化学
光催化
轨道能级差
催化作用
吡唑
配体(生物化学)
氢键
光化学
金属有机骨架
金属
吸附
分子
立体化学
物理化学
有机化学
受体
生物化学
作者
Ké Li,Sheng Ge,Xiaoqian Wei,Weibao Zou,Xiuwen Wang,Qiuhui Qian,Bin Gao,Lin Dong
出处
期刊:Inorganic Chemistry
[American Chemical Society]
日期:2023-09-18
卷期号:62 (39): 15824-15828
被引量:2
标识
DOI:10.1021/acs.inorgchem.3c02272
摘要
Metal-organic frameworks (MOFs) have been studied extensively in the catalytic field. However, the role of ligands in catalysis has been less well investigated. Here, an asymmetric ligand photocatalytic strategy for CO2 reduction in MOFs is first proposed. MOF-303(Al) with asymmetric ligands (pyrazolyldicarboxylic acid) exhibits synergistic catalytic effects. Specifically, pyrazoles participate in CO2 activation; i.e., pyrazole and μ2-OH form hydrogen bonds with CO2 to polarize C═O bonds. Furthermore, the lowest unoccupied molecular orbital (LUMO; A pyrazole) and highest occupied molecular orbital (HOMO; B pyrazole) act as the electron donor and acceptor to spatially separate the excited electron-hole, with A and B pyrazoles for CO2 and H2O adsorption to avoid competition, respectively. Owing to its advantages, MOF-303-modified g-C3N4 achieves nonsacrificial and transition-metal-free photocatalytic CO2 reduction to CO of 16.19 μmol·g-1·h-1, significantly higher than that of g-C3N4. This work provides fresh insights into asymmetric ligands in photocatalytic CO2 reduction.
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