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 ([Al 13 O 4 (OH) 24 (H 2 O) 12 ] 7+ , the structure is represented by twelve AlO 6 octahedra and one central AlO 4 tetrahedron. These octahedra are interconnected via edge sharing and bonded to the central AlO 4 unit through corner sharing.) into the interlayer framework of VO x (exfoliated V 2 O 5 , denoted as VO x ), 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 (VO x -Al 13 ) exhibited remarkable catalytic efficiency with a conversion rate of 99.7% and over 99% product selectivity, outperforming VO x . Femtosecond transient absorption (fs-TA) spectroscopic analysis revealed a dominant internal charge separation (ICS) state with a prolonged lifetime of 1.5 ns in VO x -Al 13 , 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. Download: Download high-res image (109KB) Download: Download full-size image