Applied Catalysis A: General, Vol.370, No.1-2, 16-23, 2009
Characterization of clay intercalated cobalt-salen catalysts for the oxidation of p-cresol
The intercalation of cobalt-salen complexes into the interlamelar spaces of montmorillonite clay was investigated by various characterization studies. The "neat" cobalt-salen complex showed a weight loss at 368 degrees C while the weight loss for the corresponding intercalated complex was observed at much higher temperature of 492 degrees C due to decomposition of the complex. The thermal stabilization observed was due to the host-guest interaction of clay and metal complex and thus confirmed the intercalation. The XANES spectrum of Co(salen)-mont sample revealed the change of symmetry from the tetrahedral in plane to the octahedral structure having an axial bonding of oxygen to the cobalt, indicating that cobalt atoms in Co(salen)-mont were coordinated axially with the lattice oxygen of montmorillonite. Both XANES and EXAFS results indicated that cobalt atoms in Co(salen)-mont form two additional Co-O bonds with a bond length of 0.199 nm by the intercalation while retaining the Co-salen structure. Co-salen intercalated into the montmorillonite clay showed the highest activity for the air oxidation of p-cresol, giving 88% selectivity to the oxidation products. Effects of NaOH concentration and various solvents on the conversion and selectivity patterns also have been studied. (C) 2009 Elsevier B.V. All rights reserved.
Keywords:Intercalation;Cobalt-salen;Montmorillonite;X-ray absorption near edge structure;Extended X-ray absorption fine structure;Cobalt-oxygen bond;Lattice oxygen