Investigation of Copper(II) Interference on the Anodic Stripping Voltammetry of Lead(II) and Cadmium(II) at Bismuth Film Electrode

The bismuth‐coated electrode is known to be prone to errors caused by copper(II). This study investigates copper(II) interference at bismuth film electrode for the detection of lead(II) and cadmium(II). It was conducted using glassy carbon electrode, while the bismuth film was plated in situ simultaneously with the target metal ions at ? 1200 mV. Copper(II) presented in solution significantly reduced the sensitivity of the electrode, for example there was an approximately 70 % and 90 % decrease in peak signals for lead(II) and cadmium(II), respectively, at a 10‐fold molar excess of copper(II). The decrease in sensitivity was ascribed to the competition between copper and bismuth or the metal ions for surface active sites. Scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) analysis suggested a large decrease in the amount of bismuth nanoparticles formed on the electrode surface in the presence of copper(II) occurred, validating the competition between copper and bismuth ions for surface active sites. Recovery of the stripping signal of lead(II) and cadmium(II) was obtained by adding ferrocyanide ion to the solution. Finally, the proposed method was successfully applied to determine lead(II) and cadmium(II) in water samples and the method was validated by ICP‐MS technique.     

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.     

Determination of Lead(II) Using Screen‐Printed Bismuth‐Antimony Film Electrode

This work presents a disposable bismuth‐antimony film electrode fabricated on screen‐printed electrode (SPE) substrates for lead(II) determination. This bismuth‐antimony film screen‐printed electrode (Bi‐SbSPE) is simply prepared by simultaneously in situ depositing bismuth(III) and antimony(III) with analytes on the homemade SPE. The Bi‐SbSPE can provide an enhanced electrochemical stripping signal for lead(II) compared to bismuth film screen‐printed electrodes (BiSPE), antimony film screen‐printed electrodes (SbSPE) and bismuth‐antimony film glassy carbon electrodes (Bi‐SbGC). Under optimized conditions, the Bi‐SbSPE exhibits attractive linear responses towards lead(II) with a detection limit of 0.07 µg/L. The Bi‐SbSPE has been demonstrated successfully to detect lead in river water sample.     

Simultaneous and Sensitive Detection of Cd(II) and Pb(II) Using a Novel Bismuth Film/Ordered Mesoporous Carbon‐molecular Wire Modified Graphite Carbon Paste Electrode

An electrochemical sensor for the simultaneous and sensitive detection of Cd(II) and Pb(II) is proposed on the basis of square‐wave anodic stripping voltammetry (SWASV) experiments using a novel bismuth film/ordered mesoporous carbon‐molecular wire modified graphite carbon paste electrode (Bi/OMC‐MW/GCPE). Ordered mesoporous carbon (OMC) and molecular wire (MW) (diphenylacetylene) were used as the modifier and binder, respectively. The Bi/OMC‐MW/GCPE was prepared with the addition of graphite powder, OMC and DPA at the ratio of 2 : 1 : 1. The electrochemical properties and morphology of the electrode were characterized by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), SWASV and scanning electron microscopy (SEM). The parameters affecting the stripping current response were investigated and optimized. The experimental results show that the prepared electrode exhibited excellent electrochemical performance, good electrical conductivity and a high stripping voltammetric response. Under optimized conditions, a linear range was achieved over a concentration range from 1.0 to 70.0 μg/L for both Cd(II) and Pb(II) metal ions, with detection limits of 0.07 μg/L for Cd(II) and 0.08 μg/L for Pb(II) (S/N=3) with the deposition time 150 s. Moreover, the sensor exhibited improved sensitivity and reproducibility compared to traditional CPEs. The fabricated electrode was then successfully used to satisfactorily detect Cd(II) and Pb(II) in real soil samples.     

Anodic Stripping Voltammetry Determination of Pb(II) and Cd(II) at a Bismuth/Poly(aniline) Film Electrode

Abstract

A novel voltammetric method—anodic—using a bismuth/poly(aniline) film electrode has been developed for simultaneous measurement of Pb(II) and Cd(II) at low µg L^?1 concentration levels by stripping voltammetry. The results confirmed that the bismuth/poly(aniline) film electrode offered high‐quality stripping performance compared with the bismuth film electrode. Well‐defined sharp stripping peaks were observed for Pb(II) and Cd(II), along with an extremely low baseline. The detection limits of Pb(II) and Cd(II) are 1.03 µg L^?1 and 1.48 µg L^?1, respectively. The bismuth/poly (aniline) electrode has been applied to the determination of Pb(II) in tap water samples with satisfactory results.     

Evaluation of Bismuth Modified Carbon Thread Electrode for Simultaneous and Highly Sensitive Cd (II) and Pb (II) Determination

Bismuth film modified and chemically activated carbon micro‐thread electrodes were investigated for the simultaneous determination of Cd(II) and Pb(II) using square wave anodic stripping voltammetry. The carbon thread electrode was characterised using both surface and electrochemical techniques. Electrochemical impedance spectroscopy (EIS) studies demonstrated that the H₂SO₄/IPA‐treated carbon thread electrode showed a much improved resistance response (R_ct=23 Ω) compared to the IPA‐untreated carbon thread (R_ct=8317 Ω). Furthermore, parameters such as the effect of deposition potential, deposition time and Bi(III) concentration were explored using square wave voltammetry. Detection limits (S/N=3) for Cd(II) and Pb(II) were found to be 1.08 µg L^?1 and 0.87 µg L^?1, respectively and response was found to be linear over the range 5–110 µg L^?1. The proposed Bi/IPA‐treated carbon thread electrode exhibited a high selectivity towards Cd(II) and Pb(II) even in the presence of a range of heavy metals and is capable of repetitive and reproducible measurements, being attributed to the high surface area, geometry and electrode treatment characteristics. The proposed metal ion sensor was employed to determine cadmium and lead in river water samples and % RSD was found to be 5.46 % and 5.93 % for Cd(II) and Pb(II) respectively (n=3). Such facile sensing components favour the development of cost effective portable devices for environmental sample analysis and electrochemical applications.     

Simultaneous determination of chromium(III) and cadmium(II) by differential pulse anodic stripping voltammetry on a stannum film electrode

A stannum film electrode has been developed for the simultaneous determination of trace levels of chromium(III) and cadmium(II) by differential pulse anodic stripping voltammetry (DPASV). The stannum film electrode was generated in situ by depositing simultaneously the stannum film and the metals obtained by reduction of Cd(II) and Cr(III) at −1.4 V on a glassy carbon electrode. Then, the reduced products were oxidized by scanning the potential of the electrode from −1.4 to −0.4 V using DPASV. The electrode exhibited well-defined and separated stripping signals for both metals accompanied with a low background contribution. The possible mechanism of this design was proposed. Under the optimized working conditions, the detection limit was 2.0 and 1.1 μg l⁻¹ for Cr(III) and Cd(II) at a deposition time of 3 min. Finally, the stannum film electrode was successfully applied to the determination of Cd(II) in tap water with satisfactory results.     

Performance of Ex Situ Bismuth Film Rotating Disk Electrode in Trace Metal Analysis by Stripping Chronopotentiometry: Definition of the Depletion Regime and Optimization of Experimental Parameters

The potentiality of the ex situ deposited bismuth film electrode, allied to the rotation of a glassy carbon disk electrode (BiFE‐RDE), was exploited in trace metal analyses of lead(II) and cadmium(II) by stripping chronopotentiometry (SCP). A single BiFE (6.2 nm film thickness) can be used for a 1‐day term with no significant variation in the analytical signal. The limit of detection (3σ) for a deposition time of 40 s and an oxidation current of 15×10^?9 A was 1.5×10^?8 M for Pb(II) and 3.0×10^?8 M for Cd(II). BiFE‐RDE was successfully applied to the direct SCP determination of lead(II) in a fresh water certified material.     

Resolving the copper interference effect on the stripping chronopotentiometric response of lead(II) obtained at bismuth film screen-printed electrode

As copper(II) is a common ion in a variety of analytical samples, its effect on the stripping response of lead(II) at bismuth film screen-printed carbon electrode (BFSPCE) was investigated. The study was conducted using a screen-printed three-electrode system (working, counter and reference electrodes), with the carbon-working electrode plated in situ with bismuth film. Copper present at significant concentration level in samples was found to affect the sensitivity of the electrode by reducing the constant current stripping chronopotentiometric (CCSCP) response of lead(II). Recovery of the lead stripping response at the BFSPCE in the presence of copper was obtained when 0.1 mM ferricyanide was added to the test solution. The ferricyanide added circumvents the detrimental effect of copper(II) by selectively masking the copper ions by forming a complex. The analytical utility of the procedure is illustrated by the stripping chronopotentiometric determinations of lead(II) in soil extracts.     

Hierarchical Porous Tubular Biochar Based Sensor for Detection of Trace Lead (II)

Hierarchical porous tubular biochar (PTBC) was prepared by selectively removing lignin simply according to reverse the pyrolysis sequence of cellulose. The properties of the PTBC sample were characterized by XRD, SEM, TEM, Raman spectra, cyclic voltammetry and electrochemical impedance spectroscopy. The electrochemical performances of PTBC modified on the screen-printing electrode illustrated excellent detection of lead ions (lead (II)) in water with the linear range (0.5–120 μg/L) and the detection limit (0.02 μg/L) by in-situ bismuth film square wave anode stripping voltammetry.     

Characterization and Applications of a Bismuth Bulk Electrode

A bismuth bulk electrode (BiBE), a new solid‐state electrode, is presented. The polycrystalline metal bismuth disk‐shaped electrode was examined for its anodic stripping voltammetry performance, which was found to be well comparable to that achieved with the bismuth or mercury film electrodes. Useful potential windows of the BiBE in aqueous solutions of pH 1 to 13 were found to range from approximately ?1.7 to ?0.1 V, depending on pH, where either hydrogen evolution or anodic dissolution of metallic bismuth limit the electrochemical inertness of the BiBE. Employing cyclic voltammetry (CV), the cathodic behavior of the BiBE was examined by testing inorganic (cadmium(II) ions) and organic (2‐nitrophenol) model compounds; a CV quasi‐reversible behavior was recorded in the case of the Cd(II)‐Cd(0) couple. The characteristics of the BiBE under anodic conditions, i.e., at bismuth surface coated with a thin conductive Bi₂O₃ film, was examined by testing two well‐established redox systems, potassium hexacyanoferate(III) and ruthenium(III) hexaaminechloride; a nearly reversible behavior was recorded in the latter case. Based on the presented preliminary results, BiBE can be considered as an interesting alternative to common solid and (toxic) mercury electrodes for possible use in electrochemical studies and electroanalytical applications.     

High‐Sensitivity Determination of Lead(II) and Cadmium(II) Based on the CNTs‐PSS/Bi Composite Film Electrode

A high‐sensitivity sensing platform for lead(II) and cadmium(II) based on the bismuth modified carbon nanotubes (CNTs)‐poly(sodium 4‐styrenesulfonate) composite film electrode (CNTs‐PSS/Bi) was fabricated. The composite film CNTs‐PSS/Bi provided remarkably improved sensitivity and reproducibility compared with previously reported CNTs‐modified electrodes. The detection limits were estimated to be 0.04 ppb for lead(II) and 0.02 ppb for cadmium(II) with a preconcentration time of 120 s, respectively. The linear responses of Cd²⁺ and Pb²⁺ were over the ranges of 0.5–50 ppb and 0.5–90 ppb, respectively. Finally, the practical application of the proposed method was verified in the real water sample with satisfactory results.     

Ultrasensitive Voltammetric Detection of Trace Lead(II) and Cadmium(II) Using MWCNTs‐Nafion/Bismuth Composite Electrodes

Multiwall carbon nanotubes were dispersed in Nafion (MWCNTs‐NA) solution and used in combination with bismuth (MWCNTs‐NA/Bi) for fabricating composite sensors to determine trace Pb(II) and Cd(II) by differential pulse anodic stripping voltammetry (DPASV). The electrochemical properties of the MWCNTs‐NA/Bi composites film modified glassy carbon electrode (GCE) were evaluated. The synergistic effect of MWCNTs and bismuth composite film was obtained for Pb(II) and Cd(II) detection with improved sensitivity and reproducibility. Linear calibration curves ranged from 0.05 to 100 μg/L for Pb(II) and 0.08 to 100 μg/L for Cd(II). The determination limits (S/N=3) were 25 ng/L for Pb and 40 ng/L for Cd, which compared favorably with previously reported methods in the area of electrochemical Pb(II) and Cd(II) detection. The MWCNTs‐NA/Bi composite film electrodes were successfully applied to determine Pb(II) and Cd(II) in real sample, and the results of the present method agreed well with those of atomic absorption spectroscopy.     

铋膜修饰玻碳电极伏安法测定微量铅(Ⅱ)

以铋膜修饰玻碳电极为工作电极,采用阳极溶出伏安法对微量Pb(Ⅱ)进行测定。考察了铋离子浓度、支持电解质pH、沉积时间等因素对测定的影响。实验结果表明,铋膜修饰电极对痕量Pb(Ⅱ)具有良好的电化学响应。在实验选定条件下,Pb(Ⅱ)在10～260!g/L范围内与峰电流呈良好的线性关系,检出限为1.98!g/L。用同一支铋膜电极对50!g/L Pb(Ⅱ)平行测定10次,相对标准偏差(RSD)为2.82%。该电极可应用于井水中铅的测定。     

A Novel Cell Design for the Improved Stripping Voltammetric Detection of Zn(II), Cd(II), and Pb(II) on Commercial Screen‐Printed Strips by Bismuth Codeposition in Stirred Solutions

A novel electrochemical cell design is proposed to allow fast, reproducible and highly efficient convective transport of dissolved substances to screen‐printed electrochemical three‐electrode strips mounted on miniaturized plastic vessels, with the goal of improving detection limits in disposable electrochemical stripping field sensors. The experimental configuration has been tested for accumulation of the selected heavy metals ions Zn(II), Cd(II), and Pb(II), codeposited with bismuth ions on a carbon disk screen‐printed working electrode before detection by square wave anodic stripping voltammetry. Chemical and instrumental variables of the proposed device and associate electrochemical method were optimized. Selected parameters gave detection limits in the low ng mL^?1 range with moderate deposition time (120 s). Practical applicability was tested on certified water and real samples (tap water and waste water), with acceptable results, suggesting potential usefulness for field environmental monitoring of heavy metals.     

Bismuth-dispersed xerogel-based composite films for trace Pb(II) and Cd(II) voltammetric determination

We report for the first time the synthesis of bismuth-modified (3-mercaptopropyl) trimethoxysilane (MPTMS) and its application for the determination of lead and cadmium by anodic stripping voltammetry. Xerogels made from bismuth-modified MPTMS and mixtures of it with tetraethoxysilane, under basic conditions (NH₃·H₂O), were characterized with scanning electron microscopy, energy dispersive spectroscopy, infrared spectroscopy and electrochemical methods. Bismuth-modified xerogels were mixed with 1.5% (v/v) Nafion in ethanol and applied on glassy carbon electrodes. During the electrolytic reductive deposition step, the bismuth compound on the electrode surface was reduced to metallic bismuth. The target metal cations were simultaneously reduced to the respective metals and were preconcentrated on the electrode surface by forming an alloy with bismuth. Then, an anodic voltammetric scan was applied in which the metals were oxidized and stripped back into the solution; the voltammogram was recorded and the stripping peak heights were related to the concentration of Cd(II) and Pb(II) ions in the sample. Various key parameters were investigated in detail and optimized. The effect of potential interferences was also examined. Under optimum conditions and for preconcentration period of 4 min, the 3σ limit of detection was 1.3 μg L⁻¹ for Pb(II) and 0.37 μg L⁻¹ for Cd(II), while the reproducibility of the method was 4.2% for lead (n = 5, 10.36 μg L⁻¹ Pb(II)) and 3.9% for cadmium (n = 5, 5.62 μg L⁻¹ Cd(II)). Finally, the sensors were applied to the determination of Cd(II) and Pb(II) ions in water samples.     

Influence of Pb(II) concentration and pH of acetate buffer on the potential window of a lead film electrode: an Atomic Force Microscopy Study

Atomic force microscopy (AFM) studies on observations of lead films deposited from the solutions containing an acetate buffer and different concentration of Pb(II) are presented. AFM images show considerable variability in morphology of the deposited lead layer depending on experimental conditions. To investigate effects of the Pb(II) concentration and pH of the supporting electrolyte on the accessible potential window of the lead film electrode (PbFE), voltammetric techniques were used. It was found that the useful potential window of PbFE is affected by the pH and Pb(II) concentration. Additionally, it was found that the distribution and large size of Pb particles on the electrode surface shown by AFM corresponded well to the mass of Pb expected on the glassy carbon support with respect to the voltammetric data. Results reveal that PbFE is an attractive nonmercury metallic electrode suitable for electrochemical detection of metal ions and a lot of organic compounds in a wide potential window. The accessible potential window of the PbFE in an acetate buffer (pH = 5.0) was compared to those obtained at the bismuth film electrode and antimony film electrode.     

An adsorptive stripping voltammetry of nickel and cobalt at a solid lead electrode

For the first time, a solid lead electrode (PbE) was exploited for adsorptive stripping voltammetric determination of Ni(II) and Co(II) in the presence of nioxime as a complexing agent. The calibration graphs for Ni(II) and Co(II) were linear from 0.059 to 0.59 µg L^?1 and from 0.029 to 0.29 µg L^?1 (accumulation time 120 s), respectively. The analytical parameters such as the detection limit and separation of analytical signals obtained at the solid lead electrode were comparable with those obtained using a lead film electrode while better in comparison to those reported before for the bismuth film or solid bismuth electrodes. Co(II) could be determined in the presence of a large excess of Ni(II) and Zn(II). The proposed electrode was applied to determine Co(II) and Ni(II) traces in certified reference material and a natural water sample with satisfactory results.     

A stannum-bismuth composite film electrode for simultaneous determination of zinc(II) and cadmium(II) using differential pulse anodic stripping voltammetry

The development and use of 'green' electrode materials is extremely attractive for the routine use of disposable metal sensors. Bismuth is an environmentally-friendly element and a bismuth film electrode was proposed as an alternative to mercury film electrodes. Compared with bismuth, stannum is a more 'environmentally friendly' material. The stannum-bismuth composite film electrode prepared by the in situ electrodeposition of stannum and bismuth on the glassy carbon substrate is reported for the first time. Compared with bismuth film and stannum film electrodes, the stannum-bismuth composite film electrode revealed better electroanalytical performance, and can be used as a possible alternative electrode for electrochemical stripping analysis of trace heavy metals.     

Ultrasensitive voltammetric detection of trace heavy metal ions using carbon nanotube nanoelectrode array

We describe an ultrasensitive voltammetric detection of trace heavy metal ions using nanoelectrode arrays (NEAs) that are based on low-site density carbon nanotubes (CNTs). The NEAs were prepared by sealing the side-walls of CNTs with an epoxy passive layer that reduces the current leakage and eliminates the electrode capacitance, leading to a low background current. This provides a high signal-to-noise ratio. The CNTs-NEAs coated with a bismuth film were used successfully for voltammetric detection of trace cadmium(II) and lead(II) at the sub-ppb level. The detection limit of 0.04 microg L(-1) was obtained under optimum experimental conditions. The attractive behavior of the new carbon NEA sensing platform holds great promise for onsite environmental monitoring and biomonitoring of toxic metals.