TiO2 loaded with Au–Ag bimetallic alloy particles efficiently produces H2O2 from an O2-saturated ethanol/water mixture under UV irradiation. This is achieved via the double effects created by the alloy particles. One is the efficient photocatalytic reduction of O2 on the Au atoms promoting enhanced H2O2 formation, due to the efficient separation of photoformed electron–hole pairs at the alloy/TiO2 heterojunction. Second is the suppressed photocatalytic decomposition of formed H2O2 due to the decreased adsorption of H2O2 onto the Au atoms.

Photocatalytic production of hydrogen peroxide (H2O2) on semiconductor catalysts with alcohol as a hydrogen source and molecular oxygen (O2) as an oxygen source has attracted much attention as a potential method for safe H2O2 synthesis, because the reaction can be carried out without the use of explosive H2/O2 mixed gases. Early reported photocatalytic systems with aliphatic alcohol as a hydrogen source, however, produce only a few millimolar levels of H2O2. We found that benzylic alcohols, when used as a hydrogen source for photoreaction in water with titanium dioxide (TiO2) photocatalyst, produce a very high concentration of H2O2 (ca. 40 mM). Raman spectroscopy and electron spin resonance analysis revealed that the enhanced H2O2 formation is due to the efficient formation of side-on coordinated peroxo species on the photoactivated TiO2 surface, via the reaction of benzylic alcohol and O2. The peroxo species is readily transformed to H2O2, thus facilitating highly efficient H2O2 production.

Visible light irradiation (λ >450 nm) of platinum (Pt) nanoparticles supported on anatase titanium dioxide (TiO 2 ) promotes efficient aerobic oxidation at room temperature. This occurs via the electronic excitation of Pt particles by visible light followed by the transfer of their electrons to anatase conduction band. The positively charged Pt particles oxidize substrates, whereas the conduction band electrons are consumed by the reduction of molecular oxygen. The activity of this photocatalysis depends on the height of Schottky barrier and the number of perimeter Pt atoms created at the Pt/anatase heterojunction, which are affected by the amount of Pt loaded and the size of Pt particles. The catalyst loaded with 2 wt % Pt, containing 3−4 nm Pt particles, creates a relatively low Schottky barrier and a relatively large number of perimeter Pt atoms and, hence, facilitates smooth Pt→anatase electron transfer, resulting in very high photocatalytic activity. This catalyst is successfully activated by sunlight and enables efficient and selective aerobic oxidation of alcohols at ambient temperature.

Cr/Ti/Si ternary mixed oxides (CrTiSi) were prepared by a hydrolysis of tetraethyl orthosilicate (TEOS), Cr(NO3)3, and titanium tetraisopropoxide (TTIP) followed by calcination. These oxides were used as catalysts for partial oxidation of cyclohexane with molecular oxygen under irradiation of visible light (λ > 400 nm). The CrTiSi catalysts produce cyclohexanol and cyclohexanone with high selectivity (>91%) and show much higher activity than the CrSi binary oxides. Among them, the catalyst with equimolar amounts of Cr and Ti shows the highest activity. Visible-light irradiation of the CrSi catalyst promotes a reduction of tetrahedrally coordinated Cr oxide species (T d 6+) and produces the excited state (T d 4+*), which behaves as an active site for oxidation. In contrast, the CrTiSi catalyst contains tetrahedrally coordinated Cr and Ti oxide species that are connected through the Cr–O–Ti bond. The photoformed T d 4+* species is strongly stabilized due to delocalization of excited electrons on the Cr–O–Ti species. This suppresses rapid deactivation of T d 4+* and results in enhanced photocatalytic activity.