碳纳米管表面沉积氧化镍及其超电容器的电化学行为

通过催化裂解法制备了碳纳米管并进一步制备了碳纳米管薄膜电极.基于该种材料的超电容器电极比容量达到36F/g.研究了在碳纳米管薄膜基体上使用电化学方法沉积氧化镍的新工艺,制备出碳纳米管和氧化镍的复合电极.电化学测试证明复合电极的比容量提高到52F/g以上且基于这种复合电极的超电容器具有极低的自放电率.     

原位生长缺陷碳纳米管化学修饰电极的研制

利用浸渍法将碳纳米管(CNT)催化剂附着在石墨电极表面,用化学气相沉积法制备得到原位生长碳纳米管化学修饰电极(GSCNT-CME).通过控制催化剂及反应气体的配比,在石墨电极表面得到的管壁多缺陷的CNT,研究表明这种 GSCNT-CME具有良好的电化学检测性能.研究还发现这种GSCNT-CME具有高稳定性的原因是CNT是基于石墨电极上碳原子的晶格而生长的.     

用单壁纳米碳管制备葡萄糖生物传感器的研究

以单壁纳米碳管为代表材料,对利用纳米碳管制备葡萄糖生物传感器中纳米碳管的作用和纳米碳管修饰电极的方法、酶的固定化方法及电极种类等因素对传感器性能的影响进行了研究.研究结果表明,纳米碳管的加入能有效地改善传感器的电化学性能,利用二茂铁和单壁纳米碳管共同修饰电极所制得的传感器的性能要好于仅用单壁纳米碳管修饰电极制得的传感器.在酶的固定化方法中,戊二醛交联法要略好于明胶包埋法;而利用铂电极制备出的生物传感器对葡萄糖的响应电流要明显高于利用金电极和玻碳电极制备出的生物传感器.这些结论对于开发纳米碳管在生物传感领域及生命科学相关领域的应用有参考价值.     

Bioinspired peptide nanotubes as supercapacitor electrodes

Bioinspired materials offer new routes in nanotechnology. These materials are composed from chemically synthesized biomolecules and inspired by natural biological structures. They are self assembled into highly ordered nanostructures (nanotubes, nanospheres, etc.) from elementary building blocks of biological origin such as peptide and proteins. We developed a new technique of physical vapor deposition of peptide nanotubes (PNT) and applied it to electrochemical energy storage devices—supercapacitors (SC). In this work, aligned and homogenously distributed diphenylalanine PNT have been used to modify carbon electrodes for SC devices. Electrochemical properties of PNT coatings of different density and height, modifying carbon electrodes have been studied. We have found that aligned PNT arrays significantly increase the double layer capacitance of the carbon electrodes. The found enlargement of the PNT-modified electrode capacitance has been ascribed to increasing of usable electrode surface area of the carbon electrodes coated by PNT. We show that the critical factor of the accumulation process of the electrolyte ions at the PNT-modified electrode surface is a wetting process of the PNT nanoscale hydrophilic channels by aqueous electrolyte.     

碳纳米管电极电催化氧化降解染料溶液的研究

研究了经高温焙烧结合高速球磨处理后的碳纳米管的结构及形貌, 测定了其相应的比表面积. 对碳纳米管冷压成形制得的电催化电极的表面形貌进行了分析. 分别以活性炭、石墨、碳纳米管作为电催化阳极, 处理模拟染料废水活性艳红X-3B溶液, 实验结果表明: 碳纳米管电极电催化稳定性较好, 经电催化氧化反应20min后, X-3B染料的降解率达到96.55%, 其电催化降解效率明显优于活性炭和石墨电极.     

Development of a method for total inorganic arsenic analysis using anodic stripping voltammetry and a Au-coated, diamond thin-film electrode

We demonstrate that a Au-coated, boron-doped, diamond thin-film electrode provides a sensitive, reproducible, and stable response for total inorganic arsenic (As(III) and As(V)) using differential pulse anodic stripping voltammetry (DPASV). As is preconcentrated with Au on the diamond surface during the deposition step and detected oxidatively during the stripping step. Au deposition was uniform over the electrode surface with a nominal particle size of 23 +/- 5 nm and a particle density of 109 cm-2. The electrode and method were used to measure the As(III) concentration in standard and river water samples. The detection figures of merit were compared with those obtained using conventional Au-coated glassy carbon and Au foil electrodes. The method was also used to determine the As(V) concentration in standard solutions after first being chemically reduced to As(III) with Na2SO3, followed by the normal DPASV determination of As(III). Sharp and symmetric stripping peaks were generally observed for the Au-coated diamond electrode. LODs were 0.005 ppb (S/N = 3) for As(III) and 0.08 ppb (S/N = 3) for As(V) in standard solutions. An As(III) concentration of 0.6 ppb was found in local river water. The relative standard deviation of the As stripping peak current for river water was 1.5% for 10 consecutive measurements and was less than 9.1% over a 10-h period. Excellent electrode response stability was observed even in the presence of up to 5 ppm of added humic acid. In summary, the Au-coated diamond electrode exhibited better performance for total inorganic As analysis than did Au-coated glassy carbon or Au foil electrodes. Clearly, the substrate on which the Au is supported influences the detection figures of merit.     

Performance Characteristics of Modified Paraffin Impregnated Graphite Electrodes—Testing of Different Carbon Nanotubes Binders

The electrochemical properties of modified paraffin impregnated graphite electrodes (PIGEs) were tested throughout an electrochemical determination of Cu(II). The PIGEs were modified either by casting of carbon nanotubes suspension on prepared electrode surface or its abrasive deposition was used. Ten types of PIGE-modified electrodes, differed in type of dispersing agent used for CNT treatment and manner of modification, were evaluated. Chemometric characteristics of measurements were calculated and compared.     

Fabrication of multi-wall carbon nanotube film on glassy carbon electrode surface and the determination of tyrosine

A novel chemically modified electrode has been prepared on the basis of the attachment of multi-wall carbon nanotubes (MWNT) onto the surface of a glassy carbon electrode (GCE) in the presence of a hydrophobic surfactant, dihexadecyl phosphate (DHP). This MWNT film was characterized by transmission electron microscopy images (TEM) and scanning electron microscopy (SEM). The electrochemical behavior of tyrosine at the MWNT film coated GCE was examined and it is found that this MWNT-modified GCE greatly enhances the oxidation peak current of tyrosine. Effects of some important factors, including pH, scan rate and amount of modifier, on the oxidation process of tyrosine were investigated. When the signal to noise ratio (SNR) is 3, the detection limit is 1 x 10(-7) M. The low relative standard deviations of the detection of tyrosine in human morning urine (3.3%) and white wine (5.2%) suggest a good reproducibility of the modified electrode.     

Direct electrochemical determination of ascorbic acid by a cobalt(II) tetra-neopentyloxy phthalocyanine-multi-walled carbon nanotubes glassy carbon electrode

A cobalt(II) tetra-neopentyloxy phthalocyanine-multi-walled carbon nanotubes (CoTNPPc–MWNTs) composite was synthesized and characterized by UV–Vis spectra and transmission electron microscopy. The CoTNPPc–MWNTs glassy carbon electrode (CoTNPPc–MWNTs/GCE) was prepared by drop coating. The electrocatalytic performance of the chemically modified electrode was investigated for oxidation of ascorbic acid (AA). It was found that in phosphate buffer solution at pH = 6.60, the chemically modified electrode exhibited excellent electrocatalytic activity toward the oxidation of AA. The oxidation peak current increased linearly with the concentration of AA in the range of 10 μM–1.6 mM within the detection limit of 5 μM and low response time of 4 s.     

Optimization of Conditions for Preparation of Carbon Origin Solid Electrodes Modified with Carbon Nanotubes

A multi-walled carbon nanotubes (MWCNTs) were used for modification of two solid electrode types, glassy carbon electrode (GC), which is widely used for modification in electroanalysis, and, for the first time, paraffin impregnated graphite electrode (PIGE). The optimization of MWCNT/PIGE and MWCNT/GC electrodes was carried out by altering ultrasonication parameters (ultrasonication time, ultrasound generator performance, and dispersing agent). The preparation of modified electrodes was investigated. The most electrochemically sensitive MWCNT/GC electrode was prepared with nanotubes sonicated for 30 min and the most sensitive MWCNT/PIGE for 20 min, both using ethanol/water solution as dispersing agent and 500 W ultrasound generator performance. Both electrodes were successfully used for analysis of lead performed by DC voltammetry. Current responses were measured for the concentration of lead (II) in range from 1 × 10^?5 to 5 × 10^?5 mol dm^?3 for MWCNT/PIGE and also MWCNT/GC electrode.     

Electrochemical biosensor based on multi-walled carbon nanotubes and Au nanoparticles synthesized in chitosan

A new biosensor is prepared by cross-linking glucose oxidase (GOD) with glutaradehyde at the electrode combining Au nanoparticles (AuNP) with multi-walled carbon nanotubes (MWCNTs). Au nanoparticles-doped chitosan (CS) solution (AuNP-CS) is prepared by treating the CS solution followed by chemical reduction of Au (III) with NaBH4. MWCNTs are then dispersed in AuNP-CS solution. TEM, FT-IR, and UV-Vis show that the AuNP-CS solution is highly dispersed and stable. The synergistic effect between AuNP and CNTs of the AuNP-CNTs-CS material has been investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and amperometric methods. The modified glassy carbon electrode (GCE) allows low-potential detection of H2O2 with high sensitivity and fast response time. With the immobilization of GOD, a biosensor has been constructed. In phosphate buffer solutions (PBS, pH 7.0), nearly free interference determination of glucose has been realized at 0.4 V(vs. Ag/AgCl/3.0 M KCI) with a wide linear range from 2.0 x 10(-5) to 1.5 x 10(-2) M and a fast response time within 5s. The biosensor has been used to determine glucose in human serum samples and the results are satisfactory.     

Determination of serotonin on a glassy carbon electrode modified by electropolymerization of meso-tetrakis(2-aminophenyl)porphyrin and single walled carbon nanotubes

A chemically modified electrode [poly(TAPP)-SWNT/GCE] was prepared by electropolymerization of meso-tetrakis(2-aminophenyl)porphyrin (TAPP)-single walled carbon nanotubes (SWNT) on the surface of a glassy carbon electrode (GCE). This modified electrode was employed as an electrochemical biosensor for the determination of serotonin concentration and exhibited a typical enhance effect on the current response of serotonin and lower oxidation overpotential. The biosensor was very effective to determined 5-HT in a mixture. The linear response was in the range 2.0 x 10(-7) to 1.0 x 10(-5) M, with a correlation coefficient of 0.999 [i(p)(microA) = 3.406 C (microM)+0.132] on the anodic current, with a detection limit of 1 x 10(-9) M. Due to the relatively low currents and different potentials in the electrochemical responses to ascorbic acid and dopamine, the modified electrode is a useful and effective sensing device for the selective and sensitive serotonin determination in the presence of ascorbic acid and dopamine.     

含碳纳米管导电剂改善Li_4Ti_5O_(12)电极电化学性能

采用一种较为实用的调浆方法,考察了碳纳米管与乙炔黑的复合物(CNTs/AB)导电剂、乙炔黑(AB)导电剂和碳纳米管(CNTs)导电剂对Li_4Ti_5O_(12)电化学性能的影响,并用恒流充放电、扫描电子显微镜(SEM)和交流阻抗(AC)对添加上述3种导电剂制备得到的电极片进行研究.结果表明,采用该调浆流程能够克服CNTs在使用时出现的团聚问题,CNTs/AB复合物在改善Li_4Ti_5O_(12)电化学性能尤其在容量发挥和倍率性能方面比单一AB和CNTs具有明显优势.CNTs/AB复合物中两者的质量百分比为1:2～1:1时,0.5C时,Li_4Ti_5O_(12)电极的首次放电容量可高达157.0mAh/g,10.0C时,其放电容量可达到128.3mAh/g.与单一导电剂AB和CNTs相比,CNTs与AB复合使用时,由于CNTs的高长径比和良好导电性能使之能够起到"桥梁"作用把部分没有与活性物质充分接触的颗粒状导电剂AB与活性物质连接起来,因此两者的有机结合提高了CNTs/AB与活性材料的接触面积,使电极片能够形成有效的导电网络,有利于Li_4Ti_5O_(12)导电性能的提高.     

Role of iron oxide impurities in electrocatalysis by multiwall carbon nanotubes: An investigation using a novel magnetically modified ITO electrodes

The role of iron oxide impurities in the electrocatalytic properties of multiwall carbon nanotubes (MWCNTs) prepared by catalytic chemical vapour decomposition method (CCVD) is studied in detail. A novel magnetically modified electrodes have been developed by which MWCNTs were immobilized on indium-tin oxide (ITO) electrodes, without any chemical binders. The electro-catalytic oxidation of dopamine, and reduction of hydrogen peroxide have been studied by cyclic voltammetry on magnetically modified electrodes with (i) MWCNTs with occluded iron oxide impurities (Fe-MWCNTs), (ii) MWCNTs grown on iron oxide nanoparticle particulate films (Io-MWCNTs) and (iii) pristine iron oxide nanoparticle particulate film (Io-NPs). A shift towards less positive potentials for the oxidation of dopamine was observed which is in the order of Fe-MWCNTs < Io-MWCNTs < Io-NPs. Similarly, trend towards less negative potentials for the reduction of hydrogen peroxide was observed. Thus, the electrocatalytic activities displayed by MWCNTs have been attributed to the iron oxide impurities associated with it. The systematic variation was related to the nature of interaction of iron oxide nanoparticles with MWCNT surface.     

Electrochemical impedance-based DNA sensor using a modified single walled carbon nanotube electrode

Carbon nanotubes have become promising functional materials for the development of advanced electrochemical biosensors with novel features which could promote electron-transfer with various redox active biomolecules. This paper presents the detection of Salmonella enterica serovar Typhimurium using chemically modified single walled carbon nanotubes (SWNTs) with single stranded DNA (ssDNA) on a polished glassy carbon electrode. Hybridization with the corresponding complementary ssDNA has shown a shift in the impedance studies due to a higher charge transfer in ssDNA. The developed biosensor has revealed an excellent specificity for the appropriate targeted DNA strand. The methodologies to prepare and functionalize the electrode could be adopted in the development of DNA hybridization biosensor.     

导电分子印迹膜化学修饰电极的制备及其对胭脂红的电化学检测

报道了一种聚丙烯酰胺(PAAM)-植酸(PA)-聚多巴胺(PDA)导电分子印迹膜(PAAM-PA-PDA MIP)化学修饰电极的制备、表征及其在电化学定量检测食品添加剂胭脂红(P4R)中的应用。即通过原位电聚合和碱液洗脱的方法在玻碳电极(GCE)表面制得具有分子识别作用的导电分子印迹膜(PAAM-PA-PDA MIP)化学修饰电极,并利用SEM、循环伏安法(CV)及交流阻抗法(EIS)对该导电分子印迹膜化学修饰电极的表面形貌和电化学性能进行表征。研究结果表明该方法所制备的导电分子印迹膜化学修饰电极具有良好的电化学检测性能和应用前景,其对P4R的线性检测区间为10~200 μmol/L,灵敏度为0.085 A/mol/L,检测限可达23.6 nmol/L,并可有效地应用于P4R实际样品的分析检测。      

Performance of polyacrylonitrile-carbon nanotubes composite on carbon cloth as electrode material for microbial fuel cells

The performance of carbon nanotubes composite-modified carbon cloth electrodes in two-chambered microbial fuel cell (MFC) was investigated. The electrode modified with polyacrylonitrile-carbon nanotubes (PAN-CNTs) composite showed better electrochemical performance than that of plain carbon cloth. The MFC with the composite-modified anode containing 5 mg/cm2 PAN-CNTs exhibited a maximum power density of 480 mW/m2.     

Ethylene glycol oxidation on Pt and Pt-Ru nanoparticle decorated polythiophene/multiwalled carbon nanotube composites for fuel cell applications

A novel supporting material containing polythiophene (PTh) and multiwalled carbon nanotubes (MWCNTs) (PTh-CNTs) is prepared by in?situ polymerization of thiophene on carbon nanotubes using FeCl(3) as oxidizing agent under sonication. The prepared polythiophene/CNT composites are further decorated with Pt and Pt-Ru nanoparticles by chemical reduction of the corresponding metal salts using HCHO as reducing agent at pH = 11 (Pt/PTh-CNT and Pt-Ru/PTh-CNT). The fabricated composite films decorated with nanoparticles were investigated towards the electrochemical oxidation of ethylene glycol (EG). The presence of carbon nanotubes in conjugation with a conducting polymer produces a good catalytic effect, which might be due to the higher electrochemically accessible surface areas, electronic conductivity and easier charge-transfer at polymer/electrolyte interfaces, which allows higher dispersion of Pt and Pt-Ru nanoparticles. Such nanoparticle modified PTh-CNT electrodes exhibit better catalytic behavior towards ethylene glycol oxidation. Results show that Pt/PTh-CNT and Pt-Ru/PTh-CNT modified electrodes show enhanced electrocatalytic activity and stability towards the electro-oxidation of ethylene glycol than the Pt/PTh electrodes, which shows that the composite film is more promising for applications in fuel cells.     

纳米纤维素/碳纤维-聚苯胺/碳纳米管电极的制备

目的以纳米纤维素/碳纤维复合膜为导电基底,制备纳米纤维素/碳纤维-聚苯胺/碳纳米管超级电容器电极。方法利用超声处理和真空抽滤制备纳米纤维素/碳纤维复合膜;利用原位聚合法制备聚苯胺和聚苯胺/碳纳米管复合材料;通过真空抽滤法制备纳米纤维素/碳纤维-聚苯胺电极和纳米纤维素/碳纤维-聚苯胺/碳纳米管电极。结果在纳米纤维素/碳纤维复合膜中,碳纤维形成了互穿导电网络结构,是良好的超级电容器电极导电基体;纳米纤维素/碳纤维-聚苯胺/碳纳米管电极具有良好的电化学性能,在扫描速率为5 mV/s的条件下,质量比电容为380.74 F/g,且在1000次循环测试后,电容保留率为88.05%。结论以纳米纤维素/碳纤维导电复合膜作为基体制备的纳米纤维素/碳纤维-聚苯胺/碳纳米管电极具有良好的电化学性能,可以作为超级电容器电极。     

Porous graphitized carbon monolith as an electrode material for probing direct bioelectrochemistry and selective detection of hydrogen peroxide

For the first time, graphitized carbon particles with a high surface area have been prepared and evaluated as a new material for probing direct electrochemistry of hemoglobin (Hb). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) imaging revealed that the carbon monolithic skeleton was constructed by a series of mesopores with irregular shapes and an average pore diameter of ~5.6 nm. With a surface area of 239.6 m(2)/g, carbon particles exhibited three major Raman peaks as commonly observed for carbon nanotubes and other carbon materials, i.e., the sp(3) and sp(2) carbon phases coexisted in the sample. A glassy carbon electrode modified with carbon monoliths and didodecyldimethylammonium bromide exhibited direct electron transfer between Hb molecules and the underlying electrode with a transfer rate constant of 6.87 s(-1). The enzyme electrode displayed a pair of quasi-reversible reduction-oxidation peaks at -0.128 and -0.180 V, reflecting the well-known feature of the heme [Fe(3+)/Fe(2+)] redox couple: a surface-controlled electrochemical process with one electron transfer. This reagentless biosensing approach was capable of detecting H(2)O(2), a simple molecule but plays an important role in analytical and biological chemistry, as low as 0.1 μM with linearity of 0.1-60 μM and a response time of <0.8 s, comparing favorably with other carbon based electrodes (5 s).