Graphene supported antimony nanoparticles on carbon electrodes for stripping analysis of environmental samples

>Magister Scientiae - MScPlatinum Group Metals (PGMs), particularly palladium (Pd), platinum (Pt) and rhodium (Rh) have been identified as pollutants in the environment due to their increased use in catalytic converters and mining in South Africa (as well as worldwide). Joining the continuous efforts to alleviate this dilemma, a new electrochemical sensor based on a nanoparticle film transducer has been developed to assess the level of these metals in the environment. The main goal of this study was to exploit the capabilities of nanostructured material for the development and application of an adsorptive stripping voltammetric method for reliable quantification of PGMs in environmental samples. In the study reported in this thesis, glassy carbon electrode (GCE) and screen-printed carbon electrode (SPCE) surfaces were modified with conducting films of nanostructured reduced graphene oxide-antimony nanoparticles (rGO-SbNPs) for application as electrochemical sensors. The rGO-SbNPs nanocomposite was prepared by Hummer`s synthesis of antimony nanoparticles in reaction medium containing reduced graphene oxide. Sensors were constructed by drop coating of the surfaces of the carbon electrodes with rGO-SbNPs films followed by air-drying. The nanocomposite material was characterised by: scanning and transmission electron miscroscopies; FTIR, UV-Vis and Ramanspectrosocopies; dc voltammetry; and electrochemical impedance spectroscopy. The real surface area of both electrodes were studied and estimated to be 1.66 × 10⁶ mol cm⁻² and 4.09 × 10³ mol cm⁻² for SPCE/rGO-SbNPs and GCE/rGO-SbNPs, respectively. The film thickness was also evaluated and estimated to be 0.36 cm and 1.69 × 10⁻⁶ cm for SPCE/rGO-SbNPs and GCE/rGO-SbNPs, respectively. Referring to these results, the SPCE/rGO-SbNPs sensor had a better sensitivity than the GCE/rGO-SbNPs sensor. The electroanalytical properties of the PGMs were first studied by cyclic voltammetry followed by indepth stripping voltammetric analysis. The development of the stripping voltammetry methodology involved the optimisation of experimental conditions such as selection of adequate supporting electrolyte, choice of pH and /or concentration of supporting electrolytes, deposition potential, deposition time, stirring conditions. The detection of Pd(II), Pt(II) and Rh(III) in environmental samples were performed SPCE/rGO-SbNPs and GCE/rGO-SbNPs at the optimised experimental conditions For the GCE/rGO-SbNPs sensor, the detection limit was found to be 0.45, 0.49 and 0.49 pg L⁻¹ (S/N = 3) for Pd(II), Pt(II) and Rh(III), respectively. For the SPCE/rGO-SbNPs sensor, the detection limit was found to be 0.42, 0.26 and 0.34 pg L⁻¹ (S/N = 3) for Pd(II), Pt(II) and Rh(III), respectively. The proposed adsorptive differential pulse cathodic stripping voltammetric (AdDPCSV) method was found to be sensitive, accurate, precise, fast and robust for the determination of PGMs in soil and dust samples. The simultaneous determination of PGMs was also investigated with promising results obtained. The AdDPCSV sensor performance was compared with that of inductive coupled plasma mass spectroscopy (ICP-MS) for the determination of PGM ions in soil and dust samples. It was found that though the metals could be determined by ICP-MS technique, it was limited from the standpoints of sensitivity, ease of operation and versatility compared to the AdDPCSV sensor. This study has show cased the successful construction and application of novel SPCE/rGO-SbNPs and GCE/rGO-SbNPs AdDPCSV sensors forthe determination of PGMs in environmental samples (specifically roadside dust and soil samples). The study provides a promising analytical tool for monitoring PGMs pollutants that are produced by automobiles and transported in the environment