Benzotrithiophene-Based Covalent Organic Frameworks with Rhenium Modified for Artificial Photosynthetic CO2 Reduction
Hong Dong1, Hong-Tu Che1, Li-Wen Bai1
1Heilongjiang 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.
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.
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