Dong Hong, Che Hong-Tu, Bai Li-Wen, Zhang Nan-Nan, Tian Yong-Qi, Li Bing-Zhi, Wang Ya, Zhang Xin, Zhang Feng-Ming
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.
School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China.
Inorg Chem. 2024 Dec 23;63(51):24421-24428. doi: 10.1021/acs.inorgchem.4c04599. Epub 2024 Dec 9.
Although covalent organic framework (COF)-based photocatalysts for CO 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 CO reduction by the artificial photosynthesis strategy. Herein, anchoring the Re carbonyl complex Re(CO)Cl in a benzotrithiophene-based COF has been synthesized for artificial photosynthetic CO reduction. The photocatalytic results demonstrate that BTT-bpy-COF-Re exhibits the highest CORR activity, achieving a rate of 110.9 μmol g h for the conversion of CO 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.
尽管基于共价有机框架（COF）的光催化剂用于CO还原反应已被广泛报道，但通过人工光合作用策略实现CO还原的整体反应仍存在一些问题，如可见光吸收差和活性低。在此，已合成了将铼羰基配合物Re(CO)Cl锚定在基于苯并三噻吩的COF中用于人工光合CO还原。光催化结果表明，BTT-bpy-COF-Re表现出最高的CORR活性，将CO转化为CO的速率达到110.9 μmol g h，无需任何牺牲剂或光敏剂。该性能显著超过BTT-COF和BTT-bpy-COF。此外，BTT-bpy-COF-Re在420 nm处显示出1.17%的表观量子效率。进一步的表征分析表明，增强的光催化活性可归因于Re配合物修饰的BTT-bpy-COF-Re体系中可见光吸收的改善和有效的电荷转移。
