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Identifying the Azobenzene/Aniline reaction intermediate on TiO2-(110) : a DFT Study
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Bradley, M. K. (Matthew K.), Robinson, Jim, Dr. and Woodruff, D. P. (2013) Identifying the Azobenzene/Aniline reaction intermediate on TiO2-(110) : a DFT Study. The Journal of Physical Chemistry C, Volume 117 (Number 24). pp. 12591-12599. doi:10.1021/jp402461g ISSN 1932-7447.
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Official URL: http://dx.doi.org/10.1021/jp402461g
Abstract
Density functional theory (DFT) calculations, both with and without dispersion corrections, have been performed to investigate the nature of the common surface reaction intermediate that has been shown to exist on TiO2(110) as a result of exposure to either azobenzene (C6H5N═NC6H5) or aniline (C6H5NH2). Our results confirm the results of a previous DFT study that dissociation of azobenzene into two adsorbed phenyl imide (C6H5N) fragments, as was originally proposed, is not energetically favorable. We also find that deprotonation of aniline to produce this surface species is even more strongly energetically disfavored. A range of alternative surface species has been considered, and while dissociation of azobenzene to form surface C6H4NH species is energetically favored, the same surface species cannot form from adsorbed aniline. On the contrary, adsorbed aniline is much the most stable surface species. Comparisons with experimental determinations of the local adsorption site, the Ti–N bond length, the molecular orientation, and the associated C 1s and N 1s photoelectron core level shifts are all consistent with the DFT results for adsorbed aniline and are inconsistent with other adsorbed species considered. Possible mechanisms for the hydrogenation of azobenzene required to produce this surface species are discussed.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Physics | ||||
Library of Congress Subject Headings (LCSH): | Azo compounds, Aniline, Density functionals | ||||
Journal or Publication Title: | The Journal of Physical Chemistry C | ||||
Publisher: | American Chemical Society | ||||
ISSN: | 1932-7447 | ||||
Official Date: | 30 May 2013 | ||||
Dates: |
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Volume: | Volume 117 | ||||
Number: | Number 24 | ||||
Number of Pages: | 8 | ||||
Page Range: | pp. 12591-12599 | ||||
DOI: | 10.1021/jp402461g | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Access rights to Published version: | Restricted or Subscription Access | ||||
Date of first compliant deposit: | 26 December 2015 | ||||
Date of first compliant Open Access: | 26 December 2015 | ||||
Funder: | Engineering and Physical Sciences Research Council (EPSRC), Science Research Investment Fund (SRIF) |
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