TiO2 particles loaded with silver nanoparticles with a mean diameter of 1.5 nm exhibit a high photocatalytic activity (84 % conversion after 1 h irradiation) for the reduction of nitrobenzene to aniline with 100 % selectivity in the presence of CH3OH (concentration=100 mM). High-resolution transmission electron microscopic studies of Pt-photodeposited Ag/TiO2 demonstrate that the Ag nanoparticles act as reduction sites in the photocatalytic reaction. Both spectroscopic measurements and density functional theory (DFT) calculations reveal that nitrobenzene is selectively adsorbed onto the Ag surfaces of Ag/TiO2 via partial electron transfer from Ag to nitrobenzene, whereas the interaction between aniline and Ag/TiO2 is weak. The kinetic analysis indicates that the recombination between the electrons flowing into the Ag nanoparticle and the holes left in the TiO2 valence band is significantly suppressed, particularly in the presence of CH3OH. The high activity and selectivity in the present Ag/TiO2-photocatalyzed reduction are rationalized in terms of the charge separation efficiency, the selective adsorption of the reactants on the catalyst surfaces, and the restriction of the product readsorption.

Bimetallic nanoparticles are successfully formed on the surface of TiO2 (see figure) with Ag shell layer (nL) control. Pt@Ag/TiO2 exhibits unique photocatalytic performances for reduction of nitorobenzene at nL≤1, however when nL exceeds ≈1 they are similar to those of Ag/TiO2. Furthermore at the critical value of nL≈1, the surface properties of Pt@Ag nanoparticles change from Pt to Ag.