A novel design of Cu(I) active site on the metal-organic framework for exploring the structural transformation of Fenton-like catalysts through in situ "capturing" OH

Xuheng Li; Xiang Li; Chunli Wang; Bo Wang

doi:10.1016/j.jcis.2023.05.189

A novel design of Cu(I) active site on the metal-organic framework for exploring the structural transformation of Fenton-like catalysts through in situ "capturing" OH

J Colloid Interface Sci. 2023 Oct 15:648:778-786. doi: 10.1016/j.jcis.2023.05.189. Epub 2023 Jun 2.

Authors

Xuheng Li¹, Xiang Li², Chunli Wang³, Bo Wang⁴

Affiliations

¹ School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi'an, Shanxi 710072, China.
² Advanced Research Institute of Multidisciplinary Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China. Electronic address: xiangli0369@bit.edu.cn.
³ Research Center for Environmental Materials and Pollution Control Technology, University of Chinese Academy of Sciences, Beijing 101408, China. Electronic address: wangchunli@ucas.ac.cn.
⁴ Advanced Research Institute of Multidisciplinary Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China.

PMID: 37321097
DOI: 10.1016/j.jcis.2023.05.189

Abstract

The mutual transformation of reactive oxygen species may affect the structural transformation of catalysts during the Fenton-like processes. Its in-depth understanding is essential to achieve high catalytic activity and stability. In this study, a novel design of Cu(I) active sites based on the metal-organic framework (MOF) is proposed to "capture" OH^- produced via Fenton-like processes and re-coordinate the oxidized Cu sites. The Cu(I)-MOF presents an excellent removal efficiency for sulfamethoxazole (SMX), with a high removal kinetic constant of 7.146 min^-1. Combing DFT calculations with experimental observations, we have revealed that the Cu of Cu(I)-MOF exhibits a lower d-band center, enabling efficient activation of H₂O₂ and spontaneous "capturing" of OH^- to form Cu-MOF, which can be reorganized into the Cu(I)-MOF through molecular regulation for recycle. This research demonstrates a promising Fenton-like approach for solving the trade-off between catalytic activity and stability and provides new insights into the design and synthesis of efficient MOF-based catalysts for water treatment.

Keywords: Cu(I) active sites; Cu-MOF nanosheets; Fenton-like; Phase transition; “capturing” OH(−).