Glycerol Selective Oxidation to Lactic Acid over AuPt Nanoparticles; Enhancing Reaction Selectivity and Understanding by Support Modification
Mark Douthwaite, Natasha Powell, Aoife Taylor, Grayson M. Ford, José Manuel López, Benjamín Solsona, Nating Yang, Olga Sanahuja‐Parejo, Qian He, David Morgan, Tomás García, Stuart H. Taylor
Abstract
Abstract A high surface area mesoporous TiO 2 material (110 m 2 /g) was synthesised using a nanocasting methodology, utilizing SBA‐15 as a hard template. This material was subsequently used as a support to prepare a series of 1 wt.% AuPt/TiO 2 catalysts, synthesised by conventional impregnation and sol‐immobilisation. Catalysts were tested for the oxidation of glycerol to lactic acid and their performance was compared with corresponding catalysts supported on TiO 2 −P25, TiO 2 ‐anatase and TiO 2 ‐rutile. Higher rates of reaction and higher selectivity to lactic acid were observed over nanocast TiO 2 supported catalysts. The increased performance of these catalysts was attributed to the presence of Si on the surface of the support, which likely arose from inefficient etching of the SBA‐15 template. The presence of Si in these catalysts was confirmed by X‐ray photoelectron spectroscopy and electron energy loss spectroscopy. It was proposed that the residual Si present increases the Brønsted acidity of the TiO 2 support, which can lead to the formation of Lewis acid sites under reaction conditions; both sites are known to catalyse the dehydration of a primary alcohol in glycerol. Typically, under alkaline conditions, lactic acid is formed by the nucleophilic abstraction of a hydrogen. Thus, we propose that the improved selectivity to lactic acid over the nanocast TiO 2 supported catalyst is attributed to the co‐operation of heterogeneous and homogeneous dehydration reactions, as both compete directly with a direct oxidation pathway, which leads to the formation of oxidation products such as glyceric and tartronic acid.