Au Nanostructure-Decorated TiO₂ Nanowires Exhibiting Photoactivity Across Entire UV-visible Region for Photoelectrochemical Water Splitting

Here we demonstrate that the photoactivity of Au-decorated TiO₂ electrodes for photoelectrochemical water oxidation can be effectively enhanced in the entire UV–visible region from 300 to 800 nm by manipulating the shape of the decorated Au nanostructures. The samples were prepared by carefully depositing Au nanoparticles (NPs), Au nanorods (NRs), and a mixture of Au NPs and NRs on the surface of TiO₂ nanowire arrays. As compared with bare TiO₂, Au NP-decorated TiO₂ nanowire electrodes exhibited significantly enhanced photoactivity in both the UV and visible regions. For Au NR-decorated TiO₂ electrodes, the photoactivity enhancement was, however, observed in the visible region only, with the largest photocurrent generation achieved at 710 nm. Significantly, TiO₂ nanowires deposited with a mixture of Au NPs and NRs showed enhanced photoactivity in the entire UV–visible region. Monochromatic incident photon-to-electron conversion efficiency measurements indicated that excitation of surface plasmon resonance of Au is responsible for the enhanced photoactivity of Au nanostructure-decorated TiO₂ nanowires. Photovoltage experiment showed that the enhanced photoactivity of Au NP-decorated TiO₂ in the UV region was attributable to the effective surface passivation of Au NPs. Furthermore, 3D finite-difference time domain simulation was performed to investigate the electrical field amplification at the interface between Au nanostructures and TiO₂ upon SPR excitation. The results suggested that the enhanced photoactivity of Au NP-decorated TiO₂ in the UV region was partially due to the increased optical absorption of TiO₂ associated with SPR electrical field amplification. The current study could provide a new paradigm for designing plasmonic metal/semiconductor composite systems to effectively harvest the entire UV–visible light for solar fuel production