Cations such as H(+) and Li(+) are intercalated into TiO(2) nanotube arrays by subjecting them to short-term electrochemical pulses at controlled potentials (<-1.0 V vs Ag/AgCl). The intercalation of these small cations has a profound effect toward enhancing photocurrent generation under UV light irradiation. A nearly three-fold increase in the photoconversion efficiency (IPCE) was observed upon intercalation of Li(+) ions into TiO(2) nanotube arrays. The intercalation process is visualized by the color change from gray to blue. Spectroelectrochemical measurements were carried out to monitor the absorption changes at different applied potentials. The analysis of the V(oc) decay following termination of UV light shows a significant decrease in the rate of recombination of accumulated electrons upon Li(+) ion intercalation.

Iridium oxide, a water oxidation cocatalyst, plays an important role in mediating the hole transfer process of a UV-irradiated TiO2 system. Spectroscopic identification of trapped holes has enabled their characterization in colloidal TiO2 suspension and monitoring of the transfer of trapped holes to IrO2. Titration of trapped holes with potassium iodide yields an estimate of three holes per particle during 7 min of UV irradiation of TiO2 suspension in ethanol containing 5% acetic acid. The hole transfer to IrO2 occurs with a rate constant of 6 × 105 s–1. Interestingly, IrO2 also catalyzes the recombination of trapped holes with reduced oxygen species. The results discussed here provide a mechanistic and kinetic insight into the catalytic role of IrO2 in the photogenerated hole transfer process.

Scanning electrochemical microscopy (SECM) was used to identify more efficient p-type photocatalysts for H+ reduction in the Pb–Bi–Mo trimetal oxide system. An atomic ratio of (1:1:1) between Pb, Bi, and Mo showed higher photocurrent than other spots in screening experiments. The crystal structure of Pb–Bi–Mo oxide was studied by X-ray diffraction, indicating that a composite of p-PbMoO4 and n-Bi2O3 coexisted as a heterostructure. Photoelectrochemical performance of the p-PbMoO4/n-Bi2O3 composite electrode showed enhanced stability for the H+ and O2 reduction reactions. We propose a reaction mechanism to explain this stabilization of a p-type semiconductor.

Bulk processing of porous silicon nanoparticles (nSi) of 50-300 nm size and surface area of 25-230 m(2)/g has been developed using a combustion synthesis method. nSi exhibits consistent photoresponse to AM 1.5 simulated solar excitation. In confirmation of photoactivity, the films of nSi exhibit prompt bleaching following femtosecond laser pulse excitation resulting from the photoinduced charge separation. Photocurrent generation observed upon AM 1.5 excitation of these films in a photoelectrochemical cell shows strong dependence on the thickness of the intrinsic silica shell that encompasses the nanoparticles and hinders interparticle electron transfer.

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