Advanced

Adsorption of Bi-Isonicotinic Acid on Rutile TiO2 (110)

Patthey, L.; Rensmo, H.; Persson, Petter LU ; Westermark, K.; Vayssieres, L.; Stashans, A.; Petersson, A.; Bruhwiler, P. A.; Siegbahn, H. and Lunell, S., et al. (1999) In Journal of Chemical Physics 110(12). p.5913-5918
Abstract
Bi-isonicotinic acid ~2,28-bipyridine–4,48-dicarboxylic acid! is the ligand of several organometallic

dyes, used in photoelectrochemical applications. Therefore the atomic scale understanding of the

bonding of this molecule to rutile TiO2(110) should give insight into the crucial dye–surface

interaction. High resolution x-ray photoelectron spectroscopy ~XPS!, near edge x-ray absorption

fine structure ~NEXAFS!, and periodic intermediate neglect of differential overlap ~INDO!

calculations were carried out on submonolayer bi-isonicotinic acid rutile TiO2(110). Data from

multilayers is also presented to support the submonolayer results. For a multilayer, XPS shows that

the carboxyl... (More)
Bi-isonicotinic acid ~2,28-bipyridine–4,48-dicarboxylic acid! is the ligand of several organometallic

dyes, used in photoelectrochemical applications. Therefore the atomic scale understanding of the

bonding of this molecule to rutile TiO2(110) should give insight into the crucial dye–surface

interaction. High resolution x-ray photoelectron spectroscopy ~XPS!, near edge x-ray absorption

fine structure ~NEXAFS!, and periodic intermediate neglect of differential overlap ~INDO!

calculations were carried out on submonolayer bi-isonicotinic acid rutile TiO2(110). Data from

multilayers is also presented to support the submonolayer results. For a multilayer, XPS shows that

the carboxyl groups remain in the ~pristine! protonated form, and NEXAFS show that the molecular

plane is tilted by 57° with respect to the surface normal. For the submonolayer, the molecule bonds

to the rutile TiO2(110) surface via both deprotonated carboxyl groups, with a tilt angle of 25°, and

additionally an azimuthal orientation of 44° with respect to the @001# crystallographic direction. The

adsorbant system was also investigated by quantum mechanical calculations using a periodic INDO

model. The most stable theoretical adsorption geometry involves a twist around the molecular axis,

such that the pyridine rings are tilted in opposite directions. Both oxygen atoms of each carboxyl

group are bonded to five-fold coordinated Ti atoms ~2M-bidentate!, in excellent agreement with the

experimental results. (Less)
Please use this url to cite or link to this publication:
author
, et al. (More)
(Less)
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
110
issue
12
pages
5913 - 5918
publisher
American Institute of Physics
external identifiers
  • scopus:0000287782
ISSN
0021-9606
DOI
10.1063/1.478491
language
English
LU publication?
no
id
6babeeef-d4ec-4006-afe9-9b173d74a888 (old id 1457938)
date added to LUP
2009-08-27 14:53:22
date last changed
2017-08-13 03:48:18
@article{6babeeef-d4ec-4006-afe9-9b173d74a888,
  abstract     = {Bi-isonicotinic acid ~2,28-bipyridine–4,48-dicarboxylic acid! is the ligand of several organometallic<br/><br>
dyes, used in photoelectrochemical applications. Therefore the atomic scale understanding of the<br/><br>
bonding of this molecule to rutile TiO2(110) should give insight into the crucial dye–surface<br/><br>
interaction. High resolution x-ray photoelectron spectroscopy ~XPS!, near edge x-ray absorption<br/><br>
fine structure ~NEXAFS!, and periodic intermediate neglect of differential overlap ~INDO!<br/><br>
calculations were carried out on submonolayer bi-isonicotinic acid rutile TiO2(110). Data from<br/><br>
multilayers is also presented to support the submonolayer results. For a multilayer, XPS shows that<br/><br>
the carboxyl groups remain in the ~pristine! protonated form, and NEXAFS show that the molecular<br/><br>
plane is tilted by 57° with respect to the surface normal. For the submonolayer, the molecule bonds<br/><br>
to the rutile TiO2(110) surface via both deprotonated carboxyl groups, with a tilt angle of 25°, and<br/><br>
additionally an azimuthal orientation of 44° with respect to the @001# crystallographic direction. The<br/><br>
adsorbant system was also investigated by quantum mechanical calculations using a periodic INDO<br/><br>
model. The most stable theoretical adsorption geometry involves a twist around the molecular axis,<br/><br>
such that the pyridine rings are tilted in opposite directions. Both oxygen atoms of each carboxyl<br/><br>
group are bonded to five-fold coordinated Ti atoms ~2M-bidentate!, in excellent agreement with the<br/><br>
experimental results.},
  author       = {Patthey, L. and Rensmo, H. and Persson, Petter and Westermark, K. and Vayssieres, L. and Stashans, A. and Petersson, A. and Bruhwiler, P. A. and Siegbahn, H. and Lunell, S. and Mårtensson, N.},
  issn         = {0021-9606},
  language     = {eng},
  number       = {12},
  pages        = {5913--5918},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Adsorption of Bi-Isonicotinic Acid on Rutile TiO2 (110)},
  url          = {http://dx.doi.org/10.1063/1.478491},
  volume       = {110},
  year         = {1999},
}