Unlocking Topological Effects in Covalent Organic Frameworks for High-Performance Photosynthesis of Hydrogen Peroxide.

Cheng, Jun; Wu, Yuting; Zhang, Wan; Wang, Lei; Wu, Xiaojun; Xu, Hangxun · Adv Mater · 2025

basic_science · Level V

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Abstract

Covalent organic frameworks (COFs) offer a compelling platform for the efficient photosynthesis of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>). Constructed with diverse topologies from various molecular building units, COFs can exhibit unique photocatalytic properties. In this study, three π-conjugated 2D sp<sup>2</sup> carbon-linked COFs with distinctly different topologies (hcb, sql, and hxl) are designed to investigate the topological effect on the overall photosynthesis of H<sub>2</sub>O<sub>2</sub> from water and oxygen. Despite their similar chemical and band structures, the QP-HPTP-COF with hxl topology outperformed other COFs in the photosynthesis of H<sub>2</sub>O<sub>2</sub>, demonstrating a remarkable solar-to-chemical conversion efficiency of 1.41%. Comprehensive characterizations confirmed that the hxl topology can substantially improve charge separation and transfer, thereby significantly enhancing photocatalytic performance. This study not only unravels the topology-directed charge carrier dynamics in COFs but also establishes a molecular engineering framework for developing high-performance photocatalysts for sustainable H<sub>2</sub>O<sub>2</sub> production.