Surface Chemistry of Halloysite Nanotubes. As investigated by adsorption reactions and imaging analysis

Interest in halloysite clay minerals has increased steadily over the last 20+ years, in part, due to their nanotubular shape and size, high aspect ratio and potential technological applications (Churchman et al., 2016). Throughout this thesis the surface chemistry of halloysite nanotubes is investigated by employing several analytical and advanced microscopy techniques to obtain a greater understanding of their internal and external surface features and surface adsorption reactions. This multifaceted analysis approach investigates a range of tubular halloysites of two morphologies, cylindrical and polygonal prismatic, where comparison of the two forms a framework for the presentation and discussion of the results. The results presented in Chapter 3 demonstrate the phosphate adsorption capacity of halloysite nanotubes is influenced by pH and maximum adsorptions of 1.3 mg/g and 0.5 mg/g were obtained for the cylindrical and polygonal prismatic morphologies respectively. Use of advanced microscopy techniques in Chapter 4 showed the external surface of the polygonal prismatic nanotubes have multiple steps and edges, which may act as additional adsorption sites, as has been shown for other clay minerals (Siretanu et al., 2016). In addition, use of cross-section transmission electron microscopy provided evidence of the link between the two morphologies, where the cylindrical nanotubes appear to be the template from which the larger polygonal prismatic nanotubes grow, as previously postulated by Hillier et al. (2016). In further novel work (Chapter 5), gold nanotags have been functionalised with a variety of anionic and neutral terminated linkers and used as nanoscale probes to study adsorption to the surface of halloysite nanotubes Here, transmission electron microscopy proved that the adsorption occurred primarily on the nanotube inner lumen and edges. The final technical chapter, Chapter 6, focuses on the structure and dynamics of interlayer water in halloysite through the use of neutron scattering techniques, where the initial results demonstrated that the interlayer water appears to move via both rotations and translations within the interlayer. The research presented ascertains that the surfaces of the halloysite nanotubes are more complex than often depicted for technological applications and that the specific tubular morphology is important in the functionality and behaviour of the nanotubes. This fundamental work contributes towards optimisation of halloysite nanotubes for technological applications.