The cobalt phosphate water oxidation catalyst (Co–Pi WOC) stabilized, CdS sensitized TiO2 nanowire arrays for nonsacrificial solar water splitting are reported. In this TiO2/CdS/Co–Pi photoanode, the Co–Pi WOC acts as hole transfer relay to accelerate the surface water oxidation reaction, CdS serves as light absorber for wider solar spectra harvesting, and TiO2 matrix provides direct pathway for electron transport. This triple TiO2/CdS/Co–Pi hybrid photoanode exhibits much enhanced photocurrent density and negatively shifts in onset potential, resulting in 1.5 and 3.4 times improved photoconversion efficiency compared to the TiO2/CdS and TiO2 photoanode, respectively. More importantly, the TiO2/CdS/Co–Pi shows significantly improved photoelectrochemical stability compared to the TiO2/CdS electrode, with ≈72% of the initial photocurrent retained after 2 h irradiation. The reason for the promoted performance is discussed in detail based on electrochemical measurements. This work provides a new paradigm for designing 1D nanoframework/light absorber/WOC photoanode to simultaneously enhance light absorption, charge separation, and transport and surface water oxidation reaction for efficient and stable solar fuel production.

Cobalt phosphate (Co-Pi) is photo-electrodeposited on TiO2 nanowire arrays in Co(2+) containing phosphate buffer. The resulting composite photoanode shows a generally enhanced photocurrent near the flat band potential region, and represents a 2.3 times improved photoconversion efficiency compared to that of pristine TiO2 in a neutral electrolyte. A negative effect on the photocurrent generation is also observed when loading TiO2 with a relatively thick Co-Pi layer, which is demonstrated to be due to the poor photohole transfer kinetics in the Co-Pi layer. Moreover, we find that Co-Pi can facilitate the photoelectrochemical performance of TiO2 over a wide pH range from 1-14. This improved activity is studied in detail by optical and electrochemical analyses. It is suggested that the mechanism of the overpotential-demanding water oxidation reaction is changed to a facile pathway by the Co-based electrocatalyst. At the same time, the more significant band bending is induced by the Co-Pi catalyst decreasing the charge recombination. This work provides a feasible route to reduce the external power needed to drive water splitting by coupling an electrocatalyst with a photocatalyst, as well as mechanistic insights important for other Co-Pi modified photoelectrodes for solar-driven water splitting.

This paper demonstrates the procedure for construction of nontoxic TiO2/Bi2S3 core–shell NWA photoanodes for PEC hydrogen generation.

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Core/shell heterostructured TiO2/CdSxSe1-x nanowire arrays (NWAs) were prepared via physical vapor deposition of CdSxSe1-x layer onto the hydrothermal pre-grown TiO2 NWAs with FTO as conductive substrate. By change the sulfur content (x) in the TiO2/CdSxSe1-x nano-composites, it was observed that the light absorption edge can be gradually tuned within a broad wavelength from 540 to 710 nm. When used as photoanodes for hydrogen generation, the as-prepared TiO2/CdSxSe1-x NWAs show much higher photoelectroncatalytic activity than the pristine TiO2 NWAs. Moreover, the TiO2/CdSxSe1-x photoelectrode with x = 0.52 exhibited the highest photocurrent level and outstanding stability, which is more suitable for long-time hydrogen generation. This study may be useful in the design of alloy hetrostructure photoelectrodes with optimal chemical composition toward the more efficient solar conversion devices.