Plasmonic platinum nanoparticles-tungsten oxide nanoarchitectures as visible light photocatalysts for highly efficient overall water splitting

Visible plasmonic Pt nanoparticles (NPs) have rarely been used as a photosensitizer for the semiconductor photocatalysis of overall water splitting (OWS), while they show higher probabilities of electron-hole (e-h) pair excitations and Pt catalysts are highly active for both water reduction and oxidation in comparison with plasmonic Au and Ag. Herein, we fabricate a tungsten oxide (WO3 center dot 0.5H(2)O-WO3) superstructure decorated by a series of visible plasmonic Pt NPs with a uniform diameter (120, 130, 145, and 160 nm) on nickel foam (NF) substrate. These monolithic composite Pt-WO3 center dot 0.5H(2)O-WO3 photocatalysts are capable of efficiently harvesting visible light for more efficient solar-hydrogen conversion due to the narrow bandgap of WO3 center dot 0.5H(2)O-WO3 (2.4 eV) coupled with an extension of light absorption even up to above 800 nm contributed by Pt NPs. In particular, our Pt-WO3 center dot 0.5H(2)O-WO3 photocatalysts exhibit favorable band edge positions relative to water redox potentials and intrinsic Pt catalytic activity and thus achieve an exceptional activity towards photocatalytic OWS (POWS) with apparent quantum efficiencies (AQE) of more than 10% within the range of visible light and a solar-to-hydrogen (STH) conversion efficiency of 7.6%. The dependence of the photocatalytic activity of Pt-WO3 center dot 0.5H(2)O-WO3 on the diameter of Pt NPs is attributed to a trade-off between optical absorption range and probability for interband damping of localized surface plasmon resonance (LSPR) into e-h excitations.