Regulation of Coordinating Anions around Single Co(II) Sites in a Covalent Organic Framework for Boosting CO2 Photoreduction

作者：Nan Dai, Yunyang Qian, Denan Wang, Jiajia Huang, Xinyu Guan, Zhongyuan Lin, Weijie Yang, Rui Wang, Jier Huang, Shuang‐Quan Zang, Hai‐Long Jiang · 发表于：Precision Chemistry · 年份：2024 · DOI：10.1021/prechem.4c00058 · 被引用次数：36 · 研究领域：Covalent Organic Framework Applications、Advanced Photocatalysis Techniques、Metal-Organic Frameworks: Synthesis and Applications

High Resolution Image Download MS PowerPoint Slide While photocatalytic CO 2 reduction has been intensively investigated, reports on the influence of anions coordinated to catalytic metal sites on CO 2 photoreduction remain limited. Herein, different coordinated anions (F –, Cl –, OAc –, and NO 3 – ) around single Co sites installed on bipyridine-based three-component covalent organic frameworks (COFs) were synthesized, affording TBD-COF-Co-X (X = F, Cl, OAc, and NO 3 ), for photocatalytic CO 2 reduction. Notably, the presence of these coordinated anions on the Co sites significantly influences the photocatalytic performance, where TBD-COF-Co-F exhibits superior activity to its counterparts. Combined experimental and theoretical results indicate that the enhanced activity in TBD-COF-Co-F is attributed to its efficient charge transfer, high CO 2 adsorption capacity, and low energy barrier for CO 2 activation. This study provides a new strategy for boosting COF photocatalysis through coordinated anion regulation around catalytic metal sites.