Synergistic effect of dual sites on bimetal-organic frameworks for highly efficient peroxide activation

He Liang; Ruiping Liu; Chengzhi Hu; Xiaoqiang An; Xiwang Zhang; Huijuan Liu; Jiuhui Qu

doi:10.1016/j.jhazmat.2020.124692

Synergistic effect of dual sites on bimetal-organic frameworks for highly efficient peroxide activation

J Hazard Mater. 2021 Mar 15:406:124692. doi: 10.1016/j.jhazmat.2020.124692. Epub 2020 Nov 27.

Authors

He Liang¹, Ruiping Liu², Chengzhi Hu³, Xiaoqiang An⁴, Xiwang Zhang⁵, Huijuan Liu², Jiuhui Qu⁶

Affiliations

¹ State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China; School of Environment, Northeast Normal University, Changchun 130117, Jilin, China.
² Center for Water and Ecology, State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China.
³ State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China; University of Chinese Academy of Sciences, Beijing 100039, China.
⁴ Center for Water and Ecology, State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China. Electronic address: xqan@tsinghua.edu.cn.
⁵ Department of Chemical Engineering, Monash University, Clayton, VIC 3800, Australia.
⁶ State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China; Center for Water and Ecology, State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China; University of Chinese Academy of Sciences, Beijing 100039, China.

PMID: 33310323
DOI: 10.1016/j.jhazmat.2020.124692

Abstract

Active site engineering is of significant importance for developing high activity metal-organic frameworks (MOFs) for catalytic applications. Herein, we develop a one-pot strategy to construct bimetal organic frameworks with Fe-Co dual sites for Fenton-like catalysis. Density functional theory (DFT) demonstrated that the introducing Co heteroatoms into MIL-101(Fe) (MIL represents Matérial Institute Lavoisier) was favorable for the formation of electron-deficient centers around benzene rings and electron-rich centers around Fe/Co. This synergistic effect could effectively decrease the energy barrier of H₂O₂ activation. Due to the facilitated charge transfer in the coordinated structures, MIL-101(Fe,Co) with engineered dual sites exhibited exceptionally high efficiency for the degradation of ciprofloxacin (CIP). The reaction rate of MIL-101(Fe,Co)/H₂O₂ system was 0.12 min^-1, which was nearly 7.5 times higher than that of pristine MIL-101(Fe). The reaction mechanism of heterogeneous Fenton-like catalysis was fundamentally investigated by series of in-situ techniques, such as DRIFTS and Raman. ·OH radicals generated by H₂O₂ activation endowed the inspiring ability of MIL-101(Fe,Co) for water decontamination. This work offers a facile principle of exploring MOFs-based Fenton-like catalysts with a wide working pH range for environmental applications.

Keywords: Bimetal-organic frameworks; Ciprofloxacin; Dual site engineering; Fenton-like reactions; Reaction mechanism.

Publication types

Research Support, Non-U.S. Gov't