氮化碳的氮空位与可见光催化产H2O2研究

doi:10.6023/A26020041

摘要/Abstract

光催化产H₂O₂是一种绿色安全、高效低成本的合成过程,氮化碳被认为是最有应用潜力的光催化材料之一. 但是,其光生电子-空穴对的复合几率高以及对氧气吸附能力弱的缺点,导致光催化产H₂O₂性能不佳. 本研究采用不同前驱体、不同煅烧工艺,一步法制备出三种不同的氮化碳(C₃N₄、C₂N₃和C₃N₅),其中C₂N₃呈现出优异的光催化产H₂O₂能力,在环境氧气氛和可见光(λ>420 nm)照射3 h,H₂O₂的产量可达到247.31 μmol•g^-1,是C₃N₄的3.29倍、C₃N₅的2.33倍. 实验表明,C₂N₃拥有较大比表面积并富含氮空位,理论计算显示氮空位可作为活性位点,提高催化剂对O₂的吸附能力,从而促进光催化产H₂O₂. 同时,C₂N₃的适合带隙宽,既有利于可见光的吸收,又有效抑制了光生载流子的复合,从而提高可见光催化反应的效率. 机理分析表明,吸附的O₂经光生电子还原成•O₂^-,进而可由两种不同通道转变成H₂O₂.

关键词: 氮化碳, 可见光催化, 产H₂O₂, 氮空位, 双通道机制

Photocatalytic H₂O₂ production is a green, safe, efficient and low-cost synthesis process, and carbon nitride is considered one of the most promising photocatalysts for this purpose. However, its high recombination rate of photogenerated electron-hole pairs and weak O₂ adsorption capacity result in poor performance in H₂O₂ production. In this study, three carbon nitrides of C₃N₄, C₂N₃ and C₃N₅ were synthesized via a one-step calcination route with different precursors and calcination parameters. Among them, the C₂N₃ photocatalyst was obtained by adding 1 g of 3-amino-1,2,4-triazole into a covered crucible, heating to 550 ℃ in a muffle furnace at a heating ramp of 5 ℃/min and maintaining this temperature for 3 h. It was found that C₂N₃ exhibited excellent capability of photocatalytic H₂O₂ production. Under ambient oxygen atmosphere and visible light (λ>420 nm) irradiation, the production yield of H₂O₂ reached 247.31 μmol•g^-1 after 3 h of irradiation, which was 3.29 times that of C₃N₄ and 2.33 times that of C₃N₅. Specific surface area analyzer and electron paramagnetic resonance (EPR) confirmed that the C₂N₃ catalyst possessed a large specific surface area, and was rich in nitrogen vacancies. Theoretical calculations revealed that nitrogen vacancy could serve as active site, enhancing the O₂ adsorption capacity of the catalyst, thereby promoting photocatalytic H₂O₂ production. Additionally, UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), photoluminescence (PL), electrochemical impedance spectroscopy (EIS), and photocurrent response tests indicated that C₂N₃ had a suitable band gap of 1.98 eV, which not only facilitated visible light absorption, but also effectively suppressed the recombination of photogenerated carriers, thus improving the efficiency of visible-light-driven photocatalytic reactions. Mechanistic analysis demonstrated that the adsorbed O₂ was reduced by photogenerated electrons to form •O₂^-, which could subsequently be converted into H₂O₂ through two distinct pathways. This research provides new insights into the design and fabrication of low-cost, high-performance photocatalysts, and sheds fresh light on the exploration and development of clean-energy fields.

Key words: carbon nitride, visible-light photocatalysis, H₂O₂ production, nitrogen vacancy, dual-channel mechanism

引用此文

曾子杰, 彭子凌, 王晨, 谈发堂, 王新云, 王保强, 王维. 氮化碳的氮空位与可见光催化产H₂O₂研究[J]. 化学学报, doi: 10.6023/A26020041.

Zijie Zeng, Ziling Peng, Chen Wang, Fatang Tan, Xinyun Wang, Po Keung Wong, Wei Wang. Study on the Nitrogen Vacancy in Carbon Nitride Photocatalysts for Visible-Light-Driven H₂O₂ Production[J]. Acta Chimica Sinica, doi: 10.6023/A26020041.

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氮化碳的氮空位与可见光催化产H₂O₂研究

Study on the Nitrogen Vacancy in Carbon Nitride Photocatalysts for Visible-Light-Driven H₂O₂ Production

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