Reversible Switching CuII/CuI Single Sites Catalyze High-rate and Selective CO2 Photoreduction

Herein, we first design a model of reversible redox-switching metal-organic framework single-unit-cell sheets, where the abundant metal single sites benefit for highly selective CO2 reduction, while the reversible redox-switching metal sites can effectively activate CO2 molecules. Taking the synthetic Cu-MOF single-unit-cell sheets as an example, synchrotron-radiation quasi in situ X-ray photoelectron spectra unravel the reversible switching Cu-II/Cu-I single sites initially accept photoexcited electrons and then donate them to CO2 molecules, which favors the rate-liming activation into CO2 delta-, verified by in situ FTIR spectra and Gibbs free energy calculations. As an outcome, Cu-MOF single-unit-cell sheets achieve near 100 % selectivity for CO2 photoreduction to CO with a high rate of 860 mu mol g(-1) h(-1) without any sacrifice reagent or photosensitizer, where both the activity and selectivity outperform previously reported photocatalysts evaluated under similar conditions.

Automated summary

In this study, a model of reversible redox-switching metal-organic framework single-unit-cell sheets is designed, where abundant metal single sites enable highly selective CO2 reduction, and reversible redox-switching metal sites effectively activate CO2 molecules. Using synthetic Cu-MOF single-unit-cell sheets as an example, the reversible switching of Cu-II/Cu-I single sites is found to facilitate the transfer of photoexcited electrons to CO2 molecules, leading to efficient activation of CO2. As a result, Cu-MOF single-unit-cell sheets achieve near 100% selectivity for CO2 photoreduction to CO with a high rate, outperforming previously reported photocatalysts.