Structure of a model dye/titania interface : Geometry of benzoate on rutile-TiO2 (110)(1 × 1)
(2016) In Journal of Physical Chemistry C 120(27). p.14690-14698- Abstract
Scanned-energy mode photoelectron diffraction (PhD) and ab initio density functional theory calculations have been employed to investigate the adsorption geometry of benzoate ([C6H5COO]-) on rutile-TiO2(110)(1 × 1). PhD data indicate that the benzoate moiety binds to the surface through both of its oxygen atoms to two adjacent fivefold surface titanium atoms in an essentially upright geometry. Moreover, its phenyl (C6H5-) and carboxylate ([-COO]-) groups are determined to be coplanar, being aligned along the [001] azimuth. This experimental result is consistent with the benzoate geometry emerging from DFT calculations conducted for laterally rather... (More)
Scanned-energy mode photoelectron diffraction (PhD) and ab initio density functional theory calculations have been employed to investigate the adsorption geometry of benzoate ([C6H5COO]-) on rutile-TiO2(110)(1 × 1). PhD data indicate that the benzoate moiety binds to the surface through both of its oxygen atoms to two adjacent fivefold surface titanium atoms in an essentially upright geometry. Moreover, its phenyl (C6H5-) and carboxylate ([-COO]-) groups are determined to be coplanar, being aligned along the [001] azimuth. This experimental result is consistent with the benzoate geometry emerging from DFT calculations conducted for laterally rather well-separated adsorbates. At shorter interadsorbate distances, the theoretical modeling predicts a more tilted and twisted adsorption geometry, where the phenyl and carboxylate groups are no longer coplanar; i.e., interadsorbate interactions influence the configuration of adsorbed benzoate.
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- author
- Busayaporn, W. ; Duncan, D. A. ; Allegretti, Francesco ; Wander, A. ; Bech, M. LU ; Møller, P. J. ; Doyle, B. P. ; Harrison, N. M. ; Thornton, Geoff and Lindsay, Robert
- publishing date
- 2016-07-14
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of Physical Chemistry C
- volume
- 120
- issue
- 27
- pages
- 14690 - 14698
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- scopus:84978829301
- ISSN
- 1932-7447
- DOI
- 10.1021/acs.jpcc.6b03991
- language
- English
- LU publication?
- no
- additional info
- Funding Information: The authors thank the ELETTRA staff for their support. The PhD measurements were facilitated by the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement no. 226716. In addition, through membership of the U.K.'s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work used the ARCHER U.K. National Supercomputing Service (http://www.archer.ac.uk). DAD acknowledges funding from the Alexander von Humboldt foundation. Publisher Copyright: © 2016 American Chemical Society.
- id
- c5c5b80c-19a8-4a2f-a9af-b91ee993f5ed
- date added to LUP
- 2022-03-07 14:20:42
- date last changed
- 2022-03-15 03:38:46
@article{c5c5b80c-19a8-4a2f-a9af-b91ee993f5ed, abstract = {{<p>Scanned-energy mode photoelectron diffraction (PhD) and ab initio density functional theory calculations have been employed to investigate the adsorption geometry of benzoate ([C<sub>6</sub>H<sub>5</sub>COO]<sup>-</sup>) on rutile-TiO<sub>2</sub>(110)(1 × 1). PhD data indicate that the benzoate moiety binds to the surface through both of its oxygen atoms to two adjacent fivefold surface titanium atoms in an essentially upright geometry. Moreover, its phenyl (C<sub>6</sub>H<sub>5</sub>-) and carboxylate ([-COO]<sup>-</sup>) groups are determined to be coplanar, being aligned along the [001] azimuth. This experimental result is consistent with the benzoate geometry emerging from DFT calculations conducted for laterally rather well-separated adsorbates. At shorter interadsorbate distances, the theoretical modeling predicts a more tilted and twisted adsorption geometry, where the phenyl and carboxylate groups are no longer coplanar; i.e., interadsorbate interactions influence the configuration of adsorbed benzoate.</p>}}, author = {{Busayaporn, W. and Duncan, D. A. and Allegretti, Francesco and Wander, A. and Bech, M. and Møller, P. J. and Doyle, B. P. and Harrison, N. M. and Thornton, Geoff and Lindsay, Robert}}, issn = {{1932-7447}}, language = {{eng}}, month = {{07}}, number = {{27}}, pages = {{14690--14698}}, publisher = {{The American Chemical Society (ACS)}}, series = {{Journal of Physical Chemistry C}}, title = {{Structure of a model dye/titania interface : Geometry of benzoate on rutile-TiO<sub>2</sub> (110)(1 × 1)}}, url = {{http://dx.doi.org/10.1021/acs.jpcc.6b03991}}, doi = {{10.1021/acs.jpcc.6b03991}}, volume = {{120}}, year = {{2016}}, }