Regulation of Coordinating Anions around Single Co(II) Sites in a Covalent Organic Framework for Boosting CO<sub>2</sub> Photoreduction
While photocatalytic CO<sub>2</sub> reduction has been intensively investigated, reports on the influence of anions coordinated to catalytic metal sites on CO<sub>2</sub> photoreduction remain limited. Herein, different coordinated anions (F<sup>-</sup>, Cl<sup>-</sup>, OAc<sup>-</sup>, and NO<sub>3</sub> <sup>-</sup>) 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<sub>3</sub>), for photocatalytic CO<sub>2</sub> 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<sub>2</sub> adsorption capacity, and low energy barrier for CO<sub>2</sub> activation. This study provides a new strategy for boosting COF photocatalysis through coordinated anion regulation around catalytic metal sites.
Authors
- Shuang‐Quan Zang (ORCID: https://orcid.org/0000-0002-6728-0559)
- Hai‐Long Jiang (ORCID: https://orcid.org/0000-0002-2975-7977)
- Jier Huang (ORCID: https://orcid.org/0000-0002-2885-5786)
- Nan Dai
- Jiajia Huang (ORCID: https://orcid.org/0009-0009-0374-6194)
- Denan Wang (ORCID: https://orcid.org/0000-0003-3603-6788)
- Yunyang Qian (ORCID: https://orcid.org/0000-0002-4802-1519)
- Weijie Yang (ORCID: https://orcid.org/0000-0002-0232-1129)
- Zhongyuan Lin (ORCID: https://orcid.org/0000-0003-1091-0991)
- Rui Wang (ORCID: https://orcid.org/0000-0001-5994-4952)
- Xinyu Guan (ORCID: https://orcid.org/0000-0003-2366-9375)
Institutions
- Boston College (US)
- University of Science and Technology of China (CN)
- North China Electric Power University (CN)
- Hefei Normal University (CN)
- Zhengzhou University (CN)
- Integrated Oncology (United States) (US)
- Hefei National Center for Physical Sciences at Nanoscale (CN)
- Microscale (United States) (US)
Publication Details
- Journal
- Precision Chemistry
- Published
- 2024-10-14
- DOI
- https://doi.org/10.1021/prechem.4c00058
- Citations
- 24
- Primary Topic
- Covalent Organic Framework Applications
- Type
- article
- Field-Weighted Citation Impact
- 2.81
Funders
- Boston College
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- China Postdoctoral Science Foundation
- Zhengzhou University
- Hefei Normal University
- University of Science and Technology of China
- National Key Research and Development Program of China
- Fundamental Research Funds for the Central Universities