Core–shell-structured nanoparticles, consisting of a noble metal or metal oxide core and a chromia (Cr2O3) shell, were studied as promoters for photocatalytic water splitting under visible light. Core nanoparticles were loaded by impregnation, adsorption or photodeposition onto a solid solution of gallium nitride and zinc oxide (abbreviated GaN:ZnO), which is a particulate semiconductor photocatalyst with a band gap of approximately 2.7 eV, and a Cr2O3 shell was formed by photodeposition using a K2CrO4 precursor. Photodeposition of Cr2O3 on GaN:ZnO modified with a noble metal (Rh, Pd and Pt) or metal oxide (NiOx, RuO2 and Rh2O3) co-catalyst resulted in enhanced photocatalytic activity for overall water splitting under visible light (λ>400 nm). This enhancement in activity was primarily due to the suppression of undesirable reverse reactions (H2–O2 recombination and/or O2 photoreduction) and/or protection of the core component from chemical corrosion, depending on the core type. Among the core materials examined, Rh species exhibited relatively high performance for this application. The activity for visible-light water splitting on GaN:ZnO modified with an Rh/Cr2O3 core–shell configuration was dependent on both the dispersion of Rh nanoparticles and the valence state. In addition, the morphology of the Cr2O3 photodeposits was significantly affected by the valence state of Rh and the pH at which the photoreduction of K2CrO4 was conducted. When a sufficient amount of K2CrO4 was used as the precursor and the solution pH ranged from 3 to 7.5, Cr2O3 was successfully formed with a constant shell thickness (≈2 nm) on metallic Rh nanoparticles, which resulted in an effective promoter for overall water splitting.
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