CoSALEN/APO-5复合材料的制备及其电催化还原氧的性能

将金属钴离子引入磷酸铝分子筛APO-5制得CoAPO-5分子筛,再把N,N-双水杨醛缩乙二胺(SALEN)希夫碱通过扩散进入CoAPO-5分子筛孔道并与其中的钴离子配位,形成了CoSALEN配合物,构成CoSALEN/APO-5复合材料.应用物理吸附法,以聚苯乙烯(PS)作粘结剂,将CoSALEN/APO-5涂敷在玻碳电极表面制成修饰电极PS/CoSALEN/APO-5/GCE.循环伏安法(CV)、计时电流法(CA)研究了该修饰电极在不同pH电解质溶液中的电化学行为以及对分子氧的催化还原作用.结果表明,制备的修饰电极能有效地催化分子氧的四电子还原,即氧气被电催化还原为水,据此提出可能的氧还原机理.     

Electrocatalytic reduction of dioxygen on a glassy carbon electrode modified with adsorbed cobaloxime complex.

The preparation and electrochemical properties of a glassy carbon (GC) electrode modified with cobaloxime complex were investigated. The complex of the type [CoIII(DO)(DOH)pn)Cl2] where (DO)(DOH)pn = N2,N2'-propanediylbis-2,3-butanedione-2-imine-3-oxime) was adsorbed irreversibly and strongly on the surface of preanodized glassy carbon electrode. Electrochemical behavior and stability of modified GC electrode were investigated by cyclic voltammetry. The electrocatalytic reduction of dioxygen has been studied using this modified glassy carbon electrode by cyclic voltammetry, chronoamperometry and rotating disk electrode voltammetry as diagnostic techniques. The modified electrode showed excellent eletrocatalytic ability for the reduction of dioxygen to hydrogen peroxide in acetate buffer (pH 4.0) with overpotential 1.0 V lower than the plain glassy carbon electrode. The formal potential for this modified electrode is not shifted to more negative potentials by repeated reduction-oxidation cycles in oxygen-saturated supporting electrolyte solution. The apparent electron transfer rate constant (kS), the transfer coefficent (alpha) and the catalytic rate constant of O2 reduction at a GC modified electrode were determined by cyclic voltammetry and rotating disk electrode voltammetry and were found to be around 2.6 s(-1), 0.33 and 2.25 x 10(4) M(-1) s(-1). Based on the results, a catalytic mechanism is proposed and discussed.     

Effects of surfactants on the electroreduction of dioxygen at an acetylene black electrode.

An acetylene black electrode modified by an adsorbed cationic surfactant, cetyltrimethylammonium bromide (CTAB), was developed. The influences of various types of surfactants on the electroreduction of O2 were investigated. It was demonstrated that a cationic surfactant, CTAB, on the surface of the electrode could significantly decrease the overpotential of dioxygen reduction, and the reduction peak current of O2 was also remarkably increased. The reduction of O2 at a CTAB modified acetylene black electrode was studied using cyclic voltammetry, chronocoulometry and controlled potential coulometry. The total number of electrons, the exchange current density (j(o)) and the transfer coefficient (alpha) for reduction of O2 at the surface of this modified electrode were determined.     

Catalysis of dioxygen reduction at soluble polyaniline modified electrode

A reflux-treatment of soluble polyaniline (SPA) in dimethylformamide (DMF) containing CoCl₂ yields an active catalyst for dioxygen reduction which can be adsorbed on the electrode surface firmly. The catalytic reduction of dioxygen at the glassy carbon (GC) electrode modified by the catalyst was studied with cyclic voltammetry (CV), rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE). The kinetic process of dioxygen reduction at the modified electrode was analyzed with a new RRDE theory dealing with a nondiffusion-controlled process on ring electrode. The rate constants for each scheme of dioxygen reduction were calculated, showing that only 2-electron reduction to H₂O₂ was conducted at the modified electrode. The effect of solution acidity on the electrocatalytic behaviour for dioxygen reduction was investigated. A possibility of initiating catalytic activity for dioxygen reduction was explored with ESCA method.     

Simultaneous Voltammetry Determination of Dihydroxybenzene Isomers by Nanogold Modified Electrode

A convenient electrochemical deposition method to prepare nanogold/glassy carbon modified electrode (nano‐Au/GCE) is adopted. In 0.1 mol/L HAc‐NaAc buffer solution (pH 4.61), the nano‐Au/GCE shows an excellent electrocatalytical behavior for the redox of dihydroxybenzene. A simple, rapid and highly selective voltammetry for simultaneous determination of dihydroxybenzene isomers, hydroquinone, catechol, and resorcinol, is developed using the nano‐Au/GCE. This method has been applied to the direct determination of the three dihydroxybenzene isomers in artificial wastewater.     

Electrochemical reduction of dioxygen on Alizarin modified glassy carbon electrode in acidic medium

The catalytic behaviour of glassy carbon electrode modified by 1,2-dihydroxy antraquinone (Alizarin) was investigated. The electrocatalytic ability of modified electrode for the reduction of dioxygen was examined by cyclic voltammetry and rotating disk electrode (RDE) voltammetry techniques. The Alizarin modified glassy carbon electrode possesses excellent electrocatalytic abilities for dioxygen reduction over potential 400 mV lower than at the bare glassy carbon electrode. Hydrodynamic studies were performed to determine the heterogeneous rate constant for the reduction of O₂ at the surface of modified electrode. It was determined by Koutecky-Levich plot. The apparent diffusion coefficient of O₂ in O₂ saturated acidic solutions was estimated by using Levich equation. Studies show the involvement of four electrons in dioxygen reduction at the surface of this modified electrode.     

Au/GCE电极对水中15种苯酚衍生物的测定

研究了15种不同取代基苯酚衍生物在纳米金/玻碳 (Au/GCE) 电极上的电化学响应. 测试表明：该电极对15种苯酚衍生物的电化学反应各呈现出不同程度的电催化作用;与GCE和平面金电极相比,苯酚衍生物的氧化峰电流均有所增加,氧化电位受待测物反应活性影响较大;水杨酸在Au/GCE电极上响应迅速,电流灵敏度是GCE电极的1.8倍;该电极可用于多种苯酚衍生物的痕量测定.     

Green Synthesis of Silver Nanoparticles Using Ionic Liquid and Application for the Detection of Dissolved Oxygen

The electrochemical synthesis of silver nanoparticles (nano‐Ag) has been successfully carried out on glassy carbon electrode (GCE) and indium tin oxide electrode (ITO) using 1‐butyl‐3‐methylimidazolium tetrafluoroborate (BMT) as green electrolytes. Further the electrodeposited nano‐Ag modified ITO electrode has been examined using atomic force microscopy (AFM), and X‐ray diffraction studies (XRD). The electrodeposited Ag nanoparticles on ITO were found in the size range of 5 to 35 nm. The nano‐Ag film modified GCE was further coated with nafion (Nf) and BMT (1 : 1 ratio) mixture and found to be stable in BMT and in pH 7 phosphate buffer solution (PBS). The nano‐Ag/BMT‐Nf film modified GCE successfully applied for the oxygen reduction reaction in neutral pH (pH 7.0 PBS). The proposed film modified GCE successfully reduces the over potential and show well defined reduction peaks for the detection of dissolved oxygen using cyclic voltammetry (CV) and rotating disc voltammetry (RDE). The film also applied for the detection of dissolved oxygen using electrochemical impedance spectroscopic studies (EIS).     

Ionic liquid modified GC electrode for the direct electrochemistry of chloroperoxidase

Chloropcroxidase （CPO） was immobilized by konjac glucomannan （KGM） on the 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM][BF4]/Nafion modified glassy carbon eloctrode. The electrochemical behaviors of the immobilized CPO were investigated by cyclic voltammetry. The results showed that CPO was successfully immobilized on the GCE and underwent fast direct electron transfer reactions with the formal potential at -0.3 V vs. SCE. The modified electrode showed a good catalytic activity for elcctrocatalytical reduction of O2 and H2O2.     

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...     

The determination of adrenaline on the porous gold film modified glassy carbon electrode

A simple method has been developed to prepare porous Au film-modified glassy carbon electrode (PAu/GCE). By using a simple electrodeposition process, a dense porous Au (PAu) film possessing good adhesion, large surface area, and mechanical integrity, was obtained. The surface characterization studies confirm that the formation of porous film constituted of Au nanoparticles. It was found, from the CV studies, that the prepared PAu modified electrode shows excellent catalytic activity for the electro-oxidation of adrenaline (AD) in a neutral medium. As to the electrochemical response of redox of adrenaline/adrenalinequinone couple in 0.1 M pH 7.0 phosphoate buffer solution (PBS), at the PAu/GCE, the anodic peak potential E _pa shifted by 50 mV negatively in the negative direction, compared to that on the Au film modified glassy carbon electrode (Au/GCE), indicating the extraordinary activity of PAu in electrocatalysis for the oxidation process of AD. The application of the modified electrode for the determination of AD in pharmaceutical preparations indicates that the PAu/GCE has good sensitivity and reproducibility.     

化学修饰电极的研究 ⅩⅤⅡ四苯基铁卟啉化学修饰玻碳电极的热处理及其对氧的催化还原

关于金属卟啉、酞菁等化学修饰电极的研究已有大量工作发表.这类电极很不稳定,例如著名的面-面双钴卟啉修饰电报,虽然能直接催化氧还原为水,但经受不住几次电位扫描就失去催化活性.因此,如何提高稳定性就成为研究这类电极的关键.近年来有人报道,吸附在活性碳上的金属卟啉、酞菁类化合物经热处理,可改善其稳定性。热处理后得到的粉状碳催化剂,由于完全不溶于水及有机溶剂,制备电极非常困难。曾有过用这种     

Highly sensitive electrochemical determination of Sunset Yellow based on gold nanoparticles/graphene electrode

An electrochemical sensor was prepared using Au nanoparticles and reduced graphene successfully decorated on the glassy carbon electrode (Au/RGO/GCE) through an electrochemical method which was applied to detect Sunset Yellow (SY). The as-prepared electrode was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and electrochemical measurements. The results of cyclic voltammetry (CV) proved that Au/RGO/GCE had the highest catalytic activity for the oxidation of SY as compared with GCE, Au/GCE, and RGO/GCE. Differential pulse voltammetry (DPV) showed that the linear calibration curves for SY on Au/RGO/GCE in the range of 0.002 μM–109.14 μM, and the detection limit was estimated to be 2 nM (S/N = 3). These results suggested that the obtained Au/RGO/GCE was applied to detect SY with high sensitivity, low detection limit and good stability, which provided a promising future for the development of portable sensor in food additives.     

微过氧化物酶-11修饰电极对O2和H2O2的电催化还原

运用电化学循环伏安法和旋转圆盘电极技术研究了Ｏ２和Ｈ２Ｏ２在Ｎａｆｉｏｎ膜固定的微过氧化物酶－１１修饰的玻磷（ＭＰ－１１＋Ｍａｆｉｏｎ／Ｇｃ）电极上的电化学还原,结果表明,饰电极 对Ｏ２和Ｈ２Ｏ２的还原均具电催化作用。测定和比较了Ｏ２和Ｈ２Ｏ２在ＭＰ－１１＋Ｎａｆｉｏｎ／ＧＣ的电极上电催化还原反应的一些动力学参数。发现Ｏ２在修饰电极上经历了四电子还原,且还原过程与溶液的ＰＨ值有关。     

甲基对硫磷在聚噻吩/纳米二氧化钛修饰玻碳电极上的电化学行为及其测定

用循环伏安法(CV)、线性扫描溶出伏安法(LSSV)研究了甲基对硫磷(MPT)在聚噻吩/纳米二氧化钛修饰玻碳电极(PTh-NTiO2/GCE)上的电化学行为.实验表明,该修饰电极能显著提高MPT的氧化还原峰电流,在B-R缓冲溶液(pH 5.72)中,于-0.662V( vs.SCE)处产生灵敏的不可逆还原峰,其峰电流与...     

氧化锌纳米簇-金纳米颗粒-壳聚糖复合膜修饰电极用于示差脉冲伏安法测定吗啡

将制备的氧化锌纳米簇和金纳米颗粒分散在壳聚糖中并滴涂在玻碳电极表面,制备了氧化锌纳米簇-金纳米颗粒-壳聚糖复合膜修饰电极(Au-ZnO-CHIT/GCE)。采用循环伏安法研究了吗啡在修饰电极上的电化学行为。结果表明:吗啡在该修饰电极上出现了一个氧化峰,提出了用示差脉冲伏安法测定吗啡的方法。吗啡浓度在5.3×10-6~6.5×10-4mol.L-1范围内与氧化峰电流呈线性关系,检出限(3S/N)为1.8×10-6mol.L-1。修饰电极用于尿液中吗啡的测定,回收率在80.0%~99.6%之间。     

The Electrochemical Behavior of Bleomycin at A Co/GC IonImplantation Modified Electrode

Bleomycin(BLM)isananticancerdrug.BLMhasbeenanalyzedbyosillopolarography'andadsorptivestrippingvoltammetry'.However,theelectrochemicalbehaviorofBLMataCo/GCEanditsdeterminationhavenotbeenreportedsofar.Inthiswork,theelectrochemicalbehaviorofBLMattheCo/GCEhasbeenstudiedandanewmethodforthedeterminationofBLMisproposed.Thismethodissimple,fastandreliable.Theelectrodematerialisglassycarbon(GC).JYZ8010MetalVaporVacuumArcIonSourceisusedforionimplantationatanacceleratingvoltageof40KeVinthed…     

A Novel Electrochemical Method for the Analysis of Hydrogen Peroxide with the Use of a Glassy Carbon Electrode Modified by a Prussian Blue/Copper‐Gold Bimetallic Nanoparticles Hybrid Film

A novel Prussian blue/copper‐gold bimetallic nanoparticles hybrid film modified electrode was prepared by electrochemical deposition on a glassy carbon electrode (PB/Cu‐AuNPs/GCE). Morphology and electrochemistry of this electrode were studied by UV‐vis spectroscopy, scanning electron microscopy, X‐ray diffraction, cyclic voltammetry and electrochemical impedance spectroscopy. The sensor showed significantly better electrocatalytic activity for the reduction of hydrogen peroxide in comparison with the single PB/GCE and PB/AuNPs/GCE. This was attributed to the synergistic effect of PB and Cu‐Au bimetallic nanoparticles. Also, the sensor demonstrated an overall high level of performance for the analysis of H₂O₂ in the concentration range from 0.002 to 0.84 mM.     

A catechol biosensor based on a gold nanoparticles encapsulated-dendrimer

Tyrosinase has been immobilized on a Au nanoparticles encapsulated-dendrimer bonded conducting polymer on a glassy carbon electrode for the estimation of catechol. The modified electrode was characterized by cyclic voltammetry and AFM techniques. The principle of catechol estimation was based on the reduction of biocatalytically liberated quinone species at +0.2 V versus Ag/AgCl (3 M KCl), with good stability, sensitivity, and featuring a low detection limit (about 0.002 μM) and wide linear range (0.005 μM-120 μM). The electrochemical redox peak of catechol on the GCE/PolyPATT/Den(AuNPs)/tyrosinase was also investigated. A response time of 7 s, reusability up to 5 cycles and a shelf life of more than 2 months under refrigerated conditions were reported. Various parameters influencing biosensor performance have been optimized including pH, temperature, and applied potential. The utility and application of this nanobiosensor was tested in a real water samples.     

Synthesis of 5-[(2-hydroxynaphthalen-1-yl)diazenyl]isophthalic acid and its application to electrocatalytic oxidation and determination of adrenaline,paracetamol, and tryptophan

In this study,Au nanoparticles/poly 5-[(2-hydroxynaphthalen-l-yl)diazenyl]isophthalic acid film modified glassy carbon electrode(AuNPs/poly(NDI)/GCE) has shown excellent electrocatalytic activity toward the oxidation of adrenaline(ADR),paracetamol(PAC),and tryptophan(Trp).The bare glassy carbon electrode(GCE) fails to separate the oxidation peak potentials of these molecules,while the poly(NDI) film modified electrode can resolve them.Electrochemical impedance spectroscopy(EIS)indicates that the charge transfer resistance of the bare electrode decreases as 5-[(2-hydroxynaphthalen-l-yl)diazenyl]isophthalic acid is electropolymerized on the bare electrode.Furthermore,EIS exhibits enhancement of electron transfer kinetics between analytes and the electrode after electrodeposition of Au nanoparticles.Differential pulse voltammetry results show that the electrocatalytic current increases linearly in the ranges of 0.01-680.0 μmol L~1 for ADR,0.05-498.0 μmol L~1 for PAC,and 3.0-632.0 μmol L~1 for Trp;with detection limits(S/N = 3) of 0.009 μmol L~1,0.005 μmol L~1,and 0.09 μmol L~1 for ADR,PAC,and Trp,respectively.The proposed method has been successfully applied for simultaneous determination of ADR,PAC,and Trp in biological samples.