Control of interfacial acid–metal catalysis with organic monolayers

Numerous important reactions consisting of combinations of steps (for example, hydrogenation and dehydration) have been found to require bifunctional catalysts with both a late-transition metal component and an acidic component. Here, we develop a method for preparing and controlling bifunctional sites by employing organic acid-functionalized monolayer films tethered to the support as an alternative to traditional ligand-on-metal strategies. This approach was used to create a reactive interface between the phosphonic acid monolayers and metal particles, where active-site properties such as acid strength were manipulated via tuning of the molecular structure of the organic ligands within the monolayer. After surface modification, the resultant catalysts exhibited markedly improved selectivity and activity towards hydrodeoxygenation of aromatic alcohols and phenolics. Moreover, by tuning the ligand of the acidic modifier, the rate of deactivation was significantly reduced. Bifunctional heterogeneous catalysts are usually prepared by dispersion of a metal on an acidic or basic support. Now a method has been developed to post-functionalize a catalyst and introduce tunable acidity by coating an organic acid layer on the support, resulting in improved performance as showcased for selected hydrodeoxygenation reactions.