DFT study of benzyl alcohol/TiO interfacial surface complex: reaction pathway and mechanism of visible light absorption.

We propose a new pathway for the adsorption of benzyl alcohol on the surface of TiO and the formation of interfacial surface complex (ISC). The reaction free energies and reaction kinetics were thoroughly investigated by density functional calculations. The TiO surfaces were modeled by clusters consisting of 4 Ti atoms and 18 O atoms passivated by H, OH group and HO molecules. Compared with solid-state calculations utilizing the periodicity of the materials, such cluster modeling allows inclusion of the high-order correlation effects that seem to be essential for the adsorption of organic molecules onto solid surfaces. The effects of both acidity and solvation are included in our calculations, which demonstrate that the new pathway is competitive with a previous pathway. The electronic structure calculations based on the relaxed ISC structures reveal that the chemisorption of benzyl alcohol on the TiO surface greatly alters the nature of the frontier molecular orbitals. The resulted reduced energy gap in ISC matches the energy of visible light, showing how the adsorption of benzyl alcohol sensitizes the TiO surface. Graphical Abstract The chemisorption of benzyl alcohol on TiO surface greatly alters the nature of the frontier molecular orbitals and the formed interfacial surface complex can be sensitized by visible light.