Non-oxidative dehydrogenation of hydrocarbons is an attractive alternative route for the production of CO- and CO2-free hydrogen. It will satisfy a major requirement for successful utilization of polymer electrolyte membrane (PEM) fuel cells (< 10 ppm CO) and sequestering carbon as a potentially valuable by-product, carbon nanotubes (CNTs). Due to the deposition of carbon on the surface of catalyst particles during the reaction, catalyst performance, life-time, and purification of the generated carbon product, are significant issues to solve in order to make the process practically feasible. The scope of this thesis includes: the development of novel Fe, Ni, and Fe-Ni catalysts supported on a Mg(Al)O support to achieve improved catalytic performance with easily-purified CNTs; evaluation of catalysts for ethane/methane dehydrogenation at moderate reaction temperatures; and study of activation and deactivation mechanisms by a variety of characterization techniques including TEM, HRTEM, XRD, Mössbauer spectroscopy, and x-ray absorption fine structure (XAFS) spectroscopy. The Mg(Al)O support was prepared by calcination of synthetic MgAl-hydrotalcite with a Mg to Al ratio of 5. The catalysts were prepared either by conventional incipient wetness method or by a novel nanoparticle impregnation method, where the monodisperse catalyst nanoparticles were prepared in advance by thermal decomposition of a metal-organic complex in an organic-phase solution and then dispersed onto the Mg(Al)O support. Dehydrogenation of undiluted methane was conducted in a fix-bed plug-flow reactor. Before reaction, the catalysts were activated by reduction in hydrogen. Fe-based catalysts exhibit a higher hydrogen yield at temperature above 600ºC compared with monometallic Ni catalyst. FeNi-9 nm/Mg(Al)O, Fe-10 nm/Mg(Al)O and Fe-5 nm/ Mg(Al)O nanoparticle catalysts show much improved performance and longer life-times compared with the corresponding FeNi IW/Mg(Al)O and Fe IW/Mg(Al)O catalysts prepared by incipient wetness. 10 nm is the optimum particle size for methane dehydrogenation. Addition of Ni to Fe forming a bimetallic FeNi alloy catalyst enhances the catalytic performance at the temperatures below 650ºC. Metallic Fe, Ni, FeNi alloy and Fe-Ni-C alloy, unstable iron carbide are all catalytically active components. Catalysts deactivation is due to the carbon encapsulation. The carbon products are in the form of stack-cone CNTs (SCNTs) and multi-walled CNTs (MWNTs), depending on the reaction temperature and catalyst composition. The growth of CNTs follows a tip growth mechanism and the purity of cleaned CNTs is more than 99.5%.

Cellulosic fibers sized from the macro-scale to the nano-scale were prepared hierarchically from kenaf bast fibers using chemicals. The process began with a hermetical alkaline retting followed by a bleaching treatment. The bleached fibers were hydrolyzed using inorganic acid, from which microfibers and cellulose nanowhiskers (CNWs) were fabricated. Inorganic nanoparticle impregnation (INI) was used to treat the retted fibers for the improvement of the interfacial compatibility between the fiber and polypropylene (PP) matrix. The retted fibers and INI-treated fibers were used as reinforcement for the PP polymer composites. Film casting process was used to make CNW/PVA composites. The hermetical retting process used in this study produced fibers with high cellulose contents (81-92%) by removing the lignin and hemicelluloses. Higher retting temperature resulted in higher fiber surface hardness and elastic moduli. The tensile strengths and tensile moduli of the fibers decreased as the temperature increased. The SEM images showed the micropores in the cell wall structure for the fibers retted at over 130°C, providing the possibility to anchor nanoparticles into the cell wall. Surface morphology of the INI-treated fibers was examined with SEM, and showed that the CaCO3 nanoparticle crystals grew onto the fiber surface. Energy-dispersive X-ray spectroscopy (EDS) was used to verify the CaCO3 particle deposits on the fiber surface. As the size scale of the fibers decreased, the fiber crystallinity increased from 49.9% (retted fibers) to 83.9% (CNWs). About 23% á-cellulose in the raw kenaf bast fibers had been converted into CNWs. The retted fibers without INI treatment had poor compatibility with the polypropylene matrix. The INI treatment improved the compatibility between the fibers and the PP matrix, resulting in an improvement in kenaf fiber/PP composite tensile moduli and tensile strengths. The CNWs prepared from kenaf bast fiber gave excellent reinforcement for PVA composites. A nine percent increase of CNWs in the CNW/PVA composites yielded significant improvements in tensile strength and modulus of about 46% and 152%, respectively, compared with pure PVA.