Our recent works on the photoelectrochemistry and fabrication of the water-splitting photocatalyst for solar energy conversion were reported. The S-dope midgap states were determined by monitoring the effect of the photocurrent on the addition of several reductants. The midgap states for the S-doped anatase TiO
2 has higher redox potentials than those of the Br
•/Br
− and possesses the additional multiple oxidation states of S cations. The laser ablation of the BiVO
4 and BiZn
2VO
6 photocatalytic particulates in water reduced these sizes and it was found that the thin film electrode prepared by calcining the laser-ablated BiVO
4 and BiZn
2VO
6 suspensions showed higher photocurrent efficiencies compared with the electrodes prepared without laser-ablation. The composite electrode FTO/SnO
2/BiVO
4 and FTO/WO
3/BiVO
4 were prepared by a solution method and the photocurrent efficiencies for these electrodes were found to be increased due to the mediator effect of SnO
2 and WO
3, which helps the electrons in the conduction band of BiVO
4 to transfer to the FTO. The new photocatalytic particulates that are active for oxygen evolution under the visible light irradiation was searched and the BiCu
2PO
6 was found to be active with the addition of sacrifice under the visible light irradiations.
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