Synthesis of nitrogen doped carbon nanotubes using ferrocenes

Nxumalo, Edward Ndumiso
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Nitrogen doped carbon nanotubes (N-CNTs) have become a topic of increased importance in the study of carbonaceous materials. This arises from the physical and chemical properties that are created when N is embedded into a CNT. These properties include modified chemical reactivity, modified conductivity and changed mechanical, electronic and magnetic properties. This thesis covers the analysis of the catalytic growth of N-CNTs under well defined conditions and the optimization of reaction conditions to produce N-CNTs. Herein, a range of methodologies have been devised to synthesize N-CNTs. One of the procedures used in this work uses a floating catalyst in which an organometallic complex is decomposed in the gas phase in the presence of a nitrogen containing reactant to give the N-CNTs. This thesis focuses on the use of ferrocene and ring substituted ferrocenes in the formation of N-CNTs and other shaped carbon nanostructures. It talks of the effects that physical parameters such as temperature, pressure, gas flow rates and the type and concentration of N source have on the N-CNT type, size and yields as well as the nitrogen content incorporated into the tubes that are produced using the organometallic complexes. Proposed growth models for N-CNT synthesis are also reported. This work reveals that the N-CNTs produced are less stable (thermal gravimetric analysis measurements), less graphitic and more disordered (transmission electron microscope measurements) than their undoped counterparts. The ratio of the Raman D- and G-band intensities increase with the nitrogen concentration used during the CNT growth. Furthermore, the transmission electron microscopy (TEM) studies reveal that the CNTs are multi-walled, and that the diameters of the N-CNTs can be controlled by systematically varying the concentrations of the nitrogen source. Furthermore, X-ray photoelectron spectroscopy (XPS) and CHN analysis demonstrate that substitutional N is indeed present in the CNTs mainly as pyridinic and pyrrolic xiii N (and is sp2 and sp3 coordinated). The TEM analysis also revealed that when ferrocenylaniline and ferrocene/aniline reactions are compared at similar Fe/N molar ratios, higher N doping levels are achieved when ferrocenylaniline is the catalyst. Investigations of surface and interior imaging of N-CNTs was carried out by high resolution TEM (HRTEM) and identification of N-rich regions were performed by Energy filtered TEM (EFTEM). We also investigated the solid state pyrolysis of ferrocenylmethylimidazole or a mixture of ferrocene (FcH)/methylimidazole at 800 oC at different ratios in sealed quartz tubes. TEM studies showed bamboo compartments are present in the CNTs. An investigation of the bamboo structures revealed that three methylimidazole structural isomers led to tubes with different individual bamboo compartment distances and different morphologies including different N contents. It was observed that when diverse N containing hydrocarbons were used the amount of N in the nitrogen containing reagent is more important than the source and type of the N atoms used as revealed by trends in the morphology of the N-CNTs produced. We have also studied the effect of arylferrocene ring substituents on the synthesis of CNTs and other shaped carbon nanomaterials in subsequent chapters. Magnetic properties of different N doped carbon structures produced in the earlier chapters were investigated using electron spin resonance (ESR) spectroscopy. Most importantly, we observed a large g-factor shift in samples of N-CNTs from that of the free electron. Further, the shift is temperature dependant. A facile method for attaching Au nanoparticles to the surface of pristine N-CNTs and functionalized N-CNTs has been developed. The Au nanoparticles incorporated in the N-CNTs have a wide range of diameters (10 – 35 nm) and possess different shapes. The method offers certain advantages, such as providing Au nanoparticles in good yields and ease of use. The Au/N-CNT nanohydrids are being employed in catalytic reactions e.g. the oxidation of styrene.
Ph. D., Faculty of Science, University of the Witwatersrand, 2011
nanotubes, nanostructures, nanostructured materials, nanochemistry