Covalent Organic Framework Nanosheets Embedding Single Cobalt Sites for Photocatalytic Reduction of Carbon Dioxide

• Published in: Chemistry of materials Vol. 32; no. 21; pp. 9107 - 9114
• Main Authors: Wang, Xiaoyan, Fu, Zhiwei, Zheng, Lirong, Zhao, Chengxi, Wang, Xue, Chong, Samantha Y, McBride, Fiona, Raval, Rasmita, Bilton, Matthew, Liu, Lunjie, Wu, Xiaofeng, Chen, Linjiang, Sprick, Reiner Sebastian, Cooper, Andrew I
• Format: Journal Article
• Language: English
• Published: American Chemical Society 10.11.2020
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/acs.chemmater.0c01642

Covalent organic framework nanosheets (CONs), fabricated from two-dimensional covalent organic frameworks (COFs), present a promising strategy for incorporating atomically distributed catalytic metal centers into well-defined pore structures with desirable chemical environments. Here, a series of CONs was synthesized by embedding single cobalt sites that were then evaluated for photocatalytic carbon dioxide reduction. A partially fluorinated, cobalt-loaded CON produced 10.1 μmol carbon monoxide with a selectivity of 76%, over 6 hours irradiation under visible light (TON = 28.1), and a high external quantum efficiency (EQE) of 6.6% under 420 nm irradiation in the presence of an iridium dye. The CONs appear to act as a semiconducting support, facilitating charge carrier transfer between the dye and the cobalt centers, and this results in a performance comparable with that of the state-of-the-art heterogeneous catalysts in the literature under similar conditions. The ultrathin CONs outperformed their bulk counterparts in all cases, suggesting a general strategy to enhance the photocatalytic activities of COF materials.