AVS 63rd International Symposium & Exhibition
    Surface Science Tuesday Sessions
       Session SS+HC-TuA

Paper SS+HC-TuA7
Quenching of Electron Transfer Reactions through Coadsorption: A Study of Oxygen Photodesorption from TiO2(110)

Tuesday, November 8, 2016, 4:20 pm, Room 104D

Session: Photocatalysis and Photochemistry at Surfaces
Presenter: Greg Kimmel, Pacific Northwest National Laboratory
Authors: G.A. Kimmel, Pacific Northwest National Laboratory
N.G. Petrik, Pacific Northwest National Laboratory
M. Shen, Pacific Northwest National Laboratory
M.A. Henderson, Pacific Northwest National Laboratory
Correspondent: Click to Email

Using temperature programmed desorption (TPD) and photon stimulated desorption (PSD), we show that coadsorbates of varying binding energies on the rutile TiO2(110) surface exert a commensurate inhibiting influence on the hole-mediated photodesorption of adsorbed O2. A variety of coadsorbates (Ar, Kr, Xe, N2, CO, CO2, CH4, N2O, acetone, methanol or water) were shown to quench O2 photoactivity, with the extent correlating with the coadsorbate’s gas phase basicity, which in turn determines the strength of the coadsorbate-Ti4+ bond. Coadsorbed rare gases inhibited the photodesorption of O2 by ~10-25%, whereas strongly bound species (water, methanol and acetone) nearly completely inhibited O2 PSD. We suggest that coadsorption of these molecules inhibit the arrival probability of holes to the surface. Band bending effects, which vary with the extent of charge transfer between the coadsorbate and the TiO2(110) surface, are not expected to be significant in the cases of the rare gases and physisorbed species. These results indicate that neutral coadsorbates can exert a significant influence on charge transfer events by altering the interfacial dipole in the vicinity of the target molecule.