Aluminum polycation-intercalated vanadium oxide nanosheets with modulated electronic structure for boosted photocatalytic benzyl alcohol oxidation.

Two-dimensional layered vanadium-based oxides have garnered significant attention due to their multivalent electronic configurations, abundant surface-active sites, and exceptional photocatalytic stability. However, conventional layered architectures suffer from tight interfacial stacking, which impedes charge carrier mobility and limits visible-light absorption efficiency, thereby constraining further enhancement of catalytic performance. This study employed an ultrasonic-assisted intercalation strategy to precisely embed Keggin-type Al₁₃ ([Al13O4(OH)24(H2O)12]7+, the structure is represented by twelve AlO6 octahedra and one central AlO4 tetrahedron. These octahedra are interconnected via edge sharing and bonded to the central AlO4 unit through corner sharing.) into the interlayer framework of VOx (exfoliated V2O5, denoted as VOx), thereby establishing a multiscale synergistic regulation mechanism encompassing structural morphology, electronic states, and photophysical properties. Experimental evaluation of the photocatalytic oxidation activity toward benzyl alcohol demonstrated that the exfoliated two-dimensional nanosheets (VOx-Al13) exhibited remarkable catalytic efficiency with a conversion rate of 99.7% and over 99% product selectivity, outperforming VOx. Femtosecond transient absorption (fs-TA) spectroscopic analysis revealed a dominant internal charge separation (ICS) state with a prolonged lifetime of 1.5 ns in VOx-Al13, which significantly enhanced charge transfer efficiency and catalytic reactivity. This study not only provides an effective modification strategy paradigm for optimizing layered transition metal oxides but also establishes a robust theoretical and experimental foundation for developing cost-effective, high-performance visible-light-driven photocatalytic systems with environmental sustainability.