Synthesis of sulphonated and transition metal oxide doped polymeric nanocomposites for application in design of supercapacitors

Philosophiae Doctor - PhDTo meet a fast-growing market demand for next generation portable electronic devices with higher performance and increased device functionalities, efficient electrical energy devices with substantially higher energy, power densities and faster recharge times such as supercapacitors are needed. The overall aim of this thesis was to synthesize nanostructured sulphonated polyaniline and transition metal single, binary and ternary mixed oxide doped nanocomposites with electro-conductive properties. These nanocomposites were anchored on activated graphitic carbon and used in design of asymmetric supercapacitors. Tantalum(IV)oxide, tantalum(IV)oxide-nickel(II)oxide, tantalum(II)oxide-manganese(III)oxide, tantalum(II)oxide-nickel(II)oxide-manganese(II,III)oxide nanoparticles were synthesised using modified sol-gel methods. These were then dispersed, individually, in acidic media through sonication and incorporated in-situ into the polymeric matrix during the oxidative chemical polymerization of aniline doped with poly(4-styrene sulphonic acid). These novel polymeric nanocomposites were characterised with FTIR, UV-visible, TEM, SEM, EDS, XRD to ascertain successful polymerization, doping, morphology and entrapment of the metal oxide nanoparticles. SECM approach curves and interrogation of CV revealed that these nanocomposites are conductive and electro-active. The cells showed good supercapacitor characteristics with high specific capacitances of 170.5 Fg⁻¹ in TaO₂- PANi-PSSA, 166.1 Fg⁻¹ in TaO₂-NiO-PANi-PSSA, 248.4 Fg-1 in TaO-Mn₂O₃-PANi- PSSA and 119.6 Fg⁻¹ in TaO-NiO-Mn₃O₄-PANi-PSSA. Their corresponding energy densities were calculated as 245.5 Whg⁻¹, 179.4 Whg⁻¹, 357.7 Whg⁻¹ and 172.3 Whg⁻¹ respectively. They also gave respective power densities of 0.50 Whg⁻¹, 0.61 Whg⁻¹, 0.57 Whg⁻¹ and 0.65 Whg⁻¹ and showed good coulombic efficiencies ranging between 77.97% and 83.19%. These materials are found to have a long cycle life and therefore good electrode materials for constructing supercapacitor cells.National Research Foundation (NRF

Synthesis and Characterization of Novel Nanosilicates from Kenyan Indigenous Microporous Clay

This study reports the synthesis of novel sodium nanosilicates extracted from locally available Kenyan clay. The synthetic method involved thermal calcination of the clay at 1000 0C followed by alkaline extraction with sodium hydroxide (NaOH) at 75 0C. The calcination temperature of 1000 0C was ideal for enhancing the conversion of silica components and decreasing the alumina components by making them soluble in the extracting base. Different concentrations of extraction medium (NaOH) were evaluated. The clay and the synthesized nanosilicates were characterized by X-ray fluorescence (XRF), Energy Dispersive Spectroscopy (EDS), Fourier infra-red (FTIR) spectroscopy, Field emission scanning, and transmission electron microscopy (FESEM & FETEM), and X-ray diffraction (XRD).  20% (w/v) NaOH was found to be the most appropriate concentration as revealed by XRF and EDS data which showed better silica content. &nbsp

A fumonisins immunosensor based on polyanilino-carbon nanotubes doped with palladium telluride quantum dots

An impedimetric immunosensor for fumonisins was developed based on poly(2,5-dimethoxyaniline)-multi-wall carbon nanotubes doped with palladium telluride quantum dots onto a glassy carbon surface. The composite was assembled by a layer-by-layer method to form a multilayer film of quantum dots (QDs) and poly(2,5-dimethoxyaniline)- multi-wall carbon nanotubes (PDMA-MWCNT). Preparation of the electrochemical immunosensor for fumonisins involved drop-coating of fumonisins antibody onto the composite modified glassy carbon electrode. The electrochemical impedance spectroscopy response of the FB1 immunosensor (GCE/PT-PDMA-MWCNT/anti-Fms-BSA) gave a linear range of 7 to 49 ng L−1 and the corresponding sensitivity and detection limits were 0.0162 kΩ L ng−1 and 0.46 pg L−1 , respectively, hence the limit of detection of the GCE/PT-PDMA-MWCNT immunosensor for fumonisins in corn certified material was calculated to be 0.014 and 0.011 ppm for FB1, and FB2 and FB3, respectively. These results are lower than those obtained by ELISA, a provisional maximum tolerable daily intake (PMTDI) for fumonisins (the sum of FB1, FB2, and FB3) established by the Joint FAO/WHO expert committee on food additives and contaminants of 2 μg kg−1 and the maximum level recommended by the U.S. Food and Drug Administration (FDA) for protection of human consumption (2–4 mg L−1 )

Formulation of slow release NPK fertilizer (cellulose-graft-poly(acrylamide)/nano-hydroxyapatite/soluble fertilizer) composite and evaluating its N mineralization potential

Polymer nano-composite fertilizer formulation has the potential to enhance nutrient use efficiency. Slow release fertilizer (SRF) composite was formulated by incorporating nano-hydroxyapatite (nano-HA) and water soluble fertilizers (urea, (NH4)2HPO4 and K2SO4) into water hyacinth cellulose-graft-poly(acrylamide) polymer hydrogel. Fourier Transform Infra-red spectra revealed existence of chemical interaction between the monomer, cellulose, urea and nano-HA. The release of nutrients was assessed using laboratory incubation experiment. Significantly higher content of mineral nitrogen (MN) was observed in the first 4 weeks in conventional fertilizer (CF) compared to SRF treatments and the control. MN content in SRF treatments increased considerably between the 8th and 12th week, and declined in the 16th week. The values of potentially mineralizable N estimated using first order kinetics model related well to the observed cumulative MN at 16th week. No significant difference was observed between CF and SRF treatments for available P content in the 2nd week. Significantly higher P content was observed in CF compared to SRF treatment in the 4th week, whereas in the 8th week, some SRFs released significantly higher content than CF. Available P peaked in the 8th week in all the treatments and remained constant at 12th and 16th week. Availability of P in SRFs increased with increased content of soluble P and decreased content of nano-HA. Exchangeable K showed less variation during the incubation period, suggesting short release time. The data revealed reduced chances of leaching losses and toxic effect to the plant roots, as well as synchronized nutrient release and requirement by crops. Keywords: Nano-composite, Polymer hydrogel, Chemical interaction, Incubation experiment, Kinetics mode

Antioxidant Capacity of Chitosan on Sorghum Plants under Salinity Stress

Salinity stress is one of the major environmental constraints responsible for the reductions in agricultural productivity. Salinity affects crop growth, by causing osmotic and ionic stresses, which induce oxidative damage due to increased reactive oxygen species (ROS). Exogenous application of natural compounds can reduce the negative impacts of salinity stress on plants. This study evaluated the antioxidant capacity of chitosan, a biopolymer to reduce the salt-induced oxidative damage on sorghum plants. Morpho-physiological and biochemical attributes of sorghum plants stressed with 300 mM NaCl, in combination with chitosan (0.25 and 0.5 mg/mL), were assayed. Salt stress decreased growth, fresh (66.92%) and dry (48.26%) weights, affected the shape and size of the stomata, caused deformation of the xylem and phloem layers, and increased the Na+/K+ (1.3) and Na+/Si+ (5.4) ratios. However, chitosan effectively reversed these negative effects, as supported by decreased Na+/Si+ ratio (~0.9) and formed silica phytoliths. Oxidative stress was exerted as observed by increased H2O2 (44%) and malondialdehyde (125%) contents under salt stress, followed by their reduction in chitosan-treated sorghum plants. Salt increased proline (318.67%), total soluble sugars (44.69%), and activities of SOD (36.04%) and APX (131.58%), indicating sorghum’s ROS scavenging capacity. The antioxidant capacity of chitosan was measured by determining its ability to reduce oxidative damage and minimizing the induction of the antioxidant defense system. Chitosan reduced oxidative stress markers, proline, total soluble sugars, and the antioxidant enzyme activities by more than 50%. Fourier Transform Infrared Spectra of chitosan-treated samples confirmed a reduction in the degradation of biomolecules, and this correlated with reduced oxidative stress. The results suggest that chitosan’s antioxidant capacity to alleviate the effects of salt stress is related to its role in improving silicon accumulation in sorghum plants

Antioxidant Capacity of Chitosan on Sorghum Plants under Salinity Stress

Salinity stress is one of the major environmental constraints responsible for the reductions in agricultural productivity. Salinity affects crop growth, by causing osmotic and ionic stresses, which induce oxidative damage due to increased reactive oxygen species (ROS). Exogenous application of natural compounds can reduce the negative impacts of salinity stress on plants. This study evaluated the antioxidant capacity of chitosan, a biopolymer to reduce the salt-induced oxidative damage on sorghum plants. Morpho-physiological and biochemical attributes of sorghum plants stressed with 300 mM NaCl, in combination with chitosan (0.25 and 0.5 mg/mL), were assayed. Salt stress decreased growth, fresh (66.92%) and dry (48.26%) weights, affected the shape and size of the stomata, caused deformation of the xylem and phloem layers, and increased the Na+/K+ (1.3) and Na+/Si+ (5.4) ratios. However, chitosan effectively reversed these negative effects, as supported by decreased Na+/Si+ ratio (~0.9) and formed silica phytoliths. Oxidative stress was exerted as observed by increased H2O2 (44%) and malondialdehyde (125%) contents under salt stress, followed by their reduction in chitosan-treated sorghum plants. Salt increased proline (318.67%), total soluble sugars (44.69%), and activities of SOD (36.04%) and APX (131.58%), indicating sorghum’s ROS scavenging capacity. The antioxidant capacity of chitosan was measured by determining its ability to reduce oxidative damage and minimizing the induction of the antioxidant defense system. Chitosan reduced oxidative stress markers, proline, total soluble sugars, and the antioxidant enzyme activities by more than 50%. Fourier Transform Infrared Spectra of chitosan-treated samples confirmed a reduction in the degradation of biomolecules, and this correlated with reduced oxidative stress. The results suggest that chitosan’s antioxidant capacity to alleviate the effects of salt stress is related to its role in improving silicon accumulation in sorghum plants