用X射线光电子能谱对热处理的四苯基钴卟啉修饰电极的表面表征

本文用XPS、DTA和TG分析了四苯基钴卟啉化学修饰电极的热分解行为,它不同于四苯基铁卟啉.由XPS谱图揭示了四苯基钴卟啉与玻璃碳电极之间的相互作用,进而阐述了经热处理的四苯基钴卟啉化学修饰电极的表面结构与电催化稳定性的关系.从Co2p_3/2和2p_(1/2)能级的自旋分裂间距及其Shake-up伴峰,了解经热处理后的四苯基钴卟啉修饰电极中钴自旋态变化,并且从Co的L_3VV俄歇跃迁计算出Co的双电离能,其双电离能与电催化活性有一定关系。     

用X射线光电子能谱对热处理的四苯基钴卟啉修饰电极的表面表征

本文用XPS、DTA和TG分析了四苯基钴卟啉化学修饰电极的热分解行为, 它不同于四苯基铁卟啉. 由XPS谱图揭示了四苯基钴卟啉与玻璃碳电极之间的相互作用, 进而阐述了经热处理的四苯基钴卟啉化学修饰电极的表面结构与电催化稳定性的关系. 从Co2p_3/2和2p_(1/2)能级的自旋分裂间距及其Shake-up伴峰, 了解经热处理后的四苯基钴卟啉修饰电极中钴自旋态变化, 并且从Co的L_3VV俄歇跃迁计算出Co的双电离能, 其双电离能与电催化活性有一定关系。     

有机锡化合物为中性载体的高选择性硫氰酸根离子电极

使用硫氰化银与硫化银作膜活性物质的固态硫氰酸根离子选择电极,由于受卤素离子如Cl^-、Br^-和I^-干扰很大而限制了应用.以钴(Ⅲ)卟啉或维生素B₁₂衍生物为载体的电极对SCN^-有较高的选择性^[1,2],使SCN-选择电极得到了较大的发展.     

用光透薄层电极(OTTLE)检测CO2电催化还原的中间体

光透薄层电极(OTTLE)在给定的电位下可测定介稳化合物的可见光谱,我们首次将它用于CO₂电催化还原机理的研究,并检测到CO₂钴卟啉配合物中间体和确定了催化机理。光透薄层电极池的工作电极是甩0.01mm金丝网,面积为0.5×2.0cm²,网孔密度为每厘米宽度内约含100根金丝。     

电化学氧化增强金属钴卟啉的自组装研究

应用电化学方法将钴(Ⅱ)卟啉氧化成钴(Ⅲ)卟啉以增强它与4-巯基吡啶(MP)自组装膜的轴向配位作用,从而快速制备了有序钴卟啉自组装修饰电极CoTMPP/MP/Au(E).电化学石英晶体微天平(EQCM)测试证实电化学氧化对钴卟啉膜生长过程的增强作用.Ram an光谱及修饰电极电催化还原氧研究显示,该修饰电极与经过长时间浸渍法得到的CoTMPP/MP/Au(I)修饰电极具有完全相似的有序结构和性质.与直接将钴卟啉吸附在电极表面的CoTMPP/Au修饰电极相比,以巯基吡啶为桥键得到的钴卟啉修饰电极具有更好的电催化活性和稳定性.     

染料电极的光电转换效应研究

应用一种简便的旋转涂布方法,制备了卟啉/SnO₂,酞菁/SnO₂以及卟啉/酞菁/SnO₂单层和双层电极,在双层电极研究中发现,卟啉和酞菁层的涂布次序对形成的双层电极是否出现叠加现象有很大影响。对所出现的现象进行了初步的讨论。     

化学修饰电极的研究——ⅩⅪ.聚钴原卟啉薄膜电极的电化学聚合制备及其电催化稳定性

用循环伏安法(CV)研究了钴原卟琳二甲酯(CoPP)在玻碳(GC)电极表面的电化学聚合过程,为阳离子聚合机理,中心钴离子促进乙烯基电化学氧化成为阳离子自由基而发生聚合反应。聚钴卟啉的紫外可见光谱较单体钴卟琳的光谱向长波方向移动,ESCA分析表明,聚合后钴离子仍存在于卟啉环上,有部分基团为氧取代,聚 CoPP薄膜修饰玻碳〔聚(CoPP)/GC〕电极具有催化还原氧的高稳定性,在O饱和的0.05mol/HSO_4溶液中经CV扫描400次(100mV/s),其催化峰电流不变,聚(CoPP)/GC电极主要催化O二电子还原为HO。     

四苯基钴卟啉化合物催化过亚硝酸根分解的研究

利用紫外-可见分光光度计在乙醇介质中研究了合成的4种对位取代四苯基钴卟啉对过亚硝酸根分解的催化作用. 首次发现钴卟啉可以催化ONOO^－分解, 且对位带吸电子基团的钴卟啉比对位带供电子基团的钴卟啉催化活性高. TPPCoCl, T(p-CH₃)PPCoCl, T(p-OCH₃)PPCoCl和T(p-Cl)PPCoCl在乙醇中的k_cat分别为1.69×10², 1.52×10², 1.43×10²和1.20×10³ mol^－1•L•s^－1. 动力学曲线和时间分辨谱证明这些钴卟啉是通过形成中间体催化过亚硝酸根分解的.     

酞菁钴及其衍生物修饰电极对分子氧的电催化还原

在玻碳电极上采用吸附法制备了四溴代酞菁钴(CoPcBr₄)、酞菁钴(CoPc)和四-α-(2,2,4-三甲基-3-戊氧基)酞菁钴(CoPc(OC₈H₁₇)₄)修饰电极。利用循环伏安法和线性扫描伏安法研究了修饰电极在酸性介质中对分子氧的电催化还原,比较了不同取代基的酞菁钴对电催化性质的影响。结果表明,它们对分子氧还原均具有良好的电催化活性,其中酞菁钴和四-α-(2,2,4-三甲基-3-戊氧基)酞菁钴对O₂的催化是2电子还原生成H₂O₂,与裸电极相比,O₂的还原峰电位分别向正方向移动了0.33和0.48 V。而四溴代酞菁钴修饰电极在-0.1和-0.7 V附近产生的2个还原峰,说明它催化O₂到H₂O₂的还原以后还可以促进H₂O₂继续还原到H₂O,最终实现O₂的4电子还原。     

化学修饰电极的研究 Ⅺ.吸附型四苯基金属卟啉修饰电极的制备和稳定性

本文详细研究了吸附型四苯基钴卟啉(FeTPP),四苯基结卟啉(CoTPP)和四苯基锰卟啉(MnTPP)修饰于玻碳(GC)电极表面的方法。实验证明,GC电极的表面状态是影响此类修饰电极的稳定性以及对氧还原反应的电催化活性的主要因素。在适宜条件下制备的四苯基铁卟啉化学修饰玻碳电极(FeTPP/GC)在空气以及不同pH的水溶液中稳定;进行氧的催化电还原时,在每次扫描前以空气饱和的溶液中能重复循环扫描60次,峰电流降低30％,催化氧电还原的活性顺序是FeTPP/GC>CoTPP/GC>MnTPP/GC;稳定性顺序是CoTPP/GC> FeTPP/GC>MnTPP/GC。     

Detection of H_2O_2 at a composite film modified electrode with highly dispersed Ag nanoparticles in Nafion

Ag nanoparticles were prepared by using the ion-exchange of Nafion combined with electrochemical reduction on the electrode. Ag nanoparticles are highly dispersed in Nafion film with an average size of 4.0±0.2 nm.The amount of Ag nanoparticles can be readily controlled by the amount of Nafion coated on the electrode.Thus obtained Ag nanoparticles exhibit good catalytic activity for the reduction of H₂O₂ with a linear response to H₂O₂ in the concentration range of 0.04-8.0 mmol/L with a sensitivity of 0.34μA/mmol/L and a detection limit of 1.0×10^-8 mol/L.     

Amperometric glucose-sensing electrode based on carbon paste containing poly (ethylene glycol)-modified glucose oxidase and cobalt octaethoxyphthalocyanine

An amperometric enzyme electrode for glucose was prepared by incorporating poly (ethylene glycol)-modified glucose oxidase and cobalt octaethoxyphthalocyanine [CoPc(OEt)₈], a new mediator, into a carbon paste matrix. The polymer-modified enzyme exhibited a higher activity than the native enzyme in the hydrophobic carbon paste medium. CoPc(OEt)₈ could oxidize the enzyme at more negative potentials than unsubstituted cobalt phthalocyanine (CoPc). Further, the CoPc(OEt)₈-mediated enzyme electrode showed a high stability: the electrode response to glucose did not decrease for at least 4 weeks (or for 700 assays), whereas the glucose response from a CoPc-mediated enzyme electrode fell to half of the initial value within 2 weeks (or after 300 assays). CoPc(OEt)₈, a paraffin-oil soluble derivative of CoPc, incorporated in the bulk of carbon paste, diffused towards the electrode surface so as to renew continuously the electrode surface, which resulted in the high stability of the new mediator-based enzyme electrode.     

电化学沉积制备纳米结构铜电极及其葡萄糖检测性能

利用电化学沉积法制备了高电活性的纳米结构铜电极材料, 采用扫描电子显微镜和电化学方法分别对电极表面形貌和电化学性能进行了表征, 研究了实验参数对葡萄糖电氧化活性的影响. 结果表明, 改变沉积条件可以调控沉积铜的形貌及电催化活性. 在最佳条件下制备的铜纳米结构电极对葡萄糖检测的灵敏度为1310 μA·L/mmol, 检出限为5.0×10^-7 mol/L(S/N=3).     

Immobilization of Hemoglobin on Cobalt Nanoparticles-modified Indium Tin Oxide Electrode:Direct Electrochemistry and Electrocatalytic Activity

A cobalt nanoparticles-attached indium tin oxide(CoNPs/ITO) electrode was applied to the immobilization of hemoglobin(Hb) and an Hb modified CoNPs/ITO electrode(Hb/CoNPs/ITO) was prepared. The direct electron transfer of Hb was shown by the well-behaved voltammetric responses for Hb/CoNPs/ITO electrode and the effects of scan rate and pH value were observed. Based on the catalytic activity of Hb immobilized on the CoNPs/ITO electrode toward the reduction of H₂O₂, a mediator-free H₂O₂ sensor was developed. A linear relationship existed between the catalytic current and the H₂O₂ concentration in a range of 1.0―100.0 μmol/L with a detection limit (S/N=3) of 0.2 μmol/L.     

钴卟啉修饰碳纤维束葡萄糖酶微电极的研究

生物电化学传感器的微型化研究是目前生物传感器研究中的一个很活跃的方向。我们曾用钴卟啉修饰碳纤维柱电极,并以它为基底制成了葡萄糖微传感器。为加强电极的抗折断能力,本文把约1千支碳纤维(φ9μm)做成碳纤维束盘微电极,在其表面修饰四苯基钴卟啉后,以其为基底制成了葡萄糖酶电极。将其用于流动注射分析,可以大大提高线性响应上限。     

主成分回归-络合滴定法测定混合金属离子

提出了用络合滴定法测定混合金属离子.以汞膜电极为指示电极,银-氯化银电极为参比电极,以标准EDTA溶液滴定混合金属离子溶液.采集-系列指定电位点处滴定剂的体积,并以主成分回归法处理滴定数据.利用本文方法对铜、锌、铅、钻混合溶液进行了测定,结果满意.     

基于纳米金自组装膜固定辣根过氧化物酶的生物传感研究

将辣根过氧化物酶(HRP)通过纳米技术和自组装技术固定于电极表面,制得了酶修饰电极.纳米金与HRP形成了静电复合物并高效地保持了HRP的生物活性,以对苯二酚作为电子媒介体,差示脉冲伏安法(DPV)研究生物酶电极测定H2O2的线性范围为5.0×10-6～1.0×10-3 mol/L,检测限为2.5×10-6 mol/L,线性方程为△I=0.34765+4.05553CH2O2(mM).酶电极的表观米氏常数(K(app))为0.0675 mmol/L.实验同时证明该生物酶电极具有良好的稳定性和使用寿命.     

Study of Electrochemical Non-enzyme Glucose Sensor Based on Cu(Ⅱ)Co(Ⅱ) Bimetallic Carbon Nanosheets北大核心CSCD

CuCo-MOF nanofibers are synthesized by one-step solvent blending process at room temperature. Then CuCo-MOF nanofibers are used as the precursors,carbon nanosheets（Cu（Ⅱ）Co（Ⅱ）@C）uniformly loaded with nano-sized copper oxide and cobalt oxide are obtained by calcination at high temperature in air. Cu（Ⅱ）Co（Ⅱ）@C is modified on the glassy carbon electrode to directly catalyze glucose in alkaline solution. Because CuO and CoO are uniformly and firmly embedded on the carbon nanosheets,the agglomeration of catalyst is prevented,which greatly improves the specific surface area,and increases the catalytic active site. Meanwhile,due to the synergistic effect of copper and cobalt bimetals in the carbon nanosheet material,the enzyme free glucose sensor has excellent electrical conductivity and excellent catalytic performance. The detection range of the non-enzymatic electrochemical glucose sensors for glucose is 0. 03 µμmol/L~13. 6 mmol/L, the detection limit is 0. 01 µμmol/L（S/N=3）,and the sensitivity is 10. 56 mA·L/（cm2·mmol）. In addition, the non-enzyme sensor also has good anti-interference and high stability. © 2022, Science Press (China). All rights reserved.     

聚刚果红修饰玻碳电极的制备及其电催化性能

在含刚果红的硼砂缓冲溶液中,用循环伏安法扫描,在玻碳电极上形成聚合物薄膜.在 -0. 8V~+1. 8V(vsAg/AgCl)的扫描电位范围形成的薄膜具有较高的电活性和稳定性.该电极对抗坏血酸、邻苯二酚的电化学氧化有催化作用,增大了氧化峰电流.催化峰电流与抗坏血酸和邻苯二酚浓度分别在 20 ~1 200mmol/L, 50 ~2 000mmol/L范围内呈良好的线性关系.