Interface-Enhanced Electrochemical Epoxidation Over a Core-Shell Nanozeolite TS-1@Mn-N-C Catalyst

Conventional olefin epoxidation suffers from poor atomic economy and significant environmental/economic burdens due to the reliance on harsh oxidants. While electrochemical epoxidation using water as an oxygen source presents a sustainable alternative, existing systems remain hampered by noble-metal dependence or inefficiency. To address this, we design a core-shell nanostructure integrating titanium silicalite-1 (TS-1) nanozeolite with Mn-N-C (TS-1@Mn-N-C). Critically, the interfacial synergy drives a tandem catalytic process: Mn-N-C sites electrosynthesize H₂O₂ via 2e^- water oxidation, which directly migrates to adjacent TS-1 active centers for selective epoxidation. Such spatial coupling ensures maximized H₂O₂ utilization and enhanced catalytic efficiency. As expected, TS-1@Mn-N-C achieves exceptional performance for the epoxidation of cyclooctene to 1,2-epoxycyclooctane in neutral electrolytes, outperforming both individual components and recently reported benchmarks. In situ characterizations combined with theoretical calculations reveal that the TS-1@Mn-N-C interface lowers the energy barrier for H₂O₂ activation toward reactive η-Ti-OOH intermediates, enabling efficient and sustained epoxidation. The catalyst also shows broad substrate applicability, highlighting its potential as a sustainable and cost-effective solution for electrochemical olefin epoxidation. This work pioneers a dual-site interface strategy to optimize reaction kinetics and advance green chemical synthesis.