| This thesis identifies a new and flexible route to control graphene layer structure in carbons, which is the key to carbon properties and applications, and focuses on the synthesis, structure-property relationships, and potential applications of new "supramolecular" carbon nanomaterials. This new approach begins with the studies of surface anchoring and assembly mechanisms among planar discotic liquid crystals. The results show that disk-like polyaromatics exhibit weak noncovalent interactions with most surfaces and prefer edge-on anchoring at these surfaces; only on a few surfaces such as graphite and platinum, they prefer face-on anchoring. A theory of pi-pi bond preservation has been proposed to explain the wetting, anchoring, and assembly phenomena. Based on the assembly study, a supramolecular approach was developed, which uses surfaces, flows, and confinement to create well-defined order in discotic liquid crystals, which can then be covalently captured by cross-linking and converted into a carbon material whose structure is an accurate replica of the molecular order in the precursor. This technique has been successfully applied to create innovative nanocarbons with controllable nanostructures.; The new nanomaterials synthesized by supramolecular route include organic and carbon films with precise crystal structure control using surface anchoring and flow. Lithographic techniques were employed to make micro-patterned surfaces with preprogrammed molecular orientations. Fully dense and ordered carbon thin films were prepared from lytropic liquid crystals. These films exhibit surfaces rich in edge-sites and are either anisotropic unidirectional or multi-domain. In addition, four different types of high-aspect-ratio nanocarbons were synthesized and analyzed: (1) "orthogonal" carbon nanofibers with perpendicular graphene layers, (2) "concentric" C/C-composite nanofibers with graphene layers parallel to the fiber axis, (3) "inverted" nanotubes exhibiting graphene edge planes at both inner and outer surfaces, and (4) nanoribbons. Finally, a set of mesoporous carbons were synthesized with both porous structure and interfacial structure systematically controlled by liquid crystal templating. A quantitative model was developed for carbon surface area prediction.; In addition to synthesis, this thesis includes extensive structural analysis and some surface characterization of these nanomaterials, and offers ideas to exploit their unique properties for applications in composites, displays, nanomedicine, and the environment. |
