Synergistic multiphase evolution and interface electron transfer in dual-dimensional surface engineered V2O5/TiO2 catalysts for highly selective durene oxidation

The oxidation reaction of durene (C10 feedstock) to high-value monomer, pyromellitic dianhydride (PMDA), is challenging due to the difficulties in selective C H bonds activation and controlling over-oxidation to CO x . To address this, we successfully synthesized a series of V 2 O 5 /TiO 2 catalysts co-modified with P and Ce (Ce x -P y -V/TiO 2 ), demonstrating that the optimized catalyst significantly improved PMDA selectivity by 14.08%. Mechanistic studies indicate this remarkable enhancement stems from the synergistic effect among V 2 O 5 and the new crystal phases of VOPO 4 and CePO 4 phases regulates the electronic state of surface V species via interface electron transfer, thereby optimizing the redox capability for C H activation, while the co-modification simultaneously reduces strong acidic sites, as confirmed by NH 3 -TPD, Py-IR and DFT calculation, effectively suppressing deep oxidation by weakening intermediate adsorption. In situ DRIFTS and DFT calculation confirmed that the selectivity gain is driven by an enhanced dehydration rate of the tetracarboxylic acid intermediate and the weaken ability of electron transfer. This work introduces an effective surface property design strategy based on the simultaneous fine-tuning of the active site electronic structure and the acid microenvironment, offering crucial guidance for highly selective catalytic conversions of C10 aromatics.