Quenching of electron transfer reactions through coadsorption: A study of oxygen photodesorption from TiO2(110)

Petrik, Nikolay G.; Kimmel, Greg A.; Shen, Mingmin; Henderson, Michael A.

doi:10.1016/j.susc.2015.12.038

Quenching of electron transfer reactions through coadsorption: A study of oxygen photodesorption from TiO₂(110)

Journal Article · Mon Jan 11 00:00:00 EST 2016 · Surface Science

DOI:https://doi.org/10.1016/j.susc.2015.12.038· OSTI ID:1250869

Petrik, Nikolay G. ^[1]; Kimmel, Greg A. ^[1]; Shen, Mingmin ^[1]; Henderson, Michael A. ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

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. Furthermore, 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.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1250869

Alternate ID(s):: OSTI ID: 1340844
OSTI ID: 1397340

Report Number(s):: PNNL-SA--114433; PII: S0039602816000054

Journal Information:: Surface Science, Journal Name: Surface Science Journal Issue: C Vol. 117; ISSN 0039-6028

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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