Oxygen vacancy-induced spin polarization of tungsten oxide nanowires for efficient photocatalytic reduction and immobilization of uranium(VI) under simulated solar light

Abstract

Tungsten oxide nanowires (WO3−x) with rich oxygen vacancies (OVs) were fabricated through a facile hydrothermal method, which had both high adsorptive capability and photocatalytic activity. 95.1% of total U(VI) (C0 = 10 mg/L) was removed by WO3−x at pH 5, and 79.9% was transformed to U(IV) to achieve reductive immobilization after photocatalysis under simulated solar light. Band structure and optical characterizations indicated WO3−x had narrower band gap energy, but higher charger carrier separation and transfer rates compared with conventional WO3. Density functional theory (DFT) calculations further demonstrate the spin polarization state electrons of W 5d in WO3−x due to the construction of OVs, thus greatly inhibiting recombination of electron-hole pairs. In addition, the electron density increases in WO3−x and the photogenerated e– in the conduction band of WO3−x has higher reduction ability than WO3, leading to more efficient electron transfer from WO3−x to UO22+ after photo-excitation for U(VI) reduction.