Facile Synthesis of Gold Nanoparticle-loaded Carbon Nanofiber Composites and Their Electrocatalytic Activity Towards Dopamine, Ascorbic Acid and Uric Acid

A facile approach for the synthesis of gold nanoparticle-loaded carbon nanofiber(Au/CNF) composites was developed. When applied to electrochemistry, these composites showed attractive performances such as high conductivity and facile electron transfer kinetics. Under physiological conditions, the Au/CNF composite modified electrode exhibits highly electrocatalytic activity for the oxidation of dopamine, ascorbic acid and uric acid. Owing to the good selectivity for the simultaneous detection of these three species, the novel composites are promising for the development of effective electrochemical biosensors.     

Preparation of Ti-based Yb-doped SnO2–RuO2 electrode and electrochemical oxidation treatment of coking wastewater

In this study, the Ti/SnO₂–RuO₂ electrodes with different Yb contents were prepared by sol–gel method and thermal decomposition method, and the surface morphology and crystal structure of the electrodes were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD), the electrochemical properties of the electrodes were tested by linear sweep voltammetry (LSV) and cyclic voltammetry (CV). The electrochemical oxidation device was constructed with Yb-doped Ti/SnO₂–RuO₂ electrode as the anode and titanium plate as the cathode, and the electrochemical oxidation effect and product changes of the anode on coking wastewater were investigated. The results show that the surface of the electrode is flat with high crystallinity of SnO₂ and RuO₂ crystals at 1.5% Yb doping, and the LSV and CV curves indicate that the Yb doping of 1.5% increases the oxygen precipitation potential and electrocatalytic oxidation activity of the electrode. When the electrode with Yb doping of 1.5% is the anode with current density of 10 mA/cm² electrochemical oxidation time of 30 min, the electrode can remove chemical oxygen demand (COD) up to 85.06%, total organic carbon (TOC) up to 60.59% and UV₂₅₄ from 1.594 to 0.507 for coking wastewater. Gas chromatography (GC–MS), UV–vis and three-dimensional fluorescence results of coking wastewater before and after treatment show that large toxic substances in coking wastewater are degraded to low toxic organic substances, and most soluble organic substances are degraded and transformed. This study provides the possibility of basic research for the engineering practice of electrochemical oxidation for the treatment of coking wastewater.     

聚L-天冬氨酸/多壁碳纳米管复合膜修饰玻碳电极测定亚硝酸根

采用滴涂法和电聚合法制备了聚L-天冬氨酸/多壁碳纳米管复合膜修饰玻碳电极,利用循环伏安(CV)法研究了亚硝酸根 ( NO^-₂) 在该修饰电极上的电化学行为,建立了一种电化学测定NO^-₂的新方法。实验结果表明,该修饰电极对于 NO^-₂的氧化具有良好的电催化性能,并且显著促进 NO^-₂在电极表面的电化学过程。利用差分脉冲伏安法测定,在2.0 × 10^-6~2.0 × 10^-4 mol/L浓度范围内,NO^-₂的氧化峰电流与浓度呈现良好的线性关系,相关系数为 0.998 9。信噪比为 3 时,NO^-₂的检出限为 2.0 × 10^-7 mol/L。方法成功地用于环境水样中NO^-₂测定。     

Electrooxidation of thiocyanate on the copper-modified gold electrode and its amperometric determination by ion chromatography

Cyclic voltammetry was used to investigate the electrochemical behavior of an Au/Cu electrode towards the electrooxidation of thiocyanate ion in alkaline medium. The effects of pH, copper loading, scan rate and applied potential on the electrocatalytic oxidation of thiocyanate have been investigated. Flow injection experiments and ion-chromatography (IC) were performed to characterise the electrode as an amperometric sensor for the thiocyanate determination. The effects of carbonate concentration and common interferents on the retention time were also estimated. The electrode stability, precision, limit of detection and linear range were evaluated at a constant applied potential of 0.7 V vs. Ag/AgCl. Calibration plots, obtained in IC, were linear from 1.0 to 195 microM (correlation coefficient of 0.9984). The detection limit (LOD) was 0.5 microM (29 ppb) in a 50 microlitres injection. An example of analytical application, which includes the IC separation and detection of thiocyanate ion present in human urine, is given.     

层层自组装纳米金/硫堇修饰玻碳电极测定亚硝酸根

研究了纳米金/硫堇多层膜修饰玻碳电极的制备以及亚硝酸根在该电极上的电化学行为。在稀硝酸溶液中,通过恒电位法将玻碳电极活化,使其表面产生-COH等含氧基,然后将其浸泡在硫堇溶液中,硫堇中的-NH2与玻碳电极表面的-COH基团发生席夫碱反应,将硫堇固定在电极上。最后将电极浸泡在纳米金溶液中,通过纳米金与硫堇的相互作用将纳米金修饰到电极表面,从而制得纳米金/硫堇多层膜修饰玻碳电极。实验结果表明,该修饰电极能显著促进亚硝酸根在电极表面的电化学过程,电化学响应信号与亚硝酸根的浓度在20×10-6~50×10-5 mol/L和50×10-5~20×10-3 mol/L范围内呈良好的线性关系,检出限为5×10-8 mol/L (S/N=3)。方法用于水样中亚硝酸根的测定,相对标准偏差为22%~32%,回收率在98%~104%范围。     

聚L-半胱氨酸/乙炔黑修饰玻碳电极测定水样中对苯二酚

采用滴涂和电聚合法制备了聚L-半胱氨酸/乙炔黑修饰玻碳电极(L-Cys/AB/GCE)。用电化学交流阻抗法和计时库仑法研究了该修饰电极表面的界面性质。此外,还通过循环伏安法(CV)研究了对苯二酚(HQ)在该修饰电极上的电化学行为。阻抗图谱说明L-Cys/AB/GCE修饰膜的存在能够增加电子转移速度;计时库仑分析表明,L-Cys/AB/GCE的比表面积是裸电极的6倍;CV行为表明,L-Cys/AB/GCE对HQ氧化还原具有良好的电催化作用,响应的峰电流为裸电极的4倍,提高了检测HQ的灵敏度且峰电流与电位扫描速度的平方根呈良好的线性关系,相关系数R²为0.995~0.998,说明HQ在L-Cys/AB/GCE上的电化学反应过程是受扩散速度控制的过程。在支持电解质为0.1 mol/L磷酸盐缓冲溶液(pH 7.0)的优化条件下,用差分脉冲伏安法(DPV)分析,HQ浓度在0.5~1 000 μmol/L范围内,氧化峰的峰电流(I_pa)与浓度(c)呈良好的线性关系,相关系数R²为0.998,方法检出限为0.08 μmol/L,由此建立了一种测定水样中HQ的方法。按照实验方法对环境水样中HQ进行测定,结果与高效液相色谱法基本一致,相对标准偏差(RSD,n=8)为2.3%~2.6%。     

铁氰酸镍/碳纳米管修饰电极对肼的电催化氧化

本文利用电化学沉积技术制备了铁氰酸镍/碳纳米管复合修饰电极,并用循环伏安法对修饰电极进行表征.最后,将该电极用于N2H4的电催化氧化且取得了较好的效果,NiHCF的引入明显降低了N2H4催化氧化电位.     

Flow-through amperometric immunosensor: fast 'sandwich' scheme immunoassay

A flow-through immunosensor based on a high-surface-area carbon immunoelectrode has been developed. Dispersed carbon material serves as a carrier for immobilized antibodies and at the same time as an electrode material. The 'sandwich' scheme of immunoassay has been used. Iodine formed as a result of the enzymatic oxidation of iodide by a peroxidase label has been detected amperometrically. The immunosensor consists of a disposable sensing element (immunocolumn) containing dispersed carbon material with immobilized antibodies which also acts as a working electrode. A current collector connects the working electrode to the measuring device. The electrochemical detection time of the peroxidase-labeled immuno-complex does not exceed several minutes. The overall time of analysis including flowing of analyte, flowing of antigen, washing and detection stages is as low as 22 min. This technique allows fast determination of rabbit IgG (used as a model analyte) with a low detection limit in the picomolar range and also the determination of human IgM in blood plasma with a low detection limit in the nanomolar range.     

Generation of biotin/avidin/enzyme nanostructures with maskless photolithography

Micrometer-sized domains of a carbon surface are modified to allow derivatization to attach redox enzymes with biotin/avidin technology. These sites are spatially segregated from and directly adjacent to electron transfer sites on the same electrode surface. The distance between these electron transfer sites and enzyme-loaded domains must be kept to a minimum (e.g., less than 5 microns) to maintain the fast response time and high sensitivity required for the measurement of neurotransmitter dynamics. This is accomplished through the use of photolithographic attachment of photobiotin using an interference pattern from a UV laser generated at the electrode surface. This will allow the construction of microscopic arrays of active enzyme sites on a carbon fiber substrate while leaving other sites underivatized to facilitate electron transfer reactions of redox mediators, thus maximizing enzyme activity and detection of the enzyme mediator. The ultimate sensitivity of these sensors will be realized only through careful characterization of the carbon electrode surface with respect to its chemical structure and electron transfer properties following each step of the enzyme immobilization process. The characterization of specific modifications of micrometer regions of the carbon surface requires analytical methodology that has both high spatial resolution and sensitivity. We have used fluorescence microscopy with a cooled CCD imaging system to visualize the spatial distribution of enzyme immobilization sites (indicated by fluorescence from Texas Red-labeled avidin) across the carbon surface. The viability of the enzyme attached to the surface in this manner was demonstrated by imaging the distribution of an insoluble, fluorescent product. An atomic force microscope was used to obtain high-resolution images that probe the heterogeneity of the enzyme sites.     

Drug metabolism biosensors: electrochemical reactivities of cytochrome P450cam immobilised in synthetic vesicular systems

Biosensors containing cytochrome P450cam in a didodecyldimethylammonium bromide vesicular system were prepared by cross-linking onto a glassy carbon electrode (GCE) with glutaraldehyde in the presence of bovine serum albumin. Cyclic voltammetric responses of the sensor in air-free buffer solution showed that the sensor exhibited reversible electrochemistry due to direct electron exchange between the haem Fe(3+/2+) redox system and the GCE surface. In air-saturated solution containing camphor, the biosensor gave an irreversible electrocatalytic current which is compatible with the monooxygenation of the substrate. Steady state amperometric experiments with camphor, adamantanone and fenchone were performed with a biosensor prepared by cross-linking P450cam with glutaraldehyde onto a Pt disc electrode. The sensor was characterised by fast amperometric responses, attaining steady-state in about 20 s in a cobalt sepulchrate mediated electrochemical system. The kinetic parameters of the biosensor were analysed using the electrochemical Michaelis Menten equation. The estimated apparent Michaelis-Menten constant, Km, values for the biosensors were in the range of 1.41-3.9 mM.     

谷氨酸-纳米金-石墨烯修饰的离子液体碳糊电极测定水样中铅的研究

制备了谷氨酸-纳米金-石墨烯新型修饰电极, 并用该电极实现了水样中铅的灵敏测定。用电化学方法依次将石墨烯和纳米金电沉积在以N-丁基吡啶六氟磷酸盐为粘合剂和修饰剂的碳糊电极表面, 戊二醛通过共价键合连接谷氨酸, 制备了谷氨酸-纳米金-石墨烯修饰的离子液体碳糊电极。结果表明, 该电极表面存在的石墨烯和纳米金, 极大地提高了电极的电化学性能, 谷氨酸和石墨烯分别具有良好选择性和导电性, 使传感器对Pb²⁺的信号响应和选择性均得到提高。在最佳实验条件下, pH 5.3的醋酸盐缓冲溶液中, 铅离子的浓度在1.0 × 10^-9~ 4.0 × 10^-6 mol/L范围内与峰电流呈良好的线性关系, 检出限为3.0 × 10^-10 mol/L(3σ)。建立的方法应用于工业和生活废水、井水、雨水样品的测定, 测定结果与原子吸收光谱法的测定结果一致, 相对标准偏差在3.0%～3.8%之间。     

以阵列二氧化钛纳米棒为载体制备一体化析氧电极

以碳纸为支撑体,氯铱酸为前体,利用二氧化钛纳米棒阵列作为载体,采用浸渍-热分解法成功制备IrO₂-TiO₂/C一体化析氧电极.通过扫描电镜 (SEM)、XRD、XPS和电化学方法——循环伏安 (CV)、交流阻抗 (EIS) 等手段,研究载体形貌对析氧电极性能的影响.结果表明:二氧化钛载体能有效抑制支撑体碳纸在高电位下的腐蚀,当电压为2.4 V时,极化电流才仅为13.2 mA/cm2,一体化析氧电极积分电荷由87.2 mC/cm2增至178.5 mC/cm2,电极电化学反应阻抗由3.13 Ω·cm2降低到1.62 Ω·cm2,极大地提高了析氧电极的接触面积和催化剂的电催化活性.      

Effect of CeO_2-ZrO_2 on Pt/C electrocatalysts for alcohols oxidation

The electrocatalytic activity and stability of Pt/C catalyst modified by using CeO_2-ZrO_2 mixed oxides for the alcohols electrochemical oxidation as probes were investigated. The catalyst samples were characterized by X-ray diffraction(XRD) and scanning electron microscopy(SEM). The electrochemical properties were measured by a three electrode system on electrochemical workstation(IVIUM). The results showed that the presence of CeO_2-ZrO_2 might be associated with the presence of Pt, which indicated that possibly there was synergistic effect between CeO_2-ZrO_2 and Pt nanoparticles. The electrocatalytic activity and stability of Pt-MO_x/C(M=Ce, Zr) for methanol and ethanol oxidation was better than that of Pt-CeO_2/C, which was attributed to that CeO_2-ZrO_2 composited oxides enhanced oxygen mobility and promoted oxygen storage capacity(OSC). Furthermore, the best performance was found when the molar ratio of CeO_2 to ZrO_2 was 2:1 for the oxidation of methanol and ethanol. The forward peak current density of Pt-MO_x/C(M=Ce, Zr, Ce:Zr=2:1) towards the methanol electrooxidation was about 3.8 times that of Pt-CeO_2/C. Pt-MO_x/C(M=Ce, Zr) appeared to be a promising and less expensive methanol oxidation anode catalyst.     

球形氧化镍粉末对乙醇的电催化性能的研究

通过水热-热分解法制备球形介孔氧化镍粉末,并采用X射线衍射、扫描电镜、透射电镜和比表面积仪对氧化镍粉末的形貌和结构进行表征;通过循环伏安法、计时电流法和电化学阻抗谱的测试,系统研究该种粉末在碱性介质中对乙醇的电催化氧化活性.结果表明:所得到的氧化镍粉末为球形,比表面积为35 m2·g-1,平均孔径为15.88 nm;该粉末对乙醇具有良好的催化活性,氧化电流随乙醇浓度和扫描速率的增大而增大,在0.60 V电位下保持1000 s,球形多孔氧化镍对乙醇氧化催化的电流衰减率为0.075%,稳定性比较好.循环伏安法、计时电流法和电化学阻抗谱测试表明,球形介孔NiO/玻碳电极(NiO/GCE)对乙醇的催化氧化反应机理为扩散控制.      

Fabrication of copper-ceria hybrid composite electrode for electrocatalytic oxidation of methanol

Copper-ceria hybrid composite electrode prepared by electrochemical co-deposition was examined for their redox process and electrocatalytic activities towards the oxidation of methanol.The structure and morphology of electrodes were characterized by X-ray diffraction(XRD)and scanning electron microscopy(SEM),respectively.XRD pattern of the copper-ceria hybrid composite electrode exhibited some diffraction peaks of CeO2 and SEM micrograph showed that it was composed of grains and flakes.The energy dispersive spectroscopy(EDS)spectrum of this area also showed the presence of cerium.Cyclic voltammetry,CO stripping and chronoamperometry were performed to characterize electrocatalytic property of the prepared samples.In cyclic voltammetry studies and chronoamperometry,copper-ceria hybrid composite electrode towards oxidation of methanol showed a significantly higher response and long term stability.CO stripping results indicated the facile removal of intermediate poisoning species CO in the presence of CeO2,which was helpful for CO and methanol electro-oxidation.     

钒酸钙纳米棒的生长调控及其电化学特性

以乙酸钙和钒酸钠为原料,通过水热过程合成了捆状结构的单晶钒酸钙纳米棒。电镜观察显示所得钒酸钙纳米棒的平均直径约50 nm,长度约3μm。XRD和HRTEM图像显示所得钒酸钙纳米棒由单晶六方Ca10V6O25晶相构成。在钒酸钙纳米棒的生长过程中除了形成六方Ca10V6O25主晶相外,还存在单斜Ca0.17V2O5晶相,随着水热温度和保温时间的增加,单斜Ca0.17V2O5晶相完全转变为了六方Ca10V6O25晶相。采用基于晶体分裂的核化、晶体生长过程可以解释钒酸钙纳米棒的形成与生长。酒石酸在钒酸钙纳米棒修饰玻碳电极上的电化学循环伏安特性曲线中存在一对半可逆的氧化还原电化学伏安特性峰,其检测限为2.4μm,线性范围是0.005~2 mm。     

Fast-scan cyclic voltammetry of protein films on pyrolytic graphite edge electrodes: characteristics of electron exchange

The rapid electron-exchange characteristics of metalloproteins adsorbed at a pyrolytic graphite "edge" electrode have been studied by analog dc cyclic voltammetry at scan rates up to 3000 V s-1. The voltammetry of four proteins, azurin (a "blue" copper protein) and three 7Fe ferredoxins, reveals oxidation and reduction peaks that display only modest increases in width and peak separation as the scan rate is raised. This is indicative of a substantially homogeneous population of noninteracting centers which undergo rapid electron exchange with the electrode. Both the Butler--Volmer and Marcus models have been tested. The electrochemical kinetics, as reflected by k0 (the rate at zero overpotential), are too fast to allow the determination of reorganization energies by this method. Nonetheless, the rapid and energetically coherent nature of the electron transfer enables the cyclic oxidation and reduction of protein redox centers to be examined on a time scale sufficiently short to recognize coupled processes occurring in the millisecond time domain, which are characteristic of the protein under investigation. Two of the ferredoxins display increasingly asymmetric voltammetry as the scan rate is increased, which is attributed to the coupling of electron transfer to conformational (or orientational) changes. For azurin, the use of higher electrolyte concentrations enables studies to be made at scan rates up to 3000 V s-1, from which a standard electron-transfer rate constant in the region of 5000 s-1 is obtained. At these high scan rates, azurin still shows very symmetrical voltammograms but with peak shapes displaying a more gradual decrease in current, at increasing overpotential, than is predicted using realistic values of the reorganization energy. The ability to measure even faster rate constants and access coupled reactions occurring in shorter time domains is likely to be limited by complex processes occurring on the graphite surface.     

Immunoelectrodes in protein detection: comparison between glassy carbon and a semimetallic Ni/P thin film as binding support. Biological applications

Though immunoelectrodes can allow direct detection of very low protein amounts (about 0.1 pmol) in vitro and in vivo, they are not yet widely used because they need quality improvement. Based on a few works devoted to the basic electrochemical phenomenon occurring when antibodies are linked onto a solid support and during antigen/antibody complex formation, we have coated two different supports with antibodies: the classical glassy carbon fiber or an epoxy plate covered with an amorphous semimetallic (nickel/phosphorus) thin film obtained by means of an electrochemical deposit. The antibody/antigen complex formation induces direct and/or indirect ionic movements and a current flow through the conductive support toward a very low-noise and high-sensitivity preamplifier stage in an I/V configuration. The proposed electrochemical treatment (hydrophilization), applied to both carbon and Ni/P electrodes, improves antibody binding and reliability of the response to antigens. The Ni/P probes present several advantages when compared to carbon fiber: better conductivity, possibility of surface quality control, and semimetallic nature, making them unbreakable. Several applications were proposed: somatostatin-14 detection with both carbon fiber and Ni/P plate electrodes, and histamine detection in simple and complex fluid media. Dose-response curves and analysis of the results lead us to conclude that the obtained currents are directly related to the quantity of antigen.     

用聚苏木精/TiO2-石墨烯复合膜修饰玻碳电极差分脉冲伏安法测定水样中对苯二酚

采用滴涂法和电聚合法制备了聚苏木精/TiO2-石墨烯复合膜修饰玻碳电极。用循环伏安法研究了对苯二酚（HQ)在修饰电极上的电化学行为。实验结果表明,该修饰电极对于HQ的氧化还原具有良好的电催化性能。相对于裸电极和TiO2-石墨烯修饰电极,HQ在聚苏木精/TiO2-石墨烯修饰玻碳电极上的氧化峰电流显著提高。利用差分脉冲伏安法测定,HQ在3.0×10-6~1.0×10-3 mol/L浓度范围内与氧化峰电流呈良好的线性关系,相关系数分别为0.993。信噪比为3时,HQ检出限为1.0×10-7 mol/L。将该方法用于环境水样分析,回收率为96.2% ~ 105.6%。     

镉在嵌入式碳纳米管 铋膜玻碳电极上的电化学行为及电位溶出法测定研究

制备了一种新型嵌入式碳纳米管 铋复合膜玻璃碳电极,利用循环伏安法研究了Cd在电极上的电化学行为。 Cd在电极具有一个不可逆的氧化峰,Epa=0637 V（vs．SCE）,电极对Cd具有高灵敏的电化学响应。研究了影响Cd微分电位溶出的因素,获得的最佳条件是：富集电位为-11 V,Bi3+浓度为04 mg/L,pH 46 HAc NaAc缓冲溶液。通过同位镀铋、标准加入法进一步提高了分析的可靠性。在最佳条件下,峰高与Cd质量浓度在01～20 μg/L范围呈线性,检出限为02 μg/L。对实际样品进行测定,测定值与原子吸收光谱法的结果一致, RSD在31%～72%范围,回收率在92%～102%之间。