Regulation of Coordinating Anions around Single Co(Ⅱ)Sites in a Covalent Organic Framework for Boosting CO_(2)Photoreduction  

作　　者：Nan Dai Yunyang Qian Denan Wang Jiajia Huang Xinyu Guan Zhongyuan Lin Weijie Yang Rui Wang Jier Huang Shuang-Quan Zang Hai-Long Jiang 

机构地区：[1]Hefei National Research Center for Physical Sciences at the Microscale,Department of Chemistry,University of Science and Technology of China,Hefei,Anhui 230026,China [2]College of Chemistry,Zhengzhou University,Zhengzhou,Henan 450001,China [3]School of Chemistry and Pharmaceutical Engineering,Hefei Normal University,Hefei,Anhui 230061,China [4]Department of Chemistry,Boston College,Chestnut Hill,Massachusetts 02467,United States [5]School of Energy and Power Engineering,North China Electric Power University,Baoding,Hebei 071003,China

出　　处：《Precision Chemistry》2024年第11期600-609,共10页精准化学（英文）

基　　金：supported by the National Key Research and Development Program of China(2021YFA1500400);the NSFC(U22A20401,22331009,and 22205208);the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0450302 and XDB0540000);the Fundamental Research Funds for the Central Universities(WK9990000137);the Postdoctoral Fellowship Program of CPSF(GZC20232538 and GZC20232532);the China Postdoctoral Science Foundation(2024M753086);Hefei Normal University 2023 Scientific Research Fund Project for Introducing High level Talents(2023rcjj11)。

摘　　要：While photocatalytic CO_(2)reduction has been intensively investigated,reports on the influence of anions coordinated to catalytic metal sites on CO_(2)photoreduction remain limited.Herein,different coordinated anions(F^(−),Cl^(−),OAc^(−),and NO_(3)^(−))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_(3)),for photocatalytic CO_(2)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_(2)adsorption capacity,and low energy barrier for CO_(2)activation.This study provides a new strategy for boosting COF photocatalysis through coordinated anion regulation around catalytic metal sites.

关 键 词：covalent organic framework single sites CO_(2)photoreduction coordination environment anion regulation 

分 类 号：O64[理学—物理化学]