Kinetic and DFT studies on the Ag/TiO2-photocatalyzed selective reduction of nitrobenzene to aniline.
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.
Tada
Hiroaki
H
Department of Applied Chemistry, Faculty of Science and Engineering, Kinki University, 3-4-1, Kowakae, Higashi-Osaka, Osaka. h-tada@apch.kindai.ac.jp
Ishida
Tetsuji
T
Takao
Ayako
A
Ito
Seishiro
S
Mukhopadhyay
Sudip
S
Akita
Tomoki
T
Tanaka
Koji
K
Kobayashi
Hisayoshi
H
D000814:Aniline Compounds / Q000138:chemical synthesis*; D002384:Catalysis; D007700:Kinetics; D008956:Models, Chemical; D009578:Nitrobenzenes / Q000737:chemistry*; D010084:Oxidation-Reduction; D010316:Particle Size; D010777:Photochemistry; D012834:Silver / Q000737:chemistry*; D013499:Surface Properties; D014025:Titanium / Q000737:chemistry*
D000814:Aniline Compounds; D009578:Nitrobenzenes; C009495:titanium dioxide; D012834:Silver; D014025:Titanium; C023650:aniline