Destabilizing effects of thiols on bonding to a noble metal: the effects of methanethiolate on the bonding of aldehydes and alcohols on Cu(111)

Mulligan, A. and Kadodwala, M. (2010) Destabilizing effects of thiols on bonding to a noble metal: the effects of methanethiolate on the bonding of aldehydes and alcohols on Cu(111). Journal of Physical Chemistry C, 114(49), pp. 21457-21464. (doi: 10.1021/jp106522f)

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Abstract

We demonstrate that the presence of coadsorbed methanethiolate (CH(3)S-) dramatically destabilizes the bonding toward Cu(111) of two higher alcohols (butanol and crotyl alcohol) but in contrast has little effect on the strength of interaction of the analogous aldehydes (butanal and crotonaldehyde). This behavior contrasts with the stabilizing effects that coadsorbed sulfur has on the same species. The destabilizing effects of CH(3)S- are rationalized in terms of its ability to influence bonding through the electric fields associated with its surface dipole moment. This study provides evidence for an alternative mechanism by which sulfur containing organic species can improve the selectivity of Cu catalysts toward unsaturated alcohols in the hydrogenation of a, beta-unsaturated aldehydes.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Kadodwala, Professor Malcolm
Authors: Mulligan, A., and Kadodwala, M.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of Physical Chemistry C
Publisher:American Chemical Society
ISSN:1932-7447
Published Online:22 November 2010

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