Destabilizing Effects of Thiols on Bonding to a Noble Metal: The Effects of Methanethiolate on the Bonding of Aldehydes and Alcohols on Cu(111)

作者：Mulligan A; Kadodwala M^*

来源：Journal of Physical Chemistry C, 2010, 114(49): 21457-21464.

DOI：10.1021/jp106522f

We demonstrate that the presence of coadsorbed methanethiolate (CH3S-) 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 CH3S- 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.

• 出版日期2010-12-16