Bismuth Film Microelectrode Modified with Overoxidized Poly‐1‐Naphtylamine Protective Membrane for Enhanced Stripping Voltammetric Detection

The application of protective overoxidized poly‐1‐naphtylamine membrane (ONAP) is demonstrated in combination with bismuth film microelectrode (ONAP‐BiFME) for anodic stripping voltammetric measurement of trace heavy metals in the presence of some selected surfactants. The ONAP membrane was electrochemically deposited on the surface of bare single carbon fiber microelectrode followed by the in situ or ex situ preparation of the bismuth film. The key operational parameters influencing the stripping performance of the ONAP‐BiFME were optimized and its electroanalytical performance was examined in the model solution containing Cd(II) and Pb(II) as test metal ions. The ONAP‐BiFME exhibited significantly enhanced stripping voltammetric response (approximately 70% for Cd(II) and 45% for Pb(II)) in comparison with unmodified BiFME in the absence of surfactants. In the presence of high concentrations, e.g., 20 mg L^?1, of anionic or cationic surfactants, the stripping signal for, e.g., Cd(II) decreased for less than 6% at the ONAP‐BiFME, whereas at the unmodified BiFME the signal attenuated considerably (approximately 38%). Moreover, in the presence of 10 mg L^?1 of nonionic surfactant Triton X‐100, the stripping signals at the bare BiFME were almost completely suppressed, whereas at the ONAP‐BiFME exhibited linear concentration behavior in the examined concentration range from 10 to 120 μg L^?1, with the calculated limit of detection of 5.0 μg L^?1 and 3.4 μg L^?1 for Cd(II) and Pb(II), respectively in connection with 60 s accumulation time. The attractive behavior of ONAP‐modified BiFME expands the applicability of bismuth‐based electrodes for measurement of trace heavy metals in real environments, where the presence of more complex matrix can be expected.     

Trace Determination of Chromium by Square‐Wave Adsorptive Stripping Voltammetry on Bismuth Film Electrodes

This works reports the use of adsorptive stripping voltammetry (AdSV) for the trace determination of chromium on a rotating‐disk bismuth‐film electrode (BFE). During the reductive accumulation step, all the chromium species in the sample were reduced to Cr(III) which was complexed with cupferron and the complex was accumulated by adsorption on the surface of a preplated BFE. The stripping step was carried out by using a square‐wave (SW) potential‐time voltammetric signal. Electrochemical cleaning of the bismuth film was employed, enabling the same bismuth film to be used for a series of measurements in the presence of dissolved oxygen. The experimental variables as well as potential interferences were investigated and the figures of merit of the method were established. Using the selected conditions, the 3σ limit of detection for chromium was 100 ng L^?1 (for 120 s of preconcentration) and the relative standard deviation was 3.6% at the 2 μg L^?1 level (n=8). Finally, the method was applied to the determination of chromium in real samples with satisfactory results.     

Framework‐Substituted Bismuth Zeolite‐P: Synthesis and Characterization

Bismuth‐modified zeolite‐P (Bi‐ZP) was synthesized by hydrothermal methods during the phase transformation of analcime to zeolite‐P. The evolution of phase transformation of pure analcime to Bi‐ZP was investigated. The results showed that bismuth atoms were incorporated into the framework of the microporous zeolite‐P. The effect of various Bi/Al (0–3) and Si/Bi (1–5) mole ratios on the synthesis of bismuth modified zeolite were studied by X‐ray diffraction (XRD) technique and FT‐IR spectroscopy. Evolution of the growth process of Bi‐ZP spheres was carried out at different time intervals with XRD patterns and FE‐SEM images. The energy dispersive X‐ray (EDX) spectrum indicated the existence of bismuth atoms in the synthesized Bi‐ZP. Framework substitutions of bismuth were evidenced by a set of complementary characterizations such as diffusive reflectance UV/Vis (DRS) and Raman spectroscopy on the synthesized Bi‐ZP (Si/Bi = 1).     

Screen‐Printed Disposable Sensors Modified with Bismuth Precursors for Rapid Voltammetric Determination of 3 Ecotoxic Nitrophenols

This work reports the application of screen‐printed electrodes bulk‐modified with bismuth precursors to the voltammetric determination of 2‐nitrophenol (2‐NP), 4‐nitrophenol (4‐NP) and 2,4‐dinitrophenol (2,4‐DNP) in water samples. A bismuth film was formed at the electrode surface via in situ reduction of the precursor compound contained in the electrode matrix by cathodic polarization at ?1.20 V. The formation of bismuth layer at the precursor‐modified electrodes was assessed by cyclic voltammetric (CV) at different pH values and by optical techniques. The target nitrophenols were voltammetrically determined by recording their reduction peaks in the differential pulse (DP) mode. The composition and content of the precursor compounds in the printed ink and the effect of the pH of the supporting electrolyte on the DP reduction currents of the 3 target nitrophenols were studied. The limits of quantification (LOQs) in three water matrices (distilled water, tap water and surface water) were in the range 1.1–2.2 µmol L^?1_. Using a simple solid‐phase extraction (SPE) procedure with Lichrolut EN cartridges and elution with methanol, a preconcentration factor of 100 was achieved; the LOQs were 0.021, 0.027 and 0.025 µmol L^?1 for 2‐NP, 4‐NP and 2,4‐DNP, respectively. The recoveries of samples spiked with the 3 target nitrophenols at two concentration levels (0.04 and 0.1 µmol L^?1) were always >87 %.     

Stripping Voltammetry with Bismuth Modified Graphite‐Epoxy Composite Electrodes

The attractive performance of graphite‐epoxy composite electrodes (GECE) surface‐modified with a bismuth film (Bi‐GECE) for simultaneous and separate stripping determination of trace amounts of heavy metals (lead, cadmium and zinc) is described. Several key parameters have been optimized. Bi‐GECEi electrode shows superior accumulation properties when compared to bare GECE or even to Hg‐GECE. Bi‐GECE exhibits well‐defined, undistorted, reproducible and sharp stripping signals with RSD of 2.99%, 1.56% and 2.19% for lead, cadmium and zinc respectively. Detection limits of 23.1, 2.2 and 600 μg/L for lead, cadmium and zinc were obtained. Sharp peaks with high resolution (of neighboring signals) that permit convenient multi‐elemental measurements resulted. The applicability of the electrodes to the real samples (tap water and soil sample) was also tested and promising results with good recoveries were obtained.     

Electrocatalytic Reduction of Metronidazole on Bismuth Modified Pencil‐lead Electrode

We report a new and simple approach based on an experimental design method for the preparation of pencil‐lead electrode modified with bismuth thin film. The fabrication process consists of reduction of bismuth on the surface of electrode with potentiostate method. Response surface methodology was developed as experimental strategies for modeling and optimization of the influence of some variables on the performance of modified electrode. The electrocatalytic behavior of this modified electrode was exploited as a sensitive detection system for the mercury‐free reduction and determination of metronidazole in pharmaceutical and biological samples by using differential pulse voltammetry and amperometry methods.     

Differential Pulse Voltammetric Determination of 2‐Methyl‐4,6‐Dinitrophenol using Bismuth Bulk Electrode

This work reports the application of bismuth bulk electrode (BiBE) for the determination of 2‐methyl‐4,6‐dinitrophenol (MDNP) by differential pulse voltammetry (DPV) in Britton‐Robinson buffer of pH 12.0 as an optimal medium. BiBE was prepared by transferring molten bismuth into a glass tube under constant stream of nitrogen. The linear concentration dependences were measured from 1 to 10 μmol ? L^?1 and from 10 to 100 μmol ? L^?1 by using optimum accumulation potential of ?0.7 V and optimum accumulation time 30 s. Under these conditions limit of determination and limit of quantification was 0.45 and 1.5 μmol ? L^?1, respectively. The developed method was successfully applied for the analysis of tap water as a model sample.     

Centri‐Voltammetric Folic Acid Detection

The need for practical detection of folic acid (FA) has been increased day by day. For this reason in this work, a two steps electroanalytical technique, centri‐voltammetry was utilized for FA detection for the first time. In order to get rid of the slow electrode kinetics of FA oxidation, the working electrode was modified with graphene‐Pt hibrid nanomaterial. Also for increasing the sensitivity, 1‐Chloro‐2‐[2‐(2‐methoxyethoxy) ethoxy]ethane (TEG?Cl) and 1,2‐di{2‐[2‐(2‐methoxyethoxy)ethoxy] ethoxy}‐4‐nitrobenzene (4NC?NO₂) was used as a carrier material. After the characterization of graphene‐Pt hybrid nanomaterial, experimental parameters like, 4NC?NO₂ amount, adsorption time, centri‐voltammetric parameters like centrifuge time and speed were optimized. After that, analytical characteristics such as linear range, relative standard deviation (R.S.D), limit of detection (LOD) and limit of quantification (LOQ) values were found. In this manner, linear range was obtained for FA between 1.0 μM–1000 μM with the equations of (R²=0.9977). R.S.D value was calculated for 0.83 mM FA (n=3) as 1.86 % while LOD and LOQ values were found as 1.00 μM and 3.34 μM respectively. After the examination of interference effect of substances like ascorbic acid and uric acid, established centri‐voltammetric technique was enforced for FA detection in pharmateutical tablets. As a result, the recovery value was calculated as 96.4 %.     

Voltammetric Determination of Neonicotinoid Pesticides at Disposable Screen‐Printed Sensors Featuring a Sputtered Bismuth Electrode

This work reports the determination of 5 neonicotinoid pesticides (Clothianidin, Imidacloprid, Thiamethoxam, Nitenpyram and Dinotefuran) in water samples by cathodic differential pulse (DP) voltammetry at screen‐printed disposable sensors featuring a sputtered bismuth thick‐film working electrode, a Ag reference electrode and a carbon counter electrode. The performance of the bismuth thick‐film electrodes was compared to that of a home‐made bismuth thin‐film electrode and a bismuth‐bulk electrode. The electrodes were further characterized by electrochemical and optical techniques. The effect of the pH of the supporting electrolyte on the DP reduction currents of the 5 pesticides was studied. The limits of quantification (LOQs) in 4 water matrices (distilled water, tap water, mineral water and surface water) were in the range 0.76 to 2.10 mg L^?1 but severe matrix effects were observed in the analysis of mineral and, especially, surface water samples. Using a solid‐phase extraction (SPE) procedure using Lichrolut EN cartridges and elution with methanol, the matrix effects were substantially reduced and the LOQs were in the range 9 to 17 µg L^?1_. The recoveries of surface water samples spiked with the 5 target neonicotinoids at two concentration levels (20 and 50 µg L^?1) were in the range 89 to 109 % and the % relative standard deviations ranged from 4.3 to 7.2 %.     

Bismuth Film Electrode as Sensing Platform for IgE–anti‐IgE Interactions

In this study, a bismuth film was used as a sensing platform for immunoreaction assay which includes the interactions between IgE and anti‐IgE molecules. For preparing this assay, IgE was deposited on a carbon paste electrode via bismuth(III) cations without using any membrane or functional reagent. The immobilized reagents and interaction of anti‐IgE on this formation were monitored by using atomic force microscopy technique and electrochemical impedance spectroscopy. Then some experimental parameters like the effect of IgE amount and the IgE–anti‐IgE interaction time were optimized. Under the optimal experimental conditions, the binding of anti‐IgE was also examined by following current decrease in differential pulse voltammograms of neutral red.     

Application of the Bismuth Film Electrode for Voltammetric Determination of Titanium Using Ti(IV)‐Oxalate‐Chlorate Catalytic System

The catalytic voltammetric protocol for the determination of titanium at a bismuth film electrode is presented. The method is based on the reduction of the Ti(IV)‐oxalate complex to Ti(III)‐oxalate in an acidic solution. It was proven that the addition of KClO₃ causes rapid oxidation of Ti(III)‐oxalate and, subsequently, an increase of the reduction peak current of Ti(IV) at the bismuth film electrode. Parameters that influence the Ti response, including the film preparation, solution pH, oxalate acid and chlorate concentrations, were optimized. The exploitation of the bismuth film electrode under the optimized conditions yielded a stable response for titanium, with high sensitivity (12.5 μA μM^?1), good precision (RSD=5.0%) and a low detection limit (1×10^?8 M).     

An Investigation into the Suitability of Bismuth as an Alternative to Gold‐Amalgam as a Working Electrode for the In Situ Determination of Chemical Redox Species in the Natural Environment

The suitability of the bismuth film working electrode was investigated as an alternative to the gold‐amalgam electrode used in solid state microelectrodes for in situ voltammetric analysis of redox chemistry in the natural environment (e.g., lakes, oceans, sedimentary pore waters). Chemical redox species measurable with the Au‐amalgam include O₂, H₂S, S , S₂O , Fe²⁺, Fe³⁺, Mn²⁺, I^?. Bismuth was electrochemically deposited to form a solid film analogous to the Au‐amalgam on a polished gold disk electrode. The useable potential window of the Bi‐film was found to be narrower than that of the Au‐amalgam, precluding the detection of dissolved O₂, I^? and S₂O , whose redox potentials fall outside the Bi‐film's range. The Bi‐film was able to detect free H₂S/HS^? and total sulfide (AVS), but not Fe²⁺ or Mn²⁺. The Bi‐film was less sensitive to low levels of total sulfide (<10 μM) than the Au‐amalgam; however, the Bi‐film was able to accurately quantify very high concentrations of sulfide (at least 15 mM), with a linear response up to an order of magnitude higher than that of the Au‐amalgam. Thus the Bi‐film appears to have limited application as an alternative to the Au‐amalgam microelectrode for in situ analysis of redox species in natural waters.     

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.     

Highly Sensitive and Selective Measurement of Bismuth in Seawater and Drug with 1,2‐Phenylenedioxydiacetic Acid by Cathodic Adsorptive Stripping Voltammetry

A new method is presented for determination of bismuth based on cathodic adsorptive stripping of complex bismuth with 1,2‐phenylenedioxydiacetic acid (PDA) at a hanging mercury drop electrode (HMDE). The effect of various parameters such as pH, concentration of ligand, accumulation potential and accumulation time on the selectivity and sensitivity were studied. The optimum conditions for determination of bismuth include nitric acid concentration 0.01 M, 8.0×10^?4 M PDA and accumulation time 120 s, accumulation potential of ?200 mV. The limits of detection are 0.25 and 0.05 nM, and responses are linear 1–1000 and 0.1–400 nM at t_acc of 60 and 120 s, respectively. Many common anions and cations do not interfere in the determination of bismuth. The method was applied to the determination of bismuth in some real samples such as sea – and spring water and drug.     

Ortho‐Alkylation of Phenol with Methanol Using Pb‐Cr Promoted Magnesium Oxide Catalysts

In this study, Pb‐Cr promoted magnesium oxide catalysts were used to catalyze the ortho‐alkylation of phenol in the presence of excess methanol. The Cr/MgO catalyst exhibited a high conversion of phenol and a relatively high selectivity for the ortho‐alkylation of phenol. The catalytic activity and the stability of Cr/MgO were improved by the addition of a fairly small amount of Pb. The Pb‐Cr/MgO catalyst showed specificity for the ortho‐alkylation of phenol, which was proved by a series of phenol derivative reactions with methanol.     

Electrochemical Detection of Phenol Removal by Using a Biosorbent Originated Factory Solid Waste

Biosorption is a preferable method for phenol (PNL) removal from water sources using a cheap and eco-friendly biomass. The combination of the biosorption technique with practical, affordable, sensitive, and selective monitoring tools gives a new perspective to environmental monitoring applications. Herein, as the first time, the monitoring of PNL biosorption performed using a factory waste was done by pencil graphite electrodes (PGEs) and cyclic voltammetry (CV) technique. The monitoring of the biosorption process was completed with reproducible and reliable results in just 40s. The biosorption was achieved in different water samples and the presence of different phenolic compounds.     

Voltammetric Determination of Pb(II) and Cd(II) Ions in Well Water Using a Sputtered Bismuth Screen‐Printed Electrode

A method using commercially available sputtered bismuth screen‐printed electrodes (Bi_spSPE), as substitute to mercury electrodes, for the determination of trace Pb(II) and Cd(II) ions in drinking well water samples collected in a contaminated area in The Republic of El Salvador by means of differential pulse anodic stripping voltammetry (DPASV) has been proposed. The comparable detection and quantification limits obtained for both Bi_spSPE and hanging mercury drop electrode (HMDE), together with the similar results with a high reproducibility obtained in these water samples analyses recommend the applicability of Bi_spSPE for the determination of low level of metal concentrations in natural samples.     

Stripping voltammetry with the electrode material acting as a ‘built-in' internal standard

The oxidation peak of the bismuth layer of bismuth-film electrodes is used as an internal standard in anodic stripping voltammetry. Such use of the electrode material as a ‘built-in' internal standard simplifies the analytical protocol (as it obviates the need for an external standard or long calibration and standard additions procedures) while correcting for run-to-run variations due to uncertainties (e.g., changes in mass transport, surface area, or other variables). The new internal standard strategy relies on common in situ plated film electrodes, where the deposition of both the analyte and electrode material is subject to the same variations. Such one-step quantitation and improvements are illustrated for trace measurements of lead. The use of the intrinsic signal of the system for obtaining the concentration of the target analyte is unique not only for electroanalysis, but for analytical chemistry in general.     

Zinc Detection in Serum by Anodic Stripping Voltammetry on Microfabricated Bismuth Electrodes

Zinc (Zn) homeostasis is required for a functional immune system. Critically ill patients often exhibit decreased Zn serum concentrations and could potentially benefit from Zn supplementation as a therapeutic strategy. However, the conventional approaches to monitoring Zn are time consuming and costly. This work reports on detection of Zn by anodic stripping voltammetry (ASV) on bismuth electrodes in a microfabricated electrochemical cell. The working potential window of the electrodeposited bismuth film electrode was investigated by cyclic voltammetry, while square wave ASV was used for measuring Zn in acetate buffer and blood serum. Conditions critical to sensing, such as preconcentration potential, preconcentration time, and buffer pH, were optimized for Zn detection. The sensor was successfully calibrated with pH 6 acetate buffer in the physiologically‐relevant range of 5 µM to 50 µM Zn and exhibited well‐defined and highly repeatable peaks. The sensor was used to demonstrate measurement of Zn in blood serum digested in HCl. The results of this work show that Zn detection in serum is possible with smaller sample volumes (µL vs. mL) and faster turnaround time (hours vs. days) as compared with the conventional spectroscopic methods.