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. However, the exploration of appropriate photocatalysts remains a major challenge. Combining the respective advantages of covalent organic frameworks and metal-organic frameworks to construct covalent metal-organic frameworks (CMOFs) can be a valid strategy to provide efficient, reliable, and eco-friendly photocatalysts. In this study, a CuI cluster-based CMOF (JNM-2) is used as a photocatalyst for CO2 photoreduction under visible-light irradiation. JNM-2 exhibits remarkable efficiency in 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 conversion into HCOOH/CO by using a molecularly accurate structural model.
Keywords: CO2 valorization; copper; metal-organic frameworks, photocatalysis; reduction.
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