Synthesis and characterization of MXS (M = Mo & V) and carbon supported MXS nanocomposites as Pt-free counter electrodes for electrode for DSSC application
- Authors: Bede, Asanda
- Date: 2020
- Subjects: Voltammetry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/18599 , vital:42612
- Description: It has been reported that the morphology, crystalline phase composition and electrochemical properties of counter electrode materials such MxS (Mo, V) and carbon supported MxS (Mo, V) composite nanomaterials was of considerable importance because it governs the efficiency of many photon assisted chemical and physical reactions in dye sensitized solar cells (DSSCs). The efficiency of DSSCs with composite counter electrode materials is reliant on the stability of the photochemistry reactions which can be optimized by appropriate doping levels of the composite materials. Moreover, the microstructure such as surface area, distribution of the MxS (Mo, V) and carbon supported MxS (Mo, V) composite nanomaterials, and the stability of the electrostatic bonds between the MxS (Mo, V) with the carbon support also play a significant role in the performance of the DSSCs. This work evaluates the effect of different mole ratios of the MxS (Mo, V) and carbon supported MxS (Mo, V) composite nanomaterials on the morphological, structural and electrochemical properties of the composite materials. MoS2 nanoflakes nanostructures have been synthesized by hydrothermal technique using sodium orthovanadate (Na2MoO4) as precursor. In this work Carbon supported MoS2 NFs have been prepared by physically/chemically mixing different mole ratios of MoS2 NFs with multi-walled carbon nanotubes (MWCNTs) and polyvinylidene in N-methyl-2-pyrrolidinone. The morphological, structural and electrochemical properties of the composite counter electrode materials have been investigated using SEM, XRD FTIR, TEM, RS and CV. SEM analysis has revealed the presence of large MoS2 nanoflakes (NFs) as synthesized. SEM analysis has also revealed significant change in the surface morphology of carbon supported MoS2 composite nanostructures with the change in the mole ratio of the MoS2 NFs and carbon support multi-walled carbon nanotubes. Structural analysis through HRTEM analysis revealed a d-spacing of 0.65 nm with a corresponding (002) lattice plane belonging to a trigonal crystalline phase of MoS2. Also, HRTEM analysis has revealed d-spacing of 0.291 nm corresponding to 002 plane of MWCNTs. Raman spectroscopy has revealed Characteristic Raman vibration frequencies and symmetries at 264.6 cm-1(Eg), 354.2 cm-1 (Ag ) belonging trigonal phase of MoS2 (1T-MoS2). FTIR analysis has revealed a narrow peak at 457.6 cm-1 due Mo-S vibration bond. This observation confirms the success of synthesis of MoS2 nanostructures. Cyclic voltammetry (CV), charge-discharge (CD) and electrochemical impedance spectroscopy (EIS) measurements have revealed that the ratio 6:3:1 have shown to be optimum ratio due to its large reduction rate compared to pristine MoS2 NFs and other carbon supported MoS2 NFs. Calculated Rreduction for the carbon supported MoS2 NFs is the order 3:6:1>1:8:1>6:3:1>8:1:1 indicating the trend of ratio 3:6:1 appeared to have higher reduction rate than the rest of the material and it had far less ΔEpp than the rest of other ratios. All CV curves for both pristine MoS2 NFs and carbon supported MoS2 NFs confirmed a distinct Faradic characteristic. The VS2 nanosheets (NSs) and carbon supported VS2 NSs were also effectively synthesized via hydrothermal method. The SEM micrographs for VS2 NSs and carbon supported VS2 NSs samples reveals level increased. Furthermore, SEM-EDX analysis have confirmed the presence of V and S as well as C and O on carbon supported VS2 nanocomposites, and it clearly shown a gradually blending as the ratios increases. The structural studies through XRD analysis have revealed peaks at 2θ angles of 15.4◦, 28.2◦, 34.2◦, 36.2◦, 43.3◦,48.3◦, 54.4◦, 57.7◦ and 66.2◦ which correspond to the lattice planes (001), (002), (100), (011), (102), (003), (110), (103) and (201) belonging to hexagonal VS2 (H-VS2) crystalline phase as per JCPDS card 36-1139. The HRTEM have revealed that the VS2 NSs have an edge to edge length of ~ 0.294 – 1.248 µm. Also, HRTEM micrographs of VS2 NSs have revealed interplanar d spacing of 0.571 nm belonging to the (001) lattice plane of hexagonal VS2 (H-VS2) structure. FTIR analysis have shown a peak at 558 cm-1 attributed to V-S which is evident that sulfur has bonded with the metal (V) and is in agreement with EDS. CV, CD and EIS measurements have shown that the ratio 1:8:1 is more superior to VS2 NSs and other carbon supported VS2 NSs. Based on Rreduction for the carbon supported nanosheets VS2 nanosheets are ordered as 1:8:1>3:6:1>6:3:1>8:1:1. Carbon supported VS2 NSs of the mole ratio 1:8:1 showed a small resistance of 0.32 Ω. This is further evidence that the carbon supported VS2 NSs of the mole ratio 1:8:1 in addition to revealing excellent catalytic behaviour is also more chemically stable and has good conductivity properties._________
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- Date Issued: 2020
Voltammetric investigation of microbiological growth media and carbon nanotube modified electrodes : a case study of oxytetracycline
- Authors: Kruid, Jan
- Date: 2013
- Subjects: Voltammetry , Electrodes , Oxytetracycline , Carbon nanotubes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4156 , http://hdl.handle.net/10962/d1018238
- Description: Oxytetracycline (OTC) is a broad spectrum antibiotic used extensively in the agricultural and human-health sector, and is effective against various gram positive and –negative bacteria as well as large viruses and certain pathogenic Rickettsiae. This study addresses the lack of voltammetric knowledge regarding the electroanalytical characterisation of OTC and its analysis in complex matrices. Cyclic voltammetry (CV) revealed several irreversible anodic peaks for OTC at a bare glassy carbon electrode (GCE). These current responses were improved through the selection of a diluent for OTC stock preparation, electrolyte solution and electrolyte pH, stir time and applied preconditioning potential. Under enhanced adsorptive conditions and using square wave voltammetry (SWV), a detection limit of 24.3 nM was achieved. The electrode surface could be renewed in vitro for 10 successive scans. OTC oxidation was characterised as a one electron:one proton ECiE mechanisms. Next, investigating the viability of voltammetry in various complex microbiological growth media revealed that selected growth media contained interfering redox active components, which, while simultaneously coating the electrode surface, effectively reduced GCE performance and lowered the active electrode surface area, as ascertained through CV and electrochemical impedance spectroscopy (EIS) studies. This interference lowered OTC current response in the presence of growth media which was partially recovered by appropriate growth media selection and sample dilution. In testing the use of acid functionalised multi-walled carbon nanotubes (MWCNTs) to improve anodic OTC response, charge-based attraction was observed between the MWCNT dispersal agent Nafion® and OTC, while increased surface area associated with prolonged acid functionalisation time aided in improving OTC current response.
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- Date Issued: 2013
Nanomaterial modified electrodes : optimization of voltammetric sensors for pharmaceutical and industrial application
- Authors: Brimecombe, Rory Dennis
- Date: 2011
- Subjects: Voltammetry , Electrochemistry , Nanotubes , Nanostructured materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4101 , http://hdl.handle.net/10962/d1009721
- Description: Nanomaterials, in particular carbon nanotubes have been shown to exhibit favourable properties for the enhancement of electrochemical detection of target analytes in complex matrices. There is however scope for improvement in terms of the optimization thereof in electrochemical sensors surface modification. The aim of this thesis was to examine methods that would result in increased current response, lowered passivation and application of such modified surfaces with application to pharmaceutically and industrially relevant analytes. Current methods for enhancing the performance of carbon nanotubes include acid functionalization which not only increases the hydrophilicity of the nanotubes, and consequently their ability to provide stable (aqueous) suspensions, but also introduces electrochemically active sites. This particular approach is however not normalized in the literature. Over-exposure to acid treatment results in loss of structural integrity of the carbon nanotubes, and as such a fine balance exists between achieving these dual outcomes. Guided by high resolution scanning electron microscopy, atomic force microscopy, voltammetric and impedance studies, this thesis examined the role of the length of time of the acid functionalization process as well as the impact of activation of carbon nanotubes and fullerenes on electrochemical sensor performance. Based on desired charge transfer resistances, rate transfer coefficients and sensitivity towards redox probes the optimal length of acid functionalization for multiwalled carbon nanotubes was 9 hours and 4 hours for single-walled carbon nanotubes. Further improvements in the desired outcomes were achieved through electrochemical activation of the modified electrode surface by cycling in the presence of catechol, in a novel approach. By employing electrochemical impedance spectroscopy it was observed that catechol activation resulted in lowered charge transfer resistance, before and after activation, with functionalized multi-walled carbon nanotubes (9 hours) exhibiting the greatest decrease of 90 % and functionalized single-walled carbon nanotubes (4 hours), a 50 % decrease. Corresponding increases in the heterologous rate transfer coefficient showed a 770 % increase for functionalized multi-walled carbon nanotubes (9 hours), following catechol activation. Comparative observations for fullerenes following partial reduction in potassium hydroxide yielded a 30 % decrease in charge transfer resistance, with an increased heterologous rate transfer coefficient at a fullerene modified surface The performance of the nanomaterial modified electrodes was applied to the detection of wortmannin with applications in bioprocess control and in the pharmaceutical sector as well as to the detection and monitoring of the industrial dye Reactive red. Of particular relevance to these analytes was the assessment of the nanomaterial modified electrodes for enhanced stability, reproducibility, sensitivity and decreased passivation effects. In this study the first known account of wortmannin detection through electrochemical methods is reported. Voltammetric characterization of wortmannin revealed an irreversible cathodic process with a total number of 4 electrons and a diffusion coefficient of 1.19 x 10-7 cm².s⁻¹. At a functionalized multiwalled carbon nanotubes modified glassy carbon electrode a limit of detection of 0.128 nmol.cm⁻³ was obtained, and with limited surface passivation the detection scheme afforded pertinent analyses in biological media representing a substantial improvement over chromatographic detection methods. This study also provided the first account of the voltammetric detection of reactive red, competing favourably with traditional spectroscopic methods for monitoring biodegradation of this compound in real time.
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- Date Issued: 2011
Voltammetric analysis of pesticides and their degradation: A case study of Amitraz and its degradants
- Authors: Brimecombe, Rory Dennis
- Date: 2006
- Subjects: Hydrolysis , Biodegradation , Voltammetry , Pesticides -- Biodegradation , Pesticides -- Environmental aspects , Acaricides , Acaricides -- Physiological effect
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4131 , http://hdl.handle.net/10962/d1015724
- Description: Amitraz is a formamide acaricide used predominantly in the control of ectoparasites in livestock and honeybees. Amitraz hydrolysis is rapid and occurs under acidic conditions, exposure to sunlight and biodegradation by microorganisms. The main hydrolysis product of amitraz, 2,4-dimethylaniline, is recalcitrant in the environment and toxic to humans. An electrochemical method for the determination of total amitraz residues and its final breakdown product, 2,4-dimethylaniline, in spent cattle dip, is presented. Cyclic voltammetry at a glassy carbon electrode showed the irreversible oxidation of amitraz and 2,4-dimethylaniline. A limit of detection in the range of 8.5 x 10⁻⁸ M for amitraz and 2 x 10⁻⁸ M for 2,4-dimethylaniline was determined using differential pulse voltammetry. Feasibility studies in which the effect of supporting electrolyte type and pH had on electroanalysis of amitraz and its degradants, showed that pH affects current response as well as the potential at which amitraz and its degradants are oxidised. Britton-Robinson buffer was found to be the most suitable supporting electrolyte for detection of amitraz and its degradants in terms of sensitivity and reproducibility. Studies performed using environmental samples showed that the sensitivity and reproducibility of amitraz and 2,4-dimethylaniline analyses in spent cattle dip were comparable to analyses of amitraz and 2,4-dimethylaniline performed in Britton-Robinson buffer. In addition, the feasibility qf measuring amitraz and 2,4-dimethylaniline in environmental samples was assessed and compared to amitraz and 2,4-dimethylaniline analyses in Britton-Robinson buffer. Amitraz and 2,4-dimethylaniline were readily detectable in milk and honey. Furthermore, it was elucidated that 2,4-dimethylaniline can be metabolised to 3-methylcatechol by Pseudomonas species and the proposed breakdown pathway is presented. The biological degradation of amitraz and subsequent formation of 2,4-dimethylaniline was readily monitored in spent cattle dip. The breakdown of amitraz to 2,4-dimethylaniline and then to 3-MC was monitored using cyclic voltammetry.
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- Date Issued: 2006