Benzotrithiophene-Based Covalent Organic Frameworks with Rhenium Modified for Artificial Photosynthetic CO2 Reduction

Hong Dong; Hong-Tu Che; Li-Wen Bai; Nan-Nan Zhang; Yong-Qi Tian; Bing-Zhi Li; Ya Wang; Xin Zhang; Feng-Ming Zhang

doi:10.1021/acs.inorgchem.4c04599

Benzotrithiophene-Based Covalent Organic Frameworks with Rhenium Modified for Artificial Photosynthetic CO₂ Reduction

Inorg Chem. 2024 Dec 23;63(51):24421-24428. doi: 10.1021/acs.inorgchem.4c04599. Epub 2024 Dec 9.

Authors

Hong Dong¹, Hong-Tu Che¹, Li-Wen Bai¹, Nan-Nan Zhang¹, Yong-Qi Tian¹, Bing-Zhi Li¹, Ya Wang¹, Xin Zhang², Feng-Ming Zhang¹

Affiliations

¹ Heilongjiang Provincial Key Laboratory of CO2 Resource Utilization and Energy Catalytic Materials, School of Material Science and Chemical Engineering, Harbin University of Science and Technology, Harbin 150040, China.
² School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China.

PMID: 39653606
DOI: 10.1021/acs.inorgchem.4c04599

Abstract

Although covalent organic framework (COF)-based photocatalysts for CO₂ reduction reaction has been widely reported, there are still some problems such as poor visible-light absorption and low activity to realize the overall reaction of CO₂ reduction by the artificial photosynthesis strategy. Herein, anchoring the Re carbonyl complex Re(CO)₅Cl in a benzotrithiophene-based COF has been synthesized for artificial photosynthetic CO₂ reduction. The photocatalytic results demonstrate that BTT-bpy-COF-Re exhibits the highest CO₂RR activity, achieving a rate of 110.9 μmol g^-1 h^-1 for the conversion of CO₂ to CO, without the need for any sacrificial agent or photosensitizer. This performance significantly surpasses that of BTT-COF and BTT-bpy-COF. Additionally, BTT-bpy-COF-Re shows an apparent quantum efficiency of 1.17% at 420 nm. Further characterization analyses indicate that the enhanced photocatalytic activity can be attributed to improved visible-light absorption and efficient charge transfer within the Re complex-modified BTT-bpy-COF-Re system.