Enhancing Photocatalytic Performance in Bi₂WO₆ Nanolayers via Ultrasound-Assisted Oxygen Vacancy Engineering

High-quality two-dimensional Bi₂WO₆ nanolayers were synthesized via hydrothermal processes, with oxygen vacancies introduced through an ultrasound-assisted alkali etching treatment. Comprehensive characterization using Raman spectroscopy, X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and positron annihilation spectroscopy (PAS) confirmed the presence and effects of these vacancies on the structural and electronic properties of the nanolayers. Raman spectroscopy revealed shifts in vibrational modes, particularly a blue shift in the WO₆ octahedral vibration modes, indicative of oxygen vacancy formation. XPS analysis showed a reduction in the binding energies of the Bi 4 f and W 4 f orbitals, confirming an altered electronic environment. TEM images demonstrated significant lattice distortions in the oxygen-vacancy-rich regions, particularly disordered WO₆ octahedra and disrupted Bi-O bond lengths. These distortions are consistent with the structural disorder observed in XAS measurements, which highlighted a reduction in the coordination number of W atoms and a corresponding contraction of W-O bond lengths. This charge redistribution between Bi and W atoms due to oxygen vacancies leads to localized structural perturbations, as further evidenced by PAS, which showed increased positron lifetimes associated with vacancy clusters, particularly around the Bi and W atoms. These vacancies create defective sites that trap photogenerated electrons, preventing their recombination with holes, thereby significantly enhancing photocatalytic performance. The enhanced photocatalytic activity was demonstrated by the nearly 98% degradation of Rhodamine B dye under visible-light irradiation, a substantial improvement over the 70% degradation achieved by the untreated sample. This work presents an innovative approach for generating stable oxygen vacancies in Bi₂WO₆ nanolayers and offers an in-depth understanding of the mechanisms that enhance photocatalytic performance, providing valuable insights for advancing photocatalysts designed for environmental remediation.