Porous 3 d‐4 f Coordination Clusters for Selective Visible‐Light Photocatalytic CO<sub>2</sub> Reduction to CO
Wei‐Peng Chen, Kai‐Peng Bai, Man‐Ting Lv, Shuang Ni, Chang Huang, Qing‐Yuan Yang, Yan‐Zhen Zheng
Abstract
Abstract We report herein two families of porous coordination clusters (PCCs) with 216 nuclearity (M 120 RE 96 or PCC‐216MR) and 300 nuclearity (Co 144 Gd 156 or PCC‐300CG). For the first family M could be either nickel or cobalt, and RE = Pr, Nd, Sm, Eu, and Gd; while the latter features the highest nuclearity of transition‐rare earth metal clusters. Characterized by their cube‐like, hollow structures, these clusters exhibit the ability to absorb N 2 and CO 2 . Besides, these clusters can be dissolved in both aqueous and acetonitrile/methanol solutions, and capable of acting as homogeneous catalysts for converting CO 2 to CO under visible light. The gadolinium analogues of these clusters all show turnover numbers over 10000 and turnover frequencies over 1 s −1 . In particular, the nickel based bimetallic cluster (PCC‐216NG) demonstrates nearly 100 % selectivity for the reduction product, which may open a new direction for the design and development of PCCs based catalysts.