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金属有机框架中基于沙漏形铕簇的二级建筑单元用于通过增强活性氧生成实现光催化废水净化和杀菌

Hourglass-shaped europium cluster-based secondary building unit in metal-organic framework for photocatalytic wastewater purification and sterilization via enhanced reactive oxygen species production.

作者信息

Zhang Guan-Huang, Wang Hai-Ling, Cheng Lei, Li Yun-Lan, Zhu Zhong-Hong, Zou Hua-Hong

机构信息

School of Chemistry and Pharmaceutical Sciences, State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Guangxi Normal University, Guilin 541004, PR China.

School of Chemistry and Chemical Engineering, Guangxi Key Laboratory of Electrochemical Energy Materials, Guangxi University, Nanning, 530004, PR China.

出版信息

J Colloid Interface Sci. 2025 Feb;679(Pt B):578-587. doi: 10.1016/j.jcis.2024.10.133. Epub 2024 Oct 28.

DOI:10.1016/j.jcis.2024.10.133
PMID:39471586
Abstract

A large number of diseases caused by water pollution have become a global public health issue, and the development and construction of innovative and efficient photocatalytic systems for water remediation is vital to improve water quality and prevent bacteria-induced diseases. Herein, a europium-based metal-organic framework (Eu-MOF) was self-assembled with complex hourglass-shaped Eu clusters as secondary building units (SBUs), achieving excellent photoinduced reactive oxygen species (ROS) generation ability. Moreover, Eu-MOF can quickly and efficiently degrade organic dyes and kill a variety of bacteria under low-power light irradiation conditions. Time-dependent scanning electron microscopy (SEM) and infrared absorption spectroscopy (IR) were used for the first time to track the formation process of complex clusters into cluster-based MOFs, and the gradual transformation of amorphous intermediates into crystalline Eu-MOF was clearly tracked. Electrochemical impedance spectroscopy (EIS) results showed that Eu-MOF has a smaller semicircle than the organic ligands, demonstrating its excellent charge separation ability. The excellent ROS generation capacity of Eu-MOF was jointly demonstrated by electron paramagnetic resonance (EPR) spectroscopy and the results obtained using the 2',7'-dichlorodihydrofluorescein (DCFH) indicator. More importantly, using low-power (60 mW/cm) Xe lamp irradiation, Eu-MOF can almost completely degrade 10 mg/L aqueous solutions of rhodamine B (RhB), methylene blue (MB), and crystal violet (CV) within 30, 90, and 120 min, respectively. In addition, the excellent light-induced ROS production ability of Eu-MOF contributes to its significant cell killing and antibacterial effects. Under light irradiation conditions, Eu-MOF can effectively kill Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), with average inhibition zone sizes of 2.54 ± 0.17 and 2.56 ± 0.08 cm, respectively. This work opens up new horizons for the build of efficient photocatalytic systems based on lanthanide porous materials and promotes the progress of lanthanide MOFs (Ln-MOFs) crystal engineering.

摘要

大量由水污染引起的疾病已成为全球公共卫生问题,开发和构建创新高效的光催化系统用于水修复对于改善水质和预防细菌引发的疾病至关重要。在此,一种基于铕的金属有机框架(Eu-MOF)以复杂的沙漏形铕簇作为次级构筑单元(SBUs)自组装而成,具有出色的光诱导活性氧(ROS)生成能力。此外,Eu-MOF在低功率光照射条件下能快速高效地降解有机染料并杀灭多种细菌。首次使用时间分辨扫描电子显微镜(SEM)和红外吸收光谱(IR)来追踪复杂簇形成基于簇的金属有机框架的过程,并清晰地追踪了无定形中间体向结晶Eu-MOF的逐步转变。电化学阻抗谱(EIS)结果表明,Eu-MOF的半圆比有机配体的小,表明其具有出色的电荷分离能力。电子顺磁共振(EPR)光谱和使用2',7'-二氯二氢荧光素(DCFH)指示剂获得的结果共同证明了Eu-MOF具有出色的ROS生成能力。更重要的是,使用低功率(60 mW/cm)氙灯照射,Eu-MOF能分别在30、90和120分钟内几乎完全降解10 mg/L的罗丹明B(RhB)、亚甲基蓝(MB)和结晶紫(CV)水溶液。此外,Eu-MOF出色的光诱导ROS产生能力有助于其显著的细胞杀伤和抗菌效果。在光照条件下,Eu-MOF能有效杀灭大肠杆菌(E. coli)和金黄色葡萄球菌(S. aureus),平均抑菌圈直径分别为2.54±0.17和2.56±0.08 cm。这项工作为基于镧系多孔材料构建高效光催化系统开辟了新视野,并推动了镧系金属有机框架(Ln-MOFs)晶体工程的进展。

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