Glycerol selective oxidation to lactic acid over AuPt nanoparticles; Enhancing reaction selectivity and understanding by support modification

2 Schemes, 3 Tables, 5 Figures.
A high surface area mesoporous TiO2 material (110 m2/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/TiO2 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 TiO2−P25, TiO2‐anatase and TiO2‐rutile. Higher rates of reaction and higher selectivity to lactic acid were observed over nanocast TiO2 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 TiO2 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 TiO2 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.
T. García would like to acknowledge the Spanish MICINN through its Mobility program for stays of senior researchers and professors in foreign countries (grant number PRX18/00474) for funding. O.S.P acknowledges the FPI fellowship (BES-2016-077750) funded by Spanish MINECO. B.S. also thank MINECO (MAT2017-84118-C2-1-R project) for funding. We would also like to thank the Cardiff University TEM facility for the TEM and FEG-SEM electron microscopy data acquired and Diamond Light Source for access and support in use of the electron Physical Science Imaging Centre (Instrument E01 and proposal number MG21641 and MG22766) which contributed to the results presented here.