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

Abstract

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 ^δ- , 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 μmol g^-1 h^-1 without any sacrifice reagent or photosensitizer, where both the activity and selectivity outperform previously reported photocatalysts evaluated under similar conditions.

Keywords: CO2 Activation; Selective CO2 Photoreduction; Single-Unit-Cell Sheets; Switching Cu Single Sites.