Acid and basic sites on monoclinic and tetragonal zirconia were investigated at the DFT level by computing IR and NMR properties of adsorbed probe molecules. Regular and stepped ZrO2 surfaces as well as stoichiometric zirconia nanoparticles have been considered. Acidity and basicity were probed by the adsorption of carbon monoxide and pyrrole, respectively. CO adsorption shows a positive shift of the C–O stretching frequency in IR spectra while the C atom of CO is shielded and 13C chemical shifts moves to higher field as a function of the strength of the acid site. For the study of basic sites we used a pyrrole molecule, but the interaction between the pyrrole ring and the surface leads to adsorption modes that cannot be used to titrate the surface basicity. On the other hand, at high coverage the molecule assumes an upright position and the formation of a hydrogen bond of the pyrrole NH group with the oxygen atoms of the surfaces provides a proxy of the basic properties of these sites. In particular, we focus on changes of the N–H IR frequency, 1H, 15N, and 17O NMR chemical shifts and their correlations with the surface basicity. Among the correlations found, that between the N–H stretching frequency of adsorbed pyrrole and the 17O NMR chemical shift of the O ion where the molecule is bound show a nice linear correlation. These two properties can provide useful information about the basic character of various O sites on the surface of zirconia. Graphic Abstract: [Figure not available: see fulltext.]

Maleki, F., Pacchioni, G. (2020). Characterization of Acid and Basic Sites on Zirconia Surfaces and Nanoparticles by Adsorbed Probe Molecules: A Theoretical Study. TOPICS IN CATALYSIS, 63(19-20), 1717-1730 [10.1007/s11244-020-01328-6].

Characterization of Acid and Basic Sites on Zirconia Surfaces and Nanoparticles by Adsorbed Probe Molecules: A Theoretical Study

Maleki F.;Pacchioni G.
2020

Abstract

Acid and basic sites on monoclinic and tetragonal zirconia were investigated at the DFT level by computing IR and NMR properties of adsorbed probe molecules. Regular and stepped ZrO2 surfaces as well as stoichiometric zirconia nanoparticles have been considered. Acidity and basicity were probed by the adsorption of carbon monoxide and pyrrole, respectively. CO adsorption shows a positive shift of the C–O stretching frequency in IR spectra while the C atom of CO is shielded and 13C chemical shifts moves to higher field as a function of the strength of the acid site. For the study of basic sites we used a pyrrole molecule, but the interaction between the pyrrole ring and the surface leads to adsorption modes that cannot be used to titrate the surface basicity. On the other hand, at high coverage the molecule assumes an upright position and the formation of a hydrogen bond of the pyrrole NH group with the oxygen atoms of the surfaces provides a proxy of the basic properties of these sites. In particular, we focus on changes of the N–H IR frequency, 1H, 15N, and 17O NMR chemical shifts and their correlations with the surface basicity. Among the correlations found, that between the N–H stretching frequency of adsorbed pyrrole and the 17O NMR chemical shift of the O ion where the molecule is bound show a nice linear correlation. These two properties can provide useful information about the basic character of various O sites on the surface of zirconia. Graphic Abstract: [Figure not available: see fulltext.]
Articolo in rivista - Articolo scientifico
Acid–base properties; CO and pyrrole adsorption; Density functional theory; Monoclinic and tetragonal zirconia; Oxide surfaces;
English
22-lug-2020
2020
63
19-20
1717
1730
none
Maleki, F., Pacchioni, G. (2020). Characterization of Acid and Basic Sites on Zirconia Surfaces and Nanoparticles by Adsorbed Probe Molecules: A Theoretical Study. TOPICS IN CATALYSIS, 63(19-20), 1717-1730 [10.1007/s11244-020-01328-6].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/321525
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