Inferring Protonation States of Hydroxamate Adsorbates on TiO2 Surfaces

We explore the protonation states of benzohydroxamic acid adsorbates bound to the {101} facet of TiO2 anatase by using a combination of density functional theory, simulations of UV–vis spectra based on a tight-binding Hamiltonian, and direct comparisons to experimental measurements. We find that the...

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Bibliographic Details
Published in:Journal of physical chemistry. C 2017-06, Vol.121 (22), p.11985-11990
Main Authors: Rudshteyn, Benjamin, Negre, Christian F. A, Oliboni, Robson S, Monti, Adriano, Chen, Jeffrey, Crabtree, Robert H, Rego, Luis G. C, Batista, Victor S
Format: Article
Language:English
Subjects:
CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
MATERIALS SCIENCE
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Summary:We explore the protonation states of benzohydroxamic acid adsorbates bound to the {101} facet of TiO2 anatase by using a combination of density functional theory, simulations of UV–vis spectra based on a tight-binding Hamiltonian, and direct comparisons to experimental measurements. We find that the characteristic red-shifted spectrum of nonmethylated, relative to the methylated, hydroxamic acids can only be explained by proposing a monodeprotonated monodentate mode as the main adsorption mode. The reported analysis suggests a simple, yet general, spectroscopic method based on UV–vis absorption measurements and tight-binding calculations for inferring changes of pK a of molecular adsorbates interacting with semiconductor electrode surfaces.
ISSN:1932-7447
1932-7455
DOI:10.1021/acs.jpcc.7b01272