Adsorption and Reaction of Furfural and Furfuryl Alcohol on Pd(111): Unique Reaction Pathways for Multifunctional Reagents

Abstract

Surface chemical reactions of highly functional biomass derivatives such as furans with oxygenated ligands are often considered in terms of the chemistry of their individual functional groups, with little focus on how multifunctionality affects surface chemistry. To probe these effects on functionalized furans, temperature-programmed desorption (TPD) experiments and density functional theory (DFT) calculations were used to study the thermal chemistry of furfural, C4H3(CHO)O, and furfuryl alcohol, C4H3(CH2OH)O on Pd(111). The TPD results indicate that furfural undergoes decomposition to produce furan, propylene, carbon monoxide, and hydrogen. Furfuryl alcohol forms the same products but also undergoes an unexpected C–O scission process that yields methylfuran and water. Together with DFT calculations, these results indicate that furfuryl alcohol can decompose through a surface furfural intermediate, similar to the reaction pathway observed for simple alcohols such as ethanol. The additional methylfuran pat...