O mecanismo e cinética da oxidação de etanol sobre níquel em soluções de hidróxido de sódio em condições experimentais bem definidas, que incluíram a variação da concentração do etanol, potencial final da varredura anódica, temperatura da solução (tanto na temperatura de 25 °C quanto da ordem de -15 °C), e variação da velocidade de varredura, são discutidos em termos da formação de óxidos de níquel de valência superior. Na primeira parte deste estudo foi utilizado voltametria cíclica e foram encontradas evidências para um processo de intermediação envolvendo a molécula do etanol e as espécies β-NiOOH formadas sobre a superfície do eletrodo em E ≥ 1,3 V vs. ERH. Em baixas concentrações de etanol (≤ 0,2 mol L-1) a etapa determinante da velocidade da reação é governada por um processo de difusão. Em concentrações mais altas (> 0,2 mol L-1) esta reação passou a ser governada por um processo de transferência de carga entre a molécula do etanol e as espécies Ni3+. O aumento da concentração deslocou o potencial do pico da oxidação do etanol para potenciais mais positivos. A diminuição da temperatura afetou a cinética desta reação, diminuindo a j e provocando um deslocamento do potencial de início da oxidação do etanol para potenciais mais positivos. Foi possível observar a partir das características dos perfis voltamétricos, que mesmo em temperatura de -15 °C a reação de eletro-oxidação do etanol continuou prosseguindo. No potencial de início da reação de oxidação do etanol, o valor de Ea encontrado mostrou ser característico de uma reação controlada por um processo de difusão, enquanto que o valor de Ea obtido no potencial de pico foi típico de uma reação controlada por um processo de transferência de carga. A j da oxidação do etanol não é afetada pela velocidade de varredura do potencial. Por outro lado, a velocidade de varredura do potencial tem uma influência considerável sobre as características voltamétricas referentes à formação e redução do β-NiOOH. Na segunda etapa foram realizadas análises de FTIRS in situ, os resultados mostraram que a oxidação do etanol sobre níquel converte de forma seletiva este álcool ao seu ácido carboxílico correspondente (ácido acético). / The mechanism and kinetic of the ethanol oxidation on nickel in sodium hydroxide solutions under experimental conditions well controlled that included the variation of ethanol concentration, last potential of the anodic scan, temperature of the solution, and variation of scan rate, are discussed in terms of the formation of higher valence nickel oxides. The first step of this study was performed using cyclic voltammetry and showed evidences of a mediation process involving the ethanol molecule and β-NiOOH species formed on the electrode surface at E ≥ 1,3 V vs. ERH. At low ethanol concentrations (≤ 0,2 mol L-1) the rate-determining step of the reaction is governed by a diffusion process. At higher concentrations (> 0,2 mol L-1) this reaction passed to be governed by a charge transference process between the ethanol molecule and Ni3+ species. The increase of the ethanol concentration shifted the peak potential of the oxidation of ethanol to potentials more positives. The decrease of temperature affected the kinetic of this reaction, decreasing the j and causing a shifted of the onset potential of the ethanol oxidation to potentials more positives. It was possible to observe from the CV features, which even under temperature of -15 °C, the reaction of electro-oxidation of ethanol continued pursuing. At the onset potential of the ethanol oxidation reaction, the value of Ea found showing to be characteristic of a reaction controlled by a diffusion process, while the value of Ea obtained at the peak potential was typical of a reaction controlled by a charge transference process. The j of the ethanol oxidation was not affected by potential scan rate. In the other hand, the potential scan rate has an influence considerable on the CV features associated to the processes of β-NiOOH formation and reduction. In the second step, analysis in situ FTIRS were performed, which showed that this alcohol was converted of selective form to the correspond carboxylic acid (acetic acid).

Aspectos fundamentais das reações de eletrooxidação do glicerol e álcoois similares em ouro foram estudados por meio da comparação com a eletrooxidação de álcoois similares: 1-propanol, 2-propanol, propano-1,2-diol e propano-1,3-diol, além de sorbitol e glicose. Testes eletroquímicos foram feitos em soluções ácida, neutra e alcalina. Também foram realizados testes em meio alcalino com os possíveis subprodutos de oxidação do glicerol: dihidroxiacetona, gliceraldeído, glicerato, hidroxipiruvato, mesoxalato, tartronato, oxalato e formato. Por fim, os produtos de reação foram analisados por FTIR in situ e HPLC. Conforme esperado, o ouro foi praticamente inativo para todos os álcoois nos meios neutro e ácido, e muito ativo no meio alcalino. Entretanto, os dados de RDE mostraram que a formação de alcóxido não é a responsável pela atividade, como era proposto até então. Comparando a eletrooxidação do glicerol com álcoois similares, foi possível notar que a presença de hidroxilas vizinhas na molécula é a propriedade mais importante para render altas densidades de corrente (para a eletrooxidação de álcoois em geral) sobre ouro. Ela facilita a quebra das ligações C-C favorecendo a formação de produtos mais oxidados, conforme observado por FTIR e HPLC. As medidas de FTIR in situ também mostraram que pode haver neutralização e até acidificação nas proximidades do eletrodo em meio alcalino (se a concentração de base não for suficientemente alta), devido à formação de subprodutos ácidos, o que pode levar a uma mudança no mecanismo da reação. Medidas de RDE indicam que é possível controlar a seletividade dos produtos de eletrooxidação de glicerol e outros álcoois sobre ouro pela convecção artificial, entretanto, o controle pelo potencial ou concentração são limitados, conforme constatado pela análise de produtos. Os testes realizados com os subprodutos e análise de produtos permitiram refinar a rota reacional de eletrooxidação do glicerol. / Fundamental aspects of glycerol and similar alcohols electrooxidation reactions on gold were studied by comparing with similar alcohols: 1-propanol, 2-propanol, propane-1,2-diol and propane-1,3-diol, and also sorbitol and glucose. Electrochemical measurements were performed in acidic, neutral and alkaline solutions. Moreover, CV tests were performed in alkaline environment with the main possible glycerol oxidation byproducts: dihydroxyacetone, gyceraldehyde, glycerate, hydroxypyruvate, mesoxalate, tartronate, oxalate and formate. Finally, the reaction products were analyzed by in situ FTIR and HPLC. As expected, gold was practically inactive for all alcohols in acidic and neutral conditions, but highly active in alkaline medium. However, RDE data showed that the alkoxide formation is not the responsible for the high activity, as proposed until now. By comparing the glycerol electrooxidation with the other alcohols, it was possible note that the vicinal hydroxyl groups is the key property to yield the high current densities (for alcohols electrooxidation in a general way) seen on gold. It favors the C-C bonding break, that leads to more oxidized products, as seen by FTIR and HPLC data. In addition, FTIR measurements showed that neutralization and even acidification can occur near to the electrode in alkaline medium (if the base concentration is not high enough), due to the formation of acidic byproducts that can also lead to different reaction mechanism. RDE experiments indicated that it is possible to control the selectivity of glycerol and other alcohols electrooxidation products on gold by artificial convection, but control by the potential or concentration are limited, as shown by products analysis. The CV tests with byproducts and products analysis allowed to refine the glycerol electrooxidation reaction pathways.

Eletrodos de ouro foram utilizados para preparação de eletrodos modificados com monocamadas auto arranjadas de tióis. A limpeza do substrato metálico é fundamental para que a arquitetura molecular superficial possa ser efetuada com boa estabilidade e reprodutibilidade, além de fornecer dados utilizados no cálculo de área ativa, necessários na normalização dos valores de recobrimento superficial obtidos nas determinações de dessorção do agente modificador interno, o ácido 3-mercaptopropiônico. Os eletrodos modificados consistiram no recobrimento de transdutores de ouro com ácido 3-mercaptopropiônico através da imersão do eletrodo de Au em solução 25 mmolL-1 deste composto e, em seguida, com moléculas de cisteína, através da imersão do eletrodo de Au/3-MPA em solução 0,1 molL-1 deste composto, originando um sensor do tipo Au/3-MPA/CSH. As moléculas de cisteína foram utilizadas como agente redutor para obtenção de nanopartículas de Au na superfície do eletrodo modificado, através da aplicação de 20 µL de solução de HAuCl4. Após a confirmação da ausência do par tiólico superficial responsável pela redução das nanopartículas, o eletrodo Au/3-MPA/CSH/AuNp foi utilizado na determinação de peróxido de hidrogênio em soluções de concentrações crescentes em tampão fosfato 0,1 molL-1 pH 7,2. / Gold electrodes were used for surface modification through the incorporation of self-assembled monolayers of thiols. Pre-treatment of the metal substrate is essential for achieving good stability and reproducibility of the molecular architecture in the surface developed, and provides data used in the calculation of the active area, used to normalize surface coating values, which were obtained throughout the desorption measurements of 3-mercaptopropionic acid. The modification consisted on coating gold probes with 3-mercaptopropionic acid by dipping the Au electrode in 25 mmolL-1 solution of this compound, in which were, later, anchored cysteine molecules, by dipping of the Au/3-MPA electrode in 0.1 molL-1 solution of this compound, resulting in a Au/3-MPA/CSH sensor. Cysteine molecules were used as a reducing agent to obtain gold nanoparticles on the surface of the modified electrode through application of 20 µL of HAuCl4. After confirming the absence of the thiol redox couple responsible for the reduction of gold nanoparticles, the Au/3-MPA/CSH/AuNp electrode was used to determine hydrogen peroxide in phosphate buffer 0.1 molL-1 pH 7.2.

Orientador: Rodnei Bertazzoli / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-24T00:35:31Z (GMT). No. of bitstreams: 1 Figueiredo_RaulSebastiao_D.pdf: 4040065 bytes, checksum: 3400db86cd1264a10105354e1cc73250 (MD5) Previous issue date: 2013 / Resumo: Este trabalho investiga o desempenho do chumbo anodizado e de uma mistura de óxidos de chumbo / estanho para uso em processos de eletro-oxidação. Os eletrodos foram preparados por anodização do chumbo e ligas de chumbo/estanho previamente laminados na forma de placas para obter os filmes de óxido. A camada ativa era constituída por uma película de PbO2 e PbO2/SnOx formado durante a aplicação de uma densidade de corrente de 15 mA.cm-2, o qual a polarização foi invertida a cada 1 hora , durante o processamento , a 65 ° C em 10 % ( v / v ) H2SO4 solução. A morfologia dos revestimentos foi caracterizada por microscopia eletrônica de varredura (MEV) e difração de raios-X, que foi usada para identificar as fases presentes nas camadas de anodizadas. Voltametria cíclica foi realizada para obter o intervalo de potencial entre o hidrogênio e as reações de desprendimento de oxigênio. Área ativa dos eletrodos também foi determinada usando a equação Cottrell aplicada à reação de oxidação do ferro em uma solução de ferrocianeto de potássio. Os filmes formados foram utilizados para a eletro-oxidação do glicerol em que a concentração de carbono orgânico total foi seguida. Na sequência, esponjas de chumbo foram preparadas por prensagem do chumbo derretido em meio a partículas de cloreto de sódio. Três porosidades de esponjas foram obtidas por meio de três tamanhos de partículas de NaCl . Depois, o cloreto de sódio foi removido em água por 24 h. As esponjas foram então anodizadas em ácido sulfúrico e montadas em um reator eletroquímico de fluxo de compartimentado único com placas paralelas. O reator foi usado para experimentos de eletro-oxidação em correntes constantes para a degradação dos compostos orgânicos corante laranja 2- naftol e diazepam em soluções. As variáveis estudadas foram porosidade ânodo, vazão e densidade de corrente. O decaimento da concentração dos compostos orgânicos e de carbono orgânico total foram seguidos e análises da cinética foram realizadas . Foram calculadas as constantes de velocidade de ordem zero e de pseudo-primeira ordem. O reator através de dados obtidos de transferência de massa, pode ser correlacionando com parâmetros adimensionais como Re, Sh e números Sc . A técnica utilizada para a obtenção de eletrodos porosos PbO2 provou ser eficiente. A maioria das experiências mostrou 85 % de conversão de compostos orgânicos para o CO2 após 1 h de tratamento, a baixos valores de densidades de corrente / Abstract: This work investigates the performance of anodized lead and lead/tin alloy for using in electro-oxidation processes. The electrodes were prepared by anodizing lead and lead/tin alloy rolled plates to obtain the oxide films. The active layer was constituted by a film of PbO2 and PbO2/SnOx formed during the application of a current density of 15 mA.cm-2 which polarity was inverted every 1 h during the processing at 65 oC in a 10% (v/v) H2SO4 solution. The coatings morphology was characterized by scanning electron microscopy (SEM) and the X-ray diffraction was used to identify the phases present in the layers. Cyclic voltammetry was used to obtain the potential interval between the hydrogen and oxygen evolution reactions. Active area of the electrodes was also determined using Cottrell equation applied to the oxidation reaction of iron in a potassium ferrocyanide solution. The films were used for the electro-oxidation of glycerol during which the total organic carbon concentration was followed. In the sequence, lead sponges were prepared by pressing molten lead with sodium chloride particles. Three different sponges' porosities were obtained by using three NaCl particules sizes. After, sodium chloride was removed in water by 24 h. The sponges were then anodized in sulfuric acid and mounted in a single compartmented flow electrochemical reactor with parallel plates. The reactor was used for electro-oxidation experiments at constant currents for the degradation of an orange dye 2-naphtol solution and a diazepam solution. Variables were anode porosity, flow rate and current density. The concentration decay of the organic compounds and of total organic carbon was followed and kinetic analysis was performed. Zero and first order rate constants were calculated. Mass transfer figures of merit of the reactor were obtained by correlating dimensionless parameters such as Re, Sh and Sc numbers. The technique used for obtaining porous PbO2 electrodes proved to be efficient. Most of the experiments showed 85% of conversion of organic compounds to CO2 after 1 h of processing, at low values of current densities / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

No description available.

Dans ce travail, différentes solutions aqueuses de PEDOT: polyelectrolyte ont été synthétisées à partir de polymères anioniques de types polysaccharides et polystyrènes substitués par des groupements bis(sulfonylimide). Leurs morphologies, dopages,comportements rhéologiques ainsi que leurs propriétés opto-électroniques ont notammen tété caractérisés. Une étude systématique a révélé que les polyélectrolytes de masse molaire élevée portant un groupement fortement acide et ayant un squelette rigide permettent d'obtenir un dopage élevé, une dispersion efficace du PEDOT et donc des complexes PEDOT : polyelectrolyte plus conducteurs. L'utilisation du polyelectrolyte PSTFSI en tant qu'agent de complexation pour le PEDOT donne une dispersion stable montrant les caractéristiques d'un gel, ce qui facilite la fabrication de films minces par 'spin coating' ou doctor blade. Les films de PEDOT : PSTFSI ainsi obtenus montrent une transparence élevée et une conductivité de 330S.cm-1. Ces propriétés ont permis de les intégrer avec succès comme matériaux d'électrodes dans des dispositifs OLED, OPV et OECT. / In this work different aqueous dispersions of conducting poly(3,4-ethylenedioxythiophene) :polyelectrolyte (PEDOT:polyelectrolyte) complexes,made from anionic polysaccharides and from synthetic bis(sulfonylimide) substituted polystyrenes, have been synthesized and characterized regarding their doping, morphology, rheological behavior and opto-electronic properties. A systematic study revealed, that high molar mass polyelectrolytes with strongly acidic groups and a rigid backbone structure were favorable for a high doping and an efficient dispersion of PEDOT and allowed the development of highly conducting PEDOT:polyelectrolyte complexes. The use of the polyelectrolyte poly(4-styrenetrifluoromethane(bissulfonylimide)) (PSTFSI) as complexing agent for PEDOT resultedin stable dispersions with gel character, which allowed easy processing by spin coating and doctor blading. The obtained PEDOT:PSTFSI films were highly transparent,displayed a conductivity of up to 330S.cm-1 and were successfully integrated as electrodes in OLED, OPV and OECT devices.

Les batteries lithium-ion sont aujourd’hui très utilisées pour alimenter l’électronique portable telle que les ordinateurs, les smartphones et les caméras. Cependant, de nouvelles applications telles que les véhicules électriques et les systèmes stationnaires de stockage d'énergie nécessitent des batteries à performances améliorées. En particulier, de nouveaux matériaux d'électrode avec des densités d'énergie plus élevées sont requis. Les hydrures de MgH2 et TiH2 et leurs mélanges possèdent de très fortes capacités électrochimiques (>1 Ah/g). Ils ont été étudiés comme matériaux d’électrode négative dans les batteries Li-ion. La réaction de conversion de ces hydrures avec du lithium et les changements structuraux induits ont été étudiés en détails pour mieux comprendre les mécanismes réactionnels et leur réversibilité. Les propriétés électrochimiques de couches minces de MgH2 et des poudres composites de MgH2+TiH2 ont été étudiées en utilisant à la fois des électrolytes organiques liquides et un électrolyte solide LiBH4. La capacité réversible et la tenue au cyclage dépendent fortement du rapport molaire entre les deux hydrures et des conditions de cyclage. Le transport de masse et la densité d’interfaces à l'intérieur de l'électrode sont identifiés comme les principaux facteurs affectant la réversibilité de la réaction de conversion / Today, lithium-ion batteries are widely used as power supplies in portable electronics such as laptops, smartphones and cameras. However, new applications such as full electric vehicles and energy storage stationary systems require enhanced battery performances. In particular, novel electrode materials with higher energy density are needed.MgH2 and TiH2 hydrides and mixtures of them have high electrochemical capacity (> 1 Ah/g). They have been studied as negative electrode materials in Li-ion batteries. The conversion reaction of lithium with these hydrides and the related microstructural changes have been deeply investigated to gain a better understanding of reaction mechanisms and their reversibility. The electrochemical properties of MgH2 thin films and MgH2+TiH2 composite powders have been evaluated using both liquid organic and solid (LiBH4) electrolytes. Reversible capacity and cycle-life are found to strongly depend on both molar ratio between the hydrides and cycling conditions. Mass transport and density of interfaces within the electrode are identified as the main factors affecting the reversibility of the conversion reaction

RESUME<p><p>Le travail de thèse porte sur le développement d’électrodes sélectives originales et performantes pour l’analyse de composés d’intérêt pharmaceutique. <p><p> La partie introductive traite des notions relatives à l’électrochimie mais également de notions sur les molécules médicamenteuses étudiées, en l’occurrence les principes antipaludéens et l’iode.<p><p> La partie expérimentale se subdivise en deux parties distinctes selon le type d’électrodes sélectives auxquelles font appel les techniques électrochimiques.<p><p> La première partie concerne l’élaboration, la caractérisation et l’application des électrodes potentiométriques à membrane polymérique incluant une paire d’ions et sélectives à diverses molécules organiques pharmacologiquement actives (antipaludéens). Leur application aussi bien en analyse pharmaceutique qu’en cinétique de dissolution est décrite.<p><p> La deuxième partie est consacrée à l’élaboration d’un type de senseur ampérométrique original à pâte de carbone à base d’argent micronisé ou colloïdal et à la comparaison de ses performances avec l’électrode d’argent métallique. L’intérêt analytique est mis en évidence par la détermination quantitative des iodures.<p><p> Les différents aspects susceptibles d’influencer leur comportement, dont la nature des agents précipitants (tétraphénylborate de sodium et le tétrakis (4-chlorophényl) borate de potassium) et de plastifiants ont été investigués.<p>Les bonnes performances des ces électrodes en analyse quantitative ont permis d’explorer les possibilités de leur utilisation à l’étude de la cinétique de dissolution.<p><p> L’ampérométrie à électrode à pâte de carbone modifiée à base d’argent à l’échelle micronisée (35% m/m) couplée à la chromatographie liquide ionique s’est avérée très sensible vis-à-vis des iodures en particulier et des halogénures en général. Les facteurs susceptibles d’influencer les grandeurs de séparation et la réponse de l’électrode ont été investigués et l’exploitation du signal ampérométrique permet le dosage sélectif et rapide de faibles concentrations en iodures. Les informations fournies par les mesures réalisées en voltampérométrie cyclique à l’aide des mêmes électrodes permettent une bonne compréhension mécanistique quant au mode de détection ampérométrique évitant ainsi toute confusion à ce sujet et permettant l’optimisation du processus de détection.<p>------------------------------------------------<p>ABSTRACT<p><p>This thesis describes the development of original and high performance selective electrodes for the analysis of several pharmaceutical compounds. <p><p>The introduction describes the pharmaceutical compounds of interest (antimalarial drugs and iodine) and provides an overall understanding of the electrochemical groundwork pertaining to their analysis.<p><p>The experimental aspect of the thesis is divided into two parts, each according to the type of electrode and electrochemical technique used for the analysis.<p>The first part describes the design, characterization, and application of polymer membrane based ion selective potentiometric electrodes. Selectivity was provided by including ion pairs of several antimalarial drugs into the membrane. The feasibility of use of these electrodes in pharmaceutical analysis as well as in dissolution trials is also described in this part.<p><p>The second part describes the design of an original silver-modified carbon paste amperometric sensor and compares its performances to those of a plain metallic silver electrode. The electrode has been modified by silver microparticles or by silver nanoparticles. Quantitative iodine determination serves to prove the usefulness of this new sensor in analytical chemistry.<p><p>Different aspects, such as the nature of the counter ions (sodium tetraphenylborate and potassium tetrakis (4-chlorophenyl) borate) and the plastifying agents that are likely to influence electrode behaviour have been investigated. <p><p>Since the electrodes have been shown to perform well in quantitative analysis, the possibility of use in dissolution trials was explored.<p><p>Micronized silver-modified carbon paste electrode (35% Ag m/m) coupled to anionic-exchange liquid chromatography with amperometric detection was shown to be very sensitive with regards to the assay of halogenides in general and iodide in particular. After having investigated the various factors likely to influence chromatographic separation and electrode response, it was shown that the sensor could be used to rapidly and selectively determine low iodide concentrations in complex samples. Cyclic voltammetric analysis provided information concerning the mechanisms allowing amperometric detection, thus allowing an optimisation of the detection procedures.<p> / Doctorat en Sciences biomédicales et pharmaceutiques / info:eu-repo/semantics/nonPublished

Electroanalysis offers cheap and selective analysis of interesting solutions. However, one of the most common drawbacks is the accessibility for electrochemical sensing. By using high-pressure microfluidics with an integrated three-electrode system, new possibilities open for increased accessibility. Therefore, there is a need to fabricate sustainable reference surfaces into highly pressure tolerant microchannels. In this thesis, Ag/AgCl reference surfaces were in-situ fabricated in high-pressure microfluidic chips. This was performed by electroplating Ag on thin film Pt in microchannels and then chlorinating the silver into Ag/AgCl. Electroanalysis of ferrocyanide was carried out in a microfluidic chip using one of the in-situ fabricated Ag/AgCl references. The half-wave potential showed to be around +251 mV and the electrochemical water window was measured to 1400 mV with a range between -300 mV and +1100 mV. The obtained values show to be comparable to reference data of similar experiments performed elsewhere. For some applications of electrochemistry, a catalysis surface is beneficial. Nanoporous Pt black has proved to generate high catalytic performance in electrochemistry. Therefore, attempts have been carried out to fabricate Pt black onto Pt thin films, with the vision to succeed with such fabrication within microfluidic channels. To summarize, this project work has showed a possibility to in-situ fabricate Ag/AgCl reference surfaces. The project has also showed how to use such surfaces as reference electrodes for electroanalysis in high-pressure microfluidic chips. Lastly, new challenges and ideas to fabricate catalysis surfaces on thin film electrodes in flow channels have been presented. By this thesis, one more step has been taken to increase the accessibility for electroanalysis.

Magister Scientiae - MSc / In 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.