Crystal-phase-dependent interfacial lattice matching in BiOBr/Bi2O3 S-scheme heterojunctions for efficient charge separation and levofloxacin detoxification
Abstract
Interfacial lattice commensurability is an underexplored design dimension in heterojunction photocatalysis, despite its centrality to charge-carrier dynamics at solid-solid interfaces. Here, we report the fabrication of BiOBr with vacancy oxygen employing three Bi2O3 polymorphs (α, β, γ) and systematically elucidate the role of interfacial lattice commensurability on photocatalytic performance. The α-Bi2O3 polymorph (space group P2₁/c; a = 7.79 Å, b = 7.87 Å, c = 5.48 Å) exhibits near-ideal lattice commensurability with the tetragonal BiOBr (102) plane with a lattice mismatch of 3.1% along the x direction. High-resolution transmission electron microscopy (HRTEM) provides a direct view of a coherent heterointerface with uninterrupted crystallographic registry between α-Bi2O3 (121) (d = 0.329 nm) and BiOBr (102) (d = 0.285 nm). The shifts in X-ray photoelectron spectroscopy (XPS) binding energy and density functional theory (DFT) calculations together confirm an S-scheme charge-transfer route, which is driven by an internal electric field resulting from the difference in work functions (ΦBiOBr = 5.39 eV compared to Φα-Bi2O3 = 5.06 eV). The optimized α-BOB composite achieves pseudo-first-order levofloxacin (LEV) degradation with a rate constant of k = 0.0207 min-1 under visible-light irradiation, representing a 5.2-fold improvement over BiOBr. The total organic carbon (TOC) removal efficiency of 68.3% after 120 min irradiation confirms that a significant portion of the LEV…
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