Effects of Surface Hydrophobicity on Catalytic Transfer Hydrogenation of Styrene with Formic Acid in a Biphasic Mixture.

Transfer hydrogenation (TH) of unsaturated hydrocarbons with formic acid (FA) is an attractive processing pathway for the reduction of lignocellulosic pyrolysis oils. The low solubility of hydrophobic bio-oil species in water and FA in oil necessitates the use of a biphasic system as the reaction environment. Here, we report the effects of Pd/silica catalyst surface wettability on the TH reaction rate. Modification of the surface with short chain (C1-C4) alkyl silanes resulted in an increase in the reaction rate as compared to the unmodified catalyst. In contrast, modification of the surface with sulfonate (hydrophilic) and C18 alkyl silanes (hydrophobic) resulted in a decrease in the reaction rate as compared to the unmodified catalyst. The results are discussed in terms of the catalyst interfacial activity and relative affinity of the reagents to the Pd active sites. An observed change in the apparent reaction order in styrene for a hydrophilic catalyst suggests that changing catalyst surface wettability from hydrophilic to hydrophobic resulted in a switch from a transport-limited to a kinetic-limited reaction regime.