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简便构建铜掺杂金属有机框架作为一种用于污染物降解的新型可见光响应光催化剂。

Facile construction of copper-doped metal organic framework as a novel visible light-responsive photocatalyst for contaminant degradation.

作者信息

Li Yingjie, Bi Wenyan, Yang Haoyu, Yue Yingli, Liu Sixu, Hou Guangshun

机构信息

College of Chemistry and Chemical Engineering, Collaborat Innovat Center of Coal Work Safety, Henan Polytechnic University, Jiaozuo, People's Republic of China.

China National Accreditation Service for Conformity Assessment, Beijing, People's Republic of China.

出版信息

Environ Technol. 2025 Mar;46(7):1099-1111. doi: 10.1080/09593330.2024.2376290. Epub 2024 Jul 13.

Abstract

Metal-organic frameworks (MOFs) with photocatalytic activity have garnered significant attentions in environmental remediation. Herein, copper-doped zeolitic imidazolate framework-7 (Cu-doped ZIF-7) was synthesized rapidly and easily using a microwave-assisted technique. Various analytical and spectroscopic methods were employed to access the framework, morphology, light absorption, photo-electrochemical and photocatalytic performance of the synthesized materials. Compared to ZIF-7, Cu/ZIF-7 (molar ratio of Cu to Zn is 1:1) demonstrates superior visible light absorption ability, narrower band gap, enhanced charge separation capability, and reduced electron-hole recombination performance. Under visible light irradiation, Cu/ZIF-7 serves as a Fenton-like catalyst and demonstrates exceptional activity for contaminant degradation, while virgin ZIF-7 remains inactive. With the addition of 9.8 mmol HO and exposure to visible light for 30 min, 10 mg of Cu/ZIF-7 can completely decompose RhB solution (10 mg/L, 50 mL). The synergistic effect of the Cu/ZIF-7/HO/visible light system is attributed to visible light photocatalysis and Fenton-like reactions. Cu/ZIF-7 demonstrates excellent catalytic performance stability, with only a slight decrease in degradation efficiency from an initial 97.0% to 95.4% over four cycles. Additionally, spin-trapping ESR measurements and active species trapping experiments revealed that h and ·OH occupied a significant position for Rhodamine B (RhB) degradation. Degradation intermediate products of Rhodamine B have been identified using UPLC-MS, and the degradation pathways have been proposed and discussed. This work offers a facile and efficient technique for developing MOF-based visible light photocatalysts for water purification.

摘要

具有光催化活性的金属有机框架材料(MOFs)在环境修复领域备受关注。在此,采用微波辅助技术快速简便地合成了铜掺杂的沸石咪唑酯骨架-7(Cu掺杂ZIF-7)。运用各种分析和光谱方法来研究合成材料的框架结构、形态、光吸收、光电化学和光催化性能。与ZIF-7相比,Cu/ZIF-7(Cu与Zn的摩尔比为1:1)表现出卓越的可见光吸收能力、更窄的带隙、增强的电荷分离能力以及降低的电子-空穴复合性能。在可见光照射下,Cu/ZIF-7作为类芬顿催化剂,对污染物降解表现出优异的活性,而原始的ZIF-7则无活性。添加9.8 mmol过氧化氢并在可见光下照射30分钟,10 mg的Cu/ZIF-7可完全分解罗丹明B溶液(10 mg/L,50 mL)。Cu/ZIF-7/过氧化氢/可见光体系的协同效应归因于可见光光催化和类芬顿反应。Cu/ZIF-7表现出优异的催化性能稳定性,在四个循环中降解效率仅从初始的97.0%略有下降至95.4%。此外,自旋捕获电子顺磁共振测量和活性物种捕获实验表明,空穴和·OH在罗丹明B(RhB)降解中占据重要地位。利用超高效液相色谱-质谱联用仪鉴定了罗丹明B的降解中间产物,并提出和讨论了降解途径。这项工作为开发用于水净化的基于MOF的可见光光催化剂提供了一种简便有效的技术。

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