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MoO3-Cu2O/CN三相复合光催化剂的制备及其降解四环素性能

崔春丽 郝振华 舒永春

崔春丽, 郝振华, 舒永春. MoO3-Cu2O/CN三相复合光催化剂的制备及其降解四环素性能[J]. 复合材料学报, 2024, 42(0): 1-14.
引用本文: 崔春丽, 郝振华, 舒永春. MoO3-Cu2O/CN三相复合光催化剂的制备及其降解四环素性能[J]. 复合材料学报, 2024, 42(0): 1-14.
CUI Chunli, HAO Zhenhua, SHU Yongchun. Preparation and tetracycline degradation performance of MoO3-Cu2O/CN ternary photocatalyst[J]. Acta Materiae Compositae Sinica.
Citation: CUI Chunli, HAO Zhenhua, SHU Yongchun. Preparation and tetracycline degradation performance of MoO3-Cu2O/CN ternary photocatalyst[J]. Acta Materiae Compositae Sinica.

MoO3-Cu2O/CN三相复合光催化剂的制备及其降解四环素性能

基金项目: 中原关键实验室项目 (GJJSGFYQ202302和GJJSGFZD202303)
详细信息
    通讯作者:

    郝振华,博士,副教授,硕士生导师,研究方向等离子球化;特种粉体材料;金属3D打印 E-mail: zh_hao@zzu.edu.cn

  • 中图分类号: TB331

Preparation and tetracycline degradation performance of MoO3-Cu2O/CN ternary photocatalyst

Funds: Project of Zhongyuan Critical Metals Laboratory (GJJSGFZD202303 and GJJSGFYQ202302).
  • 摘要: 本文通过水热法先在g-C3N4(CN)上原位生长MoO3,继而在其表面电沉积Cu2O构建了MoO3-Cu2O/CN三相复合光催化剂。采用XRD、SEM、TEM、XPS和FTIR等手段对催化剂进行表征,证明了复合光催化剂的成功制备。以四环素为目标污染物,探究了所制备光催化剂对四环素的降解效果及光催化剂的作用机制。结果表明,在可见光下,1.5 MoO3-Cu2O-100/CN复合材料对四环素的降解效果最佳,150 min时降解率为97.75%,分别是CN(45.28%)和1.5 MoO3/CN(63.24%)的2.2和1.5倍。采用自由基捕获实验及电子顺磁共振光谱(EPR)对机制进行了探究,证实了羟基自由基(·OH)和超氧自由基(·O2)是光催化过程的主要活性物质。综合各项测试计算 CN、MoO3 和Cu2O 的价带和导带位置,表明三相复合光催化剂形成了双Z型异质结。同时光催化活性的提高主要归因于双Z机制的构建,拓宽了可见光吸收范围,保留了氧化还原能力较高的空穴电子,降低了光生电子与空穴的复合率。稳定性实验结果表明制备的催化剂在经过四次循环后,对四环素的降解率仍达到90%以上,具有优异的稳定性,可循环使用。

     

  • 图  1  MoO3-Cu2O/ g-C3N4(CN)光催化剂的制备过程示意图

    Figure  1.  Schematic diagram of the preparation of MoO3-Cu2O/ g-C3N4 (CN) photocatalysts

    图  2  CN、1.5MoO3/CN和1.5MoO3-Cu2O-100/CN催化剂的 (a) XRD图谱和 (b) FT-IR图

    Figure  2.  (a) XRD patterns and (b) FTIR spectra of CN, 1.5MoO3/CN and 1.5MoO3-Cu2O-100/CN catalysts

    图  3  (a) CN,(b) MoO3,(c) 1.5MoO3/CN和 (d) 1.5MoO3-Cu2O-100/CN的SEM图像

    Figure  3.  SEM images of (a) CN, (b) MoO3, (c) 1.5MoO3/CN and (d) 1.5MoO3-Cu2O -100/CN

    图  4  (a) 1.5MoO3-Cu2O-100/CN的TEM图像, (b) 1.5MoO3-Cu2O-100/CN的STEM-EDX图像以及(c) 显示了C、N、O、Mo和Cu的元素分布图

    Figure  4.  (a) 1.5MoO3-Cu2O-100/CN; (b) TEM images of 1.5MoO3-Cu2O-100/CN and (c) STEM-EDX images of 1.5MoO3-Cu2O-100/CN showing the element distribution mappings of C, N, O, Mo and Cu

    图  5  1.5MoO3-Cu2O-100/CN催化剂中 (a) C,(b) N,(c) O,(d) Mo和 (e) Cu元素的高分辨率XPS光谱

    Figure  5.  High-resolution XPS spectra of (a) C, (b) N, (c) O, (d) Mo and (e) Cu in 1.5MoO3-Cu2O-100/CN catalyst

    图  6  (a) CN、1.5MoO3/CN和1.5MoO3-Cu2O-100/CN的UV -Vis DRS图。由Tauc计算出的 (b) CN, 1.5MoO3/CN和1.5MoO3-Cu2O-100/CN的带隙

    Figure  6.  UV-Vis-DRS of (a) CN, 1.5MoO3/CN and 1.5MoO3-Cu2O-100/CN. Calculated band gap from the Tauc plot of (b) CN, 1.5MoO3/CN and1.5MoO3-Cu2O-100/CN

    图  7  (a) 不同光催化剂对四环素的 (a) 降解曲线, (b) 一级动力学曲线,(c) 降解速率常数 (k, min−1), (d) 不同MoO3含量的四环素光降解效率

    Figure  7.  (a) Tetracycline degradation curves, (b) first-order kinetics curves, and (c) degradation rate constants (k, min−1) of different photocatalysts,(d) Tetracycline photo-degradation efficiency of with different MoO3 contents

    图  8  (a) 初始四环素浓度;(b)溶液pH值对1.5MoO3-Cu2O-100/CN光催化剂降解四环素的影响

    Figure  8.  Effects of (a) initial tetracycline concentration; (b) solution pH on the degradation of tetracycline in the presence of 1.5MoO3-Cu2O-100/CN photocatalyst

    图  9  (a) 1.5MoO3-Cu2O-100/CN对四环素降解的四次稳定性循环测试和降解四环素前后的XRD图谱

    Figure  9.  (a) Four cycling tests of tetracyclinphotocatalytic degradation with 1.5MoO3-Cu2O-100/CN and (b) before and after photocatalytic degradation of tetracycline

    图  10  (a) 1. MoO3-Cu2O-100/CN在不同清除剂存在下对四环素的降解曲线, (b) DMPO-捕获·OH和 (c) ·O2与1.5MoO3-Cu2O-100/CN复合材料的EPR光谱

    Figure  10.  (a) Degradation curve of tetracycline by 1.5MoO3-Cu2O-100/CN in the presence of different scavengers, EPR spectra of (b) DMPO to capture ·OH and (c)·O2 with 1.5MoO3-Cu2O-100/CN composite

    图  11  CN、1.5MoO3/CN和1.5MoO3-Cu2O-100/CN样品的 (a) PL光谱,(b) 瞬态光电流响应和 (c) EIS谱图

    Figure  11.  (a) PL spectra, (b) transient photocurrent responses, (c) EIS of CN, 1.5MoO3/CN and 1.5MoO3-Cu2O-100/CN samples

    图  12  不同MoO3含量下样品的(a) 瞬态光电流响应和 (b) EIS谱图

    Figure  12.  (a) Transient photocurrent responses and (b) EIS of the samples with different MoO3 contents

    图  13  (a) MoO3和 (b) Cu2O样品的(αhν)2对hν的曲线;(c) CN, (d) MoO3和 (e) Cu2O的XPS价带谱

    Figure  13.  (αhν)2 vs radiation energy (hv) plots for (a) MoO3 and (b) Cu2O samples. Valence-band XPS spectrum of the sample (c) CN; (d) MoO3 and(e) Cu2O

    图  14  1.5MoO3-Cu2O-100/CN复合催化剂的反应机制

    Figure  14.  Possible reaction mechanism of 1.5MoO3-Cu2O-100/CN composite catalyst

    图  15  1.5MoO3-Cu2O-100/CN 催化剂降解四环素的路径示意图

    Figure  15.  Tetracycline degradation pathway by 1.5MoO3-Cu2O-100/CN catalyst

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  • 收稿日期:  2024-04-11
  • 修回日期:  2024-06-02
  • 录用日期:  2024-06-08
  • 网络出版日期:  2024-06-26

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