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Title: Inferring Protonation States of Hydroxamate Adsorbates on TiO 2 Surfaces

Abstract

We explore the protonation states of benzohydroxamic acid adsorbates bound to the {101} facet of TiO 2 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.

Authors:
ORCiD logo [1];  [2];  [3];  [1];  [1]; ORCiD logo [1];  [3]; ORCiD logo [1]
  1. Yale Univ., New Haven, CT (United States). Dept. of Chemistry and Energy Sciences Inst.
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Federal Univ. of Santa Catarina, Florianopolis, Santa Catarina (Brazil). Dept. of Physics
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1480466
Grant/Contract Number:  
SC0001059
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 22; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

Rudshteyn, Benjamin, Negre, Christian F. A., Oliboni, Robson S., Monti, Adriano, Chen, Jeffrey, Crabtree, Robert H., Rego, Luis G. C., and Batista, Victor S. Inferring Protonation States of Hydroxamate Adsorbates on TiO2 Surfaces. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b01272.
Rudshteyn, Benjamin, Negre, Christian F. A., Oliboni, Robson S., Monti, Adriano, Chen, Jeffrey, Crabtree, Robert H., Rego, Luis G. C., & Batista, Victor S. Inferring Protonation States of Hydroxamate Adsorbates on TiO2 Surfaces. United States. doi:10.1021/acs.jpcc.7b01272.
Rudshteyn, Benjamin, Negre, Christian F. A., Oliboni, Robson S., Monti, Adriano, Chen, Jeffrey, Crabtree, Robert H., Rego, Luis G. C., and Batista, Victor S. Wed . "Inferring Protonation States of Hydroxamate Adsorbates on TiO2 Surfaces". United States. doi:10.1021/acs.jpcc.7b01272. https://www.osti.gov/servlets/purl/1480466.
@article{osti_1480466,
title = {Inferring Protonation States of Hydroxamate Adsorbates on TiO2 Surfaces},
author = {Rudshteyn, Benjamin and Negre, Christian F. A. and Oliboni, Robson S. and Monti, Adriano and Chen, Jeffrey and Crabtree, Robert H. and Rego, Luis G. C. and Batista, Victor S.},
abstractNote = {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 pKa of molecular adsorbates interacting with semiconductor electrode surfaces.},
doi = {10.1021/acs.jpcc.7b01272},
journal = {Journal of Physical Chemistry. C},
number = 22,
volume = 121,
place = {United States},
year = {2017},
month = {5}
}

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