The influence of the nature and textural properties of different supports on the thermal behavior of Keggin type heteropolyacids

In order to obtain highly dispersed heteropolyacids (HPAs) species, H3PMo12VO40 and H3PVMo11O40 were supported on various supports: silica (Aerosil - Degussa and Romsil types) and TiO2. The structure and thermal decomposition of supported and unsupported HPAs were followed by different techniques (TGA-DTA, FTIR, XRD, low temperature nitrogen adsorption, scanning electron microscopy). All the supported HPAs were prepared by impregnation using the incipient wetness technique with a 1:1 mixture of water–ethanol. Samples were prepared with different concentrations to examine the effect of loading on the thermal behavior of the supported acid catalysts. The thermal stability was evaluated with reference to the bulk solid acids and mechanical mixtures. After deposition on silica types supports, an important decrease in thermal stability was observed on the Romsil types and a small decrease on the Aerosil type. The stability of the heteropolyacids supported on titania increased due to an anion-support interaction, as the thermal decomposition proceeded in two steps. The structure of the HPAs was not totally destroyed at 450 ºC as some IR bands were still preserved. A relatively uniform distribution of HPAs on the support surface was observed for all compositions of the active phase. No separate crystallites of solid phase HPAs were found in the SEM images