Preparation Of Organic Phosphonic Acid (phosphorus) Zirconium And Its Intercalation Behavior

In this Thesis, two different methods to prepare layered zirconium phosphate/ phosphonate compounds are reported. These compounds are subsequently intercalated with amines and Rh (III) ions.Initially, new types of layered zirconium compounds containing the N-(phosphonomethyl) iminodiacetic acid group (PMIDA) were synthesized using aqueous ammonium hydroxide as solvent. The structures of the resulting layered compounds varied with the ratio of phosphoric acid to PMIDA in the reaction mixture. Sample I was obtained when a mixture of phosphoric acid and PMIDA in the ratio of 1:1 was heated with zirconyl chloride in the presence of HF. Its composition was found to beThe arrangement of metal atoms and bridging phosphate groups within the layer is similar to that found in y-ZrP, while the coordination mode of the phosphonate groups within the layer is similar to that found in ot-ZrP. When the above reaction was carried out with a phosphoric acid to PMIDA ratio of 2, a related layered structure having the composition(sample II) was obtained. When the ratio of phosphoric acid to PMIDA was 4 or 8, new phases with composition Zr(PO3C5H8O4N)x(HPO4)2-x ( samples and respectively) were obtained. These phases are staictually similar to ct-ZrP. The effects of varying the ratio of [HF] to [Zr], the pH of the phosphonate solution as well as the reaction temperature were also studied. The layered structures of the new products are stable below 300 癈.Furthermore, a new method has been suggested to prepare layered zirconium compounds containing the N-(phosphonomethyl) iminodiacetic acid group (PMIDA) using distilled water as solvent. This method is better than that using ammonium hydroxide in many respects. For example it can simplify the reaction procedures and it is easier to purify the products in the absence of ammonium ions.Primary alkylamines, CnH2X-1NH2(X=4,7,12,18), have been intercalated into thezirconium phosphate/phosphonate materials. XRD, IR, TG and DTA data suggest that in the resulting compounds the amines appear to-pack as double layers.Rh 3+ was loaded on the zirconium phosphate/phosphonate in order to prepare some novel the intercalation compounds. The structures and composition of the products were studied by XRD, ICP and XPS. A structural model has been proposed.