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• W2273363695 abstract "The formation of bridging hydroxyls (OHb) via reactions of water molecules with oxygen vacancies (VO) on reduced TiO2(110) surfaces is studied using polarized infrared reflection–absorption spectroscopy (IRAS), electron-stimulated desorption (ESD), and photon-stimulated desorption (PSD). Narrow IR peaks at 2737 and 3711 cm−1 are observed for the stretching vibrations of ODb and OHb, respectively. The IRAS spectra indicate that the bridging hydroxyls are oriented normal to the TiO2(110) surface. Using IRAS, we have studied the kinetics of water reacting with the vacancies by monitoring the formation of bridging hydroxyls as a function of the annealing temperature on the TiO2(110). Separate experiments have also monitored the loss of water molecules (using water ESD) and vacancies (using the CO photooxidation reaction) due to the reactions of water molecules with the vacancies. All three techniques show that the reaction rate becomes appreciable for T > 150 K and that the reactions are largely complete for T > 250 K. The temperature-dependent water–VO reaction kinetics are consistent with a Gaussian distribution of activation energies with Ea = 0.545 eV, ΔEa(fwhm) = 0.125 eV, and a “normal” prefactor, ν = 1012 s–1. In contrast, a single activation energy with a physically reasonable prefactor does not fit the data well. Our experimental activation energy is close to theoretical estimates for the diffusion of water molecules along the Ti5c rows on the reduced TiO2(110) surface, which suggests that the diffusion of water controls the water–VO reaction rate." @default.
• W2273363695 created "2016-06-24" @default.
• W2273363695 creator A5029632614 @default.
• W2273363695 creator A5053623972 @default.
• W2273363695 date "2015-09-24" @default.
• W2273363695 modified "2023-09-29" @default.
• W2273363695 title "Reaction Kinetics of Water Molecules with Oxygen Vacancies on Rutile TiO₂(110)" @default.
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• W2273363695 doi "https://doi.org/10.1021/acs.jpcc.5b07526" @default.
• W2273363695 hasPublicationYear "2015" @default.
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