Cheng Mingjie, Yan Pengfei, Zheng Xiaoli, Gao Bo, Yan Xinying, Zhang Gaoxiang, Cui Xiaomin, Xu Qun
College of Materials Science and Engineering, Zhengzhou University, Zhengzhou, 450052, P. R. China.
Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou, 450052, P. R. China.
Chemistry. 2023 Dec 6;29(68):e202302395. doi: 10.1002/chem.202302395. Epub 2023 Oct 24.
The inherent challenges in using metal-organic frameworks (MOFs) for photocatalytic CO reduction are the combination of wide-range light harvesting, efficient charge separation and transfer as well as highly exposed catalytic active sites for CO activation and reduction. We present here a promising solution to satisfy these requirements together by modulating the crystal facet and surface atomic structure of a porphyrin-based bismuth-MOF (Bi-PMOF). The series of structural and photo-electronic characterizations together with photocatalytic CO reduction experiment collectively establish that the enriched Bi active sites on the (010) surface prefer to promote efficient charge separation and transfer as well as the activation and reduction of CO . Specifically, the Bi-PMOFs-120-F with enriched surface Bi active sites exhibits optimal photocatalytic CO reduction performance to CO (28.61 μmol h g ) and CH (8.81 μmol h g ). This work provides new insights to synthesize highly efficient main group p-block metal Bi-MOF photocatalysts for CO reduction through a facet-regulation strategy and sheds light on the surface structure-activity relationships of the MOFs.
将金属有机框架（MOF）用于光催化CO还原存在诸多内在挑战，这些挑战包括宽范围的光捕获、高效的电荷分离与转移，以及用于CO活化和还原的高度暴露的催化活性位点。我们在此提出了一种很有前景的解决方案，即通过调节基于卟啉的铋基MOF（Bi-PMOF）的晶面和表面原子结构，来同时满足这些要求。一系列的结构和光电子表征以及光催化CO还原实验共同证实，（010）表面上富集的Bi活性位点更有利于促进高效的电荷分离与转移以及CO的活化和还原。具体而言，具有富集表面Bi活性位点的Bi-PMOFs-120-F表现出最佳的光催化CO还原性能，生成CO的量为（28.61 μmol h g ），生成CH的量为（8.81 μmol h g ）。这项工作为通过晶面调控策略合成用于CO还原的高效主族p区金属Bi-MOF光催化剂提供了新的见解，并揭示了MOF的表面结构-活性关系。
