LAUSR

The application of solar energy to convert CO2 into high-value chemicals and fuels has been considered a highly desirable approach to relieving the greenhouse effect and energy crisis, while the exploration of appropriate photocatalysts remains a major challenge. Combining the respective advantages of COFs and MOFs to construct covalent metal-organic frameworks (CMOFs) can be a valid strategy to provide efficient, reliable and eco-friendly photocatalysts. Herein, we employ a CuI cluster-based CMOF (JNM-2) as a photocatalyst for CO2 photoreduction under visible-light irradiation. JNM-2 exhibits remarkable efficiency of photocatalytic CO2 reduction with high production rates of HCOOH (9019 μmol g-1 h-1) and CO (835 μmol g-1 h-1). The active center, reaction intermediates and product generation pathways are elucidated by in-situ DRIFTS and DFT calculations. This work demonstrates the tremendous possibilities of CMOFs as photocatalysts for CO2 reduction and provides profound insights into the mechanism of CO2-to-HCOOH/CO conversion using molecularly accurate structural model.