Edge Plane Pyrolytic Graphite Electrodes for Halide Detection in Aqueous Solutions

The behavior of chloride, bromide and iodide at edge plane pyrolytic graphite electrodes has been explored in aqueous acid solutions. The voltammetric response in each case has been compared with that of basal plane pyrolytic graphite, glassy carbon and boron‐doped diamond. The electrochemical oxidation of chloride is found to only occur on boron‐doped diamond while the electrochemical reversibility for the oxidation of bromide on edge plane pyrolytic graphite is similar to that seen at glassy carbon whilst being superior to basal plane pyrolytic graphite and boron‐doped diamond. In the case of iodide oxidation, edge plane and basal plane pyrolytic graphite and glassy carbon display similar electrode kinetics but are all superior to boron‐doped diamond. The analytical possibilities were examined using the edge plane pyrolytic graphite electrode for both iodide and bromine where is was found that, based on cyclic voltammetry, detection limits in the order of 10^?6 M are possible.     

Direct Oxidation of Ascorbic Acid at an Edge Plane Pyrolytic Graphite Electrode: A Comparison of the Electroanalytical Response with Other Carbon Electrodes

The direct electrochemical oxidation of ascorbic acid at an edge plane pyrolytic graphite electrode (EPPG) is investigated and compared with other common carbon‐based electrodes, specifically glassy carbon, boron doped diamond and basal plane pyrolytic graphite. It is found that the EPPG electrode shows a significantly higher degree of electrochemical reversibility than the other electrode substrates giving rise to an analytically optimized limit of detection and sensitivity of 7.1×10^?5 M and 0.065 A M^?1 respectively.     

Manganese Detection with a Metal Catalyst Free Carbon Nanotube Electrode: Anodic versus Cathodic Stripping Voltammetry

Anodic stripping voltammetry (ASV) and cathodic stripping voltammetry (CSV) were used to determine Mn concentration using metal catalyst free carbon nanotube (MCFCNT) electrodes and square wave stripping voltammetry (SWSV). The MCFCNTs are synthesized using a Carbo Thermal Carbide Conversion method which results in a material that does not contain residual transition metals. Detection limits of 120 nM and 93 nM were achieved for ASV and CSV, respectively, with a deposition time of 60 s. CSV was found to be better than ASV in Mn detection in many aspects, such as limit of detection and sensitivity. The CSV method was used in pond water matrix addition measurements.     

The Direct Electrochemical Oxidation of Ammonia in Propylene Carbonate: A Generic Approach to Amperometric Gas Sensors

The direct electrochemical oxidation of ammonia in propylene carbonate is reported for the first time. The voltammetric responses at glassy carbon, boron‐doped diamond, edge and basal plane pyrolytic graphite electrodes are explored and compared with the outcome indicating that the optimum electrode substrate for analytical purposes in this solvent is glassy carbon. Proof‐of‐concept is shown for the amperometric detection of ammonia using basal plane pyrolytic graphite electrodes abrasively modified with glassy carbon spheres. Given the significantly lower vapor pressure of propylene carbonate in comparison to water the implications for extending the life‐time of practical sensors are evident. Propylene carbonate shows a wide potential window with glassy carbon electrodes permitting this approach to be used for a potential diversity of gaseous analytes.     

Determination of Sb(V) Using Differential Pulse Anodic Stripping Voltammetry at an Unmodified Edge Plane Pyrolytic Graphite Electrode

Antimony(V) determination at an unmodified edge plane pyrolytic graphite (EPPG) electrode using anodic stripping voltammetry (ASV) by depositing beyond the hydrogen wave is shown in this paper. By depositing beyond the hydrogen wave, we report a sensitive method to determine pentavalent antimony at a carbon electrode in 0.25 M HCl. Using differential pulse anodic stripping voltammetry (DPASV), a bare EPPG electrode gave a detection limit of 5.8±0.02 nM without the need for surface modification. This level is greatly within the EU limit for drinking water of 40 nM.     

Electroanalytical Exploitation of Nitroso Phenyl Modified Carbon‐Thiol Interactions: Application to the Low Voltage Determination of Thiols

The electrochemical generation of nitrosophenyl groups covalently attached to graphite powder (nitrosophenylcarbon) from carbon powder chemically modified with nitrophenyl groups and their subsequent reaction with thiols (glutathione, cysteine and homocysteine) has been investigated as a method by which the later can be quantified. The modified carbon powder was immobilized onto a basal plane pyrolytic graphite electrode and characterized by cyclic voltammetry by scanning between 1.0 V and ?1.0 V vs. SCE in phosphate buffer (pH 7). Square wave voltammetry (SWV) was used for the determination of thiols and the SWV parameters were optimized. The nitrosophenylcarbon is electrogenerated from nitrophenylcarbon and can chemically oxidize thiols to disulfides. Subsequent reduction of nitrosophenylcarbon to phenylhydroxylaminecarbon during the square wave voltammetric process leads to a decrease in the reductive current. This can be correlated to the concentration of thiol present within the medium. The cyclic voltammetric responses of basal plane pyrolytic graphite electrode, edge plane pyrolytic graphite electrode, glassy carbon electrode and boron‐doped diamond electrode in the direct oxidation of thiols were also investigated and all were found to have a significantly higher overpotential compared to the described method using nitrosophenylcarbon.     

Electrochemical Response of Cobalt(II) in the Presence of Ammonia

The electrochemical oxidation of cobalt(II) at gold, boron‐doped diamond, basal and edge plane pyrolytic graphite, and highly oriented pyrolytic graphite electrodes in aqueous solutions containing NH₃ has been studied using cyclic voltammetry, with subsequent chemical and electrochemical processes explained in detail. Furthermore, the electro‐reduction of [Co(NH₃)₆]³⁺ in the presence of different electrolytes has also been studied to obtain a better understanding of the oxidation pathway of the Co(II)‐ammine complexes. In aqueous solution the mechanism can be described by the following scheme:     

The Voltammetry and Electroanalysis of Some Estrogenic Compounds at Modified Diamond Electrodes

The voltammetry of some estrogenic compounds (estradiol, nonylphenol, bisphenol A, ethynylestradiol, estrone, estriol) in aqueous solution at boron doped diamond electrodes is reported. For oxidised (hydrophilic) electrodes electrochemically irreversible kinetics were observed for the diffusing molecules allowing the inference of diffusion coefficients and transfer coefficients. In contrast for hydrogen terminated (hydrophobic) surfaces significant adsorption was observed. A limit of detection of 1–100 µM for the estrogenic compounds was found using the oxidised diamond electrode. Surface modification of the oxidised diamond with nano‐Carbon (so‐called Carbon Black) allowed preconcentration of the target by adsorption onto the Carbon Black prior to analysis and a corresponding reduction of the limit of detection by ca three orders of magnitude to 5–100 nM.     

Anodic stripping voltammetry of antimony at unmodified carbon electrodes

Antimony is an element of significant environmental concern, yet has been neglected relative to other heavy metals in electroanalysis. As such very little research has been reported on the electroanalytical determination of antimony at unmodified carbon electrodes. In this paper we report the electrochemical determination of Sb(III) in HCl solutions using unmodified carbon substrates, with focus on non-classical carbon materials namely edge plane pyrolytic graphite (EPPG), boron doped diamond (BDD) and screen-printed electrodes (SPE). Using differential pulse anodic stripping voltammetry, EPPG was found to give a considerably greater response towards antimony than other unmodified carbon electrodes, allowing highly linear ranges in nanomolar concentrations and a detection limit of 3.9?nM in 0.25?M HCl. Furthermore, the sensitivity of the response from EPPG was 100 times greater than for glassy carbon (GC). Unmodified GC gave a comparable response to previous results using the bare substrate, and BDD gave an improved, yet still very high limit of detection of 320?nM compared to previous analysis using an iridium oxide modified BDD electrode. SPEs gave a very poor response to antimony, even at high concentrations, observing no linearity from standard additions, as well as a major interference from the ink intrinsic to the working electrode carbon material. Owing to its superior performance relative to other carbon electrodes, the EPPG electrode was subjected to further analytical testing with antimony. The response of the electrode for a 40?nM concentration of Sb(III) was reproducible with a mean peak current of 1.07?µA and variation of 8.4% (n?=?8). The effect of metals copper, bismuth and arsenic were investigated at the electrode, as they are common interferences for stripping analysis of antimony.     

Enhanced Performance of Edge‐Plane Pyrolytic Graphite (EPPG) Electrodes over Glassy Carbon (GC) Electrodes in the Presence of Surfactants: Application to the Stripping Voltammetry of Copper

The voltammetric performance of glassy carbon (GC) and edge‐plane pyrolytic graphite (EPPG) electrodes was investigated for the oxidation of potassium ferrocyanide in aqueous solution both with and without the addition of surfactant (sodium dodecyl sulfate and Triton X‐100). The heterogeneous electron transfer kinetics were determined for all cases, and it was found that the GC electrode surface was far more sensitive to the presence of surfactant than the more hydrophilic EPPG surface. This result was then applied to the electroanalysis of copper via adsorptive stripping voltammetry in the presence of Triton X‐100 and it was observed that the EPPG electrode response was unaffected by up to 100 μM of surfactant, whilst the voltammetry on the GC electrode was significantly affected by only 10 μM.     

Exploring the electrocatalytic sites of carbon nanotubes for NADH detection: an edge plane pyrolytic graphite electrode study

The electrocatalytic properties of multi-walled carbon nanotube modified electrodes toward the oxidation of NADH are critically evaluated. Carbon nanotube modified electrodes are examined and compared with boron-doped diamond and glassy carbon electrodes, and most importantly, edge plane and basal pyrolytic graphite electrodes. It is found that CNT modified electrodes are no more reactive than edge plane pyrolytic graphite electrodes with the comparison with edge plane and basal plane pyrolytic graphite electrodes allowing the electroactive sites for the electrochemical oxidation of NADH to be unambiguously determined as due to edge plane sites. Using these highly reactive edge plane sites, edge plane pyrolytic graphite electrodes are examined with cyclic voltammetry and amperometry for the electroanalytical determination of NADH. It is demonstrated that a detection limit of 5 microM is possible with cyclic voltammetry or 0.3 microM using amperometry suggesting that edge plane pyrolytic graphite electrodes can conveniently replace carbon nanotube modified glassy carbon electrodes for biosensing applications with the relative advantages of reactivity, cost and simplicity of preparation. We advocate the routine use of edge plane and basal plane pyrolytic graphite electrodes in studies utilising carbon nanotubes particularly if 'electrocatalytic' properties are claimed for the latter.     

Exploration of gas sensing possibilities with edge plane pyrolytic graphite electrodes: nitrogen dioxide detection

The voltammetric response of nitrogen dioxide in aqueous sulfuric acid using an edge plane pyrolytic graphite electrode has been explored and contrasted with that from basal plane pyrolytic graphite, glassy carbon or boron-doped diamond electrodes. Edge plane graphite electrode is found to produce an excellent voltammetric signal in comparison with other carbon-based electrodes exhibiting a well-defined analytically useful voltammetric redox couple in 2.5 M sulfuric acid which is absent on the alternative electrodes.     

Cathodic stripping voltammetry of trace Mn(II) at carbon film electrodes

A sensitive voltammetric method is presented for the determination of tract levels of Mn (II) using carbon film electrodes fabricated from carbon resistors of 2 Ω. Determination of manganese was made by square wave cathodic stripping voltammetry (CSV), with deposition of manganese as manganese dioxide. Chronoamperometric experiments were made to study MnO₂ nucleation and growth. As a result, it was found to be necessary to perform electrode conditioning at a more positive potential to initiate MnO₂ nucleation. Under optimised conditions the detection limit obtained was 4 nM and the relative standard deviation for eight measurements of 0.22 nM was 5.3%. Interferences from various metal ions on the response CSV of Mn(II) were investigated, namely Cd(II), Ni(II), Cu(II), Cr(VI), Pb(II), Zn(II) and Fe(II). Application to environmental samples was demonstrated.     

Gold Nanoparticle Modified Electrodes Show a Reduced Interference by Cu(II) in the Detection of As(III) Using Anodic Stripping Voltammetry

Interference by Cu(II) causes serious problems in the detection of As(III) using anodic stripping voltammetry at gold electrodes. The behavior of Cu(II) and As(III) were examined at both a gold macro electrode and two kinds of gold nanoparticle modified electrodes, one where gold particles are deposited on glassy carbon (GC) and the other where basal plane pyrolytic graphite (BPPG) is the substrate. The sensitivity of As(III) detection was higher on gold nanoparticle modified electrodes than those on a macro gold electrode by up to an order of magnitude. In addition, the stripping peak of As(III) was narrower and more symmetric on a gold nanoparticle‐modified GC electrode, leading to analytical data with a lower limit of detection. At a macro gold electrode, the peak currents of Cu(II) were higher than those on gold nanoparticle modified electrodes. Accordingly, through the use of gold nanoparticle modified electrodes, the effect of copper interference to the arsenic detection can be reduced.     

Electroanalysis at Diamond‐Like and Doped‐Diamond Electrodes

Diamond as a high performance material occupies a special place due to its in many ways extreme properties, e.g., hardness, chemical inertness, thermal conductivity, optical properties, and electric characteristics. Work mainly over the last decade has shown that diamond also occupies a special place as an electrode material with interesting applications in electroanalysis. When made sufficiently electrically conducting for example by boron‐doping, ‘thin film' and ‘free–standing' diamond electrodes exhibit remarkable chemical resistance to etching, a wide potential window, low background current responses, mechanical stability towards ultrasound induced interfacial cavitation, a low ‘stickiness' in adsorption processes, and a high degree of ‘tunability' of the surface properties. This review summarizes some of the recent work aimed at applying conductive (boron‐doped) diamond electrodes to improve procedures in electroanalysis.     

Iridium Oxide Film Electrodes for Anodic Stripping Voltammetry

The new iridium oxide film electrode, applied for the determination of lead(II), cadmium(II) and copper(II) traces using differential pulse anodic stripping voltammetry (DP ASV) is presented. The electrode display an interesting stripping voltammetric performance which compares with electrodes commonly used in voltammetry. The deposited film is known as anodically electrodeposited iridium oxide film (AEIROF). The AEIROF electrode is characterized by long‐term stability (more than 40 days) and very good reproducibility of the analytical signals in this time (≤12% for 0.5 μM of lead). The regeneration of iridium film is very simple in a time shorter than 60 seconds. The effects of various factors such as: thickness of AEIROF film, preconcentration potential and time, supporting electrolyte composition, potential interferences are optimized. The detection limit for AEIROF film electrode based on glassy carbon for an accumulation time of 30 s is as low as 7 nM for lead(II). The repeatability of the method at a concentration level of the lead(II) as low as 0.5 μM, expressed as RSD is 2.5% (n=10). The proposed method was successfully applied and validated by studying certified reference material CTA‐OTL‐1. Such an attractive use of ‘mercury–free’ ‐ environmentally friendly electrodes offers great promise to measure trace metals.     

Electroanalytical determination of cadmium(II) and lead(II) using an in-situ bismuth film modified edge plane pyrolytic graphite electrode.

A highly sensitive and simple electroanalytical methodology is presented using an in-situ bismuth film modified edge plane pyrolytic graphite electrode (BiF-EPPGE) which is exemplified with the simultaneous determination of cadmium(II) and lead(II). Square-wave anodic stripping voltammetry is utilised with the effects of several experimental variables studied. Simultaneous additions of cadmium(II) and lead(II) were investigated where two linear ranges between 0.1-100 and 0.1-300 microg/L and also detection limits of 0.062 and 0.084 microg/L were obtained, respectively. The method was then successfully applied to the simultaneous determination of cadmium(II) and lead(II) in spiked river water, where recoveries of 100.5 and 98% were obtained, respectively. This electroanalytical protocol using edge plane pyrolytic graphite electrodes is one of the simplest methodologies to date using non-mercury based electrodes and is simpler and cheaper than alternatives such as carbon nanotube electrode arrays, suggesting the use of edge plane pyrolytic graphite electrode for routine sensing.     

Direct Electrooxidation of Ascorbic Acid at the Nanocrystaline Graphite‐like Pyrolytic Carbon Film Electrode

Pyrolytic carbon films (PCFs) were prepared by chemical vapor deposition (CVD) at different deposition temperatures. As an example of using PCF electrode in electroanalysis, the direct electrooxidation of ascorbic acid (AA) at the PCF electrode was investigated and compared with common carbon‐based electrodes such as glassy carbon (GC), edge plane pyrolytic graphite (EPPG), and basal plane pyrolytic graphite (BPPG) electrodes. It was found that the PCF electrodes prepared under deposition temperatures higher than 1050 °C showed a higher sensitivity and lower overpotential compared to the other carbon electrodes. The electrode was successfully applied for determination of AA in real samples.     

Multiwalled Carbon Nanotube Modified Electrodes for the Adsorptive Stripping Voltammetric Determination and Quantification of Curcumin in Turmeric

A sensitive electrochemical method for the determination and quantification of curcumin using adsorptive stripping voltammetry (AdsSV) at a multiwalled carbon nanotube modified basal plane pyrolytic graphite electrode (MWCNT‐BPPG electrode) is presented exploiting the high surface area of the latter. Next the voltammetric behaviour of curcumin on the modified electrode is examined and AdsSV shown to be a sensitive method for quantifying curcumin. The adsorption of curcumin on the electrode surface is evidenced to follow a Langmuir adsorption isotherm. Linear calibration for curcumin in the range of 2–100 μM was obtained with a detection limit of 0.45 μM and a limit of quantification of 1.49 μM. For application to real samples of turmeric, a one‐step sample preparation in ethanol has developed providing a simple and rapid extraction procedure. The MWCNT‐BPPG electrode with AdsSV allowed the determination of curcumin equivalent in turmeric powder sample with recoveries in the range of 92–108 %. This facile and fast method will be useful for monitoring the quality of curcumin containing in commercial turmeric products.     

Simultaneous Determination of Uric Acid and Ascorbic Acid Using Edge Plane Pyrolytic Graphite Electrodes

Edge plane pyrolytic graphite electrodes have been applied for the determination of uric acid and ascorbic acid. The separate determination of uric acid was found to produce three linear ranges from 100 nM to 3400 μM with a detection limit of 30 nM found to be possible. Uric acid detection was also explored in the presence of 200 μM ascorbic acid where a detection limit of 52 nM was found to be possible. The detection of ascorbic acid in the presence of uric acid was also explored over three linear ranges of ascorbic acid with a limit of detection of 80 nM. Last the simultaneous determination of both uric acid and ascorbic acid is investigated over the range 100 nM to 1000 μM where detection limits of 50 nM and 120 nM were obtained respectively. Analysis of uric acid in a growth tissue medium was found to be successful, confirming the applicability of the methodology to real matrices. This protocol is shown to provide low detection limits, easy handling (no electrode modification), good voltammetric peak separation of uric acid and ascorbic acid and a wide linear dynamic range.