Poly(vinylbenzylchloride) (PVBC) nanofibers were fabricated by the electrospinning process. The Merrifield micropheres, silica microsparticles and PVBC nanofibers were functionalised with different quaternary diammonium groups derived from ethylenediamine (EDA), tetramethylenediamine (TMDA), hexamethylenediamine (HMDA), 1,8-diaminooctane (OMDA), 1,10-diaminodecane (DMDA) and 1,12-diaminododecane (DDMDA) and investigated for separation of [RhCl5(H2O)]2- and [IrCl6]2-. The sorbent materials were characterised by means of FTIR, XPS, SEM, BET surface area, thermogravimetric analysis and elemental analysis, and characterization results showed that the functionalization of the sorbent materials was successful. Batch equilibrium studies were carried out to assess the efficiency of these different anion exchangers using single metal aqueous solutions. The adsorption isotherms and kinetics of both [RhCl5(H2O)]2- and [IrCl6]2- adsorption onto the sorbent materials are presented. The isothermal batch adsorption studies fitted the Freundlich model indicating heterogeneous surface adsorption. The Freundlich isotherm confirmed multilayer adsorption and the Freundlich constant (kf) displayed the following ascending order for nanofibers (F-QUAT EDA, F-QUAT TMDA, F-QUAT HMDA, F-QUAT OMDA and F-QUAT DMDA), silica microparticles (Si-QUAT EDA, Si-QUAT TMDA, Si-QUAT HMDA, Si-QUAT OMDA and Si-QUAT DMDA) and microspheres (B-QUAT EDA, B-QUAT TMDA, B-QUAT HMDA, B-QUAT OMDA and B-QUAT DMDA) and a decrease in kf for F-QUAT DDMDA, Si-QUAT DDMDA and B-QUAT DDMDA has been observed. The pseudo second-order model was found to be the best fit to describe the adsorption kinetics of both metal ions complexes onto all the sorbent materials. K2 value in pseudo second-order kinetics showed that the rate constant for adsorption of [IrCl6]2- onto nanofibers was larger than for silica microparticles and Merrifield microspheres. Column sorption of [IrCl6]2- and [RhCl5(H2O)]2- was carried out and the loading capacities of [IrCl6]2- were obtained, and they showed dependence on the length of the methylene spacer between the two diammonium centres. [RhCl5(H2O)]2- was not adsorbed by the sorbent materials while [IrCl6]2- was loaded onto the column. The highest iridium loading capacities for all the sorbent materials for the diamines with decylene spacer, and were found to be 32.94 mg/g, 29.35 mg/g, and 27.09 mg/g for F-QUAT DMDA, Si-QUAT DMDA and B-QUAT DMDA respectively. It was also observed on the derivatives of DMDA supported on nanofibers that F-QUAT ethyl loading capacity for iridium (19.89 mg/g) reduced which may be due to the electron-donating nature of the ethyl group and the increase of hydrophobicity whereas F-QUAT benzyl loading capacity (244.64 mg/g) increased dramatically due to increase in the size of the cation which lowers the positive charge density of the quaternary diammonium center. The charge delocalizing ability of the benzyl group resulted in the best interaction of the diammonium group derived from this quaternizing agent, yielding the highest loading capacity for [IrCl6]2-. Reusability was conducted and the results showed that the all the sorbent materials can be used repeatedly without decreasing their adsorption capacity significantly. The neat diammonium salts were also synthesized and interacted with the chorido metal complex anions to form ion-pairs which were then studied for their solubility. The synthesis of the quaternary salts was rather challenging and resulted in some interesting species when impurities of the iodide form of the salts were present in the process of converting them to the iodide form. Some of these include I52+, which was confirmed preliminarily by X-ray structural analysis, potentiometry and cyclic voltammetry. Molecular modeling studies were also conducted to explain the interaction of the chlorido anions with the cationic diammonium centres, and to quantify these interactions by thermodynamic parameters, partial charge calculations, dipole moments and electrostatic potentials, and there was good agreement between theory and experiment. This thesis presents iridium-specific materials that could be applied in solutions of secondary PMGs sources containing rhodium and iridium as well as in feed solutions from ore processing.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:nmmu/vital:21116 |
| Date | January 2014 |
| Creators | Majavu, Avela |
| Publisher | Nelson Mandela Metropolitan University, Faculty of Science |
| Source Sets | South African National ETD Portal |
| Language | English |
| Detected Language | English |
| Type | Thesis, Doctoral, PhD |
| Format | xxxviii, 237 leaves, pdf |
| Rights | Nelson Mandela Metropolitan University |
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