Copper-Based Metal-Organic Framework with a Tetraphenylethylene-Tetrazole Linker for Visible-Light-Driven CO 2 Photoconversion.

The design of efficient and inexpensive photocatalysts for CO 2 photoreduction under visible light is of great significance for the sustainable development of the entire society. Herein, a copper-based metal-organic framework (MOF) ( CUST-804 ) using a bulky tetraphenylethylene-tetrazole linker is synthesized and successfully used as a photocatalyst for CO 2 reduction. The structural characterizations, as well as the photophysical properties, are investigated systematically. In the heterogeneous catalytic system, CUST-804 exhibits a robust CO production activity up to 2.71 mmol g -1 h -1 with excellent recyclability along with a selectivity of 82.8%, which is comparable with those of the reported copper-based MOF system. Theoretical calculations demonstrated that, among three kinds of coordinated model, only the 5-coordinated Cu site is active for CO 2 reduction, in which the *COOH intermediate is stabilized and CO is readily desorbed. The results obtained herein can provide fresh insights into the realization of efficient copper-functionalized crystalline photocatalysts for CO 2 reduction.