文献类型：期刊文献

英文题名：Delocalized Orbitals over Metal Clusters and Organic Linkers Enable Boosted Charge Transfer in Metal-Organic Framework for Overall CO2 Photoreduction

作者：Liu, Hai-Xiong[1];Zhou, Zi-Jian[2,3];Xie, Lei[1];Liu, Chen[1];Cai, Lei[1];Wu, Xin-Ping[2,3];Liu, Tian-Fu[1,4]

机构：[1]Chinese Acad Sci, State Key Lab Struct Chem, Fujian Inst Res Struct Matter, 8 Gaoxindadao Rd, Fuzhou 350108, Peoples R China;[2]East China Univ Sci & Technol, State Key Lab Green Chem Engn & Ind Catalysis, Key Lab Adv Mat & Joint Int Res Lab Precis Chem &, Feringa Nobel Prize Sci Joint Res Ctr,Ctr Computat, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[4]Univ Chinese Acad Sci, Beijing 100049, Peoples R China

年份：2024

卷号：63

期号：47

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20244117181133);WOS:【SCI-EXPANDED(收录号:WOS:001336289500001)】；

基金：We gratefully acknowledge National Key Research and Development Program of China (2023YFA1507901), the National Natural Science Foundation of China (NSFC, Grant 22071246, 22272178, 22003016, 52394271), Shanghai Sailing Program (20YF1410000).

语种：英文

外文关键词：metal-organic framework; overall CO2 photoreduction; internal charge-separated state; delocalized orbitals; direct charge transfer

摘要：The conversion of CO2 to C-2 through photocatalysis poses significant challenges, and one of the biggest hurdles stems from the sluggishness of the multi-electron transfer process. Herein, taking metal-organic framework (MOF, PFC-98) as a model photocatalyst, we report a new strategy to facilitate charge separation. This strategy involves matching the energy levels of the lowest unoccupied node and linker orbitals of the MOF, thereby creating the lowest unoccupied crystal orbital (LUCO) delocalized over both the node and linker. This feature enables the direct excitation of electrons from photosensitive linker to the catalytic centers, achieving a direct charge transfer (DCT) pathway. For comparison, an isoreticular MOF (PFC-6) based on analogue components but with far apart frontier energy level was synthesized. The delocalized LUCO caused the presence of an internal charge-separated (ICS) state, prolonging the excited state lifetime and further inhibiting the electron-hole recombination. The presence of ICS state prolongs the excited state lifetime and further inhibits the electron-hole recombination. Moreover, it also induced abundant electrons accumulating at the catalytic sites, enabling the multi-electron transfer process. As a result, the material featuring delocalized LUCO exhibits superior overall CO2 photocatalytic performance with high C(2 )production yield and selectivity.