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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/23266

Title: Binding modes of phosphonic acid derivatives adsorbed on TiO2 surfaces: Assignments of experimental IR and NMR spectra based on DFT/PBC calculations
Authors: Geldof, Davy
Tassi, Marco
Carleer, Robert
Adriaensens, Peter
Roevens, A.
Meynen, V.
Blockhuys, F.
Issue Date: 2017
Publisher: ELSEVIER SCIENCE BV
Citation: SURFACE SCIENCE, 655, p. 31-38
Abstract: A DFT study on the adsorption of a series of phosphonic acids (PAs) on the TiO2 anatase (101) and (001) surfaces was performed. The adsorption energies and geometries of the most stable binding modes were compared to literature data and the effect of the inclusion of dispersion forces in the energy calculations was gauged. As the (101) surface is the most exposed surface of TiO2 anatase, the calculated chemical shifts and vibrational frequencies of PM adsorbed on this surface were compared to experimental 31P and 170 NMR and IR data in order to assign the two possible binding modes (mono- and bidentate) to peaks and bands in these spectra; due to the corrugated nature of anatase (101) tridentate binding is not possible on this surface. Analysis of the calculated and experimental 31P chemical shifts indicates that both monodentate and bidentate binding modes are present. For the reactive (001) surface, the results of the calculations indicate that both bi- and tridentate binding modes result in stable systems. Due to the particular sensitivity of 170 chemical shifts to hydrogen bonding and solvent effects, the model used is insufficient to assign these spectra at present. Comparison of calculated and experimental IR spectra leads to the conclusion that IR spectroscopy is not suitable for the characterization of the different binding modes of the adsorption complexes.
Notes: [Geldof, D.; Blockhuys, F.] Univ Antwerp, Dept Chem, Groenenborgerlaan 171, B-2020 Antwerp, Belgium. [Geldof, D.; Tassi, M.; Carleer, R.; Adriaensens, P.] Univ Hasselt, Appl & Analyt Chem, Agoralaan, B-3590 Diepenbeek, Belgium. [Roevens, A.; Meynen, V.] Univ Antwerp, Dept Chem, Univ Pl 1, B-2610 Antwerp, Belgium.
URI: http://hdl.handle.net/1942/23266
DOI: 10.1016/j.susc.2016.09.001
ISI #: 000390496900006
ISSN: 0039-6028
Category: A1
Type: Journal Contribution
Appears in Collections: Research publications

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