HBr-Regulated Smart 2D Copper-Organic Framework for Highly Efficient and Selective Photocatalytic Oxidation.

Authors

Dan Yang, Cong Wang, Xianggang Zhou, Xia Zhao, Huaqiao Tan, Hongfei Gao, Feiyang Yu, Yonghui Wang, Yangguang Li

Published in

Angewandte Chemie (International ed. in English). Pages e4163060. Jul 03, 2026. Epub Jul 03, 2026.

Abstract

Smart covalent organic frameworks capable of modulating photocatalytic properties responsive to external stimuli represent next generation of emerging catalysts sought by researchers, yet studies on these dynamic materials and structure-activity relationships remain scarce. Herein, we report a smart metal covalent organic framework (Cu₃-MCOF) incorporating copper cyclic trinuclear clusters (Cu₃) as redox-active and structurally adaptive nodes, which exhibits dual responsiveness to hydrogen bromide (HBr) stimulation, undergoing reversible imine protonation and Br^--mediated reconstruction of copper nodes. These transformations induce pronounced narrowing of optical gap from 2.50 eV to 2.02 eV, a redshift in absorption onset from 500 nm to 613 nm, and enhanced charge separation efficiency. Consequently, Cu₃-MCOF-HBr achieves 40-fold increase in photocatalytic activity for α-terpinene oxidation, with superoxide radical selectivity exceeding 99%, compared to 41% for Cu₃-MCOF. The same stimulus-triggered enhancement is demonstrated in the photocatalytic 1,2,4-trimethoxybenzene bromination. Spectroscopic studies and density functional theory (DFT) calculations reveal that synergistic imine protonation and cluster restructuring promote electron localization within Cu₃ units, facilitate spatial charge separation, and shift oxygen adsorption to imine sites, thereby selectively promoting superoxide radical generation. This work provides the smart MCOF photocatalyst based on dynamic metal-cluster nodes and offers fundamental insights into stimulus-driven regulation of photocatalytic pathways and selectivity.

PMID:
42397875
Bibliographic data and abstract were imported from PubMed on 04 Jul 2026.

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