聚天青A膜修饰电极的电化学特性及其对亚硝酸根的电催化性能

在玻碳电极上以循环伏安法制备了聚天青A膜修饰电极(PAAE) ,天青A能够在玻碳电极上形成稳定的聚合膜 ;通过正交试验确定了电聚合天青A的最佳条件 ,研究了该修饰电极的电化学特性 ,并讨论了其对亚硝酸根的电催化还原作用 ;结果表明 ,亚硝酸根在PAAE上有很好的电流响应 ,催化峰电流与亚硝酸根浓度在1.0×10-5 ～4.0×10-3 mol/L之间呈良好的线性关系     

钯纳米粒子在电极表面的制备及其对氧的催化还原

纳米微粒的体积效应使其成为表面纳米工程及功能化纳米结构材料制备的理想研究对象 [1～ 3] .纳米粒子具有独特的电子、催化及光学特性[4 ] ,近年来关于纳米粒子的制备及其在材料科学领域中的应用受到研究者的极大关注 .而贵金属纳米粒子由于其在催化领域中的广泛应用而成为最重要的研究对象之一[5,6 ] .电催化氧还原是一直为化学家瞩目的研究领域[7～ 9] .研究主要目的之一是寻找合适的氧电极反应催化剂 ,并使之能够应用于燃料电池中 .其中催化氧电极材料研究得最多的是贵金属 Pt[10 ,11] .贵金属 Pd对氧催化还原的研究工作很少 .我们首次…     

A Simple and Efficient Electrochemical Sensor for Electrocatalytic Reduction of Nitrite Based on Poly(4‐aminoacetanilide) Film Using Carbon Paste Electrode

In this study, the electrochemical reduction of nitrite was investigated on poly(4‐aminoacetanilide) (PPAA) forming by cyclic voltammetry at the surface of carbon paste electrode. The electrochemical properties of the modified electrode have been studied by cyclic voltammetry and double potential step chronoamperometry. Results showed that in the optimum condition (pH = 0.00) the reduction of nitrite occurred at a potential about 667 mV more positive than that unmodified carbon paste electrode. This amount of electrocatalytic ability is high compared with other electrocatalysts. Using a chronoamperometric method, the catalytic rate constant (k) was calculated 8.4 × 10⁴ cm³ mol^‐1 s^‐1. Also, the electrocatalytic reduction peak currents was found to be linear with the nitrite concentration in the ranges of 5 × 10^‐4 M to 2.5 × 10^‐2 M and 2 × 10^‐5 M to 7 × 10^‐3 M with detection limits (2σ) were determined as 4.5 × 10^‐4 M and 1 × 10^‐5 M by cyclic voltammetry (CV) and hydrodynamic amperometry methods respectively. Recovery experiments exhibit the satisfactory results.     

聚吖啶橙修饰电极的电化学行为及其对肾上腺素的电催化性能

研究了聚吖啶橙 (POAO)修饰电极及其电化学性能 ,并用于肾上腺素 (EP)的电化学测定。EP在POAO修饰电极上产生一灵敏的氧化峰 ,与裸玻碳电极 (GCE)相比 ,其峰电位负移了 2 30mV ,明显降低了EP的氧化过电位。在pH 6 .0的磷酸氢二钠 柠檬酸缓冲溶液中 ,氧化峰电流与EP的浓度在 4 .5× 10 - 7～ 9.2× 10 - 5mol L范围内呈良好的线性关系 ,检出限为 1.0× 10 - 9mol L。可用于实际样品中EP的测定     

阿魏酸聚合修饰玻碳电极的制备及其对NADH的催化氧化

研究了阿魏酸修饰电极的制备、性质及对NADH的电催化作用.该电极在0.1mol/L磷酸缓冲溶液(pH=6.60)中,于-0.1～+0.50V(vs.Ag/AgCl)电位范围内呈现一对氧化还原峰,其式量电位E₀为+0.188V(vs.Ag/AgCl),且E₀随pH增加而负向移动.电子转移系数为0.496,表观电极反应速率常数(ks)为6.6s^-1.电极反应的电子数为1且有1个质子参与.该修饰电极对NADH氧化具有很好的催化作用.在NADH存在下,电极过程由扩散控制,扩散系数为1.76×10^-6cm²/s.NADH浓度在0.01～5.0mmol/L范围内与峰电流呈现良好的线性关系.通过计时安培法测得催化速率常数为6.82×10³mol^-1·L·s^-1.     

Poly(ortho‐toluidine) Modified Carbon Paste Electrode: A Sensor for Electrocatalytic Reduction of Nitrite

The electrocatalytic reduction of nitrite has been studied by poly(ortho‐toluidine) films modified carbon paste electrode (P‐OT/MCPE). Cyclic voltammetry and chronoamperometry techniques were used to investigate the suitability of poly(ortho‐toluidine) as a mediator for the electrocatalytic nitrite reduction in aqueous solution with various pH. Results showed that pH 0.00 is the most suitable for this purpose. In the optimum pH, the reduction of nitrite occurs at a potential about 600 mV more positive than unmodified carbon paste electrode. The catalytic reaction rate constant, (k_h), was calculated 8.68×10² M^?1 s^?1 by the data of chronoamperometry. The catalytic reduction peak current was linearly dependent on the nitrite concentration and the linearity range obtained was 5.00×10^?4 M–1.90×10^?2 M. Detection limit has been found to be 3.38×10^?4 M (2σ). This method has been successfully employed for quantification of nitrite in real sample.     

聚邻氨基苯甲酸-铜复合薄膜修饰电极的制备及其电化学性能

利用聚合物官能团对金属离子的配位作用,在电极表面原位制备了金属粒子。 首先在玻碳电极（GCE）表面电沉积聚邻氨基苯甲酸(PoABA),再化学吸附铜离子(Cu2+),用水合肼还原得到单质铜(Cu0)。 采用扫描电子显微镜和能谱分析表征了聚邻氨基苯甲酸 铜(PoABA-Cu0)复合薄膜的表面形貌和元素构成,研究了PoABA-Cu0修饰电极的电化学性能,并以其检测了过氧化氢（H2O2）。 结果表明,电极表面被修饰上了一层PoABA-Cu0复合薄膜;制备的修饰电极对H2O2具有良好的电催化性能,在邻氨基苯甲酸的聚合圈数为10、Cu2+的吸附时间为10 min、工作电压为-0.3 V时,该修饰电极对H2O2表现出了最佳的检测性能,其线性浓度范围为5.0×10-5～1.0×10-2 mol/L,灵敏度为96.3 μA·L/(mmol·cm),检测限为5.0×10-5 mol/L,且具有较好的稳定性。     

多巴胺在聚铬黑T修饰玻碳电极上的电化学行为及其测定

制备了聚铬黑T修饰玻碳电极,研究了多巴胺(DA)在该修饰电极上的电化学行为。实验结果表明,在pH 4.0磷酸缓冲溶液中,聚铬黑T薄膜对多巴胺的电化学氧化具有明显的催化作用。此外,实验中观察到铬黑T膜能分离检测DA、抗坏血酸(AA)和尿酸(UA)三者的电化响应,DA与AA和UA之间的电位差达到210 mV和170 mV。利用差示脉冲伏安法(DPV)测定DA,其线性范围为0.1~200μmol/L,检出限为0.02μmol/L。该法已成功用于DA注射剂的含量分析,结果令人满意。     

聚(苯胺-co-邻氨基酚)修饰玻碳电极的制备及其对抗坏血酸的电化学氧化

研究了苯胺(AN)与邻氨基酚(OAP)在玻碳电极表面的电化学共聚,由此制备了AN与OAP共聚物膜修饰的玻碳电极(PAN-OAP/GCE/CME),并研究了该电极的电化学行为及其对抗坏血酸(AA)的电催化氧化。研究表明:AN与OAP的共聚速率随溶液中OAP浓度的增大而减小。当OAP与AN的浓度比>1∶10时,聚合行为相似;在其浓度比为1∶10时得到的共聚膜具有较好的电化学活性。由此可在0.1mol/L磷酸缓冲溶液(PBS,pH6.8)中对AA进行电催化氧化。在PAN-OAP/GCE/CME上其氧化峰电位位于0.21V,比在裸玻碳电极上(0.53V)降低了0.32V。该共聚物膜在中性溶液中显示出较好的电化学活性,为生物样本中AA的测定提供了条件。AA在修饰电极上的响应电流与其浓度在0.05~16.5mmol/L范围内呈线性关系,r=0.9998。采用计时电流法对AA催化氧化的扩散系数和催化速率常数进行了研究。     

多壁碳纳米管/十六烷基三甲基溴化铵修饰丝印电极的制备及大鼠血中雌二醇水平的测定

制备了多壁碳纳米管-十六烷基三甲基溴化铵(MWCNTs/CTAB)修饰丝印电极(MWCNTs-CTAB/SPE),并将其应用于大鼠血样中雌二醇(E2)的测定。在优化条件下,应用方波伏安法测定E2的氧化峰电流的线性范围为5.0×10~(-10)~1.0×10~(-8) mol/L(R=0.9968),检测限为5.0×10~(-11) mol/L。大鼠注射外源性E2后,MWCNTs-CTAB/SPE能特异性地测定血样中的E2,该方法与放射免疫测定法(RIA)比较,MWCNTsCTAB/SPE测定步骤简单,具有较好的准确度、精密度以及稳定性。     

氮掺杂石墨烯的制备及其对氧还原反应的电催化性能

以氧化石墨烯(GO)为原料、丙酮肟(DMKO)为还原剂和氮掺杂剂,采用化学还原法制备了不同氮掺杂含量的石墨烯(NG).利用场发射透射电子显微镜(FETEM)、紫外-可见(UV-Vis)光谱、傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)、zeta电位和纳米粒度分析、循环伏安(CV)和旋转圆盘电极(RDE)等手段对材料的形貌、结构、成分和电化学性质进行表征.结果显示:DMKO能有效地还原GO,且通过调节GO与DMKO的质量比,可以得到不同还原效果的NG,其氮含量范围为4.40%-5.89%(原子分数);GO与DMKO的质量比为1:0.7时制备的氮掺杂石墨烯(NG-1)在O2饱和0.1 mol·L-1KOH溶液中对氧还原反应(ORR)的电催化性能最佳,其ORR峰电流为0.93 mA·cm-2,电子转移数为3.6,这归因于其较高含量的吡啶-N增加了材料的ORR活性位点.此外,石墨化-N由于其较高的电子导电性倾向于产生较高的氧还原峰电流,而吡啶-N较低的超电势倾向于产生较正的氧还原峰电位.与商用Pt/C相比,该材料展现出了优异的抗CH3OH"跨界效应"的特性.     

微过氧化酶-11在聚赖氨酸修饰银电极上的电化学及电催化

发现利用吸附在粗糙Ag电极上的聚赖氨酸(Ply),以静电作用方式固定微过氧化酶 11（MP 11）来制备MP 11/Ply/Ag修饰电极,不但方法简单,而且制得的修饰电极对O2 的还原有高的电催化活性和好的稳定性.另外还发现MP 11分子中血红素的第六配体被配位能力较强的配体,如咪唑取代时,其本身的氧化还原电位负移,对O2还原的电催化活性降低.     

氮掺杂石墨烯的制备及其对氧还原反应的电催化性能

以氧化石墨烯（GO）为原料、丙酮肟（DMKO）为还原剂和氮掺杂剂,采用化学还原法制备了不同氮掺杂含量的石墨烯（NG）. 利用场发射透射电子显微镜（FETEM）、紫外-可见（UV-Vis）光谱、傅里叶变换红外（FTIR）光谱、X射线光电子能谱（XPS）、zeta 电位和纳米粒度分析、循环伏安（CV）和旋转圆盘电极（RDE）等手段对材料的形貌、结构、成分和电化学性质进行表征. 结果显示：DMKO能有效地还原GO,且通过调节GO与DMKO的质量比,可以得到不同还原效果的NG,其氮含量范围为4.40%-5.89%（原子分数）;GO与DMKO的质量比为1：0.7时制备的氮掺杂石墨烯（NG-1）在O₂饱和0.1 mol·L^-1 KOH溶液中对氧还原反应（ORR）的电催化性能最佳,其ORR峰电流为0.93 mA·cm^-2,电子转移数为3.6,这归因于其较高含量的吡啶-N增加了材料的ORR活性位点. 此外,石墨化-N由于其较高的电子导电性倾向于产生较高的氧还原峰电流,而吡啶-N较低的超电势倾向于产生较正的氧还原峰电位. 与商用Pt/C相比,该材料展现出了优异的抗CH₃OH“跨界效应”的特性.     

Cu(II) Hexacyanoferrate(III) Modified Carbon Paste Electrode; Application for Electrocatalytic Detection of Nitrite

Copper hexacyanoferrate (CuHCF) film‐modified carbon paste electrode (CPE) has been prepared from various electrolytic aqueous solutions using consecutive cyclic voltammetry. The cyclic voltammograms showed the direct deposition of CuHCF films from the mixing of Cu²⁺ and Fe(CN)₆^3? ions and each time with one of the six cations: H⁺, Na⁺, K⁺, NH₄⁺, Mg²⁺, and Al³⁺. The CuHCF film showed a single redox couple that exhibited a cation effect (Na⁺, K⁺, Mg²⁺, and NH₄⁺) and anion effect (Cl^?, NO₃^?, SO₄^2?, ClO₄^?, and BrO₃^?) in the cyclic voltammograms. Voltammetric studies have indicated that in presence of nitrite, the cathodic peak current of CuHCF increases, followed by a decrease in the corresponding anodic current. This indicated that nitrite was reduced by the redox mediator immobilized on the electrode surface via an electrocatalytic mechanism. The process of reduction and its kinetics were investigated by using cyclic voltammetry, differential pulse voltammetry, chronoamperometry and chronocoulometry techniques. The electrocatalytic ability about 800 mV can be seen. The rate constant of the catalytic reduction of nitrite was found to be 7.9×10⁵ cm³ mol^?1 s^?1. Linearity range obtained was 5×10^?5?8.4×10^?3 by cyclic voltammetry and 8×10^?6?1.3×10^?3 and 4×10^?3?2×10^?2 by differential pulse voltammetry.     

Preparation and Electrochemical Behaviour of Silver Pentacyanonitrosylferrate Film Modified Glassy Carbon Electrode and Its Electrocatalytic Oxidation to L‐cysteine

A glassy carbon (GC) electrode modified with silver pentacyanonitrosylferrate (AgPCNF) film as a redox mediator was fabricated. Cyclic voltammetry was used to study the redox property of AgPCNF modified electrode. The modified electrode showed a well‐defined redox couple due to [Ag^IFe^III/II(CN)₅NO]^1‐/2‐system. The effects of scan rates, supporting electrolytes and solution pHs were studied on the electrochemical behavior of the modified electrode. The feasibility of using the AgPCNF modified electrode to measure L ‐cysteine was investigated. It showed an excellent electrocatalytic activity towards the oxidation of L ‐cysteine and the anodic currents were proportional to the L ‐cysteine concentration in the range of 0.1 μM to 20 μM, the linear regression equation is I_pa(μA) = ‐68.58 ‐ 5.78C_{L ‐cysteine} (μM), with a correlation coefficient 0.998 for N = 23. The detection limit was down to 3.5 × 10^‐8 M (three times the ratio of signal to noise).     

聚溴酚蓝膜电极对儿茶酚的电催化性能及其应用

聚溴酚蓝膜修饰电极对儿茶酚的电极反应具有良好的催化作用,儿茶酚在修饰电极上的氧化电位比在裸玻碳电极上负移了120 mV,且灵敏度大为提高.该电极具有良好的稳定性,在0.5 mol/L H2SO4中,用该修饰电极测定儿茶酚的线性范围为20～2 000 μmol/L(r=0.999 6).     

聚碱性品红修饰电极的制备及应用

研究了碱性品红在玻碳电极上聚合的最佳实验条件及其聚合机理，发现该修饰电极的多巴胺具有良好的催化作用，能大大提高多巴胺在的玻碳电极上的响应，在ｐＨ＝７．０的磷酸盐缓冲溶液中，用修饰电极测定巴胺的线性范围为２×１０＾－７～１×１０＾－５ｍｏｌ／Ｌ，检测限为１×１０＾－７ｍｏｌ／Ｌ，并且具有稳定性好，响应快，选择性等特点。     

聚吖啶红修饰电极的制备及其应用

扑热息痛;聚吖啶红修饰电极的制备及其应用     

聚对氨基苯磺酸/石墨烯电化学修饰电极检测药物中氧氟沙星

基于石墨烯纳米材料和循环伏安法技术制备了聚对氨基苯磺酸/石墨烯修饰电极并研究了氧氟沙星(OFL)在该修饰电极上的电化学行为,建立了一种简单快速灵敏测定氧氟沙星的电化学分析方法。 结果表明,与玻碳电极相比,对氨基苯磺酸/石墨烯电化学修饰电极能显著提高氧氟沙星的峰电流。 在优化条件下,其检测线性范围为1~600 μmol/L,最低检测限为(S/N=3)0.33μmol/L。 该修饰电极具有较好的重现性和稳定性,用于实际样品氧氟沙星滴眼液的测定,效果良好。     

Electrocatalytic Oxidation and Determination of Norepinephrine at Poly(Cresol Red) Modified Glassy Carbon Electrode

A glassy carbon electrode (GCE) was modified with electropolymerized films of cresol red in pH 5.6 phosphate buffer solution (PBS) by cyclic voltammetry (CV). The modified electrode shows an excellent electrocatalytic effect on the oxidation of norepinephrine (NE). The peak current increases linearly with the concentration of NE in the range of 3×10^?6–3×10^?5 M by the differential pulse voltammetry. The detection limit was 2×10^?7 M. The modified electrode can also separate the electrochemical responses of norepinephrine and ascorbic acid (AA). The separation between the anodic peak potentials of NE and AA was 190 mV by the cyclic voltammetry. And the responses to NE and AA at the modified electrode were relatively independent.