<p>This thesis describes the development and performance of novel photocatalytic inorganic polymer (geopolymer) composites for photodegradation of environmentally harmful organic materials. Nanometer-sized cubic cuprous oxide nanoparticles and spherical Cu₂O/TiO₂ nano-heterostructures were synthesized via a precipitation method and then added to a metakaolinite-based geopolymer matrix prior to curing at ambient temperature. The morphology of the homogeneous oxide nanoparticle dispersion within the geopolymer matrix was demonstrated by SEM/EDS and HRTEM. FTIR spectroscopy confirmed the formation of a well-reacted geopolymer matrix that was unaffected by the insertion of the Cu₂O and Cu₂O/TiO₂ nanoparticles. The structures of these new composites were determined by ²⁷Al and ²⁹Si MAS NMR spectroscopy. ⁶³Cu NQR spectroscopy and XRD confirmed that the metal oxide nanoparticles are unchanged by their incorporation in the geopolymer composite and after the photodegradation reactions. The nitrogen adsorption-desorption isotherms were determined, providing information about the specific surface areas and total pore volumes of the composites. The action of the composites in the adsorption and photocatalytic destruction of the model organic compound MB was determined under dark and UV illumination conditions. Experiments in dark conditions and under UV irradiation showed that these materials efficiently remove a model organic pollutant (MB dye) from solution by a dual process of adsorption on the geopolymer matrix, and photodecomposition of the dye without destroying the geopolymer structure. The adsorption kinetics of the dye are best described by a pseudo first-order model and the adsorption process by Langmuir-Freundlich isotherms. In a novel extension of this research, the metakaolinite-based geopolymer matrix was modified with a surfactant (cetyltrimethylammonium bromide, CTAB), exploiting the cation exchange capacity of the geopolymers structure. The nano oxide composites were synthesised by adding different amounts of as-prepared metal oxide nanoparticles to the modified geoplymer to produce a hydrophobic photocatalyst composite with improved photocatalytic activity arising from the dispersion of the metal oxide nanoparticles in the external surfaces and interlayers of the geopolymer matrix. This method has the advantage of producing geopolymer composites with a stable pH which are more suitable for dye degradation studies. At concentrations >20 wt%, the photo-oxide component decreases the adsorption rate by blocking the active adsorption sites of the geopolymer. Under UV radiation, the composites remove the MB by a combination of adsorption and photodegradation, without deterioration of the geopolymer structure or the photoactive metal oxide component. In addition these studies show that the metal oxide-geopolymer nano composites have significantly improved photocatalytic activity compared with the oxide nanoparticles alone, because of the unique properties of these inorganic polymers. These results demonstrate that composites of nanosized Cu₂O particles and photoreactive TiO₂ in an aluminosilicate inorganic polymer matrix constitute new and novel materials with potential environmental protection applications to efficiently remove organic pollutants from water or the atmosphere.</p>
Self-Assembly of Metal Oxide Nanoparticles in Liquid Metal toward Nucleation Control for Graphene Single-Crystal Arrays
