Composites Based on Electrodeposited WO₃ and TiO₂ Nanoparticles for Photoelectrochemical Water Splitting

Photoelectrochemically active WO₃ films were fabricated by electrodeposition from an acidic (pH 2), hydrogen-peroxide-containing electrolyte at -0.5 V vs. SCE. WO₃-TiO₂ composites were then synthesized under the same conditions, but with 0.2 g/L of anatase TiO₂ nanoparticles (⌀ 36 nm), mechanically suspended in the solution by stirring. After synthesis, the films were annealed at 400 °C. Structural characterization by XRD showed that the WO₃ films exhibit the crystalline structure of a non-stoichiometric hydrate, whereas, in WO₃-TiO₂, the WO₃ phase was monoclinic. The oxidation of tungsten, as revealed by XPS, was W⁶⁺ for both materials. Ti was found to exist mainly as Ti⁴⁺ in the composite, with a weak Ti³⁺ signal. The efficiency of the WO₃ films and composites as an oxygen evolution reaction (OER) photo-electrocatalyst was examined. The composite would generate approximately three times larger steady-state photocurrents at 1.2 V vs. SCE in a neutral 0.5 M Na₂SO₄ electrolyte compared to WO₃ alone. The surface recombination of photogenerated electron-hole pairs was characterized by intensity-modulated photocurrent spectroscopy (IMPS). Photogenerated charge transfer efficiencies were calculated from the spectra, and at 1.2 V vs. SCE, were 86.6% for WO₃ and 62% for WO₃-TiO₂. Therefore, the composite films suffered from relatively more surface recombination but generated larger photocurrents, which resulted in overall improved photoactivity.