Key Laboratory of Green Chemical Media and Reactions (Ministry of Education), Collaborative Innovation Centre of Henan Province for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan, 453007, P. R. China.
Department of Electrical and Computer Engineering, National University of Singapore, Singapore, 117583, Singapore.
Nat Commun. 2023 Feb 28;14(1):1147. doi: 10.1038/s41467-023-36779-4.
Cobalt coordinated covalent organic frameworks have attracted increasing interest in the field of CO photoreduction to CO, owing to their high electron affinity and predesigned structures. However, achieving high conversion efficiency is challenging since most Co related coordination environments facilitate fast recombination of photogenerated electron-hole pairs. Here, we design two kinds of Co-COF catalysts with oxygen coordinated Co atoms and find that after tuning of coordination environment, the reported Co framework catalyst with Co-O sites exhibits a high CO production rate of 18000 µmol g h with selectivity as high as 95.7% under visible light irradiation. From in/ex-situ spectral characterizations and theoretical calculations, it is revealed that the predesigned Co-O sites significantly facilitate the carrier migration in framework matrixes and inhibit the recombination of photogenerated electron-hole pairs in the photocatalytic process. This work opens a way for the design of high-performance catalysts for CO photoreduction.
钴配位共价有机框架由于其高电子亲和力和预定的结构，在 CO 光还原为 CO 的领域引起了越来越多的关注。然而，由于大多数与 Co 相关的配位环境促进光生电子-空穴对的快速复合，因此实现高转化率效率是具有挑战性的。在这里，我们设计了两种具有氧配位 Co 原子的 Co-COF 催化剂，并发现经过配位环境的调谐后，具有 Co-O 位的报道的 Co 框架催化剂在可见光照射下表现出 18000 µmol g h 的高 CO 生成速率，选择性高达 95.7%。通过原位/非原位光谱特性和理论计算，揭示了预定的 Co-O 位显著促进了载流子在骨架基质中的迁移，并抑制了光催化过程中光生电子-空穴对的复合。这项工作为 CO 光还原高性能催化剂的设计开辟了道路。
