碳纳米管电极上原位沉积Pt纳米颗粒

 本文利用原位离子交换法制备了碳纳米管(CNTs)载铂(Pt/CNTs)电极. X射线光电子能谱分析表明, Pt通过离子交换载于电化学功能化的CNTs表面. 扫描电镜照片显示, Pt高度分散于CNTs表面. X射线衍射分析表明, Pt的粒径约为4.0 nm. 离子交换法所制Pt/CNTs电极的电化学表面积和Pt的利用率均大于传统Pt/CNTs电极(Pt粒径约为2.5 nm), 其对氧还原的催化活性高于传统电极. 这归因于离子交换法所制电极的特殊结构,即Pt普遍载于电化学活性位上.     

In situ Detection of Microplastics: Single Microparticle‐electrode Impacts

Particle‐impact electrochemistry is employed to study spherical polyethylene microparticles suspended in an aqueous solution. This electrochemical method detects polyethylene microparticles impacting on a carbon fiber electrode generating a transient current response or “spike”. We interpret the physio‐chemical origin of the spikes and accurately identify particle size distributions and concentrations for microparticles of sizes 1–10 μm.     

Comparison of Insulin Determination on NiNPs/chitosan‐ MWCNTs and NiONPs/chitosan‐MWCNTs Modified Pencil Graphite Electrode

The rising amount of patients suffering for diabetes mellitus increases the requirements for effective insulin sensors. Carbon materials are a suitable choice for the development of insulin sensors due to their electrochemical characteristics. Pencil graphite electrodes (PGE) represent the trade‐off between price and excellent conductive properties. The modification of PGE by NiO and Ni nanoparticles fixed by chitosan results in surface area enlargement and improved electrocatalytic properties. This paper is focused on the comparison of different properties of Ni and NiO nanoparticles and their effect on redox reaction mechanism of insulin and detection characteristics. The electrode modified by Ni nanoparticles displays linear range of 1 μM–5 μM (R² 0.80), limit of detection (LOD) of 4.34 μM and sensitivity of 0.12 μA/μM. On the other hand, the electrode modified by NiO nanoparticles displays enhanced electrochemical characteristics such as linear range of 0.05 μM–5 μM (R² 0.99), limit of detection of 260 nM and sensitivity of 0.64 μA/μM. These properties make the NiO nanoparticles modified PGE the appropriate candidate for insulin determination.     

The electrochemistry of electrode edges and its relevance to partially blocked voltammetric electrodes

Analytical mathematics and digital simulation are used to predict the response, to a potential jump, of the junction between insulating and conducting regions of an electrode. The simulation is carried out differentially and employs other novel features. Concentrations in the vicinity of edges of positive and negative curvatures, as well as straight edges, are analyzed by the model and thereby the faradaic current densities and currents are predicted. It is shown that, in addition to the well-understood cottrellian current arising from the surface of the conducting electrode, currents are generated that are proportional to the length of the edge and to its curvature. These results are then applied to inlaid disks and to partially blocked electrodes. The possibility is explored of using the response to a potential step to gain information on the geometry of a partially blocked electrode.     

In Situ Growth of Hierarchical Ni-Mn-O Solid Solution on a Flexible and Porous Ni Electrode for High-Performance All-Solid-State Asymmetric Supercapacitors

To endow all-solid-state asymmetric supercapacitors with high energy density, cycling stability, and flexibility, we design a binder-free supercapacitor electrode by in situ growth of well-distributed broccoli-like Ni_0.75Mn_0.25O/C solid solution arrays on a flexible and three-dimensional Ni current collector (3D-Ni). The electrode consists of a bottom layer of compressed but still porous Ni foam with excellent flexibility and high electrical conductivity, an intermediate layer of interconnected Ni nanoparticles providing a large specific surface area for loading of active substances, and a top layer of vertically aligned mesoporous nanosheets of a Ni_0.75Mn_0.25O/C solid solution. The resultant 3D-Ni/Ni_0.75Mn_0.25O/C cathode exhibits a specific capacitance of 1657.6 mF cm⁻² at 1 mA cm⁻² and shows no degradation of the capacitance after 10 000 cycles at 3 mA cm⁻². The assembled 3D-Ni/Ni_0.75Mn_0.25O/C//activated carbon asymmetric supercapacitor has a high specific capacitance of 797.7 mF cm⁻² at 2 mA cm⁻² and an excellent cycling stability with 85.3 % of capacitance retention after 10 000 cycles at a current density of 3 mA cm⁻². The energy density and power density of the asymmetric supercapacitor are up to 6.6 mW h cm⁻³ and 40.8 mW cm⁻³, respectively, indicating a fairly promising future of the flexible 3D-Ni/Ni_0.75Mn_0.25O/C electrode for efficient energy storage applications.     

Nanostructured Screen Printed Graphite Electrode for the Development of a Novel Electrochemical Genosensor

The aim of this work is the preparation of DNA‐sensing architectures based on gold nanoparticles (AuNPs) in conjunction with an enzyme‐amplified detection to improve the analytical properties of genosensor. In order to assess the utility of study as DNA‐sensing devices, a thiolated DNA capture probe sequence was immobilized on the gold nanoparticle modified surface. After labeling of the biotinylated hybrid with a streptavidin‐alkaline phosphatase conjugate, the electrochemical detection of the enzymatic product was performed on the surface of a disposable electrode. Two different enzymatic substrates to detect the hybridization event were studied. In the first case, the enzyme catalyzed the hydrolysis of α‐naphthyl phosphate; the product is electroactive and has been detected by means of differential pulse voltammetry (DPV). In the second one, the enzyme catalyzed the precipitation of an insoluble and insulating product on the sensing interface. In this case, the electrochemical transduction of the hybridization process was performed by electrochemical impedance spectroscopy (EIS).     

基于对羟基苯硼酸为前驱体的金纳米粒子修饰电极电化学检测过氧化氢

以对羟基苯硼酸为前驱体,利用H₂O₂可以定量氧化对羟基苯硼酸产生对羟基苯酚的原理,以反应产物对羟基苯酚为电化学信号物质,结合金纳米粒子修饰玻碳电极（AuNPs/GCE）,发展了一种间接检测H₂O₂的电化学方法. 由于AuNPs/GCE具有有效电子传递性能和比表面积大等优点,对硼酸氧化产物具有较高的催化活性,因此在含1.0 mmol•L^-1对羟基苯硼酸的0.1mol•L^-1 pH 7.5 PBS中,AuNPs/GCE可以检测到1.0 ~ 1.0 × 10³ μmol•L^-1的H₂O₂,检测限为0.5μmol•L^-1. 同时,该方法具有良好的选择性和重现性,且操作简单、速度快、价格低廉,非常适用于实际样品中H₂O₂含量的测定.     

Study on the Indirect Electrochemical Detection of Ammonium Ion with In Situ Electrogenerated Hypobromous Acid

The electrochemical oxidation of bromide in the presence of ammonium ion (NH ) was studied by cyclic voltammetry and UV‐vis spectroscopy. The experimental results suggested that the anodically generated bromine (Br₂) would be hydrolyzed to hypobromous acid (HBrO) at the pH range of 5–7 and was further disproportionate to hypobromite anion (BrO^?) when pH was larger than 7. Both HBrO and BrO^? were confirmed to be participated in the following homogeneous chemical reaction with the coexisted ammonium ion. However, HBrO is electroactive whereas BrO^‐ is electroinactive at carbon electrode. Based upon the reaction of HBrO with NH , an indirect electrochemical method was proposed for determination of NH with dual‐electrode configuration in phosphate buffer solution (pH 7), where HBrO was produced at a generator electrode and the excess HBrO was subsequently detected at a collector electrode after a reaction with NH in a batch solution or in a micro flow injection analytical (micro‐FIA) system by using an interdigitated array (IDA) Pt microelectrode and a carbon film ring‐disk electrode (CFRDE), respectively. The decreasing of reduction current at the collector electrode was proportional to the concentration NH in both systems, with the detection limit below 3.0 μM. This approach shows the advantage of highly selectivity even in presence of a large amount of coexisted cations, and was successfully applied for the determination of NH in environmental water samples.     

Development of a Novel Electrochemical Sensor Based on Gold Nanoparticle-Modified Carbon-Paste Electrode for the Detection of Congo Red Dye

In this study, gold nanoparticles (AuNPs) were electrodeposited on samples of a carbon-paste electrode (CPE) with different thicknesses. The prepared AuNPs were characterized using different analysis techniques, such as FTIR, UV–Vis, SEM, EDX, TEM images, and XRD analysis. The fabricated modified electrode AuNPs/CPE was used for the sensitive detection of Congo red (CR) dye. Electrochemical sensing was conducted using square-wave voltammetry (SWV) in a 0.1 M acetate buffer solution at pH 6.5. The proposed sensor exhibited high efficiency for the electrochemical determination of CR dye with high selectivity and sensitivity and a low detection limit of 0.07 μM in the concentration range of 1–30 μM and 0.7 μM in the concentration range of 50–200 μM. The practical application of the AuNPs/CPE was verified by detecting CR dye in various real samples involving jelly, candy, wastewater, and tap water. The calculated recoveries (88–106%) were within the acceptable range.     

A Highly Selective Poly(thiophene)‐graft‐Poly(methacrylamide) Polymer Modified ITO Electrode for Neuron Specific Enolase Detection in Human Serum

In this study, an impedimetric immunosensor based on polymer poly(thiophene)‐graft‐poly(methacrylamide) polymer (P(Thi‐g‐MAm)) modified indium tin oxide (ITO) electrode is developed for the detection of the Neuron Specific Enolase (NSE) cancer biomarker. First, the P(Thi‐g‐MAm) polymer is synthesized and coated on the ITO electrode by using a spin‐coating technique. P(Thi‐g‐MAm) polymer acts as an immobilization platform for immobilization of NSE‐specific monoclonal antibodies. Anti‐NSE antibodies are utilized as biosensing molecules and they bind to the amino groups of P(Thi‐g‐Mam) polymer via glutaraldehyde cross‐linking. Spin‐coating technique is employed for bioelectrode fabrication and this technique provides a thin and uniform film on the ITO electrode surface. This bioelectrode fabrication technique is simple and it generates a suitable platform for large‐scale loadings of anti‐NSE antibodies. This immunosensor exhibits a wide linear detection range from 0.02 to 4 pg mL^?1 and with an ultralow detection limit of 6.1 fg mL^?1. It reveals a good long‐term stability (after 8 weeks, 78% of its initial activity), an excellent reproducibility (1.29% of relative standard deviation (RSD)), a good repeatability (5.55% of RSD), and a high selectivity. In addition, the developed immunosensor is proposed as a robust diagnostic tool for the clinical detection of NSE and other cancer biomarkers.     

二氧化硅/金复合膜修饰玻碳电极用于双酚A的检测

该文制备了二氧化硅/金复合膜修饰玻碳电极(SiO_2/Au/GCE),提出了一种简便检测双酚A(BPA)的电化学分析方法。采用扫描电镜(SEM)和红外光谱(FT-IR)对SiO_2和SiO_2/Au的形貌和结构进行了表征,循环伏安法(CV)和交流阻抗法(EIS)研究了SiO_2/Au/GCE的表面电化学特性,同时用CV、计时库仑法(CC)、控制电位电解库仑法、线性扫描伏安法(LSV)和差分脉冲伏安法(DPV)等研究了BPA在SiO_2/Au/GCE上的电化学行为,优化了实验参数,并得到电化学动力参数。实验发现:SiO_2/Au/GCE对BPA具有良好的电催化活性,BPA在该修饰电极上的氧化峰电流为GCE上的3倍,且BPA在SiO_2/Au/GCE上的氧化过程为2电子2质子的完全不可逆电极过程。在最佳条件下,BPA的氧化峰电流分别在0.01~0.50μmol/L和0.50~25μmol/L浓度范围内呈良好的线性关系,检出限为1.9×10-8mol/L。用于一次性手套中BPA含量的测定,回收率为98.9%~105.3%,与高效液相色谱法(HPLC)进行对照,结果满意。     

pH/Cl-复合探针技术对钢筋混凝土电化学除氯的原位检测

采用恒电流法电化学除氯处理受氯离子污染的钢筋混凝土试样,并用pH/Cl^-复合探针原位检测电化学除氯过程钢筋混凝土不同位置孔隙液的氯离子含量与pH值分布,同时用线性极化曲线和交流阻抗谱图等电化学技术考察钢筋的腐蚀性能,探讨电化学除氯过程的混凝土微环境和钢筋腐蚀速率. 研究结果表明：在电化学除氯过程,混凝土孔隙液的氯离子浓度逐降,而pH值在初期略有升高,随之其pH值略降;电化学除氯施加的阴极电流,使钢筋处于阴极极化状态而得到保护;除氯停止（即退极化）后钢筋的腐蚀电位明显正移,腐蚀电流降低,极化电阻升高,表明电化学除氯能改善钢筋的腐蚀环境,降低钢筋的腐蚀速率.     

Protein‐Directed In Situ Synthesis of Gold Nanoparticles on Reduced Graphene Oxide Modified Electrode for Nonenzymatic Glucose Sensing

A novel nonenzymatic glucose sensor was developed based on well‐dispersed gold nanoparticles, which were in situ grown under direction of protein on a reduced graphene oxide modified electrode. This electrode exhibited high electrocatalytic activity towards glucose oxidation without use of any enzyme or mediator. In application for the amperometric detection of glucose, a wide linear range of 0.02–16.6 mM, low detection limit of 5 µM and good selectivity were obtained. The attractive analytical performances of the proposed glucose sensor, coupled with the facile preparation method, provide a promising electrochemical platform for the development of effective nonenzymatic sensors.     

Electrocatalytic Determination of Nitrite on a Rigid Disk Electrode Having Cobalt Phthalocyanine Prepared In Situ

This work reports an in situ cobalt(II) phthalocyanine (CoPc) synthesis on a SiO₂/SnO₂ (SiSn) matrix surface obtained by the sol‐gel method and its electrocatalytic activity for oxidation of nitrite. A rigid disk electrode with SiSn/CoPc was used to study the electrooxidation of nitrite by the cyclic voltammetric, chronoamperometric techniques and differential pulse voltammetry (DPV). The adsorbed phthalocyanine electrocatalyzed nitrite oxidation at 0.73 V (versus SCE) using the DPV technique. The anodic peak current intensities, plotted from differential pulse voltammograms in 1 mol L^?1 KCl for the concentration range 0.002 to 3.85 mmol L^?1 of nitrite were linear, with a correlation coefficient of 0.998 and a detection limit of 0.95 μmol L^?1.     

In Situ Synthesis of MnMgFe-LDH on Biochar for Electrochemical Detection and Removal of Cd2+ in Aqueous Solution

Herein, MnMgFe-layered double hydroxides/biochar (MnMgFe-LDHs/BC) composite was fabricated by immobilizing MnMgFe-LDHs on BC via the coprecipitation method, which was employed as an effective material for the detection and removal of Cd²⁺ from aqueous media. A lamellar structure of MnMgFe-LDHs with abundant surface-hydroxyl groups and various interlayer anions inside present a greater chance of trapping Cd²⁺. Meanwhile, the conductive BC with a porous structure provides numerous channels for the adsorption of Cd²⁺. Using the MnMgFe-LDHs/BC-based sensor, Cd²⁺ can be detected with a low limit of detection down to 0.03 ng/L. The feasibility of detecting Cd²⁺ in paddy water was also carried out, with satisfactory recoveries ranging from 97.3 to 102.3%. In addition, the MnMgFe-LDHs/BC material as an adsorbent was applied to remove Cd²⁺ from water with adsorption capacity of 118 mg/g, and the removal efficiency can reach 91%. These results suggest that the as-prepared MnMgFe-LDHs/BC can serve as a favorable platform for efficient determination and removal of Cd²⁺ in water.     

头孢哌酮在玻碳电极上的电化学行为及检测方法

应用循环伏安法、线性扫描伏安法和微分脉冲伏安法研究头孢哌酮在玻碳电极上的电化学行为,建立了应用伏安法定量检测头孢哌酮的新方法。头孢哌酮的电极过程为受吸附控制的不可逆过程,电极反应转移电子数和转移质子数均为2。头孢哌酮在pH1.0的1mol/LH3PO4-NaOH介质中,在+0.13V(vs.Ag/AgCl)电位处产生一灵敏的氧化峰,应用微分脉冲伏安法进行测定,该峰电流值Ip与头孢哌酮质量浓度在5.05×10-7～1.01×10-4g/mL范围内有良好的线性关系(R=0.9996),检出限为4.95×10-9g/mL,样品测定平均加标回收率达99.50%,相对标准偏差(RSD)为3.17%。