Sonochemical regulation of oxygen vacancies for Bi2WO6 nanosheet-based photoanodes to promote photoelectrochemical performance

Abstract

Integration of oxygen vacancies (Vo) into nanostructured semiconductor-based photocatalysts has been recognized as a promising strategy for enhancing the performance of photoelectrochemical (PEC) water splitting. However, precisely controlling the Vo concentration in photocatalysts via an effective and tunable approach remains challenging. Herein, a series of optimized bismuth tungstate (Bi₂WO₆) nanosheet-based photoanodes with varying concentrations of Vo were prepared by a sonochemical method with in situ cavitation detection, which enables accurate manipulation of the acoustic cavitation intensity applied to the surface of Bi₂WO₆ photoanodes in alkaline solution. Based on the analysis of the Vo concentration and sound field characteristics, the mechanism of sonochemical regulation of Vo in Bi₂WO₆ nanosheets was interpreted. Specifically, the increase in Vo concentration can be attributed to the enhancement of Bi–O bond dissociation. This enhancement is influenced not only by the intensified impact of shear force and the generation of active radicals by transient cavitation, but also by the accelerated diffusion of the reactant, a result of stable cavitation. By optimizing the transient and stable cavitation intensity, a Vo-rich Bi₂WO₆ photoanode was obtained without altering the microstructure of Bi₂WO₆ nanosheets. The presence of high concentration Vo facilitates the interfacial chemical reactivity and the transmission of photogenerated carriers, leading to the drastic promotion of the PEC water splitting performance. The transient photocurrent density of the Vo-rich Bi₂WO₆ photoanode reaches 69.2 μA cm⁻² (1.23 V vs. RHE), 7.86 times that of the untreated Bi₂WO₆ photoanode. Additionally, the charge injection efficiency increases to 35.4%. This work provides a controllable and effective method for defect engineering of nanostructured semiconductor-based electrodes.