Silylation of Pd/SiO2 catalysts increases the selectivity toward alcohols in the reduction of aromatic ketones. This work demonstrates that the selectivity is directly related to the adsorption strength of the alcohol on the surface of the support relative to the adsorption strength of the ketone. This observation can be explained by interaction of the support coverage with the metal coverage. Silylation yields a more hydrophobic support, on which the aromatic alcohol adsorbs more weakly relative to the ketone, in turn decreasing the amount of the alcohol adsorbed on the metal and thus suppressing the consecutive reduction of the alcohol. Silylation was carried out by using di-alkyl (dichlorodimethylsilane) and trialkyl (hexamethyldisilazane and hexamethyldisi lane) silylating agents. Hexamethyldisilazarte provided to be the most effective agent in terms of incorporation of methyl groups, catalyst hydrophobicity, and stability. Selective hydrogenation of 4-isobutyl acetophenone (4-IBAP) to 4-isobutylphenyl ethanol (4IBPE) revealed that not only was the fresh hexamethyldisilazane-silylated Pd/SiO2 catalyst more selective than the untreated catalyst, but also the silylated catalyst was much more selective after a deactivationregeneration cycle than the untreated Pd/SiO2 catalyst. The change in selectivity can be explained by a change in the relative adsorption strength of 4-IBPE over 4-IBAP on silylation. (c) 2008 Elsevier Inc. All rights reserved.