The interaction of the (110) and (111) surfaces of ceria (CeO(2)) with atomic hydrogen is studied with ab initio calculations based on density functional theory. A Hubbard U term added to the standard density functional allows to accurately describe the electronic structure of the two surfaces. The minimum energy configuration for the adsorbed H on each of the two surfaces is obtained. An O-H-O bridge is formed on the (110) surface, whereas an axial tricoordinated OH group results on the (111) surface. For both surfaces, the adsorption of an H atom is accompanied by the reduction of a single Ce ion (which is one of the nearest neighbors of the adsorbed atom) and by a substantial outward protrusion of the O atom(s) directly bound to H. The adsorption of atomic H on the (110) and (111) surfaces is energetically favored by -150.8 and -128.3 kJ/mol, respectively, with respect to free molecular H(2). The calculated frequencies for the OH stretching vibrational mode are 3100 cm(-1) for the (110) surface and 3627 cm(-1) for the (111) surface. The latter value is in excellent agreement with experimental data reported in the literature.

Interaction of hydrogen with cerium oxide surfaces: a quantum mechanical computational study / Vicaro, G.; Balducci, G.; Fabris, S.; de Gironcoli, S.; Baroni, S.. - In: JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL. - ISSN 1520-6106. - 110:39(2006), pp. 19380-19385. [10.1021/jp061375v]

Interaction of hydrogen with cerium oxide surfaces: a quantum mechanical computational study

Fabris, S.;de Gironcoli, S.;Baroni, S.
2006-01-01

Abstract

The interaction of the (110) and (111) surfaces of ceria (CeO(2)) with atomic hydrogen is studied with ab initio calculations based on density functional theory. A Hubbard U term added to the standard density functional allows to accurately describe the electronic structure of the two surfaces. The minimum energy configuration for the adsorbed H on each of the two surfaces is obtained. An O-H-O bridge is formed on the (110) surface, whereas an axial tricoordinated OH group results on the (111) surface. For both surfaces, the adsorption of an H atom is accompanied by the reduction of a single Ce ion (which is one of the nearest neighbors of the adsorbed atom) and by a substantial outward protrusion of the O atom(s) directly bound to H. The adsorption of atomic H on the (110) and (111) surfaces is energetically favored by -150.8 and -128.3 kJ/mol, respectively, with respect to free molecular H(2). The calculated frequencies for the OH stretching vibrational mode are 3100 cm(-1) for the (110) surface and 3627 cm(-1) for the (111) surface. The latter value is in excellent agreement with experimental data reported in the literature.
2006
110
39
19380
19385
Vicaro, G.; Balducci, G.; Fabris, S.; de Gironcoli, S.; Baroni, S.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.11767/16361
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