Effect of small amounts of Al on the surface silanol structure and their correlation to the improved catalytic performances of WOx/SiO2–Al2O3 in the propene self-metathesis

Surface silanol structures, acid properties, and tungsten dispersion of the sol-gel-derived 7W/SiO2–xAl2O3 (x = 0.2–23 wt%) were investigated by means of 29Si, 27Al, and 1H MAS NMR, NH3-TPD, in-situ NH3-IR spectroscopy, XRD, and Raman spectroscopy. The surface silanol structure changed upon Al and tungsten loadings; however, loading of 1 wt% Al2O3 appeared to be the threshold for preserving the Si(OH)Al with isolated bridge after impregnation of 7 wt% W. The 7W/SiO2–1Al2O3 (1 wt% Al2O3) was also found to exhibit the lowest ratio of Bronsted to Lewis acid with the highest amount of Lewis acid sites and the best catalyst performances in propene self-metathesis at 550 °C in terms of both propene conversion and ethylene/butene selectivity. Despite its low tungsten dispersion, the metathesis activity was correlated well with the higher amount of tungsten carbene species, which were formed on the catalysts containing higher isolated bridge silanol and the presence of higher Lewis acid sites. [Display omitted] •High surface area spherical W/SiO2–Al2O3 catalysts with 0.2–23 wt % Al2O3.•Appropriate Al (1 wt %) led to high amount of Lewis acid with the lowest B/L ratio.•Best performances in propene metathesis at 550 °C were obtained over 7W/SiO2–1Al2O3.•Si(OH)Al with isolated bridge is important for higher tungsten carbine formation.