Symmetry Breaking Induced Amorphization of Cobalt‐Based Catalyst for Boosted CO<sub>2</sub> Photoreduction
Tianqi Guo, Xiaoxue Xu, Zhongfei Xu, Feifei You, Xiaoyu Fan, Juzhe Liu, Zhongchang Wang
Abstract
Abstract Photocatalytic reduction of CO 2 to energy carriers is intriguing in the industry but kinetically hard to fulfil due to the lack of rationally designed catalysts. A promising way to improve the efficiency and selectivity of such reduction is to break the structural symmetry of catalysts by manipulating coordination. Here, inspired by analogous CoO 6 and CoSe 6 octahedral structural motifs of the Co(OH) 2 and CoSe, a hetero‐anionic coordination strategy is proposed to construct a symmetry‐breaking photocatalyst prototype of oxygen‐deficient Se‐doped cobalt hydroxide upon first‐principles calculations. Such involvement of large‐size Se atoms in CoO 6 octahedral frameworks experimentally lead to the switching of semiconductor type of cobalt hydroxide from p to n , generation of oxygen defects, and amorphization. The resultant oxygen‐deficient Se,O‐coordinated Co‐based amorphous nanosheets exhibit impressive photocatalytic performance of CO 2 to CO with a generation rate of 60.7 µmol g −1 h −1 in the absence of photosensitizer and scavenger, superior to most of the Co‐based photocatalysts. This work establishes a correlation between the symmetry‐breaking of catalytic sites and CO 2 photoreduction performances, opening up a new paradigm in the design of amorphous photocatalysts for CO 2 reduction.