Mechanism of the formation of organic derivatives of gamma-zirconium phosphate by topotactic reactions with phosphonic acids in water and water-acetone media

The rates of the topotactic reactions between gamma-zirconium phosphate and phenylphosphonic acid in water and water-acetone mixtures at various temperatures were investigated. The slow sates of the process in aqueous medium or in water-acetone mixtures at temperatures lower than 50 degrees C were attributed to a slow interdiffusion of O2P(OH)(2)(-) and O2P(OH)(C6H5)(-) groups in the interlayer region of gamma-ZrP. Similar to ion-exchange processes, the replacement begins in the external part, of the interlayer region and progresses toward the central region with the formation of an advancing phase boundary. In water-acetone mixtures at temperatures higher than 60 degrees C an exfoliation of gamma-ZrP was found. Thus, the initial process is very fast since the substitution can take place directly on the surface of the exfoliated gamma-lamellae, However, after a certain degree of substitution, a flocculation of the colloidal dispersion, which slows down the rate of the further topotactic substitution, was observed. Some considerations on the topotactic substitution occurring on the surface of the exfoliated lamellae and on the mechanism of the diffusion of the exchanging species in the interlayer region are also reported.