An Au-mediated Cu2O-based Z-scheme heterostructure system is demonstrated for use as efficient photocathodes in photoelectrochemical (PEC) reduction. The samples are prepared by electrodepositing a Cu2O layer on the surface of Au particle-coated TiO2 nanorods. For TiO2-Au-Cu2O, the embedded Au particles function as a charge transfer mediator to enhance the electron transportation from the conduction band of TiO2 to the valence band of Cu2O. Such a vectorial charge transfer leads to the concentration of electrons at the conduction band of Cu2O and the collection of holes at the valence band of TiO2, providing TiO2-Au-Cu2O with substantially high redox abilities for reduction applications. Time-resolved photoluminescence spectra and electrochemical impedance spectroscopy analysis suggest that interfacial charge transfer is significantly improved because of the Au-mediated Z-scheme charge transfer mechanism. By virtue of the high redox ability and improved interfacial charge transfer, TiO2-Au-Cu2O performs much better as a photocathode in H2 production and CO2 reduction than pure Cu2O and binary TiO2-supported Cu2O do. Remarkably, the photocurrent density of TiO2-Au-Cu2O toward PEC CO2 reduction can reach as high as −1.82 mA/cm2 at +0.11 V vs RHE. The incident photon-to-current conversion efficiency data manifest that TiO2-Au-Cu2O surpasses both pure Cu2O and binary TiO2-supported Cu2O in PEC reduction across the whole photoactive region. The current study paves a valuable approach of devising Z-scheme photocathode for the construction of sophisticated artificial photosynthesis systems capable of solar-to-fuel conversion.

For the first time a ZnO nanorod-based Z-scheme heterostructure system was proposed and realized for efficient photoelectrochemical water splitting. The samples were prepared by depositing a thin layer of SnO2 on the Au surface of Au particle-decorated ZnO nanorods. For ZnO-Au-SnO2 nanorods, the embedded Au can mediate interfacial charge transfer by promoting electron transfer from the conduction band of SnO2 to the valence band of ZnO. This vectorial charge transfer resulted in the situation that the photoexcited electrons accumulated at ZnO while the photogenerated holes concentrated at SnO2, giving ZnO-Au-SnO2 substantially high redox powers. Time-resolved photoluminescence spectra suggested that the interfacial charge transfer across the ZnO/Au/SnO2 interface was significantly improved as a result of the Z-scheme charge transfer mechanism. With the substantially high redox powers and significantly improved interfacial charge transfer, ZnO-Au-SnO2 nanorods performed much better as a photoanode in photoelectrochemical water splitting than pristine ZnO, plasmonic Au-decorated ZnO and type-II SnO2-coated ZnO nanorods did. The present study has provided a viable approach to exploit Z-scheme photoanodes in the design of efficient artificial photosynthesis systems for solar energy conversion.

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