Fullerene Micro- And Nanostructures:Controlled Synthesis And Properties

Over the past decades, carbon nanomaterials have been widely recognized as one of the most promising materials benefiting from their unique structures and excellent properties in various fileds. Among these carbon nanomaterials, fullerenes with highly ?-conjugated zero-dimensional carbon cages are particularly important and attractive. Notably, the fabrication of regular fullerene micro- or nanostructures can substantially improve their intrinsic properties, which will fundamentally improve their applications in various fields. In this dissertation, we manly focused on the controlled synthesis of fullerene micro/nanostructures using the solution-driven self-assembly approach. Furthermore, the properties of the as-prepared fullerene architectures were also carefully studied, exhibiting excellent optoelectric, electronic and capacitive properties. The results are summarized as follows:(1) The solvent effect on the morphologies and crystalline structures of the as-prepared C6o crystals at liquid-liquid interfaces were systematically investigated by using various aromatic solvents as good solvents and alcohols as poor solvents, which leads to the finding that solvent-doping in the final crystal lattice is a critical factor that determines the morphological and crystalline characteristics of the resultant crystals. This work not only unravels the solvent effect on the formation of C60 crystals at the liquid-liquid interfaces, but also provides a dictionary for the relationship between solvents and morphologies, thus affording opportunities for the investigation of the morphology-dependent properties of these promising materials.(2) The successful preparation and morphology control of different C70 one-dimensional (1D) microstructures were realized by choosing regioisomers of xylene as good solvents and isopropyl alcohol (IPA) as the poor solvent via the liquid-liquid interfacial precipitation method. The systematic investigations reveal that the solvents participating in the formation process of these C70 1D microstructures play a critical role in determining the morphology, crystalline structure, formation process and intrinsic properties of these materials. Furthermore, these C70 1D microstructures exhibit excellent photoelectrochemical properties, proving their potential applications in related fields.(3) A two-step self-assembly strategy has been developed for the preparation of fullerene hierarchical architectures, combining the precipitation method and the drop-drying process together. Overall, this methodology is quite simple and feasible, which can be applied to prepare fullerene hierarchical structures with different morphological features, simply by choosing proper solvent. Moreover, the as-obtained fullerene hierarchical structures have many superior properties over the original fullerene micro structures such as superhydrophobicity and unique photoluminescence behaviors, promising their applications as waterproof optoelectronics.(4) K.OH activation of C70 microtubes was performed at high temperatures, which provides activated samples exhibiting excellent capacitive properties. The improved capacitive performance can be attributed to three aspects:the generation of macropores and micropores, the introduction of oxygen functionalities, and the formation of graphitic carbons from ellipsoidal fullerenes. The optimum activated state for supercapacitor application is achieved at 600?, at which the product exhibits the best electrochemical behavior with a gravimetric capacitance of 362.0 F/g at 0.1 A/g and excellent cycling stability with capacitance retention of 92.5% over 5000 cycles at 1 A/g. It will fundamentally promote the application of fullerenes in the field of energy storage.(5) Supramolecules consisting of fullerene C70 and porphyrin (four kinds of porphyrin are applied here:tetraphenylporphyrin, cobalt tetraphenylporphyrin, zinc tetraphenylporphyrin, cobalt tetramethoxyphenylporphyrin) can effectively co-assemble to two-dimensional or one-dimensional micro structures at the liquid-liquid interfaces in a controllable fashion. The functional group in the porphyrin plays a crucial role in the morphology control of the as-obtained supramolecular structure. Furthermore, the supramolecular micro-needles composed of C70 and cobalt tetramethoxyphenylporphyrin have superior properties over the original C70, showing high-temperature stability and high electron mobility, which reveals its potential application in high-temperature electronics.