Synergistic V–Nb Sites Modulate Selective Alkene Epoxidation with In Situ Photogenerated H2O2 over COF@MXene Heterostructures

Cooperative coupling of alkene epoxidation with in situ H2O2 photosynthesis is a prospective but challenging strategy for maximizing energy utilization and fabricating value-added chemicals. Herein, a covalent assembly of bipyridine-linked covalent organic framework onto VNbC solid-solution MXene heterostructures (COF-TpBpy@VNbC, TBNV-x) has been constructed, exhibiting high catalytic activity for selective styrene epoxidation (as a model reaction) with in situ photogenerated H2O2. Significantly, the optimal TBNV-3 composite achieved an impressive selectivity of 99% with nearly 100% conversion. Systematic experimental characterizations and density functional theory calculations confirm that enhanced activity and selectivity can be attributed to the synergistic effect of alloying V–Nb sites for accelerating the migration and transport of photogenerated carriers and enhancing the adsorption energy of styrene. This study provides an implication for designing innovative catalysts by optimizing structural engineering, highlighting the potential applications for coupled photocatalysis.