A MOF@MOF S‐scheme Heterojunction with Lewis Acid‐Base Sites Synergistically Boosts Cocatalyst‐Free CO₂ Cycloaddition

The photocatalytic cycloaddition reaction between CO₂ and epoxide is one of the most promising green routes for CO₂ utilization, for which high performance photocatalysts are intensely desired. Herein, we have constructed an S-scheme heterojunction of MIL-125@ZIF-67 modified by amino groups, which achieves a cyclic carbonate yield of as high as 99 % without employing any co-catalyst, outperforming the previously reported photocatalysts. In-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and in-situ electron paramagnetic resonance (EPR) spectroscopy reveal the important role of photogenerated electron migration from Lewis acid (Co) sites to the O atom of epoxide in triggering its ring-opening (the rate-determining step of CO₂ cycloaddition reaction) under the assistance of photogenerated hole. Synergistically and concurrently, the Lewis base (amino groups) sites activate CO₂ to CO₂*, facilitating the following CO₂ cycloaddition. Such a synergistic effect provides a most favorable approach to design efficient heterogeneous photocatalysts with dual/multiple-active sites for CO₂ cycloaddition reaction.