Nanomaterials (NMs) are materials in which the size of at least one dimension is less than 100 nm. Examples include quantum dots, nanoparticles, “Buckminsterfullerene (C60)”, carbon nanotubes, graphene and TiO2 thin films. Many research groups have investigated the properties of NMs, and they have reported that some of them are clearly different to those of the bulk materials, and depend on the size of the NMs. Examples include melting temperatures, phase transition pressures, fluorescence spectra, catalytic properties and magnetic properties. Recently, a high-pressure study of Te nano-cylinders revealed compressibility effects that are different to those observed in bulk-Te. Although this study reported an elevation of phase transition pressure compared to the bulk, the authors did not investigate the structures of the high-pressure phases, and it is unclear whether the incommensurate phase found at high pressures in bulk-Te was observed or not. Indeed, it is completely unknown whether the incommensurate phases observed in a number of elements at high pressure also exist in nanoparticle samples of the same materials. The search for, and study of, such phases forms the subject of this thesis. Initial studies of commercial selenium nanoparticles (nano-Se) revealed that the incommensurate phase of bulk selenium (Se-IV) is also found in nano-Se. The transition pressures in nano-Se are slightly higher than those of bulk-Se. However, the nano-Se samples were subsequently found not to have the sizes, shapes, and properties claimed by the vendor, which was confirmed by transmission and scanning electron microscopy. Further commercial samples of nano-Se and nano-Bi were also found to be of extremely poor quality. It was clear, therefore, that a detailed study of incommensurate phases in NMs would require us to make our own samples. Bismuth nanoparticles (nano-Bi) with dimensions 51(6), 52(15), 92(13), 128(45), and 138(27) nm have been successfully synthesised by the author in collaboration with the Hybrid Nano Collods group at the University of St. Andrews. On compression, the nano-Bi samples were found to have the same order of phases Bi-I, Bi-II, Bi-III, and Bi-V and phase transitions as found in bulk-Bi, but were found to exhibit larger phase coexistence. The phase transition pressures on pressure increase were higher than those of the bulk materials, and the smaller the diameter of nano-Bi, the higher the phase-transition pressure. This behaviour is similar to, but more extreme than, that found in CdSe nanoparticles. The incommensurate Bi-III structure has been found in nano-Bi under increases in pressure. However, the di↵raction patterns from Bi-III contain additional unaccounted-for peaks, and this phase is referred to as complex Bi-III. The Debye- Scherrer rings from complex Bi-III are smooth, and do not exhibit the spottiness observed in the diffraction patterns of Bi-III obtained from bulk-Bi. This enables full Rietveld refinement of Bi-III in the nano-samples. Complex Bi-III exists from 3 GPa up to 30 GPa, compared to the stable range of only 2.7 to 7.7 GPa of Bi-III in the bulk material. While such a large range of pressure enables the structure of nano-Bi-III to be studied over a much wider pressure range than bulk-Bi-III, such studies were hampered by the existence of the unaccounted-for peaks. In order to get clean, single-phase patterns of Bi-III, samples of this phase were first prepared on pressure decrease from the higher-pressure Bi-V phase, before recompressing them. Single-phase samples of Bi-III were obtained and were found to be stable up to 14-18 GPa. However, because of phase coexistence, diffraction peaks from Bi-III were still visible at pressures as high as ~30 GPa, which is ~3 times larger than the upper limit pressure of existence of bulk-Bi-III. On pressure re-increase, nano-Bi-III has a higher bulk modulus than bulk-Bi-III. The bulk modulus was found to be size-dependent as it is higher when size decreases. Moreover, nano-Bi has a smaller value of the incommensurate wave vector, which is almost pressure independent, but is found to be particles size dependent. The incommensurate wave vector thus becomes another of the structural and physical properties of nanomaterials that is found to be sample-size dependent.

The optical properties of gold in the visible are dominated by the response of the free conduction electrons to light. In gold nanostructures, the surface charge density adopts a configuration that is constrained by the shape of the nanoparticles. As a result, the scattering of light by gold nanoparticles exhibits a resonant response characterised by a strong scattering and absorption in a narrow range of frequencies. The spectral range of this \emph{localised surface plasmon resonance} (LSPR) can be tuned by varying the size and shape of the gold nanoparticle --- the nanoparticles act as nanoscale antennas for the visible light. Confirmation of this scaling rule is obtained by conducting experiments with nanoparticles of varying size and aspect ratio. Such particles are fabricated by electron-beam lithography, and characterised by dark-field spectroscopy. Not only does the LSPR shift in frequency with a change of particle size, but its spectral lineshape is also modified. The intensity and width of the LSPR are dictated by a variety of factors that are related to the intrinsic material properties (the complex dielectric function of gold), and to the particle geometry and environment. The optical response of small gold nanorods is well described by a simple oscillating dipole model --- the incident electromagnetic field induces a current in the particle that re-radiates light (scattering). A series of refinements can be made to model more accurately the optical response of realistic particles. If the dipole moment characterising the particle is allowed to vary in phase across the particle, retardation effects provide a correction for the effective dipole moment of the particle. As the particle size approaches the wave length in the surrounding medium, the dipolar approximation breaks down and higher order multipoles need to be considered. The Mie theory provides a very accurate description of the response of spheres of arbitrary size. Further, the T-matrix and other numerical techniques can be employed to accurately reproduce the scattering properties of particles of arbitrary shapes. When the scattering sample consists of a collection of gold nanoparticles, the collective optical response is affected by two key factors. First, the measured LSPR is a convolution of the distribution of particle sizes with the individual response of a single particle. This leads to an inhomogeneous broadening of the LSPR lineshape. Second, the light that is scattered by one such particle near resonance can strongly affect its neighbours which scatter light in proportion to the net field they experience, that is the sum of the incident field plus the perturbation arising from the neighbouring particles. The onset of such multiple scattering events is observed even for particle separations that are several times larger than the particle size. Several regimes of interaction can be distinguished according to the ratio separation / wavelength. First, when the particles are in close proximity (separation $\ll$ wavelength), near-field interactions dominate and result in a spectral shift of the LSPR accompanied with a spectral broadening. Second, when the separation is commensurate with the wavelength, a coherent interaction can develop that couples a large number of particles. In ordered arrays, such coupling gives rise to a geometrical resonance that can strongly affect the LSPR of the particles. In particular a sharp spectral feature is observed that depends on both the single particle response and the geometrical arrangement of the particles in the array. The coherence of such multiple scattering in diffractive arrays of gold nanoparticles can be broken by introducing disorder in the distribution of particle sizes, or in the particle positions. The optical properties of an irregular array reflect the departure from a periodic system and the spectral lineshape evolves as the level of disorder is increased. In the limit of uncorrelated positions, the diffractive coupling is suppressed and the response of the collection of the particles rejoins the response of isolated particles.

Bionanotechnology is an intersection between biology and nanotechnology, a field in which novel applications for very small materials are being realised at an alarming rate. Nanoparticles have 3 dimensions that can be measured in nanometers, their small size conferring upon them different properties from individual atoms or the bulk material. The interactions between these unique materials and microorganisms are often toxic, thus have been exploited for antimicrobial applications. However, there is a considerable paucity of data for the underlying molecular mechanisms. This study has been carried out to investigate the interactions that occur between nanoparticles and bacteria with the objective of identifying these toxicological mechanisms and novel nanoparticle effects, using the model Gram negative organism Escherichia coli K12. This study has identified metal nanoparticles that are a superior vehicle for the delivery of toxic metal ions to E. coli. The nanoparticles associate with the bacterial surface, but do not cross the cell wall. They then dissolve, releasing a concentration of metal ions that accumulate at the bacterial-nanoparticle interface, enhancing the antibacterial efficacy compared to the concentration of metal ions in the bulk solution phase. Measurement of the whole transcriptome response to silver nanoparticles in comparison to the silver ion indicates that the different modes of ion delivery may induce a differential stress response. Moreover, this data identifies molecular mechanisms that are involved in the toxicity of this metal that is now becoming increasingly prevalent in society. The dissolution based toxic effects of zinc oxide nanoparticles are augmented by an interaction with ultra-violet light, offering an alternative mode for nanoparticle toxicity.

The thermally responsive hydroxypropyl cellulose (HPC) hydrogel nanoparticles have been synthesized and characterized. The HPC particles were obtained by chemically crosslinking collapsed HPC polymer chains in water-surfactant (dodecyltrimethylammonium bromide) dispersion above the lower critical solution temperature (LCST) of the HPC. The size distributions of microgel particles, measured by dynamic light scattering, have been correlated with synthesis conditions including surfactant concentration, polymer concentration, and reaction temperature. The swelling and phase transition properties of resultant HPC microgels have been analyzed using both static and dynamic light scattering techniques. By first making gel nanoparticles and then covalently bonding them together, we have engineered a new class of gels with two levels of structural hierarchy: the primary network is crosslinked polymer chains in each individual particle, while the secondary network is a system of crosslinked nanoparticles. The covalent bonding contributes to the structural stability of the nanostructured gels, while self-assembly provides them with crystal structures that diffract light, resulting in colors. By using N-isopropylacrylamide copolymer hydrogel nanoparticles, we have synthesized nanoparticle networks that display a striking iridescence like precious opal but are soft and flexible like gelatin. This is in contrast to previous colored hydrogels, which were created either by adding dyes or fluorescent, or by organic solvent or by embedding a colloidal crystal array of polymer solid spheres . Creating such periodic 3D structures in materials allows us to obtain useful functionality not only from the constituent building blocks but also from the long-range ordering that characterizes these structures. Hydroxypropyl cellulose (HPC) and poly (acrylic acid ) (PAA) complexes were studied using turbidity measurement and laser light scattering. The phase transition temperature of the complexes is found to depend on pH and molecular weights of PAA and HPC. The driving force for this phenomenon is due to the hydrogen bonding and hydrophobic interaction of the macromolecules. Based on the principle of the PAA/HPC complexes, the PAA nanoparticles were synthesized in 0.1wt % HPC aqueous solution at room temperature.

In recent years, research has focused on reducing the cost of catalysts in a variety of ways including using less expensive materials, improving the synthetic method, and increasing the catalytic activity, recovery, and recyclability. Typically with nanoparticles, the size, shape, composition, and surface coating have an effect on catalytic activity.1-2 In this work, we focused on reducing the cost of precious metal based catalysts by altering the synthetic methods. One way to lower the cost of synthesizing precious metal nanoparticles is by debasing the precious metal with a second cheaper more abundant metal. CuPd nanoparticles were synthesized in oleylamine and displayed catalytic activity in several cross-coupling reactions. Due to copper being present in the nanoparticle, a copper halide co-catalyst was not needed for Sonogashira cross coupling to be successful.3 While this method produced reactive catalysts, low product yield hinders its application for industry. Solution based synthesis of metallic nanoparticles typically require long reaction times and high temperatures, which make large scale production of nanoparticles on an industrial scale difficult.4-5 The use of continuous flow microreactors provides greater control of synthetic parameters, leading to lower batch-to-batch variability and increasing the efficient of heat and mass transfer and have been applied to the synthesis of metals, semiconductors, zeolites, organic compounds, and semiconductors.5-7 To compare continuous flow methods to benchtop reactions, a well-characterized benchtop reaction synthesizing Cu@Ni core/shell nanoparticles was successfully transferred to a flow reactor set-up. Cu@Ni nanoparticles were synthesized using a capillary microreactor in under 1 minute compared to the 1 hour reaction on benchtop with similar properties in a green solvent.2 The Cu@Ni nanocomposites were active towards the Fischer Tropsch reaction.8 2 nm platinum nanoparticles and platinum bimetallic alloys were synthesized in water using a capillary microwave flow reactor. Investigations showed the nanoparticles were activity toward hydrogenation of octene. With further development, continuous flow synthesis of metallic nanoparticles can be applied to the synthesis of a wide variety of catalysts on an industrial scale. Continuous flow methods provide greater control of reaction parameters, increased safety by reacting smaller volumes of chemicals at a given time, and decreasing the batch-to-batch variability.

Approved for public release; distribution is unlimited / The aim of this study was to fabricate tin/carbon (Sn/C) battery anodes using a novel approach, reduction expansion synthesis (RES), and test their performance as electrodes in lithium or sodium batteries. A second preparation route, the Aerosol-Through-Plasma (ATP) method, was also employed for comparison. The specimens generated were characterized, before and after cycling, using techniques such as X-ray diffraction, scanning, and transmission electron microscopy. The RES technique was successful in creating remarkably small (ca. <5 nm) nano-scale particles of tin dispersed on the carbon support. The use of the electrodes as part of coin cell batteries resulted in capacitance values of 320 mAh/g and 110 mAh/g for lithium-ion and sodium-ion batteries, respectively. Nano-sized Sn particles were found before and after cycling. It is believed that bonds between metal atoms and dangling carbon produced via the reduction of the carbon surface during RES were responsible for the materials' ability to withstand stresses during lithiation, avoid volumetric expansion, and prevent disintegration after hundreds of cycles. When tin loading in Sn/C was increased from 10% to 20%, an increase of capacitance from 280 mAh/g to 320mAh/g was observed; thus, increased tin loading is recommended for future studies. Tin/carbon produced using ATP presented morphology consistent with stable electrodes, although battery testing was not completed because of the difficulty of producing the material in sufficient quantity. / Military Expert 5, Republic of Singapore Navy

M.Sc. (Nanoscience) / Please refer to full text to view abstract

The need for green and renewable fuels has led to the investigation of ways to exploit renewable resources. Solar among all the renewables is the most powerful and its conversion into usable energy would help in solving the energy problem our society is facing. Photocatalytic water splitting for hydrogen production is an example of solar energy storage into chemical bonds. The hydrogen produced in this way can then be employed as carbon free fuel creating the “Hydrogen Cycle”. This work investigates the structure and the activity of graphitic carbon nitride (g-C₃N₄), an organic semiconductor that proved a suitable photocatalyst for hydrogen production from water. Synthesised by thermal polycondensation of melamine it is a graphitic like material with a band gap of 2.7 eV which makes it a visible light active catalyst. In a first instance the effect of the synthesis conditions on its structure and morphology are investigated to find the optimum parameters. The temperature of condensation is varied from 450°C up to 650°C and the length from 2.5 h to 15 h. The structural changes are monitored via X-ray diffraction (XRD) and elemental analysis while the effect on the morphology and the band gap of g-C₃N₄ are investigated by mean of scanning electron microscopy and UV-Vis absorption. Subsequently, a study of the crystal structure of the catalyst is carried out. Using structures proposed in the literature, X-ray diffraction and neutron scattering simulations are used to narrow down the number of possible 3D structures. After structural characterisation, the activity of g-C₃N₄ for photocatalytic hydrogen evolution is evaluated. It is confirmed that loading 1 wt.% Pt on its surface significantly increases the hydrogen evolution rate. The attention then focuses on the loading procedures, the reduction pre treatments of the co-catalyst and the reasons of the different performances when different procedures are employed. The catalytic system is characterised by mean of X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and XRD. By investigating the composition and the morphology of the platinum nanoparticles under different conditions, the main factors responsible for the changes in activity of g-C₃N₄ for hydrogen evolution are identified. Additionally, the role of the co catalyst and its interaction with g-C₃N₄ is also elucidated. Finally, taking forward the knowledge acquired on the Pt-g-C₃N₄ system, the effect on the hydrogen evolution rate of alloying platinum with a second metal (Cu, Ag, Ni and Co) is studied. The nanoparticles are characterised by XRD and TEM. A screening of the loading procedures and bimetallic systems is performed to identify the most promising for photocatalytic hydrogen evolution with the aim of bringing them towards further investigation.

Nanotechnology is more and more present in our world today and different fields are taking advantage of its possibilities. Among others, microscopists have been interested in using nanoparticles in combination with available techniques, one of which is fluorescence microscopy. Lanthanide-doped nanoparticles for example have been studied for many years now for their interesting luminescence and upconversion characteristics. This research presents the development of upconverting biolabels operating in the near-infrared (NIR) to eventually allow scientists to probe deeper into tissues using fluorescence microscopy. Two distinct types of nanoparticles were fabricated using the lanthanide ions Yb3+ and Tm3+ for their upconversion capabilities (from 980 to 800 nm) within the biological window (700 to 1000 nm). The first one, an annealed silica-coated LaF3:Yb,Tm nanoparticle, could not be used as a biolabel due to its lack of dispersibility in aqueous environment. However, the second type, a silica-coated NaYF4:Yb,Tm nanoparticles proved to be very promising. Two surface modifications of these particles were successfully performed. The first introduced NH2 groups while the second incorporated polyethyleneglycol (PEG). The latter was achieved using two distinct methods: one through a reaction with the amino groups and one through a second silica coating involving PEGsilanes. Stable dispersions of these PEGylated nanoparticles were obtained and imaging of ovarian cancer cells grown in their presence showed that they interact with the cells although the nature of this interaction is still to be determined.

Lanthanide-based nanoparticles can be used in a variety of applications, including biomedical work such as imaging and cancer therapies, and in solar cells. This thesis presents two different potential applications for lanthanide-based nanoparticles and a possible new method for single nanoparticle analysis. Each of the projects presented in this thesis starts from the colloidal synthesis of the nanoparticles and then explores their varying properties, such as size and size distribution, crystallinity, elemental composition, and optical properties. Chapter 1 presents a short introduction to lanthanides and explores their ability to luminesce and upconvert. These optical properties make lanthanide-based nanoparticles attractive in both the visible and near-infrared (NIR) range. Chapter 2 explores the possibility of using β-LaF3:Nd3+ (5%) nanoparticles in a colloidal laser to overcome some issues that solid state lasers face due to thermal effects. A colloidal laser requires small nanoparticles that can emit a useful wavelength and that are dispersed in a high boiling point liquid. In Chapter 3, a cation exchange of ytterbium for yttrium and erbium in water-dispersible β-NaYF4:Er3+ nanoparticles across a polyvinylpyrrolidone (PVP) surface coating was tested as a possible synthesis route for radioactive nanoparticles. Incorporating radioactive materials at the end of a therapy preparation would limit the number of synthesis steps in an isotope laboratory. Chapter 4 presents single-particle analysis of β-NaYF4:Er3+ (50%) nanoparticles using X-ray absorption spectroscopy (XAS) at the Canadian Light Source (CLS). Electron beams in scanning electron transmission microscopes (STEM) can damage the samples, making quantification of nanoparticles challenging. Finally, Chapter 5 discusses some conclusions and suggests possible future work. / Graduate / 0494