(1) Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600 036, India
Abstract:
Ce3+ containing Al- and Zr-pillared clays were prepared by co-hydrolysis and co-intercalation methods, respectively. The materials were characterized by XRD, IR and near IR techniques. The expansion in the clay lattice as a result of pillaring was confirmed from X-ray diffraction study. The basal spacing for the pillared clay materials was observed typically in the range of 18–23 Å. The IR and near IR studies were employed to show the presence of acidic and non-acidic hydroxyl groups in the pillared clays. The IR peak at 3630 cm−1 corresponding to the structural hydroxyl groups was more intense in pillared clays than in the parent clay. This peak is retained even after calcination at 500∘C. Various overtone and combination bands were observed in the NIR range of 1200–2500 nm for the pillared clay materials. Pillaring with Al- and Zr-inorganic polycations enhanced the catalytic activity of the parent clays for dehydration of cyclohexanol. The presence of Ce3+ ions in the pillared clays was found to influence catalytic activity and stability of the Brønsted acidic sites. The stabilizing effect of cerium ion in the pillared clays is attributed to the competitive site occupancy and prevention of octahedral migration of the catalytically active protons.