(541g) Factors Affecting the Catalytic Activation of the Carboxylate C-O-C Bond

The hydrogenation of carboxylic acids and esters to the corresponding alcohols are industrially important processes and will likely become an integral pathway in biorefineries for the production of valuable chemicals and fuels from biomass feedstock, as carboxylic acids and esters are common components of such feedstock.  Acids, in particular, are more difficult to reduce than other classes of organic oxygenates.  Transition metals can readily decompose acids and esters but offer very limited selectivity for alcohols in vacuum and low pressure experiments.  Recently Olcay et al. have demonstrated that the activity of aqueous-phase hydrogenation (APH) of acetic acid on different metals is mainly controlled by the activity of the initial C-O bond scission step under elevated hydrogen pressure.[1]  In this contribution we explore the effects of several factors, including the metal species, surface structure, and hydrogen-rich environment, on the activity of the initial C-O bond scission step in simple carboxylic acids and esters, using acetic acid and methyl acetate as the representative compounds.

References

1.      Olcay, H., Xu, L., Xu, Y., and Huber, G.W. ChemCatChem 2, 1420 (2010).