Robust Biological Hydrogen‐Bonded Organic Framework with Post‐Functionalized Rhenium(I) Sites for Efficient Heterogeneous Visible‐Light‐Driven CO2 Reduction

• Published in: Angewandte Chemie 2021-04, Vol.133 (16), p.9065-9071
• Main Authors: Yu, Baoqiu, Li, Lianjie, Liu, Shanshan, Wang, Hailong, Liu, Heyuan, Lin, Chenxiang, Liu, Chao, Wu, Hui, Zhou, Wei, Li, Xiyou, Wang, Tianyu, Chen, Banglin, Jiang, Jianzhuang
• Format: Article
• Language: English
• Subjects: Biohydrogen; Carbon dioxide; carbon dioxide reduction; Catalytic activity; Chemistry; Crystallization; Fine structure; Guanine; heterogeneous catalysis; hydrogen-bonded organic frameworks; Irradiation; Light irradiation; Photocatalysis; Photoreduction; post-modification; Rhenium; Robustness; Selectivity; Ultrastructure; visible-light photocatalysis
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202016710

A robust 2,2′‐bipyridine (bpy)‐derived biological hydrogen‐bonded framework (HOF‐25) has been realized depending on guanine‐quadruplex with the assistance of π‐π interaction, which reacts with Re(CO)5Cl to give a post‐functionalized HOF‐25‐Re. X‐ray absorption fine structure spectroscopic study on HOF‐25‐Re confirms the covalent attachment of Re(bpy)(CO)3Cl segments to this HOF. Robust and recycled HOF‐25‐Re bearing photocatalytic Re(bpy)(CO)3Cl centers displays good heterogeneous catalytic activity towards carbon dioxide photoreduction in the presence of [Ru(bpy)3]Cl2 and triisopropanolamine in CH3CN under visible‐light irradiation, with both high CO production rate of 1448 μmol g−1 h−1 and high selectivity of 93 %. Under the same conditions, the experimental turnover number of HOF‐25‐Re (50) is about 8 times as that of the homogeneous control Re(bpy)(CO)3Cl. The sustainably regenerated HOF‐25‐Re via crystallization and post‐modification processes shows recovered photocatalytic performance. A robust porous biological HOF with bpy docking groups has been designed, prepared, and post‐modified to precisely load Re(bpy)(CO)3Cl as molecular catalyst on the basis of the hydrogen‐bonded and π‐π stacking metal‐free G‐quadruplex moieties. With the help of the sensitizer, the post‐functionalized HOF promotes efficient and selective CO2‐to‐CO conversion in a heterogeneous system under the visible‐light irradation.