The high activity of mesoporous Ga-SiO2 catalysts in the upgrading of glycerol to solketal explained by in-depth characterization

Abstract

Mesoporous Ga-silicates were prepared using a sustainable and continuous aerosol synthesis procedure. The novel solids showed record activity in the synthesis of solketal from glycerol and acetone. Three different Si/Ga ratios of 34, 74 and 148 were investigated and all materials displayed favorable features for catalytic applications such as high surface area and calibrated mesoporosity. An in-depth characterization allowed to elucidate the remarkable catalytic performance. The insertion of Ga predominantly as single site in tetrahedral coordination in the silica framework was highlighted by X-ray photoelectron spectroscopy (XPS), using the Auger parameter of Ga in a Wagner plot representation. The speciation of Ga was further clarified using solid state 71Ga NMR spectroscopy, confirming the formation of mainly isolated Ga species. Consistently, the aerosol-made Ga-silicates displayed outstanding turnover frequencies (up to 677 h−1) and selectivity, markedly outcompeting other reference metallosilicate catalysts reported in literature. Moreover, the most active catalyst was successfully reused in multiple catalytic cycles thus proving its stability under the selected reaction conditions.