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过硫酸盐活化自组装双金属 Fe/Mn-MOF 构筑 SnS 异质结用于高效四环素类抗生素光降解。

Critical trigger of self-assembled bimetallic Fe/Mn-MOF with SnS heterojunctions by persulfate activation for efficient tetracyclines photodegradation.

机构信息

School of Chemical and Environmental Engineering, China University of Mining and Technology, Beijing, 100083, China; Beijing Graphene Institute, Beijing, 100095, China.

Beijing Graphene Institute, Beijing, 100095, China.

出版信息

Environ Res. 2024 Dec 15;263(Pt 2):120060. doi: 10.1016/j.envres.2024.120060. Epub 2024 Oct 3.

DOI:10.1016/j.envres.2024.120060
PMID:39368594
Abstract

Developing advanced strategies, including exposing active site centers, regulating coordination environments, controlling crystallographic facets, optimizing electronic structures and constructing defects for enhancing photocatalytic performance is of great significance to improving the ecosystem. In this study, a novel self-assembled bimetallic Fe/Mn-MOF with SnS Z-scheme heterojunction photocatalyst was designed using a facile multistep solvothermal method. Benefiting from the interfacial heterojunction synergistic effect, the photocatalysts exhibited an outstanding catalytic performance. Nearly 91.4% efficiency of tetracyclines was degraded within 80 min through the assistance of a persulfate-based advanced oxidation process. DFT calculations utilizing the Fukui index identified the sites vulnerable to attack by the active species. As demonstrated by the trapping experiments and electron spin resonance (ESR), the involved oxygen-active species (•O and O) facilitated the rapid degradation of tetracycline. The degradation pathways were further guided in the elucidation of the rationale mechanism and the toxicity of derived intermediates was revealed. This work opens a new strategy for the rational design of bimetallic photocatalysts, emphasizing interface-modulated heterojunctions for efficient solar energy conversion.

摘要

开发先进的策略,包括暴露活性中心、调节配位环境、控制晶面、优化电子结构和构建缺陷,对于改善生态系统具有重要意义。在这项研究中,采用简便的多步溶剂热法设计了一种新型的自组装双金属 Fe/Mn-MOF 与 SnS Z 型异质结光催化剂。受益于界面异质结协同效应,光催化剂表现出了优异的催化性能。在过硫酸盐类高级氧化过程的辅助下,四环素在 80 分钟内的降解效率接近 91.4%。利用福井指数进行的 DFT 计算确定了易受活性物质攻击的位置。通过捕获实验和电子自旋共振 (ESR) 表明,涉及的氧活性物质(•O 和 O)促进了四环素的快速降解。进一步通过降解途径阐明了合理的机理,并揭示了衍生中间体的毒性。这项工作为双金属光催化剂的合理设计开辟了新的策略,强调了界面调制异质结用于高效太阳能转换。

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