PMo or PW heteropoly acids supported on MCM-41 silica nanoparticles: Characterisation and FT-IR study of the adsorption of 2-butanol

Mesoporous silica, prepared in basic conditions, has been loaded (20% weight) with 12-molybdophosphoric (PMo) or 12-tungstophosphoric (PW) acid and calcined at different temperatures ranging between 250 and 550 deg. C. The samples have been characterised by N2 adsorption-desorption at -196 deg. C, transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), UV-visible diffuse reflectance, Raman spectroscopy and temperature programmed reduction (TPR). The acidity and catalytic activity have been, respectively, examined by monitoring the adsorption of pyridine and 2-butanol by FT-IR spectroscopy. The results indicate that PW and PMo acids are highly dispersed on mesoporous silica MCM-41 spherical nanoparticles. While PMo retains its Keggin structure up to 550 deg. C, PW decomposes at this temperature into crystalline WO3 and phosphorous oxides. In both cases, the morphology, hexagonal symmetry and long-range order observed for the support are preserved with calcination up to 450 deg. C. The Broensted-type acid sites found in all samples, whose surface concentration decreases as the calcination temperature increases, are responsible for the selective formation of cis-butene detected upon adsorption of 2-butanol. The sample containing PW calcined at 450 deg. C also shows selectivity to methyl ethyl ketone. - Graphical abstract: Samples based in MCM-41 nanoparticles loaded with tungstophosphoric and molybdophosphoric acids have been synthesised. The uncalcined solids and that derived upon their calcination in the temperature range 250-550 deg. C have been characterised and evaluated in the decomposition of 2-butanol monitored by FT-IR spectroscopy