Hartnig, Christoph; Grimminger, J.; Spohr, Eckhard:
The role of water in the initial steps of methanol oxidation on Pt(211)
In: Electrochimica Acta, Jg. 52 (2007), Heft 6, S. 2236 - 2243
2007Artikel/Aufsatz in Zeitschrift
ChemieFakultät für Chemie
Damit verbunden: 1 Publikation(en)
Titel:
The role of water in the initial steps of methanol oxidation on Pt(211)
Autor*in:
Hartnig, Christoph;Grimminger, J.;Spohr, EckhardUDE
GND
143257005
LSF ID
49123
ORCID
0000-0001-8148-7575ORCID iD
Sonstiges
der Hochschule zugeordnete*r Autor*in
Erscheinungsjahr:
2007

Abstract:

We report results of quantum-chemical calculations within the framework of density functional theory for the oxidation of methanol on the (2 1 1) face of a platinum single crystal. Similar to the reaction pathway on the low indexed (1 1 1) crystal face water plays an important role as found from energy minimization calculations: the adsorption of methanol on charged and uncharged surfaces is strongly enhanced by the formation of a hydrogen bond to a coadsorbed water molecule. The methanol is adsorbed via a methyl hydrogen atom preceding scission of one of the CH-bonds as the first reaction step. In the presence of additional water, e.g., from a liquid phase, the onset of the oxidation reaction is favored by a coadsorbed neighboring water molecule which forms a hydrogen bond with the methanol OH-group. At a minimum number of adjacent water molecules (n≥2) the CH-bond as well as the OH-bond are cleaved on charged surfaces. The protonic charge stemming from the dissociation of the methanol hydroxyl group is delocalized inside the aqueous cluster and formaldehyde is formed as an intermediate product.