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材料研究学报  2025, Vol. 39 Issue (4): 241-250    DOI: 10.11901/1005.3093.2024.206
  研究论文 本期目录 | 过刊浏览 |
Co3O4/ZnO@MG-C3Nx 催化剂的合成及其可见光降解亚甲基蓝的性能
李颖1,2(), 聂学童1, 钱立国1, 朱忆仁1
1.天津工业大学化学工程与技术学院 天津 300387
2.天津工业大学 省部共建分离膜与膜过程国家重点实验室 天津 300387
Synthesis of Co3O4/ZnO@MG-C3Nx Catalysts and Their Visible Light Degradation of Methylene Blue Performance
LI Ying1,2(), NIE Xuetong1, QIAN Liguo1, ZHU Yiren1
1.School of Chemical Engineering and Technology, Tiangong University, Tianjin 300387, China
2.State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University, Tianjin 300387, China
引用本文:

李颖, 聂学童, 钱立国, 朱忆仁. Co3O4/ZnO@MG-C3Nx 催化剂的合成及其可见光降解亚甲基蓝的性能[J]. 材料研究学报, 2025, 39(4): 241-250.
Ying LI, Xuetong NIE, Liguo QIAN, Yiren ZHU. Synthesis of Co3O4/ZnO@MG-C3Nx Catalysts and Their Visible Light Degradation of Methylene Blue Performance[J]. Chinese Journal of Materials Research, 2025, 39(4): 241-250.

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摘要: 

将磁性MG-C3Nx 材料前驱体与不同Co、Zn比的CoZn-ZIF复合,在900 ℃高温煅烧制备出Co3O4/ZnO@MG-C3Nx 可见光催化剂,使用X射线衍射仪、扫描电镜、透射电镜、热重分析仪、化学吸附等多种手段表征其结构、形貌和组成,研究了这种可见光催化剂对亚甲基蓝(MB)的降解性能。结果表明,这种催化剂的可见光催化活性优良,在150 min内对MB的降解率为95.4%,负载金属离子的最佳比例为Co∶Zn = 5∶1。在G-C3N4表面进行碱活化后在其表面产生的大量N缺陷有利于加快对光生电子的捕获、促进金属活性位点之间的协同作用,以及加快光生电子-空穴的分离和迁移,从而使其光催化活性提高。这种催化剂的稳定性较高,可回收,其中的主要活性物种是羟基自由基(·OH)和单线态氧(1O2)。

关键词 复合材料氮化碳CoZn-ZIF氧化石墨烯光催化高级氧化技术    
Abstract

In response to the serious problem of trace pollutants in the natural environment, photocatalytic degradation technology has become an effective solution for trace pollutant removal. Defective carbon nitride (g-C3Nx ) materials have attracted much attention because of their superior visible light absorption properties. In this study, the Co3O4/ZnO@MG-C3Nx visible photocatalyst was prepared by mixing the magnetic MG-C3Nx material as the precursor CoZn-ZIF with different ratio of Co to Zn, and then calcinated at 900 oC. The structure, morphology and composition of the prepared photocatalyst were characterized by means of XRD, SEM, TEM, TGA and BET, to verify the successful preparation of the catalyst. It follows that the catalyst with the optimal ratio of Co∶Zn = 5∶1 possessed the excellent visible light catalytic activity, and the degradation rate of methylene blue (MB) reached 95.4% within 150 min. The catalytic efficiency of this catalyst was 4.77 and 2.2 times higher than that of G-C3N4 and Co3O4/ZnO, respectively. It was shown that the formation of a large number of nitrogen defects on the surface of G-C3Nx after alkali activation was conducive to accelerating the capture of photogenerated electrons, and the promotion of synergistic interaction between the metal active sites led to an obvious acceleration of the photogenerated electron-hole separation and migration, which in turn enhanced the photocatalytic activity. The main active species were verified to be 1O2 and ·OH by the active species capture experiments. In conclusion, the catalyst has excellent visible light absorption performance, stability and recyclability, and has a broad application prospect.

Key wordscomposite    carbon nitride    CoZn-ZIF    GO    photocatalysis    advanced oxidation technology
收稿日期: 2024-05-13     
ZTFLH:  TB383  
基金资助:国家自然科学基金(22078246)
通讯作者: 李颖,教授,ly@tiangong.edu.cn,研究方向为光电催化和功能化碳氮材料的制备
Corresponding author: LI Ying, Tel: 18722531078, E-mail: ly@tiangong.edu.cn
作者简介: 李 颖,女,1979年生,博士
图1  Co3O4/ZnO@MG-C3Nx 催化剂的制备工艺及回收
图2  G-C3N4、G-C3Nx 和MG-C3Nx 、CoZn-ZIF、Co3O4/ZnO、CoZn-ZIF@MG-C3Nx 和Co3O4/ZnO@MG-C3Nx 的XRD谱、Co3O4/ZnO@MG-C3Nx 的XPS全谱以及Co3O4/ZnO@MG-C3Nx 的元素含量分析
图3  CoZn-ZIF在N2和空气气氛中的TGA谱
图4  样品的N2吸附解吸曲线和Co3O4/ZnO@MG-C3Nx 的孔容和孔径分布
图5  CoZn-ZIF、Co3O4/ZnO样品的SEM图像以及Co3O4/ZnO@MG-C3Nx 样品的SEM照片(插图是相应的TEM图像)
图 6  样品的带隙曲线、电化学阻抗谱(EIS)曲线以及光电流响应(I-t)曲线
图7  不同KOH含量活化后G-C3Nx 对MB的光催化降解、单独ZnO,不同Co和Zn比例的Co3O4/ZnO(质量比)以及单独Co3O4的光催化降解、溶液的pH值对Co3O4/ZnO@MG-C3Nx 光催化降解的影响以及不同催化剂的光催化降解性能
图8  催化剂的循环使用、Co3O4/ZnO@MG-C3Nx 降解MB的活性物种捕获、ZnO与Co3O4功函数DFT理论计算以及Co3O4/ZnO@MG-C3Nx 光催化机理
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