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Comparative study of metal oxides and phosphate modification with different mechanisms over g-C3N4 for visible-light photocatalytic degradation of metribuzin

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Abstract

In this work, a comparative study of three frequently employed modification techniques to g-C3N4 (CN) nanosheets for the photocatalytic degradation of metribuzin (MET) under visible-light irradiation has been carried out in detail. The modification methods were coupling TiO2 nanoparticles (TO) as electron acceptors, nano-sized Fe2O3 (FO) to construct a Z-scheme nanocomposite, and phosphate (HP) modification to promote O2 adsorption. The steady-state and transient-state surface photovoltage spectra and transient photoluminescence (PL) spectra confirmed that all the three modification techniques enhanced the charge separation with prolonged lifetimes and presented degradation activities in the order of TO/CN > FO/CN > HP/CN. The TO/CN nanocomposite showed the highest photocatalytic activity for MET degradation, with a sixfold higher rate than bulk CN. Liquid chromatography–tandem mass spectrometry and radical trapping experiments indicated that the increased activity was related to the synergetic effect of two radicals (·O2− and ·OH) involved in the photocatalytic degradation pathway, which was different from the ·OH radical-dominated pathway of bulk CN. This work reveals the importance of charge separation and the influence of the radical pathway and provides guidance for the design of high-efficiency photocatalysts.

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摘要

本文以可见光催化降解嗪草酮 (MET)为应用, 通过对比研究复合宽带隙TiO2纳米颗粒(TO) 作为电子接收平台、复合纳米Fe2O3 (FO)构建Z型异质结复合体和修饰磷酸(HP)促进O2吸附的三种常用的促进g-C3N4 (CN)光生电荷分离的修饰方法, 研究提高CN基光催化性能的可行策略。通过稳态、瞬态表面光电压谱和瞬态光致发光(PL)谱等分析表明, 三种修饰策略均能促进CN的光生电荷分离, 延长光电子使用寿命。可见光催化降解MET实验表明, 降解活性依次为TO/CN > FO/CN > HP/CN。TO/CN纳米复合材料对MET的光催化降解活性最高, 是普通CN的6倍。通过液相色谱-串联质谱和自由基捕获等实验表明, TO/CN活性的提高是因为•O2−和•OH两个自由基协同参与光催化降解路径的新机制, 而普通的CN样品则表现为单一的•OH自由基主导路径。结合光物理分析, 这种新机制可能是由于TO作为高水平能级电子能量平台, 促进了电荷分离且维持了CN光生电子的热力学能力, 提高了光生电子的还原能力, 从而产生•O2−和•OH自由基。这项工作揭示了电荷分离和自由基路径影响的重要性, 并为高效光催化剂的设计提供了指导。

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 21971057 and U1805255), the Natural Science Foundation of Heilongjiang Province (Nos. YQ2019B006 and LH2020B012) and the Postdoctoral Research Foundation of Heilongjiang Province (No. LBH-Q19052), the Outstanding Youth Fund of Heilongjiang University (No. JCL201901), and the Basic Scientific Research Expenses of Colleges and Universities in Heilongjiang Province (No. 2020-KYYWF-1008).

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Authors and Affiliations

  1. Key Laboratory of Functional Inorganic Materials Chemistry, School of Chemistry and Material Sciences, Heilongjiang University, Harbin, 150080, China

    Rui Yan, Lei Sun, Zhi-Jun Li, Zhi-Yuan Mu, Shuang-Ying Chen, Fan Yang, Jian-Hui Sun, Lin-Lu Bai, Yang Qu & Li-Qiang Jing

  2. Key Laboratory of Photochemical Biomaterials and Energy Storage Materials, College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin, 150025, China

    Rui Yan

  3. Department of Chemistry, Abdul Wali Khan University Mardan, Mardan, 23200, Pakistan

    Amir Zada

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  1. Rui Yan
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Yan, R., Zada, A., Sun, L. et al. Comparative study of metal oxides and phosphate modification with different mechanisms over g-C3N4 for visible-light photocatalytic degradation of metribuzin. Rare Met. 41, 155–165 (2022). https://doi.org/10.1007/s12598-021-01857-3

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