Surface chemistry and electrocatalytic behaviour of tetra-carboxy substituted iron, cobalt and manganese phthalocyanine monolayers on gold electrode

Surface chemistry and electrocatalytic properties of self-assembled monolayers of metal tetra-carboxylic acid phthalocyanine complexes with cobalt (Co), iron (Fe) and manganese (Mn) as central metal ions have been studied. These phthalocyanine molecules are immobilized on gold electrode via the coupling reaction between the ring substituents and pre-formed mercaptoethanol self-assembled monolayer (Au-ME SAM). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy confirmed chemisorption of mercaptoethanol via sulfur group on gold electrode and also coupling reaction between phthalocyanines and Au-ME SAM. Electrochemical parameters of the immobilized molecules show that these molecules are densely packed with a perpendicular orientation. The potential applications of the gold modified electrodes were investigated towards l-cysteine detection and the analysis at phthalocyanine SAMs. Cobalt and iron tetra-carboxylic acid phthalocyanine monolayers showed good oxidation peak for l-cysteine at potentials where metal oxidation (M^III/M^II) takes place and this metal oxidation mediates the catalytic oxidation of l-cysteine. Manganese tetra-carboxylic acid phthalocyanine monolayer also exhibited a good catalytic oxidation peak towards l-cysteine at potentials where Mn^IV/Mn^III redox peak occurs and this redox peak mediates l-cysteine oxidation. The analysis of cysteine at phthalocyanine monolayers displayed good analytical parameters with good detection limits of the orders of 10⁻⁷ mol L⁻¹ and good linearity for a studied concentration range up to 60 μmol L⁻¹.     

Anodic stripping voltammetric measurement of trace heavy metals at antimony film carbon paste electrode

The antimony film carbon paste electrode (SbF-CPE) was prepared in situ on the carbon paste substrate electrode as a “mercury-free” electrochemical sensor. Its aptitude for measuring some selected trace heavy metals has been demonstrated in combination with square-wave anodic stripping voltammetry in non-deaerated model solutions of 0.01 M hydrochloric acid with pH 2. Some important operational parameters, such as deposition potential, deposition time, and concentration of antimony ions were optimized, and the electroanalytical performance of the SbF-CPE was critically compared with both bismuth film carbon paste electrode (BiF-CPE) and mercury film carbon paste electrode (MF-CPE) using Cd(II) and Pb(II) as test metal ions. In comparison with BiF-CPE and MF-CPE, the SbF-CPE exhibited superior electroanalytical performance in more acidic medium (pH 2) associated with favorably low hydrogen evolution, improved stripping response for Cd(II), and moreover, stripping signals corresponding to Cd(II) and Pb(II) at the SbF-CPE were slightly narrower than those observed at bismuth and mercury counterparts. In addition, the comparison with antimony film electrode prepared at the glassy carbon substrate electrode displayed higher stripping current response recorded at the SbF-CPE. The newly developed sensor revealed highly linear behavior in the examined concentration range from 5 to 50 μg L⁻¹, with limits of detection (3σ) of 0.8 μg L⁻¹ for Cd(II), and 0.2 μg L⁻¹ for Pb(II) in connection with 120 s deposition step, offering good reproducibility of ±3.8% for Cd(II), and ±1.2% for Pb(II) (30 μg L⁻¹, n = 10). Preliminary experiments disclosed that SbF-CPE and MF-CPE exhibit comparable performance for measuring trace concentration levels of Zn(II) in acidic medium with pH 2, whereas its detection with BiF-CPE was practically impossible. Finally, the practical applicability of SbF-CPE was demonstrated via measuring Cd(II) and Pb(II) in a real water sample.     

Linear sweep anodic stripping voltammetry of heavy metals from nitrogen doped tetrahedral amorphous carbon thin films

Nitrogen doped tetrahedral amorphous carbon (ta-C:N) thin films were deposited on p-Si (1 1 1) substrates (1 × 10⁻³ to 6 × 10⁻³ Ω cm) by a filtered cathodic vacuum arc technique with different nitrogen flow rates (3 and 20 sccm). The ta-C:N film coated samples were used as working electrodes to detect trace heavy metals such as zinc (Zn), lead (Pb), copper (Cu) and mercury (Hg) by using linear sweep anodic stripping voltammetry in 0.1 M KCl solutions (pH 1). The influence of nitrogen flow rate on the sensitivity of the films to the metal ions was investigated. The results showed that the current response of the ta-C:N film electrodes was significant to differentiate all the tested trace metal ions (Zn²⁺, Pb²⁺, Cu²⁺, and Hg²⁺) and the three ions (Pb²⁺ + Cu²⁺ + Hg²⁺) could be simultaneously identified with good stripping peak potential separations.     

Electrochemical detection of l-cysteine using a boron-doped carbon nanotube-modified electrode

A boron-doped carbon nanotube (BCNT)-modified glassy carbon (GC) electrode was constructed for the detection of l-cysteine (L-CySH). The electrochemical behavior of BCNTs in response to l-cysteine oxidation was investigated. The response current of L-CySH oxidation at the BCNT/GC electrode was obviously higher than that at the bare GC electrode or the CNT/GC electrode. This finding may be ascribed to the excellent electrochemical properties of the BCNT/GC electrode. Moreover, on the basis of this finding, a determination of L-CySH at the BCNT/GC electrode was carried out. The effects of pH, scan rate and interferents on the response of L-CySH oxidation were investigated. Under the optimum experimental conditions, the detection response for L-CySH on the BCNT/GC electrode was fast (within 7 s). It was found to be linear from 7.8 × 10⁻⁷ to 2 × 10⁻⁴ M (r = 0.998), with a high sensitivity of 25.3 ± 1.2 nA mM⁻¹ and a low detection limit of 0.26 ± 0.01 μM. The BCNT/GC electrode exhibited high stability and good resistance against interference by other oxidizable amino acids (tryptophan and tyrosine).     

The reduction of l-cystine hydrochloride at stationary and rotating disc mercury electrodes

The kinetics of l-cystine hydrochloride reduction have been studied at a mercury-plated copper rotating disc electrode (RDE) and at a stationary mercury disc electrode (SMDE) in 0.1 mol dm⁻³ HCl at 298 K. The reduction of the disulphide is irreversible and hydrogen evolution is the major side reaction. In contrast to steady state electrode kinetic studies at a mercury drop electrode (which shows a well-defined limiting current), the mercury-plated Cu RDE shows overlap between disulphide reduction and hydrogen evolution. These effects are attributable to strong reactant adsorption with a calculated surface coverage close to 100%. A Tafel slope of −185 mV per decade is found with a cathodic transfer coefficient of 0.32 and a formal rate constant of 6.7 × 10⁻⁹ m s⁻¹. The relative merits of steady state voltammetry at a mercury-plated copper RDE and linear sweep voltammetry at the SMDE are discussed, as is the mechanism of l-cysteine hydrochloride formation.     

Self-assembled nano-arrays of single-walled carbon nanotube-octa(hydroxyethylthio)phthalocyaninatoiron(II) on gold surfaces: Impacts of SWCNT and solution pH on electron transfer kinetics

The construction by sequential self-assembly process of reproducible, highly stable and pH-responsive redox-active nanostructured arrays of single-walled carbon nanotubes (SWCNTs) integrated with octa(hydroxyethylthio)phthalocyaninatoiron(II) (FeOHETPc) via ester bonds on a gold surface (Au-Cys-SWCNT-FeOHETPc) is investigated and discussed. The successful construction of this electrode is confirmed using atomic force microscopy and X-ray photoelectron spectroscopy as well as from the distinct cyclic voltammetric and electrochemical impedance spectroscopic profiles. The Au-Cys-SWCNT-FeOHETPc electrode exhibited strong dependence on the reaction of the head groups and the pH of the working electrolytes, the surface pK_a is estimated as 7.3. The high electron transfer capability of the Au-Cys-SWCNT-FeOHETPc electrode over other electrodes (Au-Cys-SWCNT or the Au-Cys-FeOHETPc or the Au-FeOHETPc) suggests that SWCNT greatly improves the electronic communication between FeOHETPc and the bare gold electrode. The electron transfer rate constant (k_app) of Au-Cys-SWCNT-FeOHETPc in pH 4.8 conditions (∼1.7 × 10⁻² cm⁻² s⁻¹) over that of the electrode obtained from SWCNT integrated with tetraaminophthalocyninatocobalt(II) (Au-Cys-SWCNT-CoTAPc) (5.1 × 10⁻³ cm⁻² s⁻¹) is attributed to the possible effect of the central metal on the phthalocyanine core and substituents on the peripheral positions of the phthalocyanine rings. We also prove that aligned SWCNT arrays exhibit much faster electron transfer kinetics to redox-active species in solutions compared to the randomly dispersed (drop-dried) SWCNTs.     

Development of a biomimetic chitosan film-coated gold electrode for determination of dopamine in the presence of ascorbic acid and uric acid

A gold electrode surface was modified using a dinuclear copper complex [Cu^II₂ (Ldtb)(μ-OCH₃)](BPh₄) and then coated with a chitosan film. This biomimetic polymer film-coated electrode was employed to eliminate the interference from ascorbic acid and uric acid in the sensitive and selective determination of dopamine. The optimized conditions obtained for the biomimetic electrode were 0.1 M phosphate buffer solution (pH 8.0), complex concentration of 2.0 × 10⁻⁴ M, 0.1% of chitosan and 0.25% of glyoxal. Under the optimum conditions, the calibration curve was linear in the concentration range of 4.99 × 10⁻⁷ to 1.92 × 10⁻⁵ M, and detection and quantification limits were 3.57 × 10⁻⁷ M and 1.07 × 10⁻⁶ M, respectively. The recovery study gave values of 95.2-102.6%. The lifetime of this biomimetic sensor showed apparent loss of activity after 70 determinations. The results obtained with the modified electrode for dopamine quantification in the injection solution matrix were in good agreement with those of the pharmacopoeia method.     

Self-assembled monolayers (SAMs) of cobalt tetracarboxylic acidchloride phthalocyanine covalently attached onto a preformed mercaptoethanol SAM: A novel method

A feasible method of fabricating phthalocyanine sensor was developed by covalent attachment of cobalt tetracarboxylic acidchloride phthalocyanine (CoTCACIPc) onto a preformed 2-mercaptoethanol (2-ME) self-assembled monolayer (SAM) modified gold electrode (designated as CoTCACIPc-2-ME-SAM). The surface concentration of the CoTCACIPc was found to be 4.58 × 10⁻¹⁰ mol/cm². The sensor gave a linear response to l-cysteine over the concentration range 0.28-20 μM with a detection limit of 5 × 10⁻⁷ M and best response time of 2 s.     

Determination of trace selenium on hanging copper amalgam drop electrode

Hanging copper amalgam drop electrode has been applied for trace determination of selenium by cathodic stripping analysis. Detection limit for Se(IV) as low as 0.25 nM (0.02 μg L⁻¹) at deposition time (120 s) could be obtained. For seven successive determinations of Se(IV) at concentration of 5 nM relative standard deviation was 2.3% (n = 7). Interferences from selected metals and surfactant substances were examined. Absence of copper ions in sample solution causes easier optimization and makes method less vulnerable on contamination. The developed method was validated by analysis of certified reference materials (BCRs) and applied to selenium determinations in natural water samples, snow, mushrooms and ox liver.     

Macrocyclic nickel(II) complex and hydrophilic polyurethane film electrodes for the electrocatalytic oxidation and selective detection of norepinephrine

Macrocyclic Ni(II) complex and hydrophilic polyurethane (PU) were used to modify activated glassy carbon (GC) electrodes for the electrocatalytic oxidation and selective detection of norepinephrine (NE). The Ni(II) complex was electropolymerized using cycling potentials, and the Ni(II) complex-modified electrode had a negatively shifted oxidation potential and increased current in phosphate buffer at pH 7.4. The linear range and detection limit were from 0.10 to 10 μM (390 nA μM⁻¹, R=0.999) and 7.7 nM (signal-to-noise ratio, S/N=3) by amperometry with flow injection, respectively. The Ni(II) complex-modified electrodes were coated with hydrophilic PU for higher selectivity. Hydrophilic anionic PU was produced by the hydrolysis of PU containing γ-benzyl l-glutamate (PUBLG) segments. The hydrophilic PU-coated electrodes increased the selectivity for NE over ascorbic acid (AA) and uric acid (UA). Moreover, NE in a human urine sample was detected with higher sensitivity, reproducibility, and stability than by using Nafion-coated electrodes. Therefore, hydrophilic PU and Ni(II) complex can be used as new electrode materials for the electrocatalysis and selective electroanalysis of NE. In particular, hydrophilic PU can be used as an alternative anionic material to Nafion for better urine compatibility.     

The characterization and bioelectrocatalytic properties of hemoglobin by direct electrochemistry of DDAB film modified electrodes

Direct electrochemistry of hemoglobin can be performed in acidic and basic aqueous solutions in the pH range 1-13, using stable, electrochemically active films deposited on a didodecyldimethylammonium bromide (DDAB) modified glassy carbon electrode. Films can also be produced on gold, platinum, and transparent semiconductor tin oxide electrodes. Hemoglobin/DDAB films exhibit one, two, and three redox couples when transferred to strong acidic, weak acidic and weak basic, and strong basic aqueous solutions, respectively. These redox couples, and their formal potentials, were found to be pH dependent. An electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ deposition of DDAB on gold disc electrodes and hemoglobin deposition on DDAB film modified electrodes. A hemoglobin/DDAB/GC modified electrode is electrocatalytically reduction active for oxygen and H₂O₂, and electrocatalytically oxidation active for S₂O₄²⁻ through the Fe(III)/Fe(II) redox couple. In the electrocatalytic reduction of S₄O₆²⁻, S₂O₄²⁻, and SO₃²⁻, and the dithio compounds of 2,2′-dithiosalicylic acid and 1,2-dithiolane-3-pentanoic acid, the electrocatalytic current develops from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in neutral and weakly basic aqueous solutions. Hemoglobin/DDAB/GC modified electrodes are electrocatalytically reduction active for trichloroacetic acid in strong acidic buffered aqueous solutions through the Fe(III)/Fe(II) redox couple. However, the electrocatalytic current developed from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in weak acidic and basic aqueous solutions. The electrocatalytic properties were investigated using the rotating ring-disk electrode method.     

Studies based on the electrochemical response of 2-(2-nitrophenyl)-1H-benzimidazole at chemically modified electrodes with over-oxidized poly-1-naphthylamine

The development of a simple and efficient method to 2-(2-nitrophenyl)-1H-benzimidazole (NB) electrochemical determination using a polymer film coated chemically modified electrode is described. A glassy carbon (GC) electrode was modified employing an electro-polymerized film of 1-naphtylamine (1-NAP) followed by an over-oxidation treatment in 0.2 M sodium hydroxide solution (poly-1-NAPox electrode).The electrochemical behaviour of NB at the poly-1-NAPox electrode was investigated in a mixture of 10% ethanol + 90% buffer solution (pH 2) by cyclic voltammetry (CV) and square-wave voltammetry (SWV). The experimental results suggested that the poly-1-NAPox electrode had a good effect on NB electrochemical response because it avoided the electrode surface fouling as a consequence of the adsorption of NB reduction products, which was found when a bare GC electrode was employed as the working electrode. The NB cathodic current was dependent on the polymeric film over-oxidation degree (α).NB could be determined in the range from 2 × 10⁻⁶ to 5 × 10⁻⁵ M. The NB detection and quantification limits were 5 × 10⁻⁷ and 1.7 × 10⁻⁶ M, respectively. The percent relative standard deviation of the peak current to 10-replicated measurement using 1.2 × 10⁻⁵ M NB solution was 1.4%. The method showed to be rapid, simple and with a good sensitivity.     

Cobalt(II) porphyrin complex immobilized on the binary oxide SiO2/Sb2O3: electrochemical properties and dissolved oxygen reduction study

In this work, SiO₂/Sb₂O₃ prepared by the sol-gel processing method, having a specific surface area, S_BET, of 790 m² g⁻¹, an average pore diameter of 1.9 nm and 4.7 wt.% of Sb, was used as substrate base for immobilization of the 5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H,23H-porphine ion. Cobalt(II) ion was inserted into the porphyrin ring with a yield of complex bonded to the substrate surface of 59.4 μ mol g⁻¹. A carbon paste electrode of this material was used to study, by linear sweeping voltammetric and chronoamperometric techniques, the electrocatalytic reduction of dissolved oxygen. The reduction, at the electrode solid-solution interface, occurred at −0.25 V versus SCE in 1.0 mol l⁻¹ KCl solution, pH 5.5, by a four electron mechanism. The electrode response was invariant under various oxidation-reduction cycles showing that the system is chemically very stable. Such characteristics allowed the study of the electrode response towards various dissolved oxygen concentrations using the chronoamperometry technique. The cathodic peak current intensities plotted against O₂ concentrations, between 1.0 and 12.8 mg l⁻¹, showed a linear correlation. The electrode response time was very fast, i.e. about 1 s. This study was extended using the electrode to determine the concentration of dissolved oxygen in sea water samples.     

Simultaneous determination of paracetamol and ascorbic acid using tetraoctylammonium bromide capped gold nanoparticles immobilized on 1,6-hexanedithiol modified Au electrode

Tetraoctylammonium bromide stabilized gold nanoparticles (TOAB-AuNPs) attached to 1,6-hexanedithiol (HDT) modified Au electrode was used for the simultaneous determination of paracetamol (PA) and ascorbic acid (AA) at physiological pH. The attachment of TOAB-AuNPs on HDT modified Au surface was confirmed by attenuated total reflectance (ATR)-FT-IR spectroscopy and atomic force microscope (AFM). The ATR-FT-IR spectrum of TOAB-AuNPs attached to the HDT monolayer showed a characteristic stretching modes corresponding to -CH₂ and -CH₃ of TOAB, confirming the immobilization of AuNPs with surface-protecting TOAB ions on the surface of the AuNPs after being attached to HDT modified Au electrode. AFM image showed that the immobilized AuNPs were spherical in shape and densely packed to a film of ca. 7 nm thickness. Interestingly, TOAB-AuNPs modified electrode shifted the oxidation potential of PA towards less positive potential by 70 mV and enhanced its oxidation current twice when compared to bare Au electrode. In addition, the AuNPs modified electrode separated the oxidation potentials of AA and PA by 210 mV, whereas bare Au electrode failed to resolve them. The amperometry current of PA was increased linearly from 1.50 × 10⁻⁷ to 1.34 × 10⁻⁵ M with a correlation coefficient of 0.9981 and the lowest detection limit was found to be 2.6 nM (S/N = 3). The present method was successfully used to determine the concentration of PA in human blood plasma and commercial drugs.     

Studies on the feasibility of electrochemical recovery of palladium from high-level liquid waste

The electrochemical behavior of palladium (II) in nitric acid medium has been studied at platinum and stainless steel electrodes by cyclic voltammetry. The cyclic voltammogram consisted of a surge in cathodic current occurring at platinum electrode at a potential of −0.1 V (vs. Pd), which culminates in a peak at −0.3 V was due to the reduction of Pd(II) to Pd. This was accompanied by a broad scant anodic peak at 0.25 V during scan reversal. Reduction of Pd(II) was irreversible and the diffusion coefficient was found to be 2.35 × 10⁻⁸ cm²/s at 298 K. At stainless steel electrode, a surge in the cathodic current occurring at −0.4 V (vs. Pd) was due to palladium deposition, which was immediately followed by a steep increase in cathodic current at −0.66 V due to H⁺ reduction. Electrolysis of palladium nitrate from 1 M to 4 M nitric acid medium at stainless steel electrode resulted in complete recovery of palladium with reasonably high Faradaic efficiency depending upon nitric acid concentration. However, the recovery and Faradaic efficiency were significantly lowered (to 40%) in the case of electrolysis from simulated high-level liquid waste due to other interfering competitive reactions.     

Highly sensitive electrochemical determination of nitric oxide using fused spherical gold nanoparticles modified ITO electrode

This paper describes the highly sensitive electrochemical determination of nitric oxide (NO) using the fused spherical gold nanoparticles (FAuNPs) modified ITO electrode. The FAuNPs were self-assembled on a (3-mercaptopropyl)-trimethoxysilane (MPTS) sol-gel film, which was preassembled on ITO electrode. The attachment of FAuNPs on MPTS sol-gel film was confirmed by UV-vis absorption spectroscopy, atomic force microscopy (AFM) and cyclic voltammetry (CV). The AFM image shows that the AuNPs retain their fused morphology after immobilized on MPTS sol-gel film. The FAuNPs modified ITO electrode shows an excellent electrocatalytic activity towards the oxidation of NO. Using FAuNPs modified electrode, the detection of 12 nM NO was achieved for the first time by amperometry method. Further, the current response was increased linearly with increasing NO concentration in the range of 1.2 × 10⁻⁸ to 7 × 10⁻⁴ M and the detection limit was found to be 3.1 × 10⁻¹⁰ M (S/N = 3). The FAuNPs modified ITO electrode displays an excellent selectivity towards the determination of 12 nM NO even in the presence of 1000-fold excess common interfering agents.     

Indium tin oxide coated conducting glass electrode for electrochemical destruction of textile colorants

Galvanostatic oxidation of 5.0 × 10⁻² mM textile dyes such as Eosin Y (EY) and Orange II (Or II) was carried out on an indium tin oxide (ITO) coated glass anode in the presence of 1.0 × 10⁻² mM KCl solution at pH 4.0 and 6.0. The degradation results of EY were compared with that of highly stable azo dyes (Or II). EY dye solution with a concentration of 5.0 × 10⁻² mM is totally decolorized in 30 min at an electrical charge (Q) 0.067 A h dm⁻³ while 5.0 × 10⁻² mM Or II degraded in a little less than an hour at the same electrical charge density. The decay kinetics of dyes follows a pseudo first-order reaction. The degradation of dyes is faster in acidic pH values than in basic pH values. Electrochemical degradation results show significant decrease in chemical oxygen demand (COD) values after electrodegradation of textile dyes. The key advantage of the ITO conducting glass anode is that the deposition of polymeric materials on the anode surface during electro-degradation of textile dyes is absent and therefore the electrode fouling is not observed. Hence, the ITO anodes can be employed an extended period without loss of activity.     

Preparation and characterization of thiocyanate-selective electrodes based on new complexes of copper(II) as neutral carriers

The complexes of hydroxycitronellal (o-aminobenzoic acid) copper(II) (Cu(II)-HXAB) and salicylaldehyde (o-aminobenzoic acid) copper(II) (Cu(II)-SHAB) were used as neutral carriers in PVC-based membrane ion-selective electrodes. The electrode based on Cu(II)-HXAB exhibited near-Nernstian potential response to thiocyanate (SCN⁻) in a linear range of 1.0 × 10^− 6 to 1.0 × 10^− 1 M with a detection limit of 8.5 × 10^− 7 M and a slope of − 57.3 mV/decade in 0.01 M phosphate buffer solution (pH 5.0). The electrode exhibited high selectivity to SCN⁻ over other tested anions with an anti-Hofmeister selectivity sequence. The selectivity behavior might be discussed in terms of UV-Vis spectrum and infrared spectrum. The transfer process of thiocyanate across the membrane interface was investigated by making use of the AC impedance technique. The electrode containing Cu(II)-HXAB could be applied to thiocyanate analysis in waste water with satisfactory results.     

Removal of Zn(II) from aqueous solution with natural Chinese loess: Behaviors and affecting factors

The Chinese loess was proved a promising adsorbent for Zn(II) removal from aqueous solution with adsorption capacities at 70.2-83.2 mg g^− 1 at 15-45 °C. Batch tests were conducted to evaluate the factors affecting the removal efficiency, of which the pH, temperature and initial Zn concentration all found in positive relevance to the increase of Zn(II) removal efficiency except for the slurry concentration. The uptake of Zn(II) on Chinese loess was considered as ion-exchange adsorption based on the calculated adsorption energy at − 12.8 to − 16.18 kJ mol^− 1 by D-R isothermal adsorption model. The adsorption kinetics follows the pseudo-second-order kinetics and the equilibrating duration was found to be > 24 h. Thermodynamic investigation shows that the enthalpy and entropy changes during adsorption are in the range of 18.27-47.83 kJ mol^− 1 and 52.7-129.6 J mol^− 1 K^− 1, respectively. The predicted Gibb's free energies were in the range of − 5.97-3.09 kJ mol^− 1, indicating that the adsorption was in favor of higher temperature and lower initial Zn(II) concentration. The optimal Zn(II) removal efficiency could be obtained under the following conditions: low or intermediate Zn(II) concentration, long reaction time, high temperature and initial pH > 3.0.     

Electrochemical study of chitosan films deposited from solution at reducing potentials

We report the electrochemical characterization of chitosan films deposited at gold electrodes from an acidic solution at reducing potentials. Cyclic voltammetry was used to characterize the deposition and electroactivity of chitosan coated gold electrodes. Chitosan films were found to deposit at gold electrodes at potentials more negative than −1.0 V versus Ag/AgCl, a potential associated with the onset of water reduction and increase in pH near the electrode. The chitosan films are electrochemically inactive; similar background charging currents are observed at bare gold and chitosan coated electrodes. The chitosan films are permeable to both cationic [Ru(NH₃)₆^3+/2+] and anionic [Fe(CN)₆^3−/4−] redox couples, but anionic complexes are retained in the chitosan film. Semiintegral analysis was used to examine adsorbed redox species at the chitosan coated electrode surface. Electrochemical parameters, including apparent diffusion coefficients for the redox probes at the electrodeposited chitosan modified electrodes are presented and are comparable to values reported for cast chitosan films.