Industrial & Engineering Chemistry Research, Vol.52, No.44, 15481-15487, 2013
Synthesis and Dehydration Activity of Novel Lewis Acidic Ordered Mesoporous Silicate: Zr-KIT-6
A zirconium-incorporated Ia3d cubic three-dimensional (3-D) mesoporous silicate, KIT-6, with different zirconium loadings, was synthesized via a one-step direct hydrothermal synthesis procedure employing Pluronic P123 triblock copolymer as the structure-directing agent under acidic conditions. Various characterization techniques, such as two-dimensional (2-D) small-angle X-ray scattering (SAXS), nitrogen sorption, temperature-programmed desorption of ammonia (NH3-TPD), and ultraviolet visible-light (UV-Vis) spectra, showed that zirconium was incorporated as Zr4+ ions in the KIT-6 framework, which retained the structural integrity with a highly ordered pore structure. The Zr-KIT-6 materials exhibit very high surface areas (810-980 m(2)/g) and large pore volumes (1.07-1.65 cm(3)/g) that decrease with an increase in zirconium content. In contrast, the pore size distribution remains relatively unaffected by zirconium loading with an average pore diameter of similar to 9.3 The Zr-KIT-6 materials possess Lewis acidity that increases with zirconium loading. In the 180-300 degrees C range, the Zr-KIT-6 materials are shown to be highly active for the test reaction of isopropanol (IPA) dehydration to propylene (selectivity >98%). The activation energy for IPA dehydration, estimated from intrinsic rate constants normalized with respect to the Lewis acid sites, was similar to 49 +/- 1 kJ/mol and found to be lower than most other Bronsted or Lewis acidic heterogeneous catalysts reported in the literature for IPA dehydration. Furthermore, these catalysts showed nearly stable activity with very little deactivation during extended runs at 260 and 300 degrees C.