High-throughput screening using porous photoelectrode for the development of visible-light-responsive semiconductors.

A high-throughput screening system for new visible-light-responsive semiconductors for photoelectrodes and photocatalysts was developed in this study. Photoelectrochemical measurement was selected to evaluate visible-light responsiveness, and an automated semiconductor synthesis system that can be used to prepare porous thin-film photoelectrodes of various materials was also developed. As an example application of our system, iron-based binary oxides were selected as target materials for n-type semiconductors. Fe-Ti, Fe-Nb, and Fe-V with various composition ratios were synthesized. Fe-Ti and Fe-Nb binary oxide systems have been studied previously, and our results showed good consistency with previous reports, demonstrating the capability of our system. In the Fe-V system, the highest photocurrent was observed with 50% vanadium. This ratio corresponds to FeVO4, which is expected to be a new visible-light-responsive material. As another example, screening targets of bismuth-based binary oxides were investigated for p-type semiconductor photoelectrodes, and CuBi2O4 was found as a new visible-light-responsive p-type semiconductor.

Photoelectrochemical decomposition of water into H2 and O2 on porous BiVO4 thin-film electrodes under visible light and significant effect of Ag ion treatment.

The photoelectrochemical properties of porous BiVO4 thin-film electrodes on conducting glass for H2 production from water under visible light were investigated. BiVO4 films were prepared by the metal-organic decomposition method, and particles were 90-150 nm in diameter. Under visible-light irradiation, H2 and O2 evolved in a stoichiometric ratio (H2/O2 = 2) from an aqueous solution of Na2SO4 with an external bias. The photocurrent increased with addition of methanol. The band structure of BiVO4 was investigated by open-circuit potential, flat-band potential, X-ray photoelectron spectroscopy, and calculations based on density functional theory. The top of the valence-band potential of BiVO4 was shifted negatively compared to the potentials of the conventional oxide semiconductors without Bi. We surmise that hybridization between the O-2p and Bi-6s orbitals might contribute to the negative shift of the BiVO4 valence band. Treatment with an aqueous solution of AgNO3 improved the photocurrent of the BiVO4 electrode significantly. The maximum incident photon-to-current conversion efficiency at 420 nm was 44%. This value was the highest among mixed-oxide semiconductor electrodes under visible light irradiation. AgNO3 treatment also improved the stability of the photocurrent. The Ag+ ion in/on the BiVO4 catalyzed the intrinsic photogeneration of oxygen with the holes.