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

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

Few-layer binder free graphene modified mercury film electrode for trace metal analysis by square wave anodic stripping voltammetry

A binding agent free graphene modified glassy carbon electrode in combination with an in situ plated mercury film electrode (Gr-GC-HgFE) was used as a highly sensitive electrochemical platform for the determination of Zn2+, Cd2+ and Pb2+ in 0.1 M acetate buffer (pH 4.6) by square-wave anodic stripping voltammetry (SWASV). Instrumental parameters such as deposition potential, deposition time and electrode rotation speed were optimized. The Gr-GC-HgFE sensing platform exhibited improved sensitivity for metal ion detection, in addition to well defined, reproducible and sharp stripping signals. Two linear calibration curves ranging from 0 –10 μg L−1 and 0 – 60 μg L−1 were identified yielding detection limits of 0.08 μg L−1, 0.05 μg L−1 and 0.14 μg L−1 for Zn2+, Cd2+ and Pb2+, respectively, for simultaneous analysis and 0.04 μg L−1, 0.11 μg L−1 and 0.14 μg L−1 for Zn2+, Cd2+ and Pb2+, respectively, for individual analysis when using a deposition time of 120 s. For practical applications recovery studies using tap water samples spiked with target metal ions gave recoveries within 10% of the spiked amount. Much better recoveries were obtained for the individual analysis in comparison with simultaneous analysis.Web of Scienc