Sensitive Determination of Trace Pb2+ in Seawater Using Columnar Glassy Carbon Electrode

We herein report a mercury‐free approach for the sensitive determination of trace Pb²⁺ in seawater using differential pulse stripping voltammetric (DPSV) method with a novel columnar glassy carbon electrode (CGCE). Compared with the conventional disk glassy carbon electrode with the same diameter, it has much larger electrochemical area (0.627 ± 0.003 cm²). The CGCE shows good accumulation ability and consequently acceptable behavior which makes it suitable as a working electrode in the DPSV determination of Pb2+ with the great advantage of the avoidance of harmful mercury. Using acidified artificial seawater as supporting electrolyte, there was a good linear relationship between the peak currents and the concentration of Pb²⁺ in the range of 0.6～140.0 μg L^‐1 with a detection limit of 0.3 μg/L (S/N = 3) when the accumulation time was 300 s. The method was employed to determine trace levels of Pb²⁺ in real seawater samples successfully.     

Voltammetric behavior and determination of bismuth on sodium humate modified carbon paste electrode

The preconcentration and voltammetric behavior of Bi^III on a sodium humate modified carbon paste electrode was studied by means of cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV). The proposed measurement involves an initial nonelectrolytic preconcentration step in which Bi^III is complexed by the surface modifier in a solution of 0.05 M KNO₃-0.0106 M HNO₃ (pH 2.0) and a subsequent electrochemical scan step in which the preconcentrated Bi^III was reduced and then oxidized promptly in supporting electrolyte of 0.5 M HNO₃. The resulting DPSV anodic current was proportional to the concentration of Bi^III ion over the range of 4.78 × 10⁻⁸–1.44 × 10⁻⁵ M. The detection limit was 4.78 × 10⁻⁸ M. The proposed method was used to determine bismuth in various samples. Various factors affecting the electrode behavior were also investigated at the same time.     

Poly(3-methylthiophene)/palladium sub-micro-modified sensor electrode. Part II: Voltammetric and EIS studies, and analysis of catecholamine neurotransmitters, ascorbic acid and acetaminophen

Promising voltammetric sensors based on the modification of Pt and poly(3-methylthiophene) (PMT) electrodes with Pd nanoparticles were achieved for the determination of catecholamine neurotransmitters, ascorbic acid and acetaminophen. Electrochemistry of the indicated compounds was studied at these electrodes and interesting electrocatalytic effects were found. Furthermore, simple, easily prepared one electrochemical step Pd-modified Pt electrode (Pt/Pd) is reported for the first time. Cyclic voltammetry (CV) and chronocoulometry (CC) were used for the determination of the apparent diffusion coefficients in different electrolytes at these electrodes and the values are in the range from 10⁻⁴ to 10⁻⁵ cm² s⁻¹. Furthermore, it was found that the method of polymer formation had a substantial effect on the synergism between the polymer film and the loaded metal particles towards the oxidation of dopamine (DA) in different supporting electrolytes. This was confirmed by the CV, CC and EIS (electrochemical impedance spectroscopy) as well as SEM (Scanning Electron Microscopy) results. Pt and PMT electrodes modified with Pd nanoparticles showed excellent results for the simultaneous determination of tertiary and quaternary mixtures of the studied compounds.     

Electrocatalytic oxidation of thiosulfate on a modified nickel hexacyanoferrate film electrode

Summary A modified nickel hexacyanoferrate film glassy carbon electrode is prepared by the electrochemical deposition technique. The film is very stable upon voltammetric scanning in the potential range of 1.0 to –0.5 V (vs. SCE) and an oxidation peak occurs at 0.35 V (vs. SCE) (1 mol/l NaNO₃). The effects of electrolyte, solvent, coexisting ions and other variables on the voltammetric behaviour of the modified film have been studied. The thickness of the resulting film can be controlled by changing the number of voltammetric cycles and the concentrations of nickel(II) and hexacyanoferrate(III) ions. The film shows catalytic activity towards electrooxidation of thiosulfate with a peak potential +0.5 V (K^–-containing media). This oxidation potential of thiosulfate on the modified electrode is shifted negatively by about 550 mV as compared to the naked glassy carbon electrode. For practical application, the modified electrode can be used for the determination of thiosulfate in concentrations from 5.0×10^–5 to 1.0×10^–1 mol/l. This method has been successfully applied to the determination of thiosulfate in photographic waste effluents.     

The cathodic stripping voltammetric determination of traces of iodide with a hanging copper amalgam drop electrode

A hanging copper amalgam drop electrode (HCADE) is used for the determination of traces of iodide by cathodic stripping voltammetry. The cathodic stripping peak of copper(I) iodide from the HCADE is better defined than that of mercury(I) iodide from a hanging mercury drop electrode. Optimum conditions and interferences are reported. With a 3-min deposition time at ?0.1 V vs. SCE, the calibration plot is linear up to 2 × 10^?6 mol dm^?3 iodide. The detection limit for iodide with the HCADE under voltammetric conditions is 4 × 10^?8 mol dm^?3; this is lowered to 8 × 10^?9 mol dm^?3 by using the differential pulse stripping technique.     

A glassy carbon electrode modified with antimony and poly(p-aminobenzene sulfonic acid) for sensing lead(II) by square wave anodic stripping voltammetry

We have developed a sensor for the square wave anodic stripping voltammetric determination of Pb(II). A glassy carbon electrode was modified with a thin film of an antimony/poly(p-aminobenzene sulfonic acid) composite in air-saturated aqueous solution of pH 2.0. Compared to a conventional antimony film electrode, the new one yields a larger stripping signal for Pb(II). The conditions of polymerization, the concentration of Sb(III), the pH value of the sample solution, the deposition potential and time, frequency, potential amplitude, and step increment potential were optimized. Under the optimum conditions, a linear response was observed for Pb(II) in the range of 0.5 to 150.0 μg?L^?1. The detection limit for Pb(II) is 0.1 μg?L^?1.

Enhanced Sensing of Carbendazim,a Fungicide on Functionalized Multiwalled Carbon Nanotube Modified Glassy Carbon Electrode and Its Determination in Real Samples

An electrochemical sensor was developed by modifying a glassy carbon electrode (GCE) with functionalized multiwalled carbon nanotubes (FMWCNTs). The fabricated electrode was used to examine the redox behavior of carbendazim (CAR) in different pH solutions (pH 1.0–13.0). Surface morphology of the modified film was studied by scanning electron microscopy (SEM). An electroanalytical procedure for the determination of CAR was developed by adsorptive differential pulse stripping voltammetry (DPSV) over the range 0.01–5 × 10⁴ µ g L^?1. The developed procedure was also validated in real samples such as soil and water samples, and the applicability of the reported method is highly encouraging.     

Electropolymerization of Acid Chrome Blue K on Glassy Carbon Electrode for the Determination of Curcumin

Acid chrome blue K (ACBK) was electropolymerized on the surface of a glassy carbon electrode (GCE) by cyclic voltammetric sweep in the potential range from –0.2 to 0.9 V. The characteristic of poly‐ACBK film was studied by different methods such as electrochemical impedance spectroscopy (EIS) and cyclic voltammetry. This modified electrode showed excellent electrocatalytic response to curcumin with the increase of the electrochemical responses. Under the optimal conditions a good linear voltammetric response could be obtained over the range of 1.0 × 10^?7‐7.0 × 10^?5 M and the detection limit was got as 4.1 × 10^?8 M (S/N = 3). The method was successfully applied for the determination of curcumin in human urinev samples.     

Determination of arsenic in gold samples using matrix exchange differential pulse stripping voltammetry

A method comprising matrix exchange differential pulse stripping voltammetry (DPSV) at a gold film electrode has been proposed for the determination of small quantities of arsenic in pure gold. A wall-jet cell (WJC) and an on-line deoxygenation system were used to facilitate matrix exchange. The gold(I) cyanide complex was formed to avoid gold deposition on the electrode together with the arsenic. The pH of the sample solutions were adjusted to 3, as alkaline solutions gold(I) cyanide produced interference and the uncomplexed cyanide led to passivation of the gold film electrode. Matrix exchange electrolytes consisting of 4 mol l⁻¹ hydrochloric acid or a combination of 2 mol l⁻¹ sulphuric acid and 0.2 mol l⁻¹ hydrochloric acid could be utilised. Arsenic concentrations as low as 0.1 mg l⁻¹, could readily be detected in a gold matrix with a 60 s deposition time. While, cobalt and silver did not interfere with the arsenic determination, copper interfered even when present at similar concentrations to that of arsenic.     

Enhanced sensing of anthraquinone dyes using multiwalled carbon nanotubes modified electrode

The voltammetric behaviour of two anthraquinone dyes such as Alizarin Red S (ARS) and Reactive blue 4 (RB4) was investigated at plain glassy carbon electrode (GCE), multiwalled carbon nano tube modified GCE (MWCNT/GCE) and zeolite modified GCE (ZE/GCE) using cyclic voltammetry. Effects of pH, scan rate and concentration were studied. The surface morphology of the modified electrode in the absence and presence of dye molecules was characterized by scanning electron microscopy (SEM). A systematic study on the variation of experimental parameters with differential pulse stripping voltammetry (DPSV) was carried out and the optimized experimental conditions were arrived. MWCNT/GCE performed well among the three electrode systems and the limit of detection (LOD) was 0.036?µg?mL^?1 for ARS and 0.05?µg?mL^?1 for RB4 on this modified system. Suitability of the differential pulse stripping voltammetric method for the trace determination of textile dyes in effluents was also realized.     

Electrocatalytic Determination of Ascorbic Acid Using a Palladium Coated Nanoporous Gold Film Electrode

Cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical behavior of ascorbic acid (AA) on palladium coated nanoporous gold film (PdNPGF) electrode. The deposition of palladium was done through oxidation of copper UPD layer by palladium ions. This low Pd‐loading electrode behaved as the nanostructured Pd for electrocatalytic reaction. The PdNPGF electrode exhibits excellent electrocatalytic behavior by enhancing the AA oxidation peak current due to synergistic influence of the Pd film and NPGF. The kinetic parameters such as electron transfer coefficient, α, was 0.47 and the voltammetric responses of the PdNPGF electrode were linear against concentration of AA in the ranges of 2.50–33.75 mM and 0.10–0.50 mM with CV and DPV respectively.     

Electrochemical Behavior of 8‐Azaguanine at DNA Langmuir–Blodgett Modified Glassy Carbon Electrode and Its Analytical Application

A highly sensitive electrochemical biosensor for the detection of trace amounts of 8‐azaguanine has been designed. Double stranded (ds)DNA molecules are immobilized onto a glassy carbon electrode surface with Langmuir–Blodgett technique. The adsorptive voltammetric behaviors of 8‐azaguanine at DNA‐modified electrode were explored by means of cyclic voltammetry and square wave voltammetry. Compared with bare glassy carbon electrode (GCE), the Langmuir–Blodgett film modified electrode can greatly improve the measuring sensitivity of 8‐azaguanine. Under the optimum experimental conditions, the Langmuir–Blodgett film modified electrode in pH 3.0 Britton–Robinson buffer solutions shows a linear voltammetric response in the range of 5.0×10^?8 to 1.0×10^?5 mol L^?1 with detection limit 9.0×10^?9 mol L^?1. The method proposed was applied successfully for the determination of 8‐azaguanine in diluted human urine with wonderful satisfactory.     

Electrochemical Properties of Electrode Modified with Langmuir‐Blodgett Film of p‐tert‐Butylcalix[4]arene Derivatives and Its Application in Determining of Silver

A new type of voltammetric sensor, Langmuir‐Blodgett (LB) film of 5,11,17,23‐tetra‐tert‐butyl‐25,27‐di(3‐thiadiazole‐propanoxy)‐26,28‐dihydroxycalix[4]arene modified glassy carbon electrode (LB_TZCA–GCE), was prepared. The electrochemical properties of LB_TZCA–GCE were researched in detail and its recognizing mechanism for silver ion in aqueous solution was discussed. Using this voltammetric sensor, a new stripping voltammetric method for determining of Ag⁺ was erected with good sensitivity, selectivity, reproducibility and recovery. The detection limit was 8×10^?9 M at accumulation time of 180 s. By this method, real samples (lake water, tap water and synthesis sample) were analyzed and the results obtained were well satisfactory.     

用聚(L-蛋氨酸)/纳米金修饰玻碳电极同时灵敏检测多巴胺和尿酸简

A novel electrochemical sensor was fabricated by electrodeposition of gold nanoparticles on a poly(L-methionine) (PMT)-modified glassy carbon electrode (GCE) to form a nano-Au/PMT composite-modified GCE (nano-Au/PMT/GCE). Scanning electron microscopy and electrochemical techniques were used to characterize the composite electrode. The modified electrode exhibited considerable electrocatalytic activity towards the oxidation of dopamine (DA) and uric acid (UA) in phosphate buffer solution (pH = 7.00). Differential pulse voltammetry revealed that the electrocatalytic oxidation currents of DA and UA were linearly related to concentration over the range of 5.0×10^-8 to 10^-6 mol/L for DA and 7.0×10^-8 to 10^-6 mol/L for UA. The detection limits were 3.7×10^-8 mol/L for DA and 4.5×10^-8 mol/L for UA at a signal-to-noise ratio of 3. According to our experimental results, nano-Au/PMT/GCE can be used as a sensitive and selective sensor for simultaneous determination of DA and UA.     

离子液体中纳米TiO2/聚3-甲基噻吩复合膜的制备及性质研究

采用溶胶凝胶法制成了纳米TiO₂电极, 在离子液体中将其应用于3-甲基噻吩的电化学聚合, 采用循环伏安法(CV), 在线紫外可见光谱(UV-Vis), 扫描电镜(SEM)和电化学阻抗谱(EIS)对TiO₂/聚3-甲基噻吩(TiO₂/PMT)复合膜进行了表征并研究了其电化学性质. 实验证明, 不论是用循环伏安法, 恒电位, 还是恒电流方法, 都能在电极上得到聚3-甲基噻吩(PMT)膜, 并伴随有明显的掺杂和去掺杂过程. 对应的在线紫外可见光谱上, 也出现了氧化和还原两种不同的吸收状态, 还原(去掺杂)过程中在480 nm处有一个吸收峰, 而氧化(掺杂)过程中此峰消失, 取而代之的是一个可见光区的逐渐增强的吸收. PMT膜是p型半导体, TiO₂是n型半导体, 两者之间能够形成p-n异质结, 使光电转换效率得以提高. SEM给出了TiO₂电极和聚合物修饰的TiO₂的形貌图, 电极的交流阻抗谱则从一个角度说明了聚合物膜修饰电极的导电性.     

Carbon Nanotubes/Poly(1,2‐diaminobenzene) Nanoporous Composite Film Electrode Prepared by Multipulse Potentiostatic Electropolymerisation and Its Application to Determination of Trace Heavy Metal Ions

A novel method for the fabrication of carbon nanotubes/poly(1,2‐diaminobenzene) nanoporous composite based electrode was proposed. By multipulse potentiostatic electropolymerization, the multi‐walled carbon nanotubes (MWNTs) and poly(1,2‐diaminobenzene) were deposited simultaneously on the electrode surface. Compared with the composite prepared by the traditional potentiodynamic method, the composite synthesized by multipulse potentiostatic method has a unique nanoporous structure, exhibits excellent conductivity and better environmental stability. The surface of the resulting electrode was characterized with scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The nanoporous composite film modified glassy carbon electrode was also used successfully for the simultaneously voltammetric determination of trace level of Cd²⁺ and Cu²⁺ at first‐time. Under the optimal conditions, the determination limits of 0.25 and 0.33 ppb for Cd²⁺ and Cu²⁺ were obtained, respectively. The calibration graphs were linear in the concentration range of 5–100 ppb. The electrode system provides an excellent platform for ultra sensitive electrochemical sensors for chemical and biological sensing.     

Electrode kinetics of Eu3+/Eu2+ reaction by cyclic voltammetry

The cyclic voltammetric behaviour of Eu³⁺/Eu²⁺ couple at hanging mercury drop electrode (HMDE) has been studied in chloride, bromide, iodide, thiocyanate and EDTA supporting electrolytes. The apparent rate constant and transfer coefficient for these systems have been calculated at various voltage scan rates, without using the data for standard or formal potential. The values have been compared with those obtained by earlier workers through other electrochemical methods.     

Ionic Liquid‐Hemoglobin‐Carbon Paste Composite Bioelectrode and Its Electrocatalytic Activity

A new carbon ionic liquid paste bioelectrode was fabricated by mixing hemoglobin (Hb) with graphite powder, ionic liquid 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIMBF₄) and liquid paraffin homogeneously. Nafion film was cast on the electrode surface to improve the stability of bioelectrode. Direct electrochemistry of Hb in the bioelectrode was carefully investigated. Cyclic voltammetric results indicated that a pair of well‐defined and quasi‐reversible electrochemical responses appeared in pH 7.0 phosphate buffer solution (PBS), indicating that direct electron transfer of Hb was realized in the modified electrode. The formal potential (E^0′) was calculated as ?0.316 V (vs. SCE), which was the typical characteristic of the electrochemical reaction of heme Fe(III)/Fe(II) redox couple. Based on the cyclic voltammetric results the electrochemical parameters of the electrode reaction were calculated. This bioelectrode showed high electrocatalytic activity towards the reduction of trichloroacetic acid (TCA) with good stability and reproducibility.     

Fabrication of Nano Flower‐shaped Platinum on Glassy Carbon Electrode as a Sensitive Sensor for Lead Electrochemical Analysis

Platinum nanoflowers modified glassy carbon electrodes (PtNFs/GCE) was fabricated simply for lead determination in water samples. The modified electrodes were prepared by electrodeposition in hexachloroplatinic acid solution at constant potential. The influence of deposition time and potential on surface morphology, chemical composition, electrochemical properties of electrode were investigated. At ?0.2 V of potential and 150 s of deposition duration, platinum developed as nanoflower shape and scattered densely all over the glassy carbon surface, producing the largest electrochemically active surface areas. The highest differential pulse stripping voltammetry (DPSV) signal of lead was obtained by using the prepared electrode. Under optimized experimental condition of electrolyte, accumulation potential and time, the peak current was found to be linear proportion to lead concentration in range of 1 to 100 μg L^?1 (slope=0.371) with a limit of detection of 0.398 μg L^?1. The method has good repeatability and reproducibility with relative standard deviations of 1.47 % and 4.83 %, respectively. The modified PtNFs/GCE also demonstrated an excellent long‐term stability with only 9 % decrease in Pb peak current over 30 days. Moreover, the performance of the modified PtNFs/GCE in determination of Pb(II) in two industrial wastewaters was good agreement with data obtained by a graphite furnace atomic absorption spectrometry (GFAAS) method.     

A Selective Film Based on Poly(3‐octylthiophene) Doped with Dihydroxyanthraquinone Sulfonate

A stable film of poly(3‐octylthiophene)–dihydroxyanthraquinone sulfonate has been synthesized electrochemically in non‐aqueous solution. The incorporation of dihydroxyanthraquinone sulfonate as an anionic complexing ligand into poly(3‐octylthiophene) film during electropolymerization was achieved and copper ions were accumulated by reduction on the electrode surface. The presence of dihydroxyanthraquinone sulfonate during the electrochemical polymerization of 3‐octylthiophene is shown to impact the sensitivity and the stability of the organic conducting film electrode response. The electroanalysis of copper(II) ions using conducting polymer electrode was achieved by differential pulse anodic stripping voltammetry with remarkable selectivity. The analytical performance was evaluated and linear calibration graphs were obtained in the concentration range of 50–400 ng mL^?1 copper(II) ion for 240 seconds accumulation time and the limit of detection was found to be 7.8 ng mL^?1. To check the selectivity of the proposed stripping voltammetric method for copper(II) ion, various metal ions as potential interferents were tested. The developed method was applied to copper(II) determination in certified reference material, NWRI‐TMDA‐61, trace elements in fortified water.