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

ABSTRACT

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 H ₂ O ₂ via 2e ⁻ water oxidation, which directly migrates to adjacent TS‐1 active centers for selective epoxidation. Such spatial coupling ensures maximized H ₂ O ₂ 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 H ₂ O ₂ 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.