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ABSTRACT
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REFERENCES
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EXAMPLE
TiO2 NANOPARTICLES WITH CONTROLLED SHAPE
AND TiO2 P25: ELUCIDATION OD THE STRUCTURE OF SURFACE CATIONS
Chiara Deiana,a,b Marco Minella,a Gloria Tabacchi,b Valter Maurino,a Ettore Fois,b Salvatore
Coluccia,a and Gianmario Martra,a (chiara.deiana@unito.it)
a)Department of Chemistry, University of Torino, Via P. Giuria 7, 10125, Torino, Italy.
b)Department of Science and High Technology, University of Insubria, Via Lucini 3, 22100 Como,
Italy.
ABSTRACT
TiO2 photocatalytic behavior is affected to a large extent by surface structure and interactions with
adsorbed molecules on TiO2 nanoparticles [1-3] Spectroscopic methods are very effective tools for
unraveling structure and reactivity of surface sites of oxides. In particular, the possibility to attain a
comparison at a “molecular resolution” level between the surface features of nanoparticles with well
shaped or irregular surfaces is offered by the IR spectroscopic studies of adsorbed probe molecules
exhibiting vibrational features sensitive to the nature and structure of adsorbing sites. As well known, this
is the case of the frequency of the internal stretching mode of adsorbed CO, that can be used to probe a
broad variety of systems, from single crystals to finely divided powders.[4,5] Now, integrated studies of CO
on truncated bipyramidal TiO2 anatase nanoparticles mainly enclosed by (101) and (001) type facets,
provide the missing link between TiO2 single crystals and commercial TiO2 nanopowders with complex
morphology.[3] On such a basis, well-shaped titania nanoparticles were prepared in selected hydrothermal
conditions (hereafter referred to as TiO2 HT). The synergy among high resolution transmission electron
microscopy, IR spectroscopy and modeling correlates
adsorbed CO stretching frequency to anatase surface
type and elucidates key aspects of the reactivity of
TiO2 P25, one of the most adopted titania
photocatalysts.
Comparison of the two TiO2 nanoparticle types
highlights the role of low coordination Ti4+ sites
selectively present on TiO2 P25 in the photocatalytic
decomposition of H2O2, an important Reactive Oxygen
Species (ROS) formed in photocatalytic processes.[6]
Such a powerful multi-disciplinary approach provided
a significant advance in the understanding of the
interactions of molecules at TiO2 surfaces, which
allowed to correlate observed properties with Figure1. Infrared spectra of CO adsorbed on TiO2
HT. Top inset right: 3D model of TiO2 HT
specific structural features of the nanoparticles.
nanoparticles. Bottom inset: model of CO
adsorbed on TiO2 anatase (101) slab.
REFERENCES
[1] Gong, X. Q.; Selloni, A. J. Catal. 2007, 249, 134-139.
[2] Augugliaro, V.; Coluccia, S.; Garcia-Lopez, E.; Loddo, V.; Marci, G.; Martra, G.; Palmisano, L.; Schiavello,
M. Top. Catal. 2005, 35, 237-244.
[3] D'Arienzo, M.; Carbajo, J.; Bahamonde, A.; Crippa, M.; Polizzi, S.; Scotti, R.; Wahba, L.; Morazzoni, F. J.
Am. Chem. Soc. 2011, 133, 17652-17661.
[4] Hadjiivanov, K. I.; Vayssilov, G. N. Adv. Catal. 2002, 47, 307-511.
[5] Spoto, G.; Gribov, E.; Damin, A.; Ricchiardi, G.; Zecchina, A. Surf. Sci. 2003, 540, L605-L610.
[6] Maurino, V.; Minero, C.; Mariella, G.; Pelizzetti, E. Chem. Commun. 2005, 2627-2629.