Synergistic Effects In Reactions of Functionalized Alcohols On Pd(111)

The surface chemistry of multifunctional oxygenates, such as unsaturated alcohols, is of interest due to the prevalence of these compounds as intermediates in the transformation of biomass to fine chemicals and fuels. This contribution focuses on recent experimental and computational studies of highly functional oxygenates such as furfuryl alcohol and furfural – furanic compounds that can readily be derived from biomass – on Pd(111). It is observed that the surface chemistry of these compounds cannot be understood by the reactivity of the individual functional groups alone. Rather, there is a synergistic effect that allows these molecules to undergo deoxygenation in addition to decarbonylation. Theoretical studies were conducted to investigate the complete decomposition mechanism for furfural and furfuryl alcohol, and to relate this chemistry to that of similar probe molecules such as 1-propanol and allyl alcohol.  Related investigations of the chemistry of polyols and halogenated alcohols point to a complex synergy between alcohols and additional functional groups in reactions on surfaces.