Bioinspired Polyoxo-titanium Cluster for Greatly Enhanced Solar-Driven CO 2 Reduction.

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.