Electrochemical hydrogen storage in single-walled carbon nanotube paper

Single-walled carbon nanotube (SWNT) papers were successfully prepared by dispersing SWNTs in Triton X-100 solution, then filtered by PVDF membrane (0.22 microm pore size). The electrochemical behavior and the reversible hydrogen storage capacity of single-walled carbon nanotube (SWNT) papers have been investigated in alkaline electrolytic solutions (6 N KOH) by cyclic voltammetry, linear micropolarization, and constant current charge/discharge measurements. The effect of thickness and the addition of carbon black on hydrogen adsorption/desorption were also investigated. It was found that the electrochemical charge-discharge mechanism occurring in SWNT paper electrodes is somewhere between that of carbon nanotubes (physical process) and that of metal hydride electrodes (chemical process), and consists of a charge-transfer reaction (Reduction/Oxidation) and a diffusion step (Diffusion).     

A carbon nanotube needle biosensor

A carbon nanotube needle biosensor was developed to provide fast, cost effective and highly sensitive electrochemical detection of biomolecules. The sensor was fabricated based on an array of aligned multi-wall carbon nanotubes synthesized by chemical vapor deposition. A bundle of nanotubes in the array was welded onto the tip of a tungsten needle under a microscope. The needle was then encased in glass and a polymer coating leaving only the tip of the needle exposed. Cyclic voltammetry was performed to examine the redox behavior of the nanotube needle. The cyclic voltammetry results showed a steady-state response attributable to radial diffusion with a high steady-state current density. An amperometric sensor was then developed for glucose detection by physically attaching glucose oxidase on the nanotube needle. The amperometric response of these nanotube needles showed a high sensitivity with a low detection limit. It is expected that the nanotube needle can be sharpened to increase the sensitivity to the point where the current is almost too small to measure. The simple manufacturing method should allow commodity level production of highly sensitive electronic biosensors.     

Carbon nanotube coating improves neuronal recordings

Implanting electrical devices in the nervous system to treat neural diseases is becoming very common. The success of these brain-machine interfaces depends on the electrodes that come into contact with the neural tissue. Here we show that conventional tungsten and stainless steel wire electrodes can be coated with carbon nanotubes using electrochemical techniques under ambient conditions. The carbon nanotube coating enhanced both recording and electrical stimulation of neurons in culture, rats and monkeys by decreasing the electrode impedance and increasing charge transfer. Carbon nanotube-coated electrodes are expected to improve current electrophysiological techniques and to facilitate the development of long-lasting brain-machine interface devices.     

Specific features of oxygen electroreduction on platinized carbon black-functionalized carbon nanotube composite

The electrochemical behavior of multiwalled carbon nanotubes (MWCNTs) containing functional surface groups has been studied by the methods of cyclic voltammetry and direct-current polarography with stationary and rotating disk electrodes. The surface catalytic activity of supported platinum in the reaction of molecular oxygen electroreduction and the influence of functionalized MWCNTs on this process were determined.     

High-performance carbon composite electrode based on an ionic liquid as a binder

Ionic liquid, n-octylpyridinum hexafluorophosphate (OPFP) has been used to fabricate a new carbon composite electrode with very attractive electrochemical behavior. This type of carbon electrode has been constructed using graphite mixed with OPFP as the binder. The electrode has combined advantages of edge plane characteristics of carbon nanotubes and edge plane pyrolytic graphite electrodes together with the low cost of carbon paste electrodes and robustness of metallic electrodes. It provides a remarkable increase in the rate of electron transfer of different organic and inorganic electroactive compounds and offers a marked decrease in the overvoltage for biomolecules such as NADH, dopamine, and ascorbic acid. It also circumvents NADH surface fouling effects as well as furnishing higher current density for a wide range of compounds tested. Depending on the choice of the electrolyte, the electrode can have the ion-exchange property and adsorptive characteristics of clay-modified electrodes. The proposed electrode thus allows sensitive, low-potential, simple, low-cost, and stable electrochemical sensing of biomolecules and other electroactive compounds. Scanning electron microscopy images indicate significant improvement in the microstructure of the proposed electrode compared to carbon paste electrodes. Such abilities promote new opportunities for a wide range of electrochemical and biosensing applications.     

Carbon composite microelectrodes fabricated by electrophoretic deposition

Single-walled carbon nanotubes were deposited on one end of the etched carbon fiber electrodes by an electrophoretic method. The carbon nanotube bundles formed a dense network on the carbon fiber surface. The electrochemical properties of the composite carbon electrodes were studied in the buffered neutral solutions. The results in cyclic voltammetry's characteristic indicate that the electrons on the electrodes transfer very fast. Furthermore, the redox reactions of dopamine (DA) on the composite electrodes show good sensitivity. When the DA concentration was 0.02 mM, the peak current in differential pulse technique reached 1.33 microA after performing the background subtraction. In addition, the simultaneous detection of DA and ascorbic acid (AA) showed that the interference effect was not observed. It was suggested that the carbon composite microelectrodes have potential applications as electrochemical sensors inside a single cell.     

Reproducible fabrication of robust, renewable vertically aligned multiwalled carbon nanotube/epoxy composite electrodes

We describe the reproducible fabrication of robust, vertically aligned multiwalled carbon nanotube (VACNT)/epoxy composite electrodes. The electrodes are characterized by cyclic voltammetry, impedance spectroscopy, and scanning electron and atomic force microscopies. Low background currents are obtained at the electrodes, and common redox probe molecules and NADH show excellent voltammetric behavior. When electrode performance deteriorates due to fouling, the electrode surfaces can be reproducibly renewed by mechanical polishing followed by O(2) plasma treatment. The electrochemical performance of the electrodes is maintained after more than 100 cycles of use and renewal.     

Carbon nanotubes grown on stainless steel to form plate and probe electrodes for chemical/biological sensing

This paper describes the fabrication and evaluation of carbon nanotube (CNT) electrodes grown on stainless steel (SS) plate and wire for electrochemical sensor applications. Multi-wall carbon nanotubes with different diameters were grown on the SS plate and wire by chemical vapor deposition from an ethylene precursor. The SS provides a good electrical and mechanical connection to the CNT, and the SS is a tough substrate. The SS part of the electrode was electrically insulated from the analyte so that only the CNT were active in sensing. Cyclic voltammetry for the reduction of 6 mM K3Fe(CN)6 in a 1.0 M KNO3 supporting electrolyte was performed to examine the redox behavior of the CNT-SS electrode. The cyclic voltammograms showed sigmoidal-like shapes, indicating that mass transport around the electrodes is dominated by radial diffusion. Based on the cyclic voltammograms, the effective area of the CNT-SS electrodes and the number of individual CNTs were estimated. These results indicate that the CNT-SS plate and wire electrodes are good candidates to develop practical in vivo biosensors.     

Polyisoprene-multi wall carbon nanotube composite structure for flexible pressure sensor application

The major problem of conventional rigid sensor materials is difficulty to integer them into soft flexible structures. Piezoresistive polyisoprene/nanostructured carbon composite appears as promising materials for such application. Previous research approved high structure carbon black and carbon nanotube filled composites as finger pressure sensitive piezoresistive materials. Carbon nanotubes originate with variable length to width ratio and high electric conductivity in longitudinal direction of the tubes, which theoretically should make it possible to obtain electric percolation in polymercarbon nanotube composites at very low loads of filler. However recent experience with mechanically dispersed carbon nanotubes shows quite high values of percolation threshold and specific sensing properties. In this work we present an attempt to use ultrasound for improved dispersion of the filler in a piezoresistive polyisoprene-multi wall carbon nanotube composite as well polyisoprene-high structure carbon black composite. The noticeable shift of percolation threshold for both types of composites have been achieved. The piezoresistive behavior of sonicated composites have been determined and compared with mechanically mixed ones. The differences have been evaluated and explained.     

Influence of raw carbon nanotubes diameter for the optimization of the load composition ratio in epoxy amperometric composite sensors

In this work, it is reported the necessity to characterize the raw carbon materials before their application in composite electrodes based on multiwall carbon nanotubes (MWCNTs) dispersed in epoxy resin for the development of improved amperometric sensors. These sensors must contain an optimum MWCNT/epoxy ratio for their best electroanalytical response. The main drawback in MWCNTs composite materials resides in the lack of homogeneity of the different commercial nanotubes largely due to different impurities content, as well as dispersion in their diameter/length ratio and state of aggregation. The optimal composite electrode composition takes into account the high electrode sensitivity, low limit of detection, fast response, and electroanalytical reproducibility. These features depend on carbon nanotube physical properties as the diameter. Three different commercial carbon nanotubes with different diameters were characterized by transmission electron microscopy and the results were significantly different from the ones provided by the manufacturers. Then, the three MWCNTs were used for the MWCNT/epoxy sensors construction. After an accurate electrochemical characterization by cyclic voltammetry and electrochemical impedance spectroscopy, they were employed as working electrodes using ascorbic acid as a reference analyte. Percolation theory was applied in order to verify the electrochemical results. It is demonstrated that the optimum interval load of raw carbon material in the optimized-composite electrodes closely depends on the MWCNTs diameter, needing 5 % in carbon content for the narrowest MWCNTs containing composite electrodes versus 12 % for the widest MWCNTs.     

Electrochemical impedance measurement of prostate cancer cells using carbon nanotube array electrodes in a microfluidic channel

Highly aligned multi-wall carbon nanotubes were synthesized in the shape of towers and embedded into fluidic channels as electrodes for impedance measurement of LNCaP human prostate cancer cells. Tower electrodes up to 8 mm high were grown and easily peeled off a silicon substrate. The nanotube electrodes were then successfully soldered onto patterned printed circuit boards and cast into epoxy under pressure. After polishing the top of the tower electrodes, RF plasma was used to enhance the electrocatalytic effect by removing excess epoxy and activating the open end of the nanotubes. Electrodeposition of Au particles on the plasma-treated tower electrodes was done at a controlled density. Finally, the nanotube electrodes were embedded into a polydimethylsiloxane (PDMS) channel and electrochemical impedance spectroscopy was carried out with different conditions. Preliminary electrochemical impedance spectroscopy results using deionized water, buffer solution, and LNCaP prostate cancer cells showed that nanotube electrodes can distinguish the different solutions and could be used in future cell-based biosensor development.     

Carbon nanotube fiber microelectrodes: design, characterization, and optimization

We report on the preparation and interesting electrochemical behavior of carbon nanotube fiber microelectrodes (CNTFM). By combining the advantages of carbon nanotubes (CNT) with those of fiber electrodes, this type of microelectrode differs from CNT modified or CNT containing composite electrodes, because it's made of only CNT without any other components like additives or binders. The active CNT surface is easily regenerated. The performance of CNTFMs has been characterized, among others, by surface modification with phosphomolybdic acid. It is shown that adsorption behavior of these catalyst molecules is highly improved with a controlled orientation of CNT. A better CNT alignment inside the fiber can be achieved by a hot stretching procedure.     

Electrochemical determination of pharmaceuticals in spiked water samples

The electrochemical behaviour of acidic and neutral pharmaceutical active compounds (PhACs) was studied by cyclic voltammetry and pulse voltammetric techniques on mercury, carbon nanotube paste, carbon paste and gold electrodes. The best results, in terms of sensitivity, linearity range and detection limits, were obtained by differential pulse voltammetry (DPV) for ofloxacin (LOD 5.2 microM), differential pulse polarography (DPP) for clofibric acid (LOD 4.7 microM) and normal pulse voltammetry (NPV) for diclofenac (LOD 0.8 microM) and propranolol (LOD 0.5 microM). An enrichment step of approximately two orders of magnitude was performed by a solid-phase extraction procedure (SPE) in order to concentrate the samples. The developed method was optimized and tested on spiked river water samples.     

Rapid, Sensitive Detection of Neurotransmitters at Microelectrodes Modified with Self-assembled SWCNT Forests

Carbon nanotube (CNT) modification of microelectrodes can result in increased sensitivity without compromising time response. However, dip coating CNTs is not very reproducible and the CNTs tend to lay flat on the electrode surface which limits access to the electroactive sites on the ends. In this study, aligned CNT forests were formed using a chemical self-assembly method, which resulted in more exposed CNT ends to the analyte. Shortened, carboxylic acid functionalized single-walled CNTs were assembled from a dimethylformamide (DMF) suspension onto a carbon-fiber disk microelectrode modified with a thin iron hydroxide-decorated Nafion film. The modified electrodes were highly sensitive, with 36-fold higher oxidation currents for dopamine using fast-scan cyclic voltammetry than bare electrodes and 34-fold more current than electrodes dipped in CNTs. The limit of detection (LOD) for dopamine was 17 ± 3 nM at a 10 Hz repetition rate and 65 ± 7 nM at 90 Hz. The LOD at 90 Hz was the same as a bare electrode at 10 Hz, allowing a 9-fold increase in temporal resolution without a decrease in sensitivity. Similar increases were observed for other cationic catecholamine neurotransmitters, and the increases in current were greater than for anionic interferents such as ascorbic acid and 3,4-dihydroxyphenylacetic acid (DOPAC). The CNT forest electrodes had high sensitivity at 90 Hz repetition rate when stimulated dopamine release was measured in Drosophila . The sensitivity, temporal resolution, and spatial resolution of these CNT forest modified disk electrodes facilitate enhanced electrochemical measurements of neurotransmitter release in vivo.     

Application of titanium oxide nanotube films containing gold nanoparticles for the electroanalytical determination of ascorbic acid

Au/TiO₂/Ti electrodes have been prepared by galvanic deposition of gold particles on TiO₂ nanotube substrates. Titanium oxide nanotubes are fabricated by anodizing titanium foil in a Dimethyl Sulfoxide electrolyte containing fluoride. The scanning electron microscopy results indicated that gold particles are homogeneously deposited on the surface of TiO₂ nanotubes. The TiO₂ layers consist of individual tubes of about 40-80 nm diameters. The electro-catalytic behavior of Au/TiO₂/Ti and flat gold electrodes for the ascorbic acid electro-oxidation was studied by cyclic voltammetry. The results showed that the flat gold electrode is not suitable for the oxidation of ascorbic acid. However, the Au/TiO₂/Ti electrodes are shown to possess catalytic activity toward the oxidation reaction. Catalytic oxidation peak current showed a linear dependence on the ascorbic acid concentration and a linear calibration curve is obtained in the concentration range of 1-5 mM of ascorbic acid. Also, determination of ascorbic acid in real samples was evaluated. The obtained results were found to be satisfactory. Finally the effects of interference on the detection of ascorbic acid were investigated.     

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.     

Arc process parameters for single-walled carbon nanotube growth and production: experiments and modeling

Collarets rich in single-walled carbon nanotubes (SWCNTs) have been grown using a direct current arc method. Arc process parameters such as current, pressure, and anode to cathode distance were varied experimentally and by modeling to provide an optimal working window. The best collaret yields were obtained when helium was used as a buffer gas. Mixing helium with argon in the buffer permits controlling nanotube diameters. In addition to an experimental study, a modeling approach was developed assuming local thermal equilibrium and homogenous and heterogeneous neutral chemistry. The gas-phase chemical model involves 81 neutral carbon species (C1, C2, . . ., C79, C60F, C70F) and 554 reactions with rates taken from data of Krestinin and Moravsky. Axial profiles of temperature, C atom, C2 radical, and fullerene distributions in the reactor are predicted as a function of process parameters. Carbon nanotube growth is considered by a set of surface reactions simulating open nanotube growth. Because nanotube surface chemistry is controlled by the local terminated bond and not by the bulk nanotube bond, a mechanistic approach based on the formal resemblance between the bonding and the structure of open nanotube and other carbon surfaces is proposed to explain nanotube growth. Predicted growth rates are in the range of 100 to 1000 microm/min.     

Field emission from a selected multiwall carbon nanotube

The electron field emission characteristics of individual multiwalled carbon nanotubes were investigated by a piezoelectric nanomanipulation system operating inside a scanning electron microscopy chamber. The experimental set-up ensures a precise evaluation of the geometric parameters (multiwalled carbon nanotube length and diameter and anode-cathode separation) of the field emission system. For several multiwalled carbon nanotubes, reproducible and quite stable emission current behaviour was obtained, with a dependence on the applied voltage well described by a series resistance modified Fowler-Nordheim model. A turn-on field of ～30?V?μm(-1) and a field enhancement factor of around 100 at a cathode-anode distance of the order of 1?μm were evaluated. Finally, the effect of selective electron beam irradiation on the nanotube field emission capabilities was extensively investigated.     

One-step fabrication of ordered Pt-Cu alloy nanotube arrays for ethanol electrooxidation

Novel one dimensional (1D) nanostructured metallic electrodes have received much attention in the area of the fuel cell because of their extremely high surface-to-volume ratios and excellent activities. Here, we report the one-step fabrication of Pt-Cu alloy nanotube arrays. As determined by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, ordered Pt-Cu alloy nanotubes have been successfully fabricated utilizing a nanochannel alumina template. The electrocatalytic activities of the Pt-Cu alloy nanotubes for the oxidation of ethanol in acidic medium were investigated by cyclic voltammetry. The results show that the Pt-Cu alloy nanotubes can be used as effective electrocatalysts for ethanol oxidation in direct alcohol fuel cells.     

Electrochemical biosensing based on polypyrrole/titania nanotube hybrid

The glucose oxidase (GOD) modified polypyrrole/titania nanotube enzyme electrode is fabricated for electrochemical biosensing application. The titania nanotube array is grown directly on a titanium substrate through an anodic oxidation process. A thin film of polypyrrole is coated onto titania nanotube array to form polypyrrole/titania nanotube hybrid through a normal pulse voltammetry process. GOD-polypyrrole/titania nanotube enzyme electrode is prepared by the covalent immobilization of GOD onto polypyrrole/titania nanotube hybrid via the cross-linker of glutaraldehyde. The morphology and microstructure of nanotube electrodes are characterized by field emission scanning electron microscopy and Fourier transform infrared analysis. The biosensing properties of this nanotube enzyme electrode have been investigated by means of cyclic voltammetry and chronoamperometry. The hydrophilic polypyrrole/titania nanotube hybrid provides highly accessible nanochannels for GOD encapsulation, presenting good enzymatic affinity. As-formed GOD-polypyrrole/titania nanotube enzyme electrode well conducts bioelectrocatalytic oxidation of glucose, exhibiting a good biosensing performance with a high sensitivity, low detection limit and wide linear detection range.