Intercalation of amines and exchange of transition metal comlexes into the layered structure of zirconium phosphate

Abstract

520-00The intercalation of ten different amines in ??-Zr (HPO4)2*H2O and the exchange of some transition metal complexes into some of the amine intercalates and other forms of zirconium phosphates has been investigated. It has been found that two moles of an n-alkylamine are intercalated per formula weight of ??-ZrP while half as much ethylenediamine is intercalated. X-ray powder diffraction data indicates that the n-alkylamines are arranged as bimolecular layers with their carbon chain backbone roughly inclined at 60?? angle to the plane of the layer. The intercalation behavior of two aromatic amines (aniline and pyridine) has also been investigated. Two moles of aniline are intercalated per formula weight of ??-zirconium bis(monohydrogenorthophosphate)monohydrate while only one mole of pyridine is intercalated. It is suggested that differences in the hybridization on the nitrogen atoms in these two amines cause the observed differences in the amount of amine intercalated. A maximum of one mole of diethylamine is intercalated per formula weight of zirconium phosphate and the crosssectional size of this molecule is offered as the reason for the low uptake. The amine intercalates, [ethiopic]-zirconium phosphate, and the half exchanged sodium form have been shown to be host layer lattices for some transition metal complexes. These guest transition metal complexes have been characterized by X-ray diffraction, diffuse reflectance spectroscopy and by thermal and chemical methods. It is suggested that the exchange of transition metal complexes (that show catalytic behavior in a homogeneous medium) may produce catalysts with altered behavior. It has also been shown that Ni(II) and Cu(II) are exchanged quantitatively with the butylamine intercalate at room temperature and new Ni(II) phase has been identified. Finally it is suggested that the intercalates will have the potential of being used as gas chromatograph supports, industrial ion exchangers, and heterogeneous catalysts when transition metal complexes are exchanged into the layers. A new gel-like phase formed by intercalation of n-propylamine shows the potential of being a inorganic membrane.