Electrocatalytic Oxidation of Hydrogen Peroxide on Poly(m‐toluidine)‐Nickel Modified Carbon Paste Electrode in Alkaline Medium

The poly(m‐toluidine) film was prepared by using the repeated potential cycling technique in an acidic solution at the surface of carbon paste electrode. Then transition metal ions of Ni(II) were incorporated to the polymer by immersion of the modified electrode in a 0.2 M NiSO₄, also the electrochemical characterization of this modified electrode exhibits stable redox behavior of the Ni(III)/Ni(II) couple. The electrocatalytic ability of Ni(II)/poly(m‐toluidine)/modified carbon paste electrode (Ni/PMT/MCPE) was demonstrated by electrocatalytic oxidation of hydrogen peroxide with cyclic voltammetry and chronoamperometry methods in the alkaline solution. The effects of scan rate and hydrogen peroxide concentration on the anodic peak height of hydrogen peroxide oxidation were also investigated. The catalytic oxidation peak current showed two linear ranges with different slopes dependent on the hydrogen peroxide concentration and the lower detection limit was 6.5 μM (S/N=3). The catalytic reaction rate constant, (k_h), was calculated 5.5×10² M^?1 s^?1 by the data of chronoamperometry. This modified electrode has many advantages such as simple preparation procedure, good reproducibility and high catalytic activity toward the hydrogen peroxide oxidation. This method was also applied as a simple method for routine control and can be employed directly without any pretreatment or separation for analysis cosmetics products.     

Trace Level Determination of Hydrogen Peroxide at a Carbon Ceramic Electrode Modified with Copper Oxide Nanostructures

An electrochemical sensor was developed for determination of hydrogen peroxide based on nanocopper oxides modified carbon sol‐gel or carbon ceramic electrode (CCE). The modified electrode was prepared by electrodeposition of metallic copper on the CCE surface and derivatized in situ to copper oxides nanostructures and characterized by scanning electron microscopy (SEM) and X‐ray diffraction (XRD) techniques. The modified electrode responded linearly to the hydrogen peroxide (H₂O₂) concentration over the range 0.78–193.98 µmol L^?1 with a detection limit of 71 nmol L^?1 (S/N=3) and the sensitivity of 0.697 A mol^?1 L cm^?2. This electrode was used as selective amperometric sensor for determination of H₂O₂ contents in hair coloring creams.     

Effect of Various Deposition Techniques,Electrode Materials and Posttreatment with Tetrabutylammonium and Tetrabutylphosphonium Salts on the Electrochemical Behavior and Stability of Various Prussian Blue Modified Electrodes

The effect of various deposition techniques, electrode materials and posttreatment with tetrabutylammonium and tetrabutylphosphonium salts on the electrochemical behavior and stability of various Prussian blue (PB) modified electrodes, namely PB modified glassy carbon electrodes, silicate‐film supported PB modified glassy carbon electrodes, PB‐doped silicate glassy carbon electrodes, PB modified carbon ceramic electrodes using electrochemical deposition and PB modified carbon ceramic electrodes using chemical deposition is reported. Cyclic voltammetry and amperometric measurements of hydrogen peroxide were performed in a flow injection system while the carrier phosphate buffer (pH 7.0) with a flow rate of 0.8 mL min^?1 was propelled into the electrochemical flow through cell housing the PB modified working electrode as well as an Ag|AgCl|0.1 M KCl reference and a Pt auxiliary electrode. The results showed that the deposition procedure, electrode material and posttreatment with additional chemicals can significantly alter the stability and electrochemical behavior of the PB film. Among the studied PB modified electrodes, those based on carbon ceramic electrodes modified with a film of electropolymerized PB showed the best electrochemical stability.     

Carbon Nanostructured Screen‐printed Electrodes Modified with CuO/Glucose Oxidase/Maltase/SiO2 Composite Film for Maltose Determination

A sensitive voltammetric method was developed to determine maltose in beverage products using a carbon nanostructured screen‐printed electrode modified with CuO/glucose oxidase/maltase/SiO₂ biocomposite film. Adding CuO particles was done to possess catalytic activity toward hydrogen peroxide. Electrode modified by glucose oxidase and maltase shows a good response to maltose. A well‐defined reduction peak was registered at the potential of ?0.55 V (vs. Ag/AgCl) which intensity increases linearly with the concentration of maltose ranging from 0.01 to 0.1 mmol L^?1. The calculated limit of detection was 0.005 mmol L^?1. Tested on the beer samples, the developed CuO/glucose oxidase/maltase/SiO₂ biocomposite film covered carbon nanostructured screen‐printed electrode is showed to be a prospective sensitive element of the third generation biosensor for maltose.     

Carbon Electrodes Modified by Nanoscopic Iron(III) Oxides to Assemble Chemical Sensors for the Hydrogen Peroxide Amperometric Detection

In this study we show that nanoparticles of various ferric oxides (hematite, maghemite, amorphous Fe₂O₃, β‐Fe₂O₃ and ferrihydrite) incorporated into carbon paste exhibit electro‐catalytic properties towards hydrogen peroxide reduction. The modified paste electrode performances were evaluated and compared with those obtained with Prussian Blue‐modified carbon paste electrode, which represents an excellent chemical mediator towards the H₂O₂ redox reaction (as widely described in literature). The best catalytic activity was found for carbon paste modified by amorphous ferric oxide with 2–4 nm particle size, which was further tested for possible application as hydrogen peroxide sensor. At pH 7, the limit of detection was 2×10^?5 M H₂O₂ (S/N=3), the calibration curves were linear upto 8.5 mM H₂O₂ (R²=0.998), the measurement reproducibility (RSD=97%, n=4), the interelectrode reproducibility (RSD=16%, n_electrodes=5) and <3 s response time.     

Amperometric Biosensors Based on Platinum Nanowires

Abstract

Platinum nanowires (PtNW) were prepared by an electrodeposition strategy using nanopore alumina template. The nanowires prepared were dispersed in chitosan (CHIT) solution and stably immobilized onto the surface of glassy carbon electrode (GCE). The electrochemical behavior of PtNW‐modified electrode and its application to the electrocatalytic reduction of hydrogen peroxide (H₂O₂) are investigated. The modified electrode allows low potential detection of hydrogen peroxide with high sensitivity and fast response time. As an application example, the glucose oxidase was immobilized onto the surface of PtNW‐modified electrode through cross‐linking by glutaric dialdehyde. The detection of glucose was performed in phosphate buffer at –0.2 V. The resulting glucose biosensor exhibited a short response time (<8 s), with a linear range of 10^?5?10^?2 M and detection limit of 5×10^?6 M.     

Electrocatalytic Activity of Nanohybrids Based on Carbon Nanomaterials and MFe2O4 (M=Co,Mn) towards the Reduction of Hydrogen Peroxide

We report the advantages of hybrid nanomaterials prepared with electrogenerated ferrites (MFe₂O₄; M: Co, Mn) and multi‐walled carbon nanotubes (MWCNTs) or thermally reduced graphene oxide (TRGO) on the electro‐reduction of hydrogen peroxide. Glassy carbon electrodes (GCE) modified with these hybrid nanomaterials dispersed in Nafion/isopropanol demonstrated a clear synergism on the catalytic reduction of reduction of hydrogen peroxide at pH 13.00. The intimate interaction between MFe₂O₄ and carbon nanomaterials allowed a better electronic transfer and a facilitated regeneration of M²⁺ at the carbon nanomaterials, reducing the charge transfer resistances for hydrogen peroxide reduction and increasing the sensitivities of the amperometric response.     

Nanobiocomposite Modified Carbon‐Ceramic Electrode Based on Nano‐TiO2‐Plant Tissue and Its Application for Electrocatalytic Oxidation of Dopamine

A new modified carbon‐ceramic electrode was prepared by incorporating TiO₂ nanoparticle into sol‐gel network by accompanying apple tissue. A mixture of fine graphite powder with 15 wt% of TiO₂ nanoparticle was used for the preparation of the carbon matrix and finally modification with a known amount weighted of apple tissue. The apple tissue containing polyphenol oxidase enzyme acts as molecular recognition element. The electrocatalytic oxidation of dopamine was investigated on the surface of the nanobiocomposite modified carbon‐ceramic electrode using cyclic voltammetry, chronoamperometry and amperometry techniques. Effect of pH, scan rate, TiO₂ percentage on the response of modified electrode was studied. The prepared modified electrode presented a linear range for dopamine from 5.0×10^?6 to 1.2×10^?3 M in buffered solutions with pH 7.4 by amperometry. The detection limit was 3.41×10^?6 M dopamine. The response of the modified carbon‐ceramic electrode and unmodified carbon‐ceramic electrode was compared.     

Electrocatalytic Dioxygen Reduction at Glassy Carbon Electrode Modified with Polyaniline Grafted Multiwall Carbon Nanotube Film

The work details the electrocatalysis of oxygen reduction reaction (ORR) in 0.5 M H₂SO₄ medium on a modified electrode containing a film of polyaniline (PANI) grafted multi‐wall carbon nanotube (MWNT) over the surface of glassy carbon electrode. We have fabricated a novel modified electrode in which conducting polymer is present as connected unit to MWNT. The GC/PANI‐g‐MWNT modified electrode (ME) is fabricated by electrochemical polymerization of a mixture of amine functionalized MWNT and aniline with GC as working electrode. Cyclic voltammetry and amperometry are used to demonstrate the electrocatalytic activity of the GC/PANI‐g‐MWNT‐ME. The GC/PANI‐g‐MWNT‐ME exhibits remarkable electrocatalytic activity for ORR. A more positive onset potential and higher catalytic current for ORR are striking features of GC/PANI‐g‐MWNT‐ME. Rapid and high sensitivity of GC/PANI‐g‐MWNT‐ME to ORR are evident from the higher rate constant (7.92×10² M^?1 s^?1) value for the reduction process. Double potential chronoamperometry and rotating disk and rotating ring‐disk electrode (RRDE) experiments are employed to investigate the kinetic parameters of ORR at this electrode. Results from RDE and RRDE voltammetry demonstrate the involvement of two electron transfer in oxygen reduction to form hydrogen peroxide in acidic media.     

Electropolymerized Diphenylamine on Functionalized Multiwalled Carbon Nanotube Composite Film and Its Application to Develop a Multifunctional Biosensor

Diphenylamine (DPA) monomers have been electropolymerized on the amino‐functionalized multiwalled carbon nanotube (AFCNT) composite film modified glassy carbon electrode (GCE) by cyclic voltammetry (CV). The surface morphology of PDPA‐AFCNT was studied using field‐emission scanning electron microscopy (FE‐SEM). The interfacial electron transfer phenomenon at the modified electrode was studied using electrochemical impedance spectroscopy (EIS). The PDPA‐AFCNT/GCE represented a multifunctional sensor and showed good electrocatalytic behavior towards the oxidation of catechol and the reduction of hydrogen peroxide. Rotating‐disk electrode technique was applied to detect catechol with a sensitivity of 1360 µA mM^?1 cm^?2 and a detection limit of 0.01 mM. Amperometric determination of hydrogen peroxide at the PDPA‐AFCNT film modified electrode results in a linear range from 10 to 800 µM, a sensitivity of 487.1 µA mM^?1 cm^?2 and detection limit of 1 µM. These results show that the nano‐composite film modified electrode can be utilized to develop a multifunctional sensor.     

Amperometric hydrogen peroxide sensor based on a sol-gel-derived ceramic carbon composite electrode with toluidine blue covalently immobilized using 3-aminopropyltrimethoxysilane

A carbon composite amperometric hydrogen peroxide sensor has been developed using a sol-gel technique. Toluidine blue (TB), which acts as the redox mediator, was covalently immobilized via glutaraldehyde crosslinking with an organically modified silane, namely 3-aminopropyltrimethoxysilane (APTMOS). Methyltrimethoxysilane (MTMOS) was used as the additional monomer; this controls the hydrophobicity of the electrode surface, thus limiting the wettability. The immobilization of TB within the sol-gel matrix was confirmed with FTIR studies. The sol-gel mixture containing TB immobilized in APTMOS and MTMOS was mixed with graphite powder in order to prepare the carbon composite electrode. The electrode was characterized using voltammetric techniques and its electrocatalytic activity for the reduction of hydrogen peroxide was also studied. The carbon composite electrode has the advantage of sensing H₂O₂ at a lower potential and with a higher sensitivity, and interferences due to ascorbic acid, uric acid and acetaminophen were greatly minimized. The linear range for the determination of H₂O₂ extends from 5.37 × 10⁻⁶ to 6.15 × 10⁻³ M, with a correlation coefficient of 0.9981. The detection limit was found to be 2.15 × 10⁻⁶ M. The covalent immobilization of TB effectively prevents the leakage of the water-soluble mediator during measurements. The modified electrode, aside from electrocatalyzing the reduction of H₂O₂, exhibits distinct advantages in terms of surface renewal in the event of surface fouling, as well as simple preparation, good chemical and mechanical stability, and good reproducibility. Figure Amperometric hydrogen peroxide sensor based on sol-gel-derived ceramic carbon composite electrode with toluidine blue covalently immobilized using 3-aminopropyltrimethoxysilane Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Preparation, Electrochemical Behavior and Electrocatalytic Activity of a Copper Hexacyanoferrate Modified Ceramic Carbon Electrode

A copper hexacyanoferrate modified ceramic carbon electrode （CuHCF/CCE） had been prepared by two-step sol-gel technique and characterized using electrochemical methods. The resulting modified electrode showed a pair of well-defined surface waves in the potential range of 0.40 to 1.0 V with the formal potential of 0.682 V （vs. SCE） in 0.050 mol·dm^-3 HOAc-NaOAc buffer containing 0.30 mol·dm^-3 KCl. The charge transfer coefficient （a） and charge transfer rate constant （ks） for the modified electrode were calculated. The electrocatalytic activity of this modified electrode to hydrazine was also investigated, and chronoamperometry was exploited to conveniently determine the diffusion coefficient （D） of hydrazine in solution and the catalytic rate constant （kcat）. Finally, hydrazine was determined with amperometry using the resulting modified electrode. The calibration plot for hydrazine determination was linear in 3.0 × 10^-6--7.5 × 10^-4 mol·dm^-3 with the detection limit of 8.0 × 10^-7 molodm^-3. This modified electrode had some advantages over the modified film electrodes constructed by the conventional methods, such as renewable surface, good long-term stability, excellent catalytic activity and short response time to hydrazine.     

Immobilization of [Cu(bpy)2]Br2 complex onto a glassy carbon electrode modified with α-SiMo12O40 and single walled carbon nanotubes: Application to nanomolar detection of hydrogen peroxide and bromate

A simple procedure has been used for preparation of modified glassy carbon electrode with carbon nanotubes and copper complex. Copper complex [Cu(bpy)₂]Br₂ was immobilized onto glassy carbon (GC) electrode modified with silicomolybdate, α-SiMo₁₂O₄₀⁴⁻ and single walled carbon nanotubes (SWCNTs)_. Copper complex and silicomolybdate irreversibly and strongly adsorbed onto GC electrode modified with CNTs. Electrostatic interactions between polyoxometalates (POMs) anions and Cu-complex, cations mentioned as an effective method for fabrication of three-dimensional structures. The modified electrode shows three reversible redox couples for polyoxometalate and one redox couple for Cu-complex at wide range of pH values. The electrochemical behavior, stability and electron transfer kinetics of the adsorbed redox couples were investigated using cyclic voltammetry. Due to electrostatic interaction, copper complex immobilized onto GC/CNTs/α-SiMo₁₂O₄₀⁴⁻ electrode shows more stable voltammetric response compared to GC/CNTs/Cu-complex modified electrode. In comparison to GC/CNTs/Cu-complex the GC/CNTs/α-SiMo₁₂O₄₀⁴⁻ modified electrodes shows excellent electrocatalytic activity toward reduction H₂O₂ and BrO₃⁻ at more reduced overpotential. The catalytic rate constants for catalytic reduction hydrogen peroxide and bromate were 4.5(±0.2) × 10³ M⁻¹ s⁻¹ and 3.0(±0.10) × 10³ M⁻¹ s⁻¹, respectively. The hydrodynamic amperommetry technique at 0.08 V was used for detection of nanomolar concentration of hydrogen peroxide and bromate. Detection limit, sensitivity and linear concentration range proposed sensor for bromate and hydrogen peroxide detection were 1.1 nM and 6.7 nA nM⁻¹, 10 nM-20 μM, 1 nM, 5.5 nA nM⁻¹ and 10 nM-18 μM, respectively.     

Reduced Graphene Oxide|Carbon Ceramic Electrode Modified with CdS‐Hemoglobin as a Sensitive Hydrogen Peroxide Biosensor

A sensitive hydrogen peroxide (H₂O₂) biosensor was developed based on a reduced graphene oxide|carbon ceramic electrode (RGO|CCE) modified with cadmium sulfide‐hemoglobin (CdS‐Hb). The electron transfer kinetics of Hb were promoted due to the synergetic function of RGO and CdS nanoparticles. The transfer coefficient (α) and the heterogeneous electron transfer rate constant (k_s) were calculated to be 0.54 and 2.6 s^?1, respectively, indicating a great facilitation achieved in the electron transfer between Hb and the electrode surface. The biosensor showed a good linear response to the reduction of H₂O₂ over the concentration range of 2–240 µM with a detection limit of 0.24 µM (S/N=3) and a sensitivity of 1.056 µA µM^?1 cm^?2. The high surface coverage of the CdS‐Hb modified RGO|CCE (1.04×10^?8 mol cm^?2) and a smaller value of the apparent Michaelis? Menten constant (0.24 mM) confirmed excellent loading of Hb and high affinity of the biosensor for hydrogen peroxide.     

Self‐Assembled Prussian Blue Nanoparticles Based Electrochemical Sensor for High Sensitive Determination of H2O2 in Acidic Media

In this paper, self‐assembled Prussian blue nanoparticles (PBNPs) on carbon ceramic electrode (CCE) were developed as a high sensitive hydrogen peroxide (H₂O₂) electrochemical sensor. The PBNPs film was prepared by a simple dipping method. The morphology of the PBNPs‐modified CCE was characterized by scanning electron microscopy (SEM). The self‐assembled PB film exhibited sufficient mechanical, electrochemical stability and high sensitivity in compare with other PB based H₂O₂ sensors. The sensor showed a good linear response for H₂O₂ over the concentration range 1 μM–0.26 mM with a detection limit of ca. 0.7 μM (S/N=3), and sensitivity of 754.6 mA M^?1 cm^?2. This work demonstrates the feasibility of self‐assembled PBNPs‐modified CCE for practical sensing applications.     

Carbon paste electrode modified by cobalt ions dispersed into poly (N-methylaniline) preparing in the presence of SDS: application in electrocatalytic oxidation of hydrogen peroxide

Conducting and stable poly (N-methylaniline) film was prepared by using the repeated potential cycling technique in aqueous solution containing N-methylaniline, sulfuric acid, and sodium dodecyl sulfate (SDS) at the surface of carbon paste electrode (CPE). The transition metal ions of Co(ІІ) were incorporated to the polymer by immersion of the modified electrode in 0.1 M cobalt chloride solution for 10 min. The electrochemical characterization of this modified electrode exhibits stable redox behavior of Co(ІІ)→Co(ІІІ) and formation of insoluble oxide/hydroxide cobalt species on the CPE surface. The modified electrode showed well-defined and stable redox couples in alkaline aqueous solution. The modified electrode showed excellent electrocatalytic activity for oxidation of hydrogen peroxide. The response of modified electrode toward the H₂O₂ oxidation was examined using cyclic voltammetry, differential pulse voltammetry, square wave voltammetry, and chronoamperometry. This modified electrode has many advantages such as simple preparation procedure, good reproducibility, and high catalytic activity toward the hydrogen peroxide oxidation. Such characteristics were explored for the specific determination of hydrogen peroxide in cosmetics product sample, giving results in excellent agreement with those obtained by standard method.     

Development of Silver Nanowires Based Highly Sensitive Amperometric Glucose Biosensor

The fabrication of a highly sensitive amperometric glucose biosensor based on silver nanowires (AgNWs) is presented. The electrochemical behavior of glassy carbon electrode modified by Ag NWs exhibits remarkable catalytic performance towards hydrogen peroxide (H₂O₂) and glucose detection. The biosensor could detect glucose in the linear range from 0.005 mM to 10 mM, with a detection limit of 50 µM (S/N=3). The glucose biosensor shows high and reproducible sensitivity of 175.49 µA cm^?2 mM and good stability. In addition, the biosensor exhibits a good anti‐interference ability and favorable stability over relatively long‐term storage (more than 21 days).     

Catalase Like Activity of Iron Phthalocyanine Incorporated in a Carbon Paste Electrode

Abstract

The electrochemical oxidation of hydrogen peroxide has been investigated using a modified carbon paste electrode, by incorporating iron phthalocyanine. This offers interesting properties due to the catalase like activity of the electrode.

The utilization of this type of electrode permits the quantitative determination of hydrogen peroxide at concentrations down to 5x10^?5 M.     

Electrocatalytic Reduction of Dioxygen at Carbon Paste Electrode Modified with a Novel Cobalt(III) Schiff's Base Complex

A carbon paste modified electrode with a new cobalt(III) Schiff's base complex (CPME) and its application to electrocatalytic activity for dioxygen reduction is developed. The electrochemical behavior and stability of the CPME as well as the two‐electron reduction of O₂ at the electrode were investigated using cyclic voltammetry, chronoamperometry and rotating disk electrode methods. At the CPME, the reduction of dioxygen to hydrogen peroxide occurs at potentials where it is not observed at a bare carbon paste electrode. The CPME exhibited potent and persistent electrocatalysis for O₂ reduction in acetate buffer solutions of pH 4.0 with an overpotential of about 800 mV lower than unmodified CPE and drastic increase in the peak current. The heterogeneous rate constant for the reduction of O₂ at the surface of CPME was determined by hydrodynamic voltammetry using the Koutecky–Levich plot. A possible catalytic mechanism is proposed and discussed.     

Sandwich-type amperometric immunosensor for human immunoglobulin G using antibody-adsorbed Au/SiO2 nanoparticles

A novel sandwich-type electrochemical immunosensor for human immunoglobulin G (hIgG) was developed using Au/SiO₂ nanoparticles (NPs) with adsorbed horseradish peroxidase-anti-hIgG as the secondary antibody layer. The signal readout is based on the amperometric response to the catalytic reduction of hydrogen peroxide at an AuNPs-polythionine modified glassy carbon electrode. Under optimized conditions, the linear range is from 0.1 to 200 ng·mL^?1, with a detection limit of 0.035 ng·mL^?1 (at an S/N of 3). The immunosensor exhibited a performance that is better than that based on Au/SiO₂NPs-excluded secondary antibody.