纳米银-磷酸锆复合膜修饰电极的制备和电化学

合成了新型纳米银-磷酸锆复合材料并用其修饰玻碳电极,用循环伏安法对修饰电极进行电化学研究.结果表明,此复合膜保持了银的纳米尺寸的微粒性质和磷酸锆对碱性染料的电位调制能力.复合膜中的纳米银提高了磷酸锆对中性红的吸附能力,增强了中性红的氧化还原反应活性.复合膜修饰电极表现出更灵敏的电化学响应.复合膜比单纯的磷酸锆膜表现出更好的机械强度,用其制备的修饰电极表现出更好的稳定性.     

钼钒磷酸四乙胺纳米粒子体修饰碳糊电极及其对过氧化氢的电催化还原

首次研究了无机 有机杂化的钼钒磷酸基的多金属氧酸盐纳米粒子 [(C2 H5) 4N]4PMo1 1 VO40 ·H2 O体修饰碳糊电极在 0 .5mol LH2 SO4+0 .1mol LNa2 SO4溶液中的电化学行为 ,结果表明该修饰电极对H2 O2 的电化学还原表现出很好的催化作用 ,而且具有优良的稳定性 ,这主要归因于该多金属氧酸盐纳米粒子的难溶性及其在石墨表面的强吸附。该修饰电极最独特的优点是电极表面可以重复更新。     

天青I修饰电极的电化学性质及对血红蛋白的电催化还原

天青I修饰电极在pH=5.5的HAc-NaAc缓冲溶液中,在0.3～-0.7V电位范围内表现出可逆的氧化还原行为,其表面式量电位E^0'=-0.21V,表观电极反应速率常数k_s'=0.69s^-1,该电极对血红蛋白的还原过程具有良好的催化作用。实验结果表明,由电沉积构成的修饰电极较吸附法制备的修饰电极具有更好的稳定性。     

碳纳米管／纳米TiO2复合膜修饰电极的制备及其对马来酸的电催化还原

制备了碳纳米管/纳米TiO2复合膜修饰电极(B)和纯纳米膜修饰电极(A).用XRD,TEM和循环伏安及计时库仑比较了A和B的电化学性能差异.结果表明,大量细小的碳纳米管的存在,可起到阻碍TiO2纳米粒子的团聚作用.碳纳米管独特的原子结构,能在电化学反应中促进电子传递,大大提高了B的电化学性能;B的循环伏安图中氧化还原峰电流比A的高出两倍多,单位时间通过电极的电量大幅度增加;通过对马来酸的异相电催化还原反应进一步证明了B比A具有更高的电催化活性.     

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.     

锇-聚乙烯吲哚配合物修饰电极对肾上腺素的电催化氧化

研究了配位聚合物锇 -聚乙烯吲哚 [Os( bpy) 2 ( PVI) 1 0 Cl]Cl和 Nafion双层膜修饰玻碳电极的电化学特性 ,该膜对肾上腺素 ( EP)的电化学氧化有催化作用 ,在通常的生理条件下 ( p H7.0 ) ,催化电流与 EP浓度在1 .0× 1 0 - 6～ 8.6× 1 0 - 5 mol/L范围内呈良好的线性关系 ,相关系数为 0 .9987.Nafion膜排除了抗坏血酸( AA)的干扰 ,表现出较高的灵敏度、选择性及良好的稳定性 .该电极可在 +2 50 m V下进行 EP的安培法测定 .用旋转圆盘电极对电催化过程的动力学进行了研究 ,催化速率常数 kch为 3 .53× 1 0 3mol- 1 · L· s- 1 .在较高 EP浓度下 ,催化电流与浓度的关系表现出 Michaelis-Menten型响应 ,Michaelis-Menten常数 Km 为1 .4 7mmol/L.     

NanoTiO2-CNT复合膜电极在DMF溶液中对糠醛的异相电催化还原

通过在乙醇中电化学溶解Ti金属阳极合成前驱体Ti(OEt)4和溶胶-凝胶法在Ti表面修饰一层纳米TiO2-碳纳米管(nanoTiO2-CNT)复合膜, 采用循环伏安和电解合成法研究了nanoTiO2-CNT复合膜电极在N, N-二甲基甲酰胺(DMF)中的氧化还原行为以及对糠醛(furfural)还原的电催化活性. 结果发现, nanoTiO2-CNT电极在阴极扫描时有两对氧化还原峰, 可逆半波电位E r1/2 分别为－1.27 V和－2.44 V(vs SCE, 扫描速度100 mV•s-1), 分别对应于TiO2/Ti2O3氧化还原电对的可逆电极过程和TiO2/Ti(OH)3电对的准可逆电极过程；在DMF电解液中nanoTiO2-CNT复合膜中的Ti(IV)/Ti(III)氧化还原电对作为媒质间接电还原糠醛为糠醇, 反应机理为电化学偶联随后化学催化反应(EC′)机理.     

壳聚糖-铜复合物修饰电极对过氧化氢电催化性能的研究

将壳聚糖与铜盐通过配位结合制得壳聚糖-铜复合物(CTS-Cu),并用其修饰玻碳电极,使用循环伏安法和计时安培法研究了该修饰电极对H2O2的电催化性能,对其催化机理进行了探讨.优化的实验条件为:以0.1 mol/L.磷酸缓冲溶液(PBS,pH 7.0)为反应介质,CTS-Cu修饰液中的铜离子浓度为6 mmol/L,工作电...     

聚中性红作电子转移介体的过氧化氢生物传感器

提出一种新的第二代电流型生物传感器。将易溶于水的电子转移介体中性红经电聚合在石墨电极表面形成一层致密、稳定的膜 ,有效的减少了其流失。并在辣根过氧化酶的表面覆盖一层明胶 ,再用戊二醛交联制备了H2 O2 传感器 ,使固定化酶保持了较高活性。该生物传感器具有较宽的线性范围 :2 .0× 10 - 5～ 2 .5×10 - 2 mol L ;检出限为 1.8× 10 - 5mol L ,达到 95 %稳态电流所用时间 <2 0s。     

L-半胱氨酸修饰Ag-nano-TiO2/CNT复合膜电极的制备及其对苯乙酮的电催化还原

在nano-TiO2/CNT电极表面镀一层银,制备了Ag-nano-TiO2/CNT电极.用L-半胱氨酸(L-Cys)修饰Agnano-TiO2/CNT制备了L-Cys-Ag-nano-TiO2/CNT 电极.研究了Ag-nano-TiO2/CNT和L-cys-Ag-nano-TiO2/CNT的电化学性质,结果表明,L-Cys-Ag-nano-TiO2/CNT对苯乙酮有较强的催化还原作用.     

An Unmediated Hydrogen Peroxide Sensor Based on a Hemoglobin-sds Film Modified Electrode

ABSTRACT

An unmediated hydrogen peroxide sensor is designed in this paper by employing a hemoglobin-SDS film modified electrode. Hemoglobin exhibits direct (unmediated) electrochemistry at the modified electrode. The protein also shows elegant catalytic activity towards the electrochemical reduction of hydrogen peroxide. Consequently, a prototype hydrogen peroxide sensor is prepared. Under optimum conditions, this sensor provides a linear response over the hydrogen peroxide concentrations in the range of 1×10^-5～1×10^-4 mol/L. The detection limit was 2×10^-6 mol/L The relative standard deviation was 4.2% for 6 successive determinations of the hydrogen peroxide at 1×10^-5 mol/L. This configuration is shown to be sensitive, stable and easily fabricated. It might be useful in the biological and industrial fields.     

Palladium-Substituted Keggin Type Polyoxotungstate Chemically Modified Electrode and Its Catalytic Activity Toward Hydrogen Peroxide Reduction

Abstract

Keggin type heteropolytungstate, in which one of the positions normally occupied by a tungsten cation is occupied by a palladium cation instead, is used to prepare a chemically modified electrode (CME). The electrochemical and electrocatalytic properties of such a CME are investigated. The electron transfer between the palladium-substituted heteropolytungstate and the glassy carbon electrode is fast. The palladium-substituted heteropolyanion CME, with a surface apparent coverage about 1.94 x 10^?9 mol.cm^?2, is shown to be an excellent catalyst for the electrochemical reduction of hydrogen peroxide, while the perfect and lacunary heteropolyanions show no catalytic activity. The effect of solution pH on the stability of the CME, as well as on the electrocatalytic activity toward H₂O₂, was also investigated. The catalytic current increases linearly with increasing concentration of H₂O₂ up to 150mmol.L^?1, and the detection limit is 4.0 x 10^?6mol.L^?1. Due to its sensitivity and durability, this CME could be used as analytical sensor for detecting H₂O₂ in real samples.     

Novel Enzymatic Rhodium Modified Poly(styrene‐g‐oleic amide) Film Electrode for Hydrogen Peroxide Detection

Newly synthesized poly(styrene‐g‐oleic amide) was coated onto a rhodium nanoparticle modified glassy carbon (GC) surface for the fabrication of horseradish peroxidase based biosensor used for hydrogen peroxide detection. The rhodium modifed electrode presented ten times higher signal than unmodified electrode even at low elecrtroactive enzyme quantity by enhancing the electron transfer rate at the applied potential of −0.65 V. The biosensor designed by under the optimized rhodium electrodeposition time exhibited a fast response less than 5 s, an excellent operational stability with a relative standard deviation of 0.6 % (n=6), an accuracy of 96 % and a large linear range between 50 μM and 120 mM for hydrogen peroxide. Detection limit and the sensitivity parameters were calculated to be 44 μM and 57 μA mM⁻¹ cm⁻², respectively by preserving its entire initial response up to the 15 days, while only 20 % of its initial response was lost at the end of one month.     

基于硫堇/碳纳米管修饰电极的新型过氧化氢电化学传感器

基于碳纳米管(CNTs)和硫堇(Th)的协同效应,将辣根过氧化物酶(HRP)通过戊二醛(GA)交联作用固定在硫堇(Th)/CNTs修饰电极上,构造了一种新型酶电极(HRP/GA-Th/CNTs/GC)。CNTs静电吸附正电荷的Th,而Th不仅可以促进电极和酶的氧化还原活性中心之间的电子传递,而且能使CNTs氨基(—NH2)功能化,从而利于HRP的固定。基于HRP/GA-Th/CNTs/GC电极的过氧化氢传感器具有较好的传感性能,且检出限低(0.3μmol.L-1)、响应时间短(5 s内)、抗干扰能力强。     

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。     

Electrocatalytic Activity of Riboflavin Chemically Modified Electrode Toward Dioxygen Reduction

Abstract

A chemically modified electrode (CME) exhibiting electrocatalytic response toward dioxygen was constructed by adsorbing the mediator riboflavin onto spectroscopic graphite. The electron transfer between the riboflavin functionality and the graphite was fast. The surface apparent coverage was at most 9.6 × 10^?10 mol cm^?2. The modified electrode permitted the dioxygen electroreduction to take place at the reduction potential of the mediator molecule. Dioxygen accepted two electrons from a reduced mediator to form hydrogen peroxide. Characterisation of the performance of the CME was carried out. After 30 min of continuous electrochemical cycling of pH 6.8, 30% of the original coverage remained for the CME. The effect of the solution pH and temperature on the electrocatalytic activity of the CME for oxygen reduction was also investigated.     

基于热解ZIF-8的氮掺杂碳电化学氧还原合成过氧化氢催化剂

氧气的两电子还原反应(2e-ORR)是绿色、安全的H₂O₂合成路线. 本工作以Zn²⁺和2-甲基咪唑合成的沸石型咪唑酸框架-8 (ZIF-8)为前驱体, 通过高温热解炭化, 利用ZIF-8中的锌在高温下的可挥发性, 制备了非金属氮掺杂石墨化多孔碳材料(p-ZIF), 系统考察了ZIF-8热解炭化温度(900、950和1000 ℃)对催化剂结构和2e-ORR催化性能的影响. p-ZIF不仅保留了ZIF-8规整的菱形十二面体形貌, 而且氮含量高, 拥有高的比表面积和多级孔结构. 在酸性条件下的2e-ORR反应中, 三个p-ZIF催化剂均显示了较低的过电位和较低的Tafel斜率, 而且稳定性良好. 其中在H₂O₂选择性最高的p-ZIF-950催化剂上, 过电位为86 mV, H₂O₂选择性最高可达89.2%. 在6 h恒电位反应中, p-ZIF-950催化剂能够以87 mmol•g_cat^-1•h^-1的恒定速率产生H₂O₂. 根据多种表征结果, 推测p-ZIF催化剂的孔径尺寸和石墨N含量是影响其2e-ORR催化性能的主要因素.     

Precise Design of Covalent Organic Frameworks for Electrocatalytic Hydrogen Peroxide Production

Electrochemical synthesis of H₂O₂ with high productivity is a significant challenge in electrocatalysis. Herein, we develop Mg-ion contained covalent organic frameworks (MgP-DHTA-COF), comprising stacked 2D layers, well-defined skeletons, and well-ordered monodispersed active sites, for the electrocatalytic production of H₂O₂ directly from O₂ and H₂O. The precise-designed MgP-DHTA-COF achieves H₂O₂ selectivity up to 96%, high Faradaic efficiency of 91% and reliable stability for H₂O₂ synthesis in 0.10 mol L⁻¹ KOH aqueous solution. Both experiments and simulations demonstrate that the pyrrolic-N fixed Mg ions in the knots promote the reactivity of COF and enhance the adsorption ability of OOH*. This work provides a valuable example for the design of an efficient electrocatalyst based on COFs for H₂O₂ production.     

Microperoxidase-11 Modified Electrode and Its Electrocatalytic Activity on the Reduction of O2 and H2O2

Microperoxidase-11(MP-11) was immobilized on the surface of a silanized glass carbon electrode by means of the covalent bond with glutaraldehyde.The measurements of cyclic voltammetry demonstrated that the formal redox potential of immobilized MP-11 was -170mV.which is significantly more positive than that of MP-11 in a solution or immobilized on the surface of electrodes prepared with other methods.This MP-11 modified electrode showed a good electrocatalytic activity and stability for the reduction of oxygen and hydrogen peroxide.     

炭载微过氧化物酶-11电极对O2和H2O2还原的电催化性能

氧还原;生物燃料电池;炭载微过氧化物酶-11电极对O2和H2O2还原的电催化性能