Inferring Protonation States of Hydroxamate Adsorbates on TiO2 Surfaces
Abstract
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.
- Authors:
-
[1];
[1];
[1]
- Yale Univ., New Haven, CT (United States). Dept. of Chemistry and Energy Sciences Inst.
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- 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); Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- 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
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
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. https://doi.org/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. https://doi.org/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 = {Wed May 24 00:00:00 EDT 2017},
month = {Wed May 24 00:00:00 EDT 2017}
}
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Works referencing / citing this record:
Snapshots of Dynamic Adaptation: Two‐Dimensional Molecular Architectonics with Linear Bis‐Hydroxamic Acid Modules
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Snapshots of Dynamic Adaptation: Two‐Dimensional Molecular Architectonics with Linear Bis‐Hydroxamic Acid Modules
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