EPR of VO2+ ions in Al-pillared montmorillonite

Abstract

AbstractA pillared smectite clay has been formed by treating Na-montmorillonite with a hydroxy-aluminium solution with an OH/Al ratio of two. Heating the pillared clay for four h at 500°C reduces the interlayer spacing, measured at ambient humidity, from ∼ 9·4 to 8·0 Å. Hydrated VO2+ (and Mg2+) ions have been introduced into the region between the pillars by immersing the pillared clay in VOSO4-MgCl2 solutions and EPR measurements show that in general both immobile and mobile VO2+ ions are present. The immobile ion is probably VO2+(OH)x(H2O)5·x where x = 2–4, and is adsorbed on the pillars with a concentration that saturates at about 1 per 8 Al13 pillars in the unfired clay, and 1 per 4·3 pillars in the fired clay. The mobile species is VO2+(H2O)5 and for both fired and unfired clay in the wet state at room temperature it has a rotational correlation time of (9 ± 1) × 10−11s rad−1.