Carbon nano-onions (CNOs) discovered by Ugarte in 1992 are multi-layered fullerenes that are spherical analogs of multi-walled carbon nanotubes with diameters varying from 6 nm to 30 nm. Among the various methods of synthesis, CNOs prepared by graphitization of nanodiamonds (N-CNOs) and underwater electric arc of graphite rods (A-CNOs) are the subject of our research. N-CNOs are considered as more reactive than A-CNOs due to their smaller size, high curvature and surface defects. This dissertation focuses on structural analysis and surface functionalization of N- CNOs with diameters ranging from 6—10 nm. Synthetic approaches such as oleum- assisted oxidation, Freidel-Crafts acylation and Billups reductive alkylation were used to functionalize N-CNOs to improve their dispersion properties in aqueous and organic solvents. Functionalized N-CNOs were characterized using various techniques such as TGA, TG-MS, Raman spectroscopy and pH-titrimetry. We designed an experimental method to isolate polycyclic aromatic adsorbates formed on the surface of oleum oxidized N-CNOs (ON-CNOs) and characterized them. A-CNOs, on the other hand are bigger than N-CNOs with diameters ranging from 20—40 nm. In this dissertation, we discuss the preparation of graphene structures by unzipping of A-CNOs using KMnO4 as oxidizing agent. These graphene structures were characterized using powder X-ray diffraction, TGA, BET nitrogen adsorption/desorption studies and compressed powder conductivity. This dissertation also focuses on lithiation/delithiation studies of N-CNOs, A- CNOs and A-CNO-derived graphene structures to use them as negative electrode materials in lithium-ion batteries. The cycling performances of these materials at a charge/discharge rate of C/10 were discussed. The cycling performance of N-CNOs was tested at faster charge/discharge rate of C.

Carbon nano-onions (CNOs), concentrically multilayered fullerenes, are prepared by several different methods. We are studying the properties of two specific CNOs: A-CNOs and N-CNOs. A-CNOs are synthesized by underwater arc discharge, and N-CNOs are synthesized by high-temperature graphitization of commercial nanodiamond. In this study the synthesis of A-CNOs are optimized by designing an arc discharge aparatus to control the arc plasma. Moreover other synthesis parameters such as arc power, duty cycles, temperature, graphitic and metal impurities are controlled for optimum production of A-CNOs. Also, a very efficient purification method is developed to screen out A-CNOs from carboneseous and metal impurities. In general, A-CNOs are larger than N-CNOs (ca. 30 nm vs. 7 nm diameter). The high surface area, appropriate mesoporosity, high thermal stability and high electrical conductivity of CNOs make them a promising material for various applications. These hydrophobic materials are functionalized with organic groups on their outer layers to study their surface chemistry and to decorate with metal oxide nanoparticles. Both CNOs and CNO nanocomposites are investigated for application in electrochemical capacitors (ECs). The influences of pH, concentration and additives on the performance of the composites are studied. Electrochemical measurements demonstrate high specific capacitance and high cycling stability with high energy and power density of the composite materials in aqueous electrolyte.

New derivatives of carbon nanostructures: nanotubes, nano-onions and nanocrystalline diamonds were obtained through fluorination and subsequent functionalization with sucrose. Chemically modified nanocarbons show high solubility in water, ethanol, DMF and can be used as biomaterials for medical applications. It was demonstrated that sucrose functionalized nanostructures can find applications in nanocomposites due to improved dispersion enabled by polyol functional groups. Additionally, pristine and chemically derivatized carbon nanotubes were studied as nanofillers in epoxy composites. Carbon nanotubes tailored with amino functionalities demonstrated better dispersion and crosslinking with epoxy polymer yielding improved tensile strength and elastic properties of nanocomposites. Reductive functionalization of nanocarbons, also known as Billups reaction, is a powerful method to yield nanomaterials with high degree of surface functionalization. In this method, nanocarbon salts prepared by treatment with lithium or sodium in liquid ammonia react readily with alkyl and aryl halides as well as bromo carboxylic acids. Functionalized materials are soluble in various organic or aqueous solvents. Water soluble nanodiamond derivatives were also synthesized by reductive functionalization of annealed nanodiamonds. Nanodiamond heat pretreatment was necessary to yield surface graphene layers and facilitate electron transfer from reducing agent to the surface of nanoparticles. Other carbon materials such as activated carbon and anthracite coal were also derivatized using reductive functionalization to yield water soluble activated carbon and partially soluble in organic solvents anthracite. It was shown that activated carbon can be effectively functionalized by Billups method. New derivatives of activated carbon can improve water treatment targeting specific impurities and bio active contaminants. It was demonstrated that functionalized carbon nanotubes are suitable for real time radiation measurements. Radiation sensor incorporating derivatized carbon nanotubes is lightweight and reusable. In summary, functionalization of carbon nanomaterials opens new avenues for processing and applications ranging from biomedicine to radiation sensing in space.