Abstract

AbstractThe pillaring process of montmorillonite and beidellite with Al and Ga polymers has been studied using XRD, IR,27Al,71Ga, and29Si MAS NMR, TGA, TEM, N2adsorption and chemical analyses. The Al adsorption maximum for montmorillonite is close to 5.5 mEq Al/g clay, whereas the maximum for Ga is higher. Basal spacings of both Ga- and Al-pillared clays vary between 16.7 and 18.8 Å. Freeze-drying of pillared products followed by calcination yielded more regular pillared structures. Pillaring montmorillonite increased the BET surface area from 35 m2/g to 350 m2/g mainly by the creation of micropores <20 Å in diameter. The Al-pillared clays are thermally stable to ∼700°C. Calcination of pillared montmorillonite liberates protons from the pillar, which diffuse into the clay sheet, lowering the thermal stability. In pillared beidellite, mainly silanol groups are formed by breaking Si-O-Al bonds. No reaction is observed between pillars and montmorillonite upon calcination, whereas in pillared beidellite a structural transformation links the pillar to inverted tetrahedra of the tetrahedral sheet. The basal spacing of Ga-pillared montmorillonite collapses to 9.5 Å at 350°C due to the Ga polymer decomposing to Ga3+cations.

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