Critical Roles of Doping Cl on Cu₂O Nanocrystals for Direct Epoxidation of Propylene by Molecular Oxygen

Direct epoxidation of propylene by molecular oxygen alone is one of the "dream reactions" in heterogeneous catalysis. Despite much effort, the yield of propylene epoxide is still too low to be commercially attractive due to the trade-off between conversion and selectivity. Here, we demonstrate that doping Cl into the lattice of Cu₂O nanocrystals by the intergrowth method not only can enhance the catalytic selectivity and conversion of direct propylene epoxidation but also can solve the long-existing Cl loss problem. In particular, Cl-doped rhombic dodecahedral Cu₂O with (110) exposing facets exhibited 63% PO selectivity with a 12.0 h^-1 turnover frequency at 200 °C, outperforming any other coinage metal-based catalysts under mild conditions. Comprehensive characterization and theoretical calculations revealed that the Cl-decorated Cu(I) facilitated formation of electrophilic oxygen species, thus boosting the production of propylene oxide. This work provides a general strategy to develop catalysts and explore the promoter effect by creating uniform isolated anion doping to activate a nearby metal center by virtue of well-defined nanocrystals.