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Materials Science and Engineering

First Advisor

Barbara Knutson


The synthesis of highly ordered carbonaceous materials, including carbon nanofibers, has been the subject of a disparate and burgeoning literature over the past decade. Growth of carbon nanotubes via an atypical catalytic route, the decomposition of halogenated reactants as chlorobenzene (CB) over 10% (w/w) Ni/SiO2 is investigated. The C (carbon) yield and structural order are a function of reaction time and temperature. Greater degree of structural order and C yield is observed from CB relative to benzene, suggesting Cl/catalyst interaction(s) and metal site restructuring. Evaluation of the effect of H2 on C growth from CB reveals that C yield is sensitive to % (v/v) H2 with selectivity maxima at 40% (v/v) H2. Further, C yield is significantly influenced by the nature of the heteroatom substituent on the benzene ring; presence of strong electron withdrawing groups favors C yield and weak electron withdrawing or donating groups favors competing side reactions. The effect of the strong electron withdrawing group, Cl, varies with the chemical structure of the carbon source. Presence of Cl promotes C yield in the case of aromatic and straight chained (aliphatic) compounds whereas it promotes formation of benzene in the case of cyclic (aliphatic) compounds. Results are interpreted in term of substituent/ catalyst interaction and the mechanism of solid C formation. Further, effect of % (v/v) H2 on C growth characteristics varies significantly with the precursor. The C growth characteristics are strongly dependent on the nature of the support used, as demonstrated for the following supports: SiO2, Ta2O5, Al2O3, NaY, activated carbon and graphite at 10% (w/w) Ni loading. Ni/SiO2 results in maximum C yield. Variation in Ni loading significantly influences the C yield; higher loading favors greater C yield. C grown on Ni/NaY was found to be relatively more structured to C obtained on the other supports. EDX analysis of the carbon product was used to assess the possibility of Cl intercalation and it reveals presence of 0.4 at% Cl on carbon grown on Ni/Al2O3.