Electrochemical preparation of effective and low cost catalyst for electrooxidation of ethanol

A nanocatalyst coating was prepared at surface of a glassy carbon electrode by electropolymerization of pyrrole by cycling the electrode potential between ?0.8 and 0.8 V (vs. Ag/AgCl). Then, polypyrrole film was potentiostatically coated with platinum nanoparticles at constant potential of ?0.2 V (vs. Ag/AgCl). The resulting electrode was denoted as GCE/PPy/Pt. This modified electrode was characterized by IR, SEM, TEM and EDX. The electrocatalytic oxidation of ethanol at the GCE/PPy/Pt has been investigated using cyclic voltammetric and chronoamperometric methods. The effects of various parameters on electrocatalytic oxidation of the ethanol, such as the thickness of PPy film, the amount of platinum nanoparticles, ethanol concentration, potential scan rate and working potential limit in anodic direction, were investigated. The kinetic of the ethanol oxidation is discussed on the GCE/PPy/Pt. The stability and reproducibility of this modified electrode were also studied.     

Fabrication of Trimetallic Pt−Pd−Co Porous Nanostructures on Reduced Graphene Oxide by Galvanic Replacement: Application to Electrocatalytic Oxidation of Ethylene Glycol

In present work, reduced graphene oxide nanosheets (rGO) decorated with trimetallic three‐dimensional (3D) Pt−Pd−Co porous nanostructures was fabricated on glassy carbon electrode (Pt−Pd−Co/rGO/GCE). First, GO suspension was drop‐casted on the electrode surface, then GO film reduction was carried out by cycling the potential in negative direction to form the rGO film modified GCE (rGO/GCE). Then, electrodeposition of the cobalt nanoparticles (CoNPs) as sacrificial seeds was performed onto the rGO/GCE by using cyclic voltammetry. Afterward, Pt−Pd−Co 3D porous nanostructures fabrication occurs through galvanic replacement (GR) method based on a spontaneous redox process between PtCl₂, PdCl_2, and CoNPs. The morphology and structure of the Pt−Pd−Co/rGO porous nanostructure film was characterized by scanning electron microscopy, energy dispersive spectroscopy and X‐ray diffraction method. The performance of the prepared electrode was investigated by various electrochemical methods including, cyclic voltammetry and electrochemical impedance spectroscopy. The electrocatalytic activity of the as‐prepared modified electrode with high surface areas was evaluated in anodic oxidation of ethylene glycol. The study on electrocatalytic performances revealed that, in comparison to various metal combinations in modified electrodes, trimetallic Pt−Pd−Co/rGO/GCE exhibit a lower onset potential, significantly higher peak current density, high durability and stability for the anodic oxidation of ethylene glycol. The excellent performances are attributed to the rGO as catalysts support and resulting synergistic effects of the trimetallic and appropriate characteristics of the resulted 3D porous nanostructures. Moreover, the influence of various concentrations of ethylene glycol, the potential scan rate and switching potential on the electrode reaction, in addition, long‐term stability have been studied by chronoamperometric and cyclic voltammetric methods.     

Direct electrochemistry and electrocatalysis of hemoglobin in gelatine film modified glassy carbon electrode

Direct electrochemical and electrocatalytic behavior of hemoglobin (Hb) immobilized on glass carbon electrode (GCE) containing gelatine (Gel) films was investigated. The characteristics of Hb/Gel film modified GC electrode were performed by using SEM microscopy, UV-vis spectroscopy and electrochemical methods. The immobilized Hb showed a couple of quasi-reversible redox peak with a formal potential of −0.38 V (versus SCE) in 0.1 M pH 7.0 PBS. The formal potential changed linearly from pH 4.03 to 8.41 with a slope value of −52.0 mV pH⁻¹, which suggested that a proton transfer was accompanied with each electron transfer (ET) in the electrochemical reaction. The Hb/gelatine/GCE displayed a rapid amperometric response to the reduction of H₂O₂ and nitrite.     

石墨烯的制备及石墨烯修饰电极对p-苯二酚的催化氧化

采用氨水还原氧化石墨烯(GO)制备石墨烯(GN), 并考察石墨烯修饰玻碳电极(GN/GCE)电催化氧化p-苯二酚(HQ)的性能. 利用傅里叶红外光谱(FTIR)、拉曼光谱(Raman)、X射线衍射(XRD)、扫描电子显微镜(SEM)、原子力显微镜(AFM)、比表面分析(BET)和电分析化学测试等技术对GN结构、表面形貌和电化学行为进行了表征. 采用循环伏安法(CV)和差分脉冲溶出伏安法(DPV)研究GN/GCE对HQ的电催化氧化性能. 结果表明, 与裸玻碳电极(GCE)相比, [Fe(CN)₆]^3-/4-在GN/GCE上电荷转移电阻为75.0 Ω·cm², 减小约9倍, 说明GN具有良好导电性; 同时HQ在GN/GCE上氧化峰电位负移, 还原峰电位正移, 峰电位差ΔE_p减小165 mV, 且氧化还原峰电流(I_pa和I_pc)均增大, HQ电化学氧化可逆性明显改善, 表明GN/GCE对HQ氧化具有显著电催化作用.     

Voltammetric Determination of Phosphate in Brazilian Biodiesel Using Two Different Electrodes

The presence of contaminants, such as phosphate, in biodiesel, has several drawbacks for instance: current engines perform poorly, fuel tanks deteriorate, catalytic conversion is damaged, and particles emission is increased. Therefore, biodiesel quality control is extremely important for biodiesel acceptance and commercialization worldwide. In this context, a bare glassy carbon electrode (GCE) and another chemically modified electrode with iron hexacyanoferrate (Prussian Blue – PB) were developed for determination of phosphate in biodiesel. The LODs of 6.44 and 1.19 mg kg^?1, and LOQs of 21.43 and 3.97 mg kg^?1 were obtained for the bare GCE and the PB‐modified GCE, respectively. The methodology was employed for analysis of Brazilian biodiesel samples, and it led to satisfactory results, demonstrating its potential application for biodiesel quality control. Additionally, recovery and interference tests were conducted, which revealed that the developed methods are suitable for analysis of phosphate in biodiesel samples.     

The effects of abrasive particles on the electrochemical behavior of adrenaline at different electrodes

Cyclic voltammetry (CV), double-potential step chronocoulometry (DPSCC), and electrochemical impedance spectroscopy (EIS) techniques have been performed to study the effects of abrasive particles on the electrochemical reaction of adrenaline at glassy carbon electrode (GCE) and platinum electrode in 0.5 mol/L H₂SO₄ solution. For the electrochemical reaction of adrenaline, it was shown that abrasive particles have a more marked electrocatalytic effect at GCE compared to that at platinum electrode. The electrocatalytic effect of SiC coated GCE is more obvious comparing to that of Al₂O₃ coated GCE. With the coarse degree of the abrasive paper increasing, the peak current (i _p) increases significantly and the peak-to-peak potential separation (ΔE _p) changes a little at the pretreated GCE. The electron transfer process of adrenaline at the different pretreated GCE is controlled by the diffusion in this system.     

Fabrication of an electrochemical sensor based on the electrodeposition of Pt nanoparticles on multiwalled carbon nanotubes film for voltammetric determination of ceftriaxone in the presence of lidocaine, assisted by factorial-based response-surface methodology

A glassy carbon electrode (GCE) is modified with platinum nanoparticle (PtNPs) decorated multiwalled carbon nanotube (MWCNT). The modified electrode is applied for the determination of ceftriaxone (CFX) in the presence of lidocaine. Different methods were used to characterize the surface morphology of the modified electrode. The electrochemical behavior of CFX was investigated at GCE, MWCNT/GCE and PtNPs/MWCNT/GCE. A factorial-based response-surface methodology was used to find out the optimum conditions with minimum number of experiments. Under the optimized conditions, oxidation peak currents increased linearly with CFX concentration in the range of 0.01–10.00 μM with a detection limit of 9.01 nM. The results prove that the modified electrode is also suitable for the determination of CFX in pharmaceutical and clinical preparations.     

Determination of Mercury by Anodic Stripping Voltammetry with a Gold Nanoparticle‐Modified Glassy Carbon Electrode

The aim of this work is the development of a procedure for the determination of aqueous Hg(II) by anodic stripping voltammetry at a gold nanoparticle‐modified glassy carbon electrode (AuNPs‐GCE). The signal of aqueous Hg(II) was measured in the square wave mode; the effect of potential scan parameters, deposition potential and deposition time on the analytical signal was examined. The supporting electrolyte was 0.06 M HCl. The repeatability, the linearity, the accuracy, the detection limit of the procedure and the interferences of other cations and of anions were evaluated. The performance of the AuNPs‐GCE was compared with those of a solid (SGE) and a film (FGE) gold electrode: the AuNPs‐GCE showed to provide lower detection limits and higher repeatability. The renewable surface permits to eliminate memory effects, to maintain a stable baseline and response, and to avoid frequent mechanical cleaning steps. The applicability of the AuNPs‐GCE for Hg(II) determination in drinking waters, sediments and pharmaceuticals was demonstrated.     

Amperometric Urea Biosensor Using Aminated Glassy Carbon Electrode Covered with Urease Immobilized Carbon Sheet,Based on the Electrode Oxidation of Carbamic Acid

A large oxidation current can be observed when ammonium carbamate aqueous solution is electrolyzed using a glassy carbon electrode (GCE) at a potential exceeding 1.0 V vs. Ag/AgCl and amino groups are introduced at the surface of the GCE. Aminated GCE exhibits the electrocatalytic activity of the oxidation of ammonium carbamate that is produced from urea as an intermediate product of urease reaction, and a distinct oxidation current is observed when the aminated GCE is used to oxidize the urea in the urease solution. A novel amperometric determination method to detect urea has been developed. This method is based on the electrooxidation of carbamic acid produced during urease reactions. Urease is immobilized to polymaleimidostyrene (PMS) coated on the insulated amorphous carbon sheet set on the aminated GCE surface. A good linear relationship is observed between urea concentration and the electrolytic current of the urease‐immobilized electrode in the concentration range from 0.5 mM to 21.0 mM. The proposed urea biosensor has an effective merit in that the interference resulting from ammonia and pH change caused by the urease reaction can be eliminated, differing from conventional urea biosensors.     

Electroanalysis of some common pesticides using conducting polymer/multiwalled carbon nanotubes modified glassy carbon electrode

The cyclic voltammetric behaviour of three common pesticides such as isoproturon (ISO), voltage (VOL) and dicofol (DCF) was investigated at glassy carbon electrode (GCE), multiwalled carbon nanotubes modified GCE (MWCNTs/GCE), polyaniline (PANI) and polypyrrole (PPY) deposited MWCNT/GCE. The modified electrode film was characterized by scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). The electroactive behaviour of the pesticides was realized from the cyclic voltammetric studies. The differential pulse voltammetric principle was used to analyze the above-mentioned pesticides using MWCNT/GCE, PANI/MWCNT/GCE and PPY/MWCNT/GCE. Effects of accumulation potential, accumulation time, Initial scan potential, amplitude and pulse width were examined for the optimization of stripping conditions. The PANI/MWCNT/GCE performed well among the three electrode systems and the determination range obtained was 0.01-100 mgL(-1) for ISO, VOL and DCF respectively. The limit of detection (LOD) was 0.1 microgL(-1) for ISO, 0.01 microgL(-1) for VOL and 0.05 microgL(-1) for DCF on PANI/MWCNT/GCE modified system. It is significant to note that the PANI/MWCNT/GCE modified system results in the lowest LOD in comparison with the earlier reports. Suitability of this method for the trace determination of pesticide in spiked samples was also realized.     

Myoglobin‐Clay Electrode for Nitric Oxide (NO) Detection in Solution

Sodium montmorillonite was prepared via a colloidal chemical approach and deposited onto glassy carbon electrodes (GCE). Myoglobin was immobilized on the clay membrane modified electrode by spontaneous adsorption. Characterization of the myoglobin/clay/glassy carbon electrode (Mb/clay/GCE) showed a quasi‐reversible, electrochemical redox behavior of the adsorbed protein with a formal potential of ?0.380±0.010 V (vs. Ag/AgCl). The heterogeneous electron transfer rate constant was found to be strongly influenced by the buffer concentration. The Mb/clay/GCE was stable for several days in solution. The interaction of the immobilized Mb with nitric oxide (NO) is characterized by coordination chemistry. The reaction was found to be reversible and could be applied for NO detection in the nanomolar concentration range by a voltammetric analysis. In addition a mixed protein electrode with co‐immmobilized myoglobin (Mb) and cytochrome c (Cyt.c) was developed. By choice of the electrode potential both proteins can be addressed independently.     

Charge transfer in duplex DNA containing mismatch

A theory for charge transfer between the electrode and the donor/acceptor molecule coupled through a DNA bridge in solution is developed. We explore the crossover between the coherent tunneling and the incoherent sequential transfer regimes by varying the electrode potential and discuss the effects of single-base mismatches in DNA duplex in both regimes. In the former regime a single-base mismatch in DNA duplex causes a reduction in the charge transfer rate simply by decreasing the electron tunneling matrix element, however, in the latter regime the effects are rather complicated.     

基于多壁碳纳米管/二茂铁接枝壳聚糖的核/壳结构组合物多层膜电极的组装及其电催化

以聚二烯丙基二甲基氯化铵(PDDA)修饰的玻碳电极(GCE)为基础电极, 利用静电层-层自组装的方法将多壁碳纳米管/二茂铁接枝壳聚糖的核/壳结构组合物(MWCNTs@CHIT-Fc)和聚苯乙烯磺酸钠(PSS)在该电极表面进行交替多层组装. 用循环伏安(CV)、紫外-可见光谱(UV-Vis)和扫描电子显微镜(SEM)等方法对组装过程进行了跟踪表征. 用CV方法研究了抗坏血酸(AA)在该多层膜电极上的电催化氧化. 研究结果表明, 当MWCNTs@CHIT-Fc为6个双层时, AA在该修饰电极上的氧化峰电位与裸GCE相比降低了约0.4 V. 用控制电位电流法研究了不同MWCNTs@CHIT-Fc双层时AA的电流响应. 用该电极测定了AA的灵敏度, 检测限及线性范围等性能参数可通过控制组装的MWCNTs@CHIT-Fc双层数进行调节.     

Direct electrochemistry of DNA,guanine and adenine at a nanostructured film-modified electrode

A nanostructured film electrode, a multi-wall carbon nanotubes (MWNT)-modified glassy carbon electrode (GCE), is described for the simultaneous determination of guanine and adenine. The properties of the MWNT-modified GCE were investigated by scanning electron microscopy (SEM) and cyclic voltammetry. The oxidation peak currents of guanine and adenine increased significantly at the MWNT-modified GCE in contrast to those at the bare GCE. The experimental parameters were optimized and a direct electrochemical method for the simultaneous determination of guanine and adenine was proposed. Using the MWNT-modified GCE, a sensitive and direct electrochemical technique for the measurement of native DNA was also developed, and the value of (G+C)/(A+T) of HCl-digested DNA was detected.     

Fe_3O_4 Magnetic Nanoparticles Modified Electrode as a Sensor for Determination of Nimesulide

A novel type of Fe3O4 nanoparticles modified glass carbon electrode(Fe3O4/GCE) was constructed and the electrochemical properties of N-(4-nitro-2-phenoxyphenyl)methanesulfonamide(nimesulide) were studied on the Fe3O4/GCE.In 0.4mol/L HAc-NaAc buffer solution(pH=5.0),the electrode process of nimesulide was irreversible at bare GCE and Fe3O4/GCE.The Fe3O4/GCE exhibited a remarkable catalytic and enhancement effect on the reduction of nimesulide.The reduction peak potential of nimesulide shifted positively from...     

Direct electrochemical behavior of cytochrome c, and its determination on phytic acid modified electrode

Phytic acid (PA) with its unique structure was attached to a glassy carbon electrode (GCE) to form PA/GCE modified electrode which was characterized by electrochemical impedance. The electrochemical behavior of cytochrome c (Cyt c) on the PA/GCE modified electrode was explored by cyclic voltammetry and differential pulse voltammetry. The Cyt c displayed a quasi-reversible redox process on PA modified electrode pH 7.0 phosphate buffer solution with a formal potential (E ^0′) of 57 mV (versus Ag/AgCl). The peak currents were linearly related to the square root of the scan rate in the range of 20–120 mV·s^?1. The electron transfer rate constant was determined to be 12.5 s^?1. The PA/GCE modified electrode was applied to the determination of Cyt c, in the range of 5?×?10^?6 to 3?×?10^?4 M, the currents increase linearly to the Cyt c concentration with a correlation coefficient 0.9981. The detection limit was 1?×?10^?6 M (signal/noise?=?3).     

Electrochemical oxidation of morin and interaction with DNA

A poly (tetrafluroethylene)-deoxyribonucleate acid (PTFE-DNA) film-modified glassy carbon electrode (GCE) has been fabricated. The electrochemical oxidation behaviors of morin as well as its interaction with DNA have been studied at PTFE-DNA film-modified GCE and bare GCE by electrochemical methods. This modified electrode shows an enhanced effectiveness towards the oxidation of morin. Importantly, as to the interaction between morin and DNA in solution, characteristic parameters such as the binding stoichiometry and association equilibrium constant according to the Hill model for cooperative binding have been determined on the basis of linear sweep voltammetry and chronocoulometry.     

Enhanced electron transfer by bovine serum albumin covalently attached to glassy carbon electrode and its application to determination of hydroquinone

Bovine serum albumin (BSA) was covalently attached to glassy carbon electrode (GCE) surface by the electrochemical method. An enhancement for the redox of hydroquinone (HQ) on BSA/GCE was confirmed by cyclic voltammetry and electrochemical impedance spectroscopy measurement. The electron transfer rate constant (k _s) on the BSA/GCE electrode is almost three orders of magnitude higher than that on bare GCE. The enhancing effect can be attributed to the electrostatic force between the positively charged HQ and negatively charged BSA. It is found that the enhanced redox process of HQ can be used to determine HQ sensitively. The oxidation current can reach 95% of its steady-state value within 30 s. The linear range for HQ determination is from 2.5 × 10^?8 M to 1.325 × 10^?6 M with a detection limit of 8.6 × 10^?9 M at a signal-to-noise ratio of 3. The study may provide a simple, rapid and sensitive method for determination of HQ which is present in the natural environment and in chemical industry effluent.     

纳米银/石墨烯修饰电极测定青蒿素

本文建立一种新型的青蒿素传感器。首先,在玻碳电极上滴涂氧化石墨,通过电化学方法将氧化石墨还原为石墨烯,然后,在石墨烯上沉积纳米银得到石墨烯/纳米银修饰电极,它作为检测青蒿素的电化学传感器。用此电极对青蒿素进行测定,并通过循环伏安法、差分脉冲伏安法、交流阻抗法等研究其电化学行为。该修饰电极在测定青蒿素溶液时,表现出较正的还原电位和较大的峰电流等优势;对其实验条件如电解质溶液的p H、应用电势等进行了探查,该电化学传感器在青蒿素溶液浓度范围为1.0×10-8~3.0×10-5mol/L时与其还原峰电流呈现良好的线性关系,最低检出限为1.2×10-9mol/L(S/N=3)。此外,对该传感器的稳定性和重现性等也进行了研究,获得令人满意的结果。     

纳米结构的钯与金-钯薄膜的制备及其电催化活性

应用电位扫描法将Pd(II)离子沉积到玻碳电极表面,形成纳米结构的金属钯薄膜电极.然后在酸性溶液中控制适当的阴极电位,使该薄膜电极的钯吸收足量的活性氢,进而以吸收的氢作还原剂将Au(III)离子还原,制得Au-Pd双金属薄膜电极.扫描电镜、循环伏安法等测试表明,该电极Au-Pd沉积层对乙醇的氧化具有很高的电催化活性.