- Title
- Development of silver-based polyaniline nanocomposite for electrochemical oxidation and detection of organosulfur compounds
- Creator
- Shoba, Siyabonga
- Subject
- Polyethylene -- Analysis
- Subject
- Composite materials Nanocomposites (Materials)
- Date Issued
- 2019
- Date
- 2019
- Type
- Thesis
- Type
- Masters
- Type
- MSc
- Identifier
- http://hdl.handle.net/10948/43600
- Identifier
- vital:36928
- Description
- Human activities such as combustion of fossil fuels through automobiles, factories and electricity generation using coal results in major productions of sulfur dioxide to the atmosphere. The sulfur dioxide gas chemically reacts with other substances (i.e. water and oxygen) in the atmosphere and produces acidic pollutants. These acidic pollutants exist in both wet and dry form and before they are deposited on the earth’s surface, they can travel long distances carried by the wind. They are deposited in a wet form as rain, snow, fog and sleet and in a dry form as gases or particles. This has led to the mandated 10 ppm S in fuel by the environmental protection agency (EPA). Electrochemical desulfurization (ECDS) has been reported as an innovative technique for removing sulfur via redox processes. ECDS technique is a low costs process as no catalysts and oxidant are involved and it is a green technology (environmental benignity), thus making the process more economical than conventional hydrodesulfurization (HDS) technologies. Modification of electrodes for electrochemistry as well as electrodeposition of metal nanoparticles offers interesting electrochemical activities due to their reduced size and high surface area to volume ratio. Electrochemical oxidation of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was analysed in acetonitrile using carbon electrodes modified with silver (Ag)-polyaniline (PAni) based nanocomposites (GCE/PAni/Ag and GCE/Ag). The PAni, PAni/Ag composites were characterized using spectroscopic (FT-IR, XRD, XPS) and microscopic (SEM and TEM) techniques. SEM confirmed that the synthesized PAni and PAni/Ag presented an amorphous granular morphology with the aggregation of small irregular particle sizes. Cyclic voltammetry of BT, DBT and 4,6-DMDBT on the modified glassy carbon (GCE) electrode show chemically irreversible anodic peaks which corresponds to electron transfer of sulfur to form sulfoxide and lastly sulfone containing compounds. The overall conversion yield of DBT and 4,6-DMDBT to respective sulfones increased as water content increases. Products were characterized by means of gas chromatograph coupled to mass spectrometer (GC-MS), 1H and 13C NMR. Similarly, silver-modified Glassy Carbon (GCE) electrode was used for the electrochemical detection of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) in the presence of naphthalene (NP) and carbazole (CR). The electrochemical response of BT, DBT and 4,6-DMDBT on the modified electrode was determined using Differential Pulse Voltammetry (DPV) in acetonitrile. The electrochemical behaviour of BT, DBT and 4,6-DMDBT showed that the modified electrode exhibited excellent oxidation electro-catalytic activity. The dynamic range for the organosulfur compounds determination was from 1 to 11 ppm with detection limits (LOD) of 0.60 ppmS, 0.41 ppmS and 0.21 ppmS for BT, DBT and 4,6-DMDBT, respectively. Electrochemical sensor showed excellent selectivity of the compounds in the presence of interfering compounds such as naphthalene, carbazole and thiourea over the studied range of concentrations. The prepared electrode exhibited satisfactory reusability and stability after four successive measurement. It has been demonstrated in this study that modified glassy carbon (GCE) electrode (GCE/PAni/Ag) can be successfully used for the assay of sulfur containing compounds such as BT, DBT and 4, 6-DMDBT in petroleum samples.
- Format
- xviii, 118 leaves
- Format
- Publisher
- Nelson Mandela University
- Publisher
- Faculty of Science
- Language
- English
- Rights
- Nelson Mandela University
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NMU School of BioMolecular and Chemical Sciences
| Thumbnail | File | Description | Size | Format | |||
|---|---|---|---|---|---|---|---|
| View Details Download | SOURCE1 | Thesis Final 31-10-2019.pdf | 7 MB | Adobe Acrobat PDF | View Details Download |