Photoelectrochemical (PEC) water splitting promises a solution to the problem of large-scale solar energy storage. However, its development has been impeded by the poor performance of photoanodes, particularly in their capability for photovoltage generation. Many examples employing photovoltaic modules to correct the deficiency for unassisted solar water splitting have been reported to-date. Here we show that, by using the prototypical photoanode material of haematite as a study tool, structural disorders on or near the surfaces are important causes of the low photovoltages. We develop a facile re-growth strategy to reduce surface disorders and as a consequence, a turn-on voltage of 0.45 V (versus reversible hydrogen electrode) is achieved. This result permits us to construct a photoelectrochemical device with a haematite photoanode and Si photocathode to split water at an overall efficiency of 0.91%, with NiFeOx and TiO2/Pt overlayers, respectively.

A stand-alone, wireless solar water splitting device without external energy supply has been realized by combining in tandem a CH3NH3PbI3 perovskite single junction solar cell with a cobalt carbonate (Co-Ci)-catalyzed, extrinsic/intrinsic dual-doped BiVO4 (hydrogen-treated and 3 at% Mo-doped). The photoanode recorded one of the highest photoelectrochemical water oxidation activity (4.8 mA/cm(2) at 1.23 VRHE) under simulated 1 sun illumination. The oxygen evolution Co-Ci co-catalyst showed similar performance to best known cobalt phosphate (Co-Pi) (5.0 mA/cm(2) at 1.23 VRHE) on the same dual-doped BiVO4 photoanode, but with significantly better stability. A tandem artificial-leaf-type device produced stoichiometric hydrogen and oxygen with an average solar-to-hydrogen efficiency of 4.3% (wired), 3.0% (wireless) under simulated 1 sun illumination. Hence, our device based on a D4 tandem photoelectrochemical cell represents a meaningful advancement in performance and cost over the device based on a triple-junction solar cell-electrocatalyst combination.

Hematite prepared by atomic layer deposition (ALD) was found to exhibit photocurrents when illuminated by near-infrared light (λ = 830 nm), whose energy is smaller than the band gap of hematite. The phenomenon was inferred to be a result of valence band to surface state transition. The influence of surface states on the thermodynamics of the hematite/water interface was studied under open-circuit conditions. It was discovered that the equilibrium potential of the hematite surface was more negative than water oxidation potential by at least 0.4 V. With a NiFeO x coating by photochemical decomposition of organometallic precursors, the equilibrium potential of hematite was restored to water oxidation potential, and the photoresponse under 830 nm illumination was annihilated. Therefore, the states were rationalized by the chemical status at the electrode surfaces, and this hypothesis was supported by similar observations on other metal oxide electrodes such as TiO2.

Au coupled ZnTe/ZnO-NW array is a new photocathode for selective CO production from CO2. The remarkable effects of an Au are to form of a Schottky junction with ZnTe to improve band bending and provide the reaction center for CO2 reduction suppressing water reduction.

Nickel-intercalated titanate nanotube was hydrothermally synthesized and evaluated for photocatalytic hydrogen production from methanol-water solution under UV light irradiation. The nickel intercalated into the nanotube was present as a hydrated Ni complex of [Ni x II (OH) 2x-1 (OH 2 )] + and was responsible for a dramatic enhancement of hydrogen evolution rate relative to that of titanate nanotube itself. The nickel species in the interlayer provided active sites for proton reduction and caused fast diffusion of photoelectrons generated from titanate layers toward the nickel sites, leading to a high photocatalytic activity. Upon annealing at 400 °C, the hydrated nickel complex was partly converted to NiO and the hydrogen evolution rate was reduced, indicating that the nickel hydroxide was a more efficient cocatalyst for titanate nanotube. A high and stable photocurrent generation was also observed from a film made of the nickel-intercalated titanate nanotube immersed in a NaOH solution.