Bioinspired Polyoxo-titanium Cluster for Greatly Enhanced Solar-Driven CO<sub>2</sub> Reduction
Xin Wu, Qiaohong Li, Shouwei Zuo, Yang Li, Xiaodong Yi, Lv‐Bing Yuan, Lirong Zheng, Jing Zhang, Jing Zhang, Juncai Dong, Sibo Wang, Huabin Zhang, Jian Zhang, Jian Zhang
Abstract
Developing artificial enzymes with excellent catalytic activities and uncovering the structural and chemical determinants remain a grand challenge. Discrete titanium-oxo clusters with well-defined coordination environments at the atomic level can mimic the pivotal catalytic center of natural enzymes and optimize the charge-transfer kinetics. Herein, we report the precise structural tailoring of a self-assembled tetrahedral Ti 4 Mn 3 -cluster for photocatalytic CO 2 reduction and realize the selective evolution of CO over specific sites. Experiments and theoretical simulation demonstrate that the high catalytic performance of the Ti 4 Mn 3 -cluster should be related to the synergy between active Mn sites and the surrounding functional microenvironment. The reduced energy barrier of the CO 2 photoreduction reaction and moderate adsorption strength of CO* are beneficial for the high selective evolution of CO. This work provides a molecular scale accurate structural model to give insight into artificial enzyme for CO 2 photoreduction.