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Molecules 2015, 20(2), 3371-3388; doi:10.3390/molecules20023371

A Density Functional Tight Binding Study of Acetic Acid Adsorption on Crystalline and Amorphous Surfaces of Titania

1
Department of Mechanical Engineering, National University of Singapore, Block EA #07-08, 9 Engineering Drive 1, Singapore 117576, Singapore
2
Department of Chemical System Engineering, School of Engineering, University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
3
CREST-JST, 7 Gobancho, Chiyoda-ku, Tokyo 102-0076, Japan
*
Author to whom correspondence should be addressed.
Academic Editor: Derek J. McPhee
Received: 4 January 2015 / Revised: 12 February 2015 / Accepted: 13 February 2015 / Published: 17 February 2015
(This article belongs to the Special Issue Molecular Engineering for Electrochemical Power Sources)
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Abstract

We present a comparative density functional tight binding study of an organic molecule attachment to TiO2 via a carboxylic group, with the example of acetic acid. For the first time, binding to low-energy surfaces of crystalline anatase (101), rutile (110) and (B)-TiO2 (001), as well as to the surface of amorphous (a-) TiO2 is compared with the same computational setup. On all surfaces, bidentate configurations are identified as providing the strongest adsorption energy, Eads = −1.93, −2.49 and −1.09 eV for anatase, rutile and (B)-TiO2, respectively. For monodentate configurations, the strongest Eads = −1.06, −1.11 and −0.86 eV for anatase, rutile and (B)-TiO2, respectively. Multiple monodentate and bidentate configurations are identified on a-TiO2 with a distribution of adsorption energies and with the lowest energy configuration having stronger bonding than that of the crystalline counterparts, with Eads up to −4.92 eV for bidentate and −1.83 eV for monodentate adsorption. Amorphous TiO2 can therefore be used to achieve strong anchoring of organic molecules, such as dyes, that bind via a -COOH group. While the presence of the surface leads to a contraction of the band gap vs. the bulk, molecular adsorption caused no appreciable effect on the band structure around the gap in any of the systems. View Full-Text
Keywords: titanium dioxide; anatase; rutile; (B)-TiO2; amorphous TiO2; acetic acid; adsorption; dye-sensitized solar cells; density functional tight binding titanium dioxide; anatase; rutile; (B)-TiO2; amorphous TiO2; acetic acid; adsorption; dye-sensitized solar cells; density functional tight binding
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Manzhos, S.; Giorgi, G.; Yamashita, K. A Density Functional Tight Binding Study of Acetic Acid Adsorption on Crystalline and Amorphous Surfaces of Titania. Molecules 2015, 20, 3371-3388.

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