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合适的带隙宽度, 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⁻¹ 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, 2026, 84(6): 879-887.

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, 2026, 84(6): 879-887.

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图/表 7

图1. C3N4、C2N3和C3N5的制备流程和SEM图片

Figure 1. Preparation processes and SEM images of C3N4, C2N3 and C3N5

图2. C3N4、C2N3和C3N5的EPR谱图

Figure 2. EPR spectra of C3N4, C2N3 and C3N5

图3. C3N4、C2N3和C3N5的XRD图(a), FT-IR光谱图(b), C 1s XPS谱图(c)和N 1s XPS谱图(d)

Figure 3. XRD patterns (a), FT-IR spectra (b), C 1s XPS spectra (c) and N 1s XPS spectra (d) of C3N4、C2N3和C3N5

图4. C3N4、C2N3和C3N5的UV-Vis DRS光谱(a), Tauc plots图(b), PL光谱(c), EIS曲线(d)和光电流响应曲线(e)

Figure 4. UV-Vis DRS spectra (a), Tauc plots (b), PL spectra (c), EIS patterns (d), and photocurrent responses (e) of C3N4, C2N3, and C3N5

图5. C3N4、C2N3和C3N5的光催化产H2O2的产量(a), C2N3的循环实验(b), C2N3-Ar的EPR谱图(c)和光催化产H2O2的产量(d)

Figure 5. Photocatalytic H2O2 production yields of C3N4, C2N3, and C3N5 (a), reuse experiment of C2N3 (b), EPR spectra (c) and photocatalytic H2O2 production yield (d) of C2N3-Ar

图6. C2N3在空气和Ar气氛中光催化产H2O2的性能对比(a), 不含氮空位C2N3 (b)和含氮空位C2N3 (c)的O2吸附模型

Figure 6. Comparison of H2O2 production yields by C2N3 in air and Ar (a), the O2 adsorption model of C2N3 without nitrogen vacancies (b) and C2N3 with nitrogen vacancies (c)

图7. 不同淬灭剂对C2N3光催化制备H2O2的影响(a), C2N3上DMPO-•O2−的EPR信号(b)和TEMP-1O2的EPR信号(c), C2N3光催化产H2O2反应路径示意图(d)

Figure 7. Effects of different scavengers on photocatalytic H2O2 production by C2N3 (a), EPR spectra of DMPO-•O2− (b) and TEMP-1O2 (c) over C2N3, schematic diagram of the reaction pathway for photocatalytic H2O2 production by C2N3 (d)

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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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