Phosphonic acid modifiers for enhancing selective hydrodeoxygenation over Pt catalysts: The role of the catalyst support.

• Phosphonic acids were deposited onto four different platinum catalyst supports. • Deposited modifiers provide Brønsted acid sites, creating an acid-metal catalyst. • The strength of Brønsted acid sites is dependent on the modifier tail functionality. • On supports with weak or no Brønsted acidity, modifiers enhance deoxygenation. • On strongly acidic supports, modification leads to a loss of deoxygenation activity. Bifunctional catalysts comprised of both noble metal and Brønsted acid sites are of growing interest for many reactions, such as the hydrodeoxygenation (HDO) of oxygenates produced by the deconstruction of lignocellulosic biomass. One method of preparing a bifunctional metal-acid catalyst is to modify the supporting material of a metal catalyst with acid-containing ligands, such as phosphonic acids (PAs), which provide tunable Brønsted acid sites at the metal-support interface. Here, we explore the potential for PA modification to improve HDO rates on Al 2 O 3 , TiO 2 , CeO 2 , and SiO 2 -Al 2 O 3 supports. PAs containing either alkyl or carboxylic acid (CA) tails were used to modify Pt catalysts on each support. PA modification improved HDO rates for the model compound benzyl alcohol when applied to Pt supported by Al 2 O 3 , TiO 2 , and CeO 2 , but had a negative effect on the HDO rate of Pt/SiO 2 -Al 2 O 3. Measurements of the relative strength of Brønsted acid sites present on the modified and unmodified catalysts suggested that PAs improved HDO when they provided new or stronger Brønsted acid sites. Additionally, the strength of the Brønsted acid sites provided by PA modifiers were tunable by altering the tail functionality, which affected the rates of HDO. These results suggest that PAs can be used to modify a variety of supports to prepare bifunctional acid-metal catalysts. [ABSTRACT FROM AUTHOR]