown are SEM images and EDS spectra of titanium-doped ruthenium dioxide obtained in Example 1 of this invention; where a is the SEM image and b is the EDS spectrum. Figure 2 The above is a comparison curve of the OER performance of titanium-doped ruthenium dioxide as a catalyst and commercial ruthenium dioxide in Example 1 of this invention. Figure 3 The stability curve of titanium-doped ruthenium dioxide as a catalyst in Example 1 of the present invention; Figure 4 The XRD patterns of ruthenium dioxide catalysts prepared by titanium doping with different proportions in Examples 1-5 of this invention are shown. Figure 5 The OER performance curves of ruthenium dioxide catalysts prepared with different proportions of titanium doping in Examples 1-5 of this invention are shown. Detailed Implementation
[0022] To make the technical problem to be solved, the technical solution, and the beneficial effects of the present invention clearer, the present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.
[0023] The present invention provides a method for preparing titanium-doped ruthenium dioxide, comprising the following steps: S1. Weigh ruthenium trichloride and tetrabutyl titanate and dissolve them in an alcohol solvent. Mix them thoroughly by sonication for 15 minutes at room temperature to obtain a precursor solution. The mass ratio of ruthenium trichloride to tetrabutyl titanate is 1:(0.07~3.24). The alcohol solvent is ethylene glycol. In some specific embodiments, in step S1, the mass of ruthenium trichloride is 10.4 mg, the mass of tetrabutyl titanate is 0.8~33.7 mg, and the volume of 99.5% ethylene glycol is 8 mL.
[0024] S2. Transfer the precursor solution to the reaction vessel and place it in an oil bath at 180°C for 5 hours. After the reaction is completed and cooled to room temperature, perform multiple washing and centrifugation purification processes. The washing solvent is acetone, the centrifugation time is 2-5 minutes, the speed is 10000-12000 rpm, and the process is repeated at least twice to obtain the purified sample. S3. Disperse the conductive carrier in an ethanol solution, add the purified sample, mix thoroughly by ultrasonication, centrifuge again to collect the precipitate, and dry the precipitate at 60~80℃ for 6~24h to obtain a powder sample. The conductive carrier is one of carbon black, carbon nanotubes, or porous carbon.
[0025] S4. The powdered sample was placed in a muffle furnace and calcined at a temperature of 350℃, a heating rate of 10℃ / min, and a calcination time of 2h to obtain titanium-doped ruthenium dioxide.
[0026] In this embodiment of the invention, the titanium-doped ruthenium dioxide is used as a catalyst in water electrolysis for hydrogen production. In some specific embodiments, the titanium-doped ruthenium dioxide is used as a catalyst at the anode in an acidic water electrolysis hydrogen production device.
[0027] The following detailed description is based on several specific embodiments. Example 1
[0028] A method for preparing titanium-doped ruthenium dioxide specifically includes the following steps: S1. Weigh 10.4 mg of ruthenium trichloride and take 5.0 mg of tetrabutyl titanate and dissolve them in 8 mL of ethylene glycol solvent. Mix them evenly by sonication for 15 min to obtain the precursor solution. S2. Transfer the precursor solution to the reaction vessel and place it in an oil bath at 180°C for 5 hours. After the reaction is complete and cooled to room temperature, transfer the solution to a centrifuge tube, add ethanol, and centrifuge the sample for 3 minutes at 12,000 rpm. Repeat twice. S3. Disperse 10 mg of carbon black in an ethanol solution, add the washed sample, sonicate for 15 min to mix evenly, centrifuge again to collect the precipitate, and place the precipitate in a drying oven at 80 °C for 12 h to obtain a powder sample. S4. Place the sample in a muffle furnace and calcine at 350°C for 2 hours to obtain titanium-doped ruthenium dioxide. Example 2
[0029] Titanium-doped ruthenium dioxide was prepared using the same method as in Example 1, except that the amount of tetrabutyl titanate used in step S1 was 0.8 mg. Example 3
[0030] Titanium-doped ruthenium dioxide was prepared using the same method as in Example 1, except that the amount of tetrabutyl titanate used in step S1 was 1.7 mg. Example 4
[0031] Titanium-doped ruthenium dioxide was prepared using the same method as in Example 1, except that the amount of tetrabutyl titanate used in step S1 was 10.1 mg. Example 5
[0032] Titanium-doped ruthenium dioxide was prepared using the same method as in Example 1, except that the amount of tetrabutyl titanate used in step S1 was 33.7 mg.
[0033] Structural characterization and performance analysis were performed on the above specific embodiments 1 to 5.
[0034] Figure 1 The images show the SEM morphology and EDS energy dispersive spectroscopy of titanium-doped ruthenium dioxide in Example 1 of this invention; from... Figure 1The SEM image of 'a' shows that titanium-doped ruthenium dioxide exhibits a sparse, porous, cluster-like nanostructure, which exposes more active sites. Figure 1 The EDS spectrum of b indicates that the titanium doping content is 2.9 at.
[0035] To further verify the practical application effect of the titanium-doped ruthenium dioxide catalyst prepared in this invention, it was applied to the anode of an acidic water electrolysis hydrogen production device to conduct water electrolysis hydrogen production experiments. Figure 2 and Figure 3 The figures show the OER performance comparison curves and stability curves of titanium-doped ruthenium dioxide as a catalyst and commercial ruthenium dioxide in Example 1 of this invention; from Figure 2 The OER performance comparison curves show that titanium-doped ruthenium dioxide at 10 mA·cm⁻¹ -2 With an overpotential of only 234 mV, it exhibits excellent catalytic performance, with activity far exceeding that of commercial ruthenium dioxide. Furthermore, the stability of the titanium-doped ruthenium dioxide catalyst prepared in this invention was tested. Figure 3 It can be seen that the catalyst can operate stably for 400 hours without significant degradation.
[0036] The performance test comparison analysis above shows that after introducing titanium, the difference in electronegativity between titanium and ruthenium is used to regulate electron transfer, which lowers the reaction energy barrier of OER, improves catalytic activity, and induces a change in the reaction mechanism, thereby improving catalytic stability.
[0037] Figure 4 The images show the XRD patterns of ruthenium dioxide catalysts prepared with different proportions of titanium doping in Examples 1-5 of this invention. Figure 4 It can be seen that the specific embodiments all have rutile phase crystal structure. The diffraction peaks that appear at 2θ angles of 28° and 35° in the embodiments correspond to the (110) crystal plane of ruthenium dioxide, indicating that the present invention has successfully synthesized ruthenium dioxide.
[0038] Figure 5 The OER performance curves of ruthenium dioxide catalysts prepared with different proportions of titanium doping in Examples 1-5 of this invention are shown. Figure 5 It can be seen that ruthenium dioxide with different doping ratios all have good activity, but too high or too low titanium doping content will lead to reduced activity.
[0039] For those skilled in the art, the specific embodiments are merely illustrative descriptions of the present invention. Obviously, the specific implementation of the present invention is not limited to the above-described manner. Any non-substantial improvements made using the inventive concept and technical solution, such as changing the mass of a substance or a reaction parameter, or directly applying the inventive concept and technical solution to other situations without modification, are all within the protection scope of the present invention.
Claims
1. A method for preparing titanium-doped ruthenium dioxide, characterized in that, Specifically, the following steps are included: S1. Weigh ruthenium trichloride and tetrabutyl titanate and dissolve them in an alcohol solvent. Mix them evenly by ultrasonication to obtain a precursor solution. S2. Transfer the precursor solution to the reaction vessel and place it in an oil bath for reaction. After the reaction is completed and cooled to room temperature, perform multiple washing and centrifugation to obtain the purified sample. S3. Disperse the conductive carrier in an ethanol solution, add the purified sample, mix thoroughly by ultrasonication, centrifuge again to collect the precipitate, and dry the precipitate to obtain a powder sample. S4. The powdered sample is placed in a muffle furnace and calcined to obtain titanium-doped ruthenium dioxide.
2. The method for preparing titanium-doped ruthenium dioxide according to claim 1, characterized in that, In step S1, the mass ratio of ruthenium trichloride to tetrabutyl titanate is 1:(0.07~3.24).
3. The method for preparing titanium-doped ruthenium dioxide according to claim 1, characterized in that, In step S1, the alcohol solvent is ethylene glycol, and the concentration of ruthenium trichloride in ethylene glycol after dissolution is 1.3 mg / mL.
4. The method for preparing titanium-doped ruthenium dioxide according to claim 1, characterized in that, In step S2, the reaction temperature is 160~200℃, the reaction time is 1~10h, the washing solvent is acetone, the centrifugation time is 2~5min, the speed is 10000~12000rpm, and it is repeated at least twice.
5. The method for preparing titanium-doped ruthenium dioxide according to claim 1, characterized in that, In step S3, the conductive carrier is one of carbon black, carbon nanotubes, or porous carbon; the drying temperature is 60~80℃, and the drying time is 6~24h.
6. The method for preparing titanium-doped ruthenium dioxide according to claim 1, characterized in that, In step S4, the calcination temperature is 350℃, the heating rate is 10℃ / min, and the calcination time is 2h.
7. Titanium-doped ruthenium dioxide prepared by the preparation method according to any one of claims 1-6.
8. The application of the titanium-doped ruthenium dioxide as a catalyst in water electrolysis for hydrogen production as described in claim 7.