Electrochemically reduced graphene oxide pencil-graphite in situ plated bismuth-film electrode for the determination of trace metals by anodic stripping voltammetry

An electrochemical platform was developed based on a pencil-graphite electrode (PGE) modified with electrochemically reduced graphene oxide (ERGO) sheets and in conjunction with an in situ plated bismuth-film (ERGO-PG-BiE). The ERGO-PG-BiE was used as a sensing platform for determining Zn2+, Cd2+ and Pb2+ by square wave anodic stripping voltammetry (SWASV). ERGO sheets were deposited on to pencil-graphite electrodes by cyclic voltammetric reduction from a graphene oxide (GO) solution. The GO, with flake thicknesses varying between 1.78 to 2.10 nm (2 sheets) was characterized using FT-IR, HR-SEM, HR-TEM, AFM, XRD and Raman spectroscopy. Parameters influencing the electroanalytical response of the ERGO-PG-BiE such as, bismuth-film concentration, deposition potential, deposition time and rotation speed were investigated and optimized. The ERGO-PG-BiE gave well-defined, reproducible peaks with detection limits of 0.19 μg L-1, 0.09 μg L-1 and 0.12 μg L-1 for Zn2+, Cd2+ and Pb2+ respectively, at a deposition time of 120 seconds. For real sample analysis, the enhanced voltammetric sensor proved to be suitable for the detection and quantitation of heavy metals below the US EPA prescribed drinking water standards of 5 mg L-1, 5 μg L-1 and 15 μg L-1 for Zn2+, Cd2+ and Pb2+ respectively

Graphene-modified pencil graphite mercury-film electrodes for the determination of trace metals by cathodic adsorptive stripping voltammetry

>Magister Scientiae - MScThis project focuses on the simple, fast and highly sensitive adsorptive stripping voltammetry detection of Nickel and Cobalt complexed with DMG and Nioxime respectively at a Reduced Graphene Oxide modified pencil graphite electrode in water samples. This research as well demonstrates a novel electrochemically reduced graphene oxide (ERGO)/mercury film (MF) nanocomposite modified PGE, prepared through successive electrochemical reduction of graphene oxide (GO) sheets and in-situ plated mercury film. The GO and graphene were characterized using FT-IR, HR-SEM, HR-TEM, XRD and Raman spectroscopy. The FT-IR results supported by Xray diffraction analysis confirmed the inclusion of oxygen moieties within the graphitic structure during the chemical oxidation step. Microscopic and spectroscopic analysis was used to confirm the stackings of graphene on the pencil electrode. The ERGO-PG-MFE, in combination with a complexing agents of [dimethylglyoxime (DMG) and Nioxime] and square-wave cathodic stripping voltammetry (SW-CSV), was evaluated towards the individual determination of Ni2+ and Co2+ respectively and simultaneous determination of both metals from the combination of DMG and Nioxime mixture. A single-step electrode pre-concentration approach was employed for the in-situ Hg-film electroplating, metal-chelate complex formation and its non-electrolytic adsorption at – 0.7 V for the individual analysis of Ni2+ and Co2+. The current response due to metal-ligand(s) complex reduction were studied as a function of experimental variables; deposition/accumulation potential, deposition/accumulation time, rotation speed, frequency and amplitude and carefully optimized for the individual determination of Ni2+and Co2+ and simultaneous determination of Ni2+ and Co2+ at low concentration levels (μg L-1) in 0.1 M NH3- NH4Cl buffer solution (pH 9.4) solution. The recorded limit of detection for the individual analysis of Ni2+and Co2+ was found to be 0.120 μg L-1 and 0.220 μg L-1 respectively, at an accumulation time of 120 s for both metals. The recorded limit of detection of the simultaneous analysis of Ni2+ and Co2+ was found to be 6.1 μg L-1 and 1.8 μg L-1 respectively. The ERGO-PG-MFE further demonstrated a highly selective stripping response toward all trace metal analysis. The testing of the applicability of graphene-based sensor and method in laboratory tap water samples was evaluated. This electrode was found to be sensitive enough to detect metal ions in the tap water samples at the 0.2 μg L-1 level for individual analysis and 0.001 μg L-1 for simultaneous, well below WHO standards

Graphene-modified pencil graphite bismuth-film electrodes for the determination of heavy metals in water samples using anodic stripping voltammetry

>Magister Scientiae - MScElectrochemical platforms were developed based on pencil graphite electrodes (PGEs) modified with electrochemically deposited graphene (EG) sheets and Nafion-graphene (NG) nanocomposites in conjunction with an in situ plated bismuth-film (EG-PG-BiE and NG-PG-BiE). The EG- and NG-PG-BiEs were used as sensing platforms for determining Zn2+, Cd2+ and Pb2+ by square wave anodic stripping voltammetry (SWASV). EG sheets were deposited onto pencil graphite electrodes by cyclic voltammetric reduction from a graphene oxide (GO) solution, while a dip coating method was used to prepare the NG-PG-BiE. The GO and graphene, with flake thicknesses of 1.78 (2 sheets) and 2.10 nm (5 sheets) respectively, was characterized using FT-IR, HR-SEM, HR-TEM, AFM, XRD and Raman spectroscopy. Parameters influencing the electroanalytical response of the EG-PG-BiE and NG-PG-BiE such as, bismuth ion concentration, deposition potential, deposition time and rotation speed were investigated and optimized. The EG-PG-BiE gave well-defined, reproducible peaks with detection limits of 0.19 μg L-1, 0.09 μg L-1 and 0.12 μg L-1 for Zn2+, Cd2+ and Pb2+ respectively, at a deposition time of 120 seconds. The NG-PG-BiE showed similar detection limits of 0.167 μg L-1, 0.098 μg L-1 and 0.125 μg L-1 for Zn2+, Cd2+ and Pb2+ respectively. For real sample analysis, the enhanced voltammetric sensor proved to be suitable for the detection and quantitation of heavy metals below the US EPA prescribed drinking water standards of 5 mg L-1, 5 μg L-1 and 15 μg L-1 for Zn2+, Cd2+ and Pb2+ respectively

Electromembrane extraction and electrochemical measurement system for heavy metal ions detection in aquatic environmental samples

Water contamination is a worldwide problem which deserves attention due to its negative impact on ecosystem, human health as well as economic growth. Heavy metals are a group of the pollutants that have received particular attention due to their high toxicity even at concentration as low as parts per billion (ppb). Technology advancement in the field of separation and detection of heavy metals has introduced sensitive and selective analytical instruments for real aquatic environmental samples. However, real sample matrices can reduce the quality of results. In modern analytical chemistry, there is a high demand for accurate quantification of trace and ultra-trace of heavy metals from real aqueous samples. In the present study, electromembrane extraction (EME) and electrochemical techniques were combined to develop effective electrodes which can separate, pre-concentrate and determine heavy metals such as Pb(II), Cr(VI) and Cd(II) in real aqueous samples. Electrochemically reduced graphene oxide-graphite reinforced carbon (ErGO-GRC) was utilised in conjunction with square wave anodic stripping voltammetry (SWASV) for the determination of Pb(II). Meanwhile, selective and sensitive determinations of Cr(VI) was carried out using ex-situ prepared nafion-coated antimony film on graphite reinforced carbon (NSbFE-GRC) by square wave adsorptive stripping voltammetry (SWAdSV) in the presence of diethyltriamine pentacetic acid (DTPA). Ex-situ prepared NSbFE-GRC was also used for simultaneous determination of Pb(II) and Cd(II) by SWASV. Simple polyvinylidene fluoride (PVDF) flat sheet membranes were synthesised and characterised in order to combine these developed electrochemical techniques with EME. Heavy metals were extracted from an aqueous sample solution into an acidic acceptor phase in the lumen of a PVDF membrane bag by the application of voltage across the supported liquid membrane (SLM), consisting of organic solvent and complexing carriers. Parameters affecting the EME were optimised for heavy metals. The PVDF–ErGO–GRC electrode system attained enrichment factors of 40 times and 80% extraction with relative standard deviation (n = 5) of 8.3% for Pb(II). Good linearity in the range of 0.25-2 nM was obtained with correlation coefficient of 0.999. The Pb(II) ions detection limit of PVDF–ErGO–GRC electrode was 0.09 nM. Meanwhile, the PVDF–NSbFE–GRC system attained enrichment factors of 86.6 times, 95.6% extraction, and good linearity in the range of 10-60 pM with correlation coefficient of 0.9933. Furthermore, the limit of Cr(VI) detection was found to be around 0.83 pM for the developed PVDF–NSbFE–GRC electrode. On the other hand, the PVDF–NSbFE–GRC was able to attain enrichment factors of 49.3 and 68.4 times, 82.6% and 114.0% extractions, and good linearity ranging from 2 to 10 pM with correlation coefficients of 0.9953 and 0.9883 for Pb(II) and Cd(II), respectively. Furthermore, the limits of detection for Pb(II) and Cd(II) were found to be around 0.65 pM and 0.60 pM, respectively. A chargeable battery operated portable EME system was developed for quantitative determination of heavy metals. The newly developed single setup electrochemical system was applied to the analysis of real aqueous samples such as tap water, industrial waste water, river water and sea water, and it was able to extract with percentage of extraction in the range of 78.7 -103.0% compared to commercially available direct current power supply

Microfluidic graphenised-paper electroanalytical devices (μGPED) for adsorptive cathodic stripping voltammetric detection of metal contaminants

Philosophiae Doctor - PhDThe need for clean, non-toxic drinking water supplies, free of pollutants and metal contamination is vital in impoverished areas and the developing world alike. With this in mind, the development of accurate, inexpensive, portable and simple devices for remote sensing applications is therefore pivotal for early detection and the prevention of illnesses. Over the last two decades, adsorptive stripping voltammetry (AdSV) has emerged as a superior detection method over common analytical techniques due to its low-cost instrumentation, unskilled labour and ability to detect a wide range of analytes

Electrochemical deposition of Graphene Oxide- metal nano-composite on Pencil-Graphite Electrode for the high sensitivity detection of Bisphenol A by Adsorptive Stripping Differential Pulse Voltammetry

Magister Scientiae - MSc (Chemistry)Electrochemical platforms were developed based on pencil graphite electrodes (PGEs) modified electrochemically with reduced graphene oxide metal nanoparticles (ERGO–metalNPs) composite and used for the high-sensitivity determination of Bisphenol A (BPA) in water samples. Synergistic effects of both reduced Graphene Oxide sheets and metal nanoparticles on the performance of the pencil graphite electrode (PGE) were demonstrated in the oxidation of BPA by differential pulse voltammetry (DPV). A solution of graphene oxide (GO) 1 mg mL-1 and 15 ppm of metal stock solutions (1,000 mg L-1, atomic absorption standard solution) (Antimony or Gold) was prepared and after sonication deposited onto pencil graphite electrodes by cyclic voltammetry reduction. Different characterization techniques such as FT-IR, HR-SEM, XRD and Raman spectroscopy were used to characterize the GO and ERGO–metalNPs. Parameters that influence the electroanalytical response of the ERGO–SbNPs and ERGO–AuNPs such as, pH, deposition time, deposition potential, purging time were investigated and optimized. Well-defined, reproducible peaks with detection limits of 0.0125 μM and 0.062 μM were obtained for BPA using ERGO–SbNPs and ERGO–AuNPs respectively. The rGO-metalNPs–PGE was used for the quantification of BPA in tap water sample and proved to be suitable for the detection of BPA below USEPA prescribed drinking water standards of 0.087 μM

Voltammetric determination of metal ions beyond mercury electrodes. A review

For a long time mercury electrodes have been the main choice for the analysis of metal ions and some metalloids. However, in the last years, safety and environmental considerations have restricted their use and encouraged the search for alternative materials more environmentally friendly and with more possibilities for in-situ and flow analysis. This research has been reinforced by the popularisation of nanomaterials, biomolecules and screen-printed electrodes, as well as for the new advances in sensor miniaturization and integration of the electrodes in multi-sensor platforms and electronic tongues. The present review critically summarizes and discusses the progress made since 2010 in the development and application of new electrodes for the analysis of metals and metalloids

Determination of paracetamol at the electrochemically reduced graphene oxide-metal nanocomposite modified pencil graphite (ERGO-MC-PGE) electrode using adsorptive stripping differential pulse voltammetry

>Magister Scientiae - MScThis project focuses on the development of simple, highly sensitive, accurate, and low cost electrochemical sensors based on the modification of pencil graphite electrodes by the electrochemical reduction of graphene oxide-metal salts as nanocomposites (ERGO-MC-PGE; MC = Sb or Au nanocomposite). The electrochemical sensors ERGO-Sb-PGE and ERGO-Au-PGE were used in the determination of paracetamol (PC) in pharmaceutical formulations using adsorptive stripping differential pulse voltammetry. The GO was prepared from graphite via a modified Hummers’ method and characterized by FTIR and Raman spectroscopy to confirm the presence of oxygen functional groups in the conjugated carbon-based structure whilst, changes in crystalline structure was observed after XRD analysis of graphite and GO.2023-10-0

Multilayer graphene modified metal film electrodes for the determination of trace metals by anodic stripping voltammetry

Magister Scientiae - MScIn this study multilayer graphene nanosheets was synthesize by oxidizing graphite to graphene oxide using H2SO4 and KMnO4 followed by reduction of graphene oxide to graphene using NaBH4. The graphene nanosheets were characterized by Fourier Transform Infrared (FTIR) and Raman spectroscopy, high resolution transmission electron microscopy (HRTEM), Scanning electron microscopy (SEM) and X-ray diffraction (XRD). HRTEM images showed that the multilayer graphene were obtained. The graphene was immobilized directly onto a glassy carbon electrode using the drop coating technique followed by the in situ deposition of mercury, bismuth or antimony thin films to afford graphene modified glassy carbon metal film electrodes (Gr-GC-MEs). The experimental parameters (deposition potential, deposition time, rotation speed, frequency and amplitude) were optimized, and the applicability of the modified electrode was investigated towards the individual and simultaneous determination of Zn2+, Cd2+ and Pb2+ at the low concentration levels (μg L-1) in 0.1 M acetate buffer (pH 4.6) using square wave anodic stripping voltammetry (SWASV). The detection limits values for the Gr-GC-HgE was 0.08, 0.05 and 0.14 μg L-1 for Zn2+, Cd2+ and Pb2+, respectively. The Gr-GC-BiE the detection limits for was 0.12, 0.22 and 0.28 μg L-1 for Zn2+, Cd2+ and Pb2+ while the detection limits for the Gr-GC-SbE was 0.1, 0.3 and 0.3 μg L-1 for Zn2+, Cd2+ and Pb2+, respectively. A Gr-GCE prepared without any binding agents or metal film had detection limits for Zn2+, Cd2+ and Pb2+ of 3.9, 0.8 and 0.2 μg L-1 for Zn2+, Cd2+ and Pb2+. Real sample analysis of which was laboratory tap water was performed using the Gr-GCMEs. Only Gr-GC-HgE was sensitive enough to detect metal ions in the tap water samples at the 3ppb level whereas, the GC-BiE and GC-SbE detected the metal ions at the 10 μg L-1 to 30 μg L-1 level

Determination of paracetamol on electrochemically reduced graphene oxide–antimony nanocomposite modified pencil graphite electrode using adsorptive stripping differential pulse voltammetry

A simple, highly sensitive, accurate, and low-cost electrochemical sensor was developed for the determination of over-the-counter painkiller, paracetamol (PC). The enhanced sensing capabilities of the developed sensor were fabricated by the single-step modification of disposable pencil graphite electrodes (PGEs) with the simultaneous electrochemical reduction in graphene oxide and antimony (II) salts. For this purpose, an electrochemically reduced graphene oxide–antimony nanoparticle (ERGO-SbNP) nanocomposite material was prepared by trapping metallic nanoparticles between individual graphene sheets in the modification of PGEs