3D‐printed Metal Electrodes for Heavy Metals Detection by Anodic Stripping Voltammetry

Heavy metals, being one of the most toxic and hazardous pollutants in natural water, are of great public health concern. Much effort is still being devoted to the optimization of the electroanalytical methods and devices, particularly for the development of novel electrode materials in order to enhance selectivity and sensitivity for the analysis of heavy metals. The ability of 3D‐printing to fabricate objects with unique structures and functions enables infinite possibilities for the creation of custom‐made electrochemical devices. Here, stainless steel 3D‐printed electrodes (3D‐steel) have been tested for individual and simultaneous square wave anodic stripping analysis of Pb and Cd in aqueous solution. Electrodeposition methods have also been employed to modify the steel electrode surface by coating with a thin gold film (3D−Au) or a bismuth film (3D−Bi) to enhance the analytical performance. All 3D‐printed electrodes (3D‐steel, 3D−Au and 3D−Bi) have been tested against a conventionally employed glassy carbon electrode (GC) for comparison. The surface modified electrodes (3D−Au and 3D−Bi) outperformed the GC electrode demonstrating higher sensitivity over the studied concentration ranges of 50–300 and 50–500 ppb for Pb and Cd, respectively. Owing to the bismuth property of binary alloys formation with heavy metals, 3D−Bi electrode displayed well‐defined, reproducible signals with relatively low detection limits of 3.53 and 9.35 ppb for Pb and Cd, respectively. The voltammetric behaviour of 3D−Bi electrode in simultaneous detection of Pb and Cd, as well as in individual detection of Pb in tap water was also monitored. Overall, 3D‐printed electrodes exhibited promising qualities for further investigation on a more customizable electrode design.     

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.     

Anodic Stripping Voltammetry Combined with Sequential Injection Analysis for Measurements of Trace Metal Ions with Bismuth‐ and Antimony Film Electrodes under Comparable Conditions

Anodic stripping voltammetry combined with sequential injection analysis (ASV‐SIA) was selected to examine the use of bismuth‐ and antimony‐film plated glassy carbon electrodes under comparable conditions for the determination of Pb(II) and Cd(II) ions. Of interest were the conditions for film deposition, as well as the composition of sample/carrier solutions, including concentrations of Sb(III) or Bi(III) and HCl. Then, by the optimized procedure, one could determine Pb(II), Cd(II), and Zn(II) ions at the low µg L^?1 level and ASV‐SIA configuration with both electrodes tested on analysis of a water sample.     

Mercury Films on Commercial Carbon Screen‐Printed Devices for the Analysis of Heavy Metal Ions: a Critical Evaluation

The suitability of mercury films on commercial screen‐printed electrodes for the analysis of heavy metal ions is critically tested for the particular case of Pb(II)‐ions. Although determination is possible by anodic stripping voltammetry with a reasonable detection limit (8.9 µg L^?1), important drawbacks are noticed as a consequence of the heterogeneous deposition of mercury on the rough surface of screen‐printed devices.     

Use of 3-D plots to avoid mutual interference in bianalyte ASV determinations: application to cadmium and lead detection

We have examined the anodic stripping voltammetry (ASV) of Cd and Pb at carbon screen printed electrodes modified by an in situ deposited Bi film, and have demonstrated significant cross talk between the stripping peaks of the two metals. A simple and generally applicable method for dealing with this problem is described, based on curve-fitting three-dimensional calibration plots using MATLAB. Non-linear fitting to the calibrations produced coefficients of determination R² > 0.99 for both metals. We have illustrated use of the plots in conjunction with Bi-plated electrodes by measuring 15 randomly selected mixtures of Cd and Pb of known concentration.     

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.     

A Zirconium Oxide Nanoparticle Modified Screen‐printed Electrode for Anodic Stripping Determination of Daclatasvir Dihydrochloride

A novel, sensitive and rapid voltammetric method applied for daclatasvir dihydrochloride (DSV.2HCl) detection in raw material, human plasma and urine using square wave voltammetry at a nano‐screen printed electrode (SPE) based on synthesized zirconium oxide nanoparticles (ZrO₂ NPs). The attention to zirconium oxide nanoparticle syntheses arises from its likely use in making an electrode material in the electroanalytical process. Anodic stripping square wave voltammetric peaks have been recorded at the optimum conditions of drug solution as pH, scan rate, accumulation time and accumulation potential. Morphology of the used nanoparticles has been performed by scanning electron microscope (SEM) and transmission microscope (TEM). ZrO₂ NPs were applied to screen printed electrode (ZrO₂‐MSPE) giving a new sensor to detect the DSV.2HCl drug. ZrO₂ NPs were tested for their electroactivity in improving electrodes sensitivity. The modified electrode has been used for the analysis of DSV.2HCl in spiked serum, spiked urine and pharmaceutical formulation.     

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.     

Electrochemical Detection of TNT at Cobalt Phthalocyanine Mediated Screen‐Printed Electrodes and Application to Detection of Airborne Vapours

We describe the use of cobalt phthalocyanine as a mediator to improve the sensitivity for the electrochemical detection of TNT. Commercial screen‐printed electrodes containing cobalt phthalocyanine were employed for determination of TNT. Improved sensitivities compared to screen‐printed carbon electrodes without phthalocyanine were observed, current response for cyclic voltammetric measurements at modified electrodes being at least double that of unmodified electrodes. A synergistic effect between oxygen and TNT reduction was also observed. Correlation between TNT concentrations and sensor output was observed between 0–200 µM TNT. Initial proof‐of‐concept experiments combining electrochemical determinations, with the use of an air‐sampling cyclone, are also reported.     

Sensitive Determination of Nitrofurantoin by Flow Injection Analysis Using Carbon Nanofiber Screen Printed Electrodes

In this work, a new method to quantify nitrofurantoin in aqueous media using a flow injection system connected to commercially available screen‐printed carbon nanofibers was developed. A pretreatment of the screen‐printed carbon nanofibers electrode with Britton? Robinson buffer/N,N‐dimethylformamide was applied to enhance the nitrofurantoin peak current signal in one step. The developed method was demonstrated to be sensible, reproducible, easy, and inexpensive. With a low detection limit, it is applicable to real samples. The results indicate that it is highly applicable for the detection of nitrofurantoin in several matrices. When urine samples without any pretreatment were analyzed, the method proved reproducible and sensible and had a low detection limit. The use of screen‐printed electrodes has advantages over other modified electrodes as a glassy carbon due to its versatility.     

AgNP/Bi/Nafion‐modified Disposable Electrodes for Sensitive Zn(II), Cd(II), and Pb(II) Detection in Aerosol Samples

A new method for modifying electrodes with Ag nanoparticles (AgNPs) using electrospray deposition for sensitive, selective detection of Zn(II), Cd(II), and Pb(II) in aerosol samples when combined with Bismuth and Nafion coating and square‐wave anodic stripping voltammetry (SWASV) is reported. Carbon stencil‐printed electrodes (CSPEs) fabricated on a polyethylene transparency (PET) sheet were produced for an inexpensive, simple to fabricate, disposable sensor that can be used with the microliter sample volumes for analysis. Sensor performance was improved by modifying the electrode surface with electrospray‐deposited AgNPs. The use of electrospray deposition resulted in more uniform particle dispersion across the electrode surface when compared to drop‐casting. Using AgNP‐modified electrodes combined with Bi and Nafion, experimental detection limits (LODs) of 5.0, 0.5, and 0.1 μg L⁻¹ for Zn(II), Cd(II), and Pb(II), respectively, were achieved. The linear working ranges were 5.0–400.0 μg L⁻¹, 0.5–400.0 μg L⁻¹, and 0.1–500.0 μg L⁻¹ for Zn(II), Cd(II), and Pb(II), respectively. Interference studies showed Cu(II) was the only metal that interfered with this assay but inference could be eliminated with the addition of ferricyanide directly to the sample solution. This electrochemical sensor was applied for the simultaneous determination of Zn(II), Cd(II), and Pb(II) within source particulate matter (PM) samples collected on filters using an aerosol test chamber.     

Graphene Oxide‐Modified Electrode Coated with in‐situ Antimony Film for the Simultaneous Determination of Heavy Metals by Sequential Injection‐Anodic Stripping Voltammetry

The proposed chemically modified electrode was graphene oxide that was synthesized via Hummer's method followed by reduction of antimony film by in‐situ electrodeposition. The experimental process could be concluded in three main steps: preparation of antimony film, reduction of analyte ions on the electrode surface and stripping step under the conditions of square wave anodic stripping voltammetry (SWASV). A simple and rapid approach was developed for the determination of heavy metals simultaneously based on a sequential injection (SI), an automated flow‐based system, coupled with voltammetric method using antimony‐graphene oxide modified screen‐printed carbon electrode (SbF‐GO‐SPCE). The effects of main parameters involved with graphene oxide, antimony and measurement parameters were also investigated. Using SI‐SWASV under the optimal conditions, the proposed electrode platform has exhibited linear range from 0.1 to 1.5 M. Calculated limits of detection were 0.054, 0.026, 0.060, and 0.066 μM for Cd(II), Pb(II), Cu(II) and Hg(II), respectively. In addition, the optimized method has been successfully applied to determine heavy metals in real water samples with acceptable accuracy of 94.29 – 113.42 % recovery.     

Double deposition/accumulation and double stripping steps system as a new way of decreasing the detection limit and elimination of interferences in stripping voltammetry of inorganic ions: A review

The article reviews an application of double deposition/accumulation and stripping steps as a new and beneficial manner of decreasing a detection limit and/or interferences elimination in stripping voltammetric determination of inorganic ions: Pb(II), Cd(II), Tl(I), U(VI), Au(III), As(III), Se(IV), In(III), Co(II), Cu(II), Bi(III) and Ga(III). A simple design of four-electrodes system, containing two working electrodes differing in their surface area, allows for conducting two preconcentration and two stripping steps in one measurement cycle and in one voltammetric cell. Considerable analytes preconcentration and, consequently, an increase of sensitivity of determinations was obtained by conducting the first stripping step in a small volume of a solution near the microelectrode surface. An appropriate selection of the conditions of the first deposition/accumulation and the first stripping steps allowed for a minimization/elimination of interference effects. The proposed procedures allows for ultra-trace levels determinations of mentioned inorganic ions (often impossible to determine by means of traditional three-electrodes systems) without additional preconcentration outside the electrochemical cell and with the use of mercury-free electrodes.     

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.     

Electrochemical Determination of Pyrogallol at Conducting Poly(3,4‐ethylenedioxythiophene) Film‐Modified Screen‐Printed Carbon Electrodes

The electrochemical oxidation of pyrogallol at electrogenerated poly(3,4‐ethylenedioxythiophene) (PEDOT) film‐modified screen‐printed carbon electrodes (SPCE) was investigated. The voltammetric peak for the oxidation of pyrogallol in a pH 7 buffer solution at the modified electrode occurred at 0.13 V, much lower than the bare SPCE and preanodized SPCE. The experimental parameters, including electropolymerization conditions, solution pH values and applied potentials were optimized to improve the voltammetric responses. A linear calibration plot, based on flow‐injection amperometry, was obtained for 1–1000 µM pyrogallol, and a slope of 0.030 µA/µM was obtained. The detection limit (S/N=3) was 0.63 µM.     

Trace Analysis of Heavy Metals (Cd,Pb, Hg) Using Native and Modified 3D Printed Graphene/Poly(Lactic Acid) Composite Electrodes

Here we investigate the use of 3D printed graphene/poly(lactic acid) (PLA) electrodes for quantifying trace amounts of Hg, Pb, and Cd. We prepared cylindrical electrodes by sealing a 600 μm diameter graphene/PLA filament in a pipette tip filled with epoxy. We characterized the electrodes using scanning electron microscopy, Raman spectroscopy, and cyclic voltammetry in ferrocene methanol. The physical characterization showed a significant amount of disorder in the carbon structure and the electrochemical characterization showed quasi‐reversible behavior without any electrode pretreatment. We then used unmodified graphene/PLA electrode to quantify Hg, and Pb and Cd in 0.01 M HCl and 0.1 M acetate buffer using square wave anodic stripping voltammetry. We were able to quantify Hg with a limit of detection (LOD) of 6.1 nM (1.2 ppb), but Pb and Cd did not present measurable peaks at concentrations below ～400 nM. We improved the LODs for Pb and Cd by depositing Bi microparticles on the graphene/PLA and, after optimization, achieved clear stripping peaks at the 20 nM level for both ions (4.1 and 2.2 ppb for Pb²⁺ and Cd²⁺, respectively). The results obtained for all three metals allowed quantification below the US Environmental Protection Agency action limits in drinking water.     

Recent Advances in Anodic Stripping Voltammetry with Bismuth‐Modified Carbon Paste Electrodes

In this article, the results of some recent investigations on two types of bismuth‐modified carbon paste electrodes are presented. In the first study, the bismuth‐film carbon paste electrode (BiF‐CPE) operated in situ and employed in anodic stripping voltammetry of Cd(II) and Pb(II) at the low μg L^?1 level was of interest in view of choosing the proper Bi(III)‐to‐Me(II) concentration ratios (where Me: Pb or Cd). Such optimization has resulted in significant improvement of detection limits down to 1.0 μg L^?1 Cd and 0.8 μg L^?1 for Pb, which allowed us to apply the BiF‐CPE for analysis of selected real samples of tap and sea water. The BiF‐CPE was also further investigated for its application in highly alkaline media. In this case, attention was focused on the complex‐forming capabilities of the OH ^– ions and their effect on the anodic stripping characteristics of some heavy metals (i.e. Cd, Pb, Tl) as well as upon the formation of the bismuth film itself. The last example deals with the continuing characterization of the recently introduced carbon paste electrodes modified with bismuth powder (Bi‐CPEs) which combine the advantageous properties of carbon paste material with the favorable electrochemical properties of bismuth. Three series of electrodes, differing either in the content of metallic bismuth (from 8 to 50% w/w) or in the type of the carbon powder used (two spectroscopic types of graphite and powdered glassy carbon), were compared and the respective relations to the optimal carbon paste composition evaluated. Attractive electroanalytical performance of the Bi‐CPE in anodic stripping voltammetry is demonstrated for selected model mixtures of heavy metals (Mn, Zn, Cd, Pb, Tl, and In).     

Screen printed graphite macroelectrodes for the direct electron transfer of cytochrome c

We report the direct electrochemistry of cytochrome c at screen printed graphite electrodes which exhibits quasi-reversible voltammetric responses without the need for any chemical or electrochemical pre-treatment, use of mediators or nanomaterials. Through voltammetric studies and X-ray photoelectron spectroscopy (XPS) it is shown that carbonyl and carboxylic surface oxygenated species likely residing at edge plane like- sites/defects of the graphite comprising the screen printed electrodes are responsible for the favourable interaction of the cytochrome c with that of the screen printed electrochemical sensing platform.     

On‐Site Determination of Carbendazim,Cathecol and Hydroquinone in Tap Water Using a Homemade Batch Injection Analysis Cell for Screen Printed Electrodes

In this work, we present a simple homemade batch‐injection analysis cell for screen‐printed electrodes (BIA‐SPE). The potential of the proposed system for on‐site analysis was demonstrated by the determination of carbendazim, catechol, and hydroquinone in tap water. The system provided reduced injection volume (30 µL), high analytical frequency (≈200 h^?1) and low detection limits (nanomolar level). Moreover, the BIA‐SPE cell presented better stability (RSD≈0.4 %) than a conventional flow injection cell for SPE (RSD≈5.0 %) in organic media. The proposed homemade BIA‐SPE cell is very simple, inexpensive and can be easily constructed in any laboratory.     

Voltammetric Determination of Trace Heavy Metals by Sequential-injection Analysis at Plastic Fluidic Chips with Integrated Carbon Fiber-based Electrodes

This work describes a sequential injection analysis (SIA) method for on-line strippping voltammetric determination of Pb(II), Cd(II) and Zn(II) using an injection-moulded electrochemical fluidic chip consisting of 3 conductive carbon fiber-loaded polymer electrodes embedded in a plastic fluidic holder. The sample containing the target metals and a solution containing Bi(III) were aspirated in the holding coil of the SIA manifold. Then, the flow was reversed and the two solutions were directed to the fluidic cell through a mixing coil which induced mixing of the two zones. Upon reaching the cell, simultaneous reduction of the target metals and Bi(III) occurred resulting in the formation of a metal-Bi alloy on the working electrode. Finally, the accumulated metals were stripped off the bismuth-film electrode via a positive potential scan and the oxidation current was recorded. The experimental variables (concentration of the bismuth plating solution, deposition potential, sample volume, stripping mode) were investigated and the potential interferences were assessed. The limits of quantification were 2.8 μg L⁻¹ for Pb(II), 3.6 μg L⁻¹ for Cd(II) and 4.2 μg L⁻¹ for Zn(II) and the the within-chip and between-chip % relative standard deviations were ≤6.3 % and ≤14 %, respectively. Finally, the sensor was applied to the determination of trace metals in a fish food sample.