Aluminum polycation-intercalated vanadium oxide nanosheets with modulated electronic structure for boosted...

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 VO_x (exfoliated V₂O₅, 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-Al₁₃) 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-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.