CN-121976239-A - Tantalum monoatomic doped bismuth sulfide catalyst loaded by carbon nano tube and preparation method and application thereof

Abstract

The invention discloses a tantalum monoatomic doped bismuth sulfide catalyst loaded by a carbon nano tube and a preparation method and application thereof, and aims to solve the problems that the yield of H 2 O 2 prepared by the existing bismuth-based catalyst through electrocatalytic reaction is low and the selectivity of H 2 O 2 is low. The preparation method comprises the steps of dispersing trimesic acid, tantalum pentachloride and bismuth nitrate pentahydrate in methanol, carrying out solvothermal reaction at the temperature of 110-140 ℃ to obtain a tantalum-doped bismuth metal organic frame material, grinding and mixing the tantalum-doped bismuth metal organic frame material and dibenzyl disulfide to obtain a mixture, and heating to 750-950 ℃ in an argon atmosphere for heat preservation carbonization treatment. The bismuth sulfide catalyst prepared by the invention has H 2 O 2 selectivity exceeding 90% in a wide voltage range of 0-0.65V, and the H 2 O 2 yield can reach 8.76 mol.g ‑1 ·h ‑1 under the industrial current density of 75 mA/cm 2 .

Inventors

• ZHANG SEN
• YANG WENSI
• LIU LINLIN
• YANG YUNPENG
• KE YUAN
• LIU KANG
• Fan Saifei
• LI YICUN
• ZHU JIAQI
• LI TAO
• Zhang Gufei
• LIU BENJIAN
• DAI BING
• ZHAO JIWEN
• CHEN RUI
• CAO DONGLIN
• Chen Zuanquan

Assignees

• 哈尔滨工业大学
• 哈工大郑州研究院
• 河南碳真芯材科技有限公司

Dates

Publication Date

20260505

Application Date

20260204

Claims (10)

1. 1. The bismuth sulfide catalyst is characterized by being prepared from a tantalum-doped bismuth metal organic frame material and dibenzyl disulfide through thermal insulation carbonization treatment at the temperature of 750-950 ℃ in an argon atmosphere, wherein the tantalum-doped bismuth metal organic frame material is prepared from trimesic acid, tantalum pentachloride and bismuth nitrate pentahydrate serving as raw materials through solvothermal reaction.
2. 2. The preparation method of the carbon nano tube supported tantalum monoatomic doped bismuth sulfide catalyst is characterized by comprising the following steps of: Dispersing trimesic acid, tantalum pentachloride and bismuth nitrate pentahydrate in methanol for ultrasonic treatment, transferring into a high-pressure reaction kettle, carrying out solvothermal reaction at 110-140 ℃, collecting a solid phase after the reaction is finished, and washing and drying to obtain tantalum-doped bismuth metal organic frame material powder; Grinding and mixing the tantalum-doped bismuth metal organic framework material powder and dibenzyl disulfide to obtain a mixture; And thirdly, heating the mixture to 750-950 ℃ in an argon atmosphere, and performing heat preservation carbonization treatment to obtain the tantalum monoatomic doped bismuth sulfide catalyst loaded by the carbon nano tube.
3. 3. The method for preparing a tantalum monoatomic doped bismuth sulfide catalyst loaded by a carbon nano tube according to claim 2, wherein the molar ratio of tantalum pentachloride to bismuth nitrate pentahydrate in the step one is (1-3): 30.
4. 4. The preparation method of the carbon nanotube-supported tantalum monoatomic doped bismuth sulfide catalyst according to claim 2, wherein the mass ratio of trimesic acid to tantalum pentachloride to bismuth nitrate pentahydrate is controlled to be (350-450): 2-6): 75 in the first step.
5. 5. The method for preparing the tantalum monoatomic doped bismuth sulfide catalyst loaded by the carbon nano tube according to claim 2, wherein the ultrasonic treatment is carried out for 20-50 min in the first step.
6. 6. The method for preparing a tantalum monoatomic doped bismuth sulfide catalyst loaded by a carbon nanotube according to claim 2, wherein the solvothermal reaction time is 20-26 h at the temperature of 110-140 ℃.
7. 7. The method for preparing a tantalum monoatomic doped bismuth sulfide catalyst loaded by a carbon nano tube according to claim 2, wherein the temperature is raised to 750-950 ℃ at a rate of 2-5 ℃ per minute in the third step.
8. 8. The method for preparing the tantalum monoatomic doped bismuth sulfide catalyst supported by the carbon nano tube according to claim 2, wherein the thermal insulation carbonization treatment time in the step three is 1-3 hours.
9. 9. The application of the carbon nanotube-supported tantalum monoatomic doped bismuth sulfide catalyst prepared in the method of claim 2, wherein the carbon nanotube-supported tantalum monoatomic doped bismuth sulfide catalyst is used for preparing hydrogen peroxide in a two-electron oxygen reduction reaction.
10. 10. The application of the carbon nanotube-supported tantalum monoatomic doped bismuth sulfide catalyst according to claim 9, wherein the carbon nanotube-supported tantalum monoatomic doped bismuth sulfide catalyst is prepared into slurry, the slurry is uniformly coated on a rotating disk electrode or a gas diffusion electrode to prepare a working cathode, and the working cathode is placed in an electrochemical reactor provided with KOH electrolyte, and oxygen is introduced to perform a two-electron oxygen reduction reaction, so that hydrogen peroxide is prepared.

Description

Tantalum monoatomic doped bismuth sulfide catalyst loaded by carbon nano tube and preparation method and application thereof Technical Field The invention belongs to the technical field of electrocatalytic materials and nanocomposite materials, and particularly relates to a carbon nanotube-supported bismuth-tantalum sulfide catalyst for preparing hydrogen peroxide by a double-electron oxygen reduction reaction (2 e - ORR), a preparation method thereof and application of the catalyst in electrochemical synthesis of hydrogen peroxide. Background The global sustainable development has faced dual challenges of energy shortage and environmental pollution since the 21 st century, and the development of green low-carbon energy conversion technology and efficient environmental remediation means has become the heart of research in academia and industry. Hydrogen peroxide (H 2O2) is an important green chemical, has the characteristics of strong oxidability and no carbon energy carrier, has irreplaceable application value in the fields of environmental pollutant degradation, public health disinfection, fine chemical synthesis, new energy storage and the like, and has great significance in pushing the construction of a green manufacturing system through the breakthrough of the efficient preparation technology. In the field of public health, H 2O2 becomes an important disinfection material because of the advantages of broad-spectrum bactericidal property and no residual pollution, and can effectively realize the deep sterilization of the surfaces of public places, medical equipment and environments. In the field of environmental remediation, advanced oxidation technology (AOPs) based on H 2O2 is a core means for treating refractory organic pollutants (such as phenols, polycyclic aromatic hydrocarbons, pesticide residues and the like), and can mineralize the pollutants into CO 2 and H 2 O by generating strong oxidative free radicals such as OH and the like, thereby remarkably improving the water purification efficiency. In the aspect of industrial application, H 2O2 replaces the traditional chlorine-containing bleaching agent in the paper industry, can reduce the emission of toxic pollutants, and simultaneously improve the whiteness and the fiber strength of paper pulp, is used for bleaching and dyeing pretreatment of fabrics in the textile industry, can improve dyeing uniformity and reduce wastewater treatment difficulty, and is used as a safe disinfectant in the packaging material sterilization and food preservation in the food industry. In particular, in the field of semiconductor manufacturing, electronic grade high purity H 2O2 is a key reagent in the process of chip cleaning and etching, and its purity directly affects the yield and performance of chips, and the annual average growth rate of market demands exceeds 15%. In the field of new energy, H 2O2 is used as a fuel cell oxidant or liquid fuel, has the advantages of high energy density, clean reaction products and the like, and provides a new direction for portable energy equipment and hydrogen energy storage. At present, the industrial mass production of H 2O2 mainly depends on an anthraquinone method, and the process has the inherent defects that firstly, the process is complex (including multi-step reactions such as hydrogenation, oxidation, extraction, purification and the like), the energy consumption is as high as 1.2-1.5 kWh.kg -1, and each 1 ton of H 2O2 is produced along with the discharge of about 2.5 tons of organic waste liquid, the treatment cost accounts for 15-20% of the total production cost, secondly, the process is highly dependent on a Pd noble metal catalyst, the Pd loading amount is as high as 0.3-0.5 wt%, the production stability is limited due to the scarcity of Pd (the crust abundance is only 1X 10 -6 g·t-1) and the price fluctuation, thirdly, the product needs to be concentrated to 30-70% from low concentration of about 5%, and the H 2O2 is easy to decompose and explode in the concentration process, so that serious safety hazards exist. The direct oxyhydrogen synthesis method is used as an alternative technology of the anthraquinone method, has the advantages of high atom economy (theoretical atom utilization rate is 100%), simple reaction path and the like, and faces double challenges of safety and efficiency in practical application. Because the explosion limit range of H 2/O2 mixed gas is wide (4-94 vol%), more than 50% of inert gas (such as N 2、CO2) needs to be introduced for dilution, so that the concentration of effective reactants in the reactor is reduced, the yield of H 2O2 is only 60% -70% of that of an anthraquinone method, and the production cost is increased by more than 30%. The electrochemical two-electron oxygen reduction reaction (2 e - ORR) is considered as the most development potential H 2O2 preparation technology because O 2 can be directly converted into H 2O2 at normal temperature and normal pressure, and the elec