Atomically Precise Iron Catalysis for Efficient Electrochemical Cycloaddition of CO₂ With Low-Cost Feedstocks to...

Electrocatalytic CO₂ cycloaddition provides a green route for the synthesis of cyclic carbonates under mild conditions. However, activating sterically hindered styrene oxide (SO) remains challenging due to its weak electron-withdrawing phenyl group. Herein, we report an atomically dispersed Fe/N-C single-atom catalyst (Fe_1.98─N─C) for the efficient conversion of SO and CO₂ to styrene carbonate (SC). The catalysts deliver a 78% yield and 99% selectivity within 6 h, outperforming most reported electrocatalytic systems. Fe_1.98─N─C exhibits higher activity than an Fe nanoparticle catalyst and Fe-free ZIF-NC. Aberration-corrected STEM and XAFS confirm the atomic dispersion of Fe and the formation of Fe─N₄ coordination sites. In situ FTIR, EPR, and DFT calculations reveal that Fe─N₄ sites promote SO ring-opening and CO₂ activation through a synergistic Lewis acid-base mechanism. Controlled Fe incorporation enhances the surface area and porosity, facilitating the cycloaddition process. This work provides a robust strategy for designing MOF-derived single-atom catalysts for sustainable electrochemical CO₂ utilization.