Loading-Controlled Photoactivity in TiO₂@BiVO₄ Heterostructures

In this study, we have investigated heterostructural TiO₂/BiVO₄ anodes to determine the effect of the amount and form of BiVO₄ nanoparticles on TiO₂ on the response of photoanodes under UV and visible illumination. BiVO₄ nanopowders were prepared and annealed at temperatures ranging from 200 to 500 °C. Structural and optical characterization indicates that as the annealing temperature is increased, a phase transition from a weakly ordered to a dominant monoclinic BiVO₄ phase is observed, which is accompanied by an increase in visible light absorption. Subsequently, the most crystalline powder was utilized to deposit BiVO₄ on nanostructured TiO₂ either as a compact overlayer (drop-casting) or as a progressively grown nanoparticle (TiO₂@S series) in the successive ionic layer adsorption and reaction process (SILAR). Photoelectrochemical measurements were performed, revealing a morphology-dependent photocurrent response under UV and visible illumination. A further increase in the number of cycles systematically increases the photocurrent in the visible light range while limiting the response to UV radiation. The TiO₂@d photoanode demonstrates the highest relative activity within the visible range; however, it also generates the lowest absolute photocurrent, indicating the presence of significant transport and recombination losses within the thick BiVO₄ layer. The results demonstrate that the presence of BiVO₄ nanoparticles on TiO₂ exerts a substantial influence on the separation of charge between semiconductors and the synergistic utilization of photons from the UV and visible ranges. This research yielded a proposed scheme of mutual band arrangement and charge carrier transfer mechanism in TiO₂@BiVO₄ heterostructures.