The effects of the lengths and orientations of single-walled carbon nanotubes on the electrochemistry of nanotube-modified electrodes

The influence of both nanotube orientation and length on the electrochemical properties of electrodes modified with single-walled carbon nanotubes was investigated. Gold electrodes were modified with either randomly dispersed or vertically aligned nanotubes to which ferrocenemethylamine was attached. Electron transfer kinetics were found to depend strongly on the orientation of the nanotube, with electron transfer between the gold electrode and the ferrocene moiety being 40 times slower through randomly dispersed nanotubes than through vertically aligned nanotubes. The difference is hypothesized to be due to electron transfer being more direct through a single tube than that with electrodes modified with randomly dispersed nanotubes. With the vertically aligned nanotubes the rate constant for electron transfer varied inversely with the mean length of the nanotubes. The results indicate there is an advantage in using aligned carbon nanotube arrays over randomly dispersed nanotubes for achieving efficient electron transfer to bound redox active species such as in the case of bioelectronic or photovoltaic devices.

[1]  R. R. Moore,et al.  Basal plane pyrolytic graphite modified electrodes: comparison of carbon nanotubes and graphite powder as electrocatalysts. , 2004, Analytical chemistry.

[2]  A. Mau,et al.  PATTERNED GROWTH OF WELL-ALIGNED CARBON NANOTUBES : A PHOTOLITHOGRAPHIC APPROACH , 1999 .

[3]  C. Chidsey,et al.  Chemical functionality in self-assembled monolayers: structural and electrochemical properties , 1990 .

[4]  Carolyn R. Bertozzi,et al.  Coadsorption of ferrocene-terminated and unsubstituted alkanethiols on gold: electroactive self-assembled monolayers , 1990 .

[5]  Harry O. Finklea,et al.  Electron-transfer kinetics in organized thiol monolayers with attached pentaammine(pyridine)ruthenium redox centers , 1992 .

[6]  M. Meyyappan,et al.  Ultrasensitive label-free DNA analysis using an electronic chip based on carbon nanotube nanoelectrode arrays , 2003, Nanotechnology.

[7]  James F. Rusling,et al.  Peroxidase activity of enzymes bound to the ends of single-wall carbon nanotube forest electrodes , 2003 .

[8]  Pulickel M. Ajayan,et al.  Carbon nanotube electrode for oxidation of dopamine , 1996 .

[9]  Yuehe Lin,et al.  Solubilization of carbon nanotubes by Nafion toward the preparation of amperometric biosensors. , 2003, Journal of the American Chemical Society.

[10]  J. Justin Gooding,et al.  Nanostructuring electrodes with carbon nanotubes: A review on electrochemistry and applications for sensing , 2005 .

[11]  R. Murray,et al.  Chemically modified electrodes: Part XIV. Attachment of reagents to oxide-free glassy carbon surfaces. Electroactive RF polymer films on carbon and platinum electrodes , 1978 .

[12]  Wei‐De Zhang,et al.  Direct Electron Transfer of Glucose Oxidase Molecules Adsorbed onto Carbon Nanotube Powder Microelectrode , 2002, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[13]  Mei Gao,et al.  Biosensors Based on Aligned Carbon Nanotubes Coated with Inherently Conducting Polymers , 2003 .

[14]  J. C. Hoogvliet,et al.  Electrochemical pretreatment of polycrystalline gold electrodes to produce a reproducible surface roughness for self-assembly: a study in phosphate buffer pH 7.4 , 2000, Analytical chemistry.

[15]  Z. Gu,et al.  Investigation of the electrochemical and electrocatalytic behavior of single-wall carbon nanotube film on a glassy carbon electrode. , 2001, Analytical chemistry.

[16]  J. Justin Gooding,et al.  Achieving Direct Electrical Connection to Glucose Oxidase Using Aligned Single Walled Carbon Nanotube Arrays , 2005 .

[17]  Ray H. Baughman,et al.  Direct electron transfer of glucose oxidase on carbon nanotubes , 2002 .

[18]  Joseph Wang,et al.  Carbon nanotube/teflon composite electrochemical sensors and biosensors. , 2003, Analytical chemistry.

[19]  Itamar Willner,et al.  Long-range electrical contacting of redox enzymes by SWCNT connectors. , 2004, Angewandte Chemie.

[20]  Zhongfan Liu,et al.  Chemical Alignment of Oxidatively Shortened Single-Walled Carbon Nanotubes on Silver Surface , 2001 .

[21]  A. Bard,et al.  A Stable Surface Modified Platinum Electrode Prepared by Coating with Electroactive Polymer , 1978 .

[22]  E. Laviron General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems , 1979 .

[23]  Dusan Losic,et al.  Protein electrochemistry using aligned carbon nanotube arrays. , 2003, Journal of the American Chemical Society.

[24]  Jun Li,et al.  Novel Three-Dimensional Electrodes: Electrochemical Properties of Carbon Nanotube Ensembles , 2002 .

[25]  H. Kraatz Synthesis and electrochemistry of ferrocenemethylamine and its conjugated acid. Crystal structure of ferrocenemethylammonium chloride , 1999 .

[26]  H. Finklea,et al.  Electrolyte and temperature effects on long range electron transfer across self-assembled monolayers , 1993 .

[27]  R. Murray,et al.  Consequences of Kinetic Dispersion on the Electrochemistry of an Adsorbed Redox-Active Monolayer , 1995 .

[28]  Richard G Compton,et al.  Carbon nanotubes contain metal impurities which are responsible for the "electrocatalysis" seen at some nanotube-modified electrodes. , 2006, Angewandte Chemie.

[29]  J. Gooding,et al.  Heterogeneous Electron-Transfer Kinetics for Flavin Adenine Dinucleotide and Ferrocene through Alkanethiol Mixed Monolayers on Gold Electrodes , 2004 .

[30]  Joseph Wang Carbon‐Nanotube Based Electrochemical Biosensors: A Review , 2005 .

[31]  A. M. Fennimore,et al.  Rotational actuators based on carbon nanotubes , 2003, Nature.

[32]  N. Wu,et al.  The study of the attachment of a single-walled carbon nanotube to a self-assembled monolayer using X-ray photoelectron spectroscopy , 2000 .

[33]  Zhennan Gu,et al.  Investigation of the electrocatalytic behavior of single-wall carbon nanotube films on an Au electrode , 2002 .

[34]  Zhennan Gu,et al.  Organizing Single-Walled Carbon Nanotubes on Gold Using a Wet Chemical Self-Assembling Technique , 2000 .

[35]  D. B. Hibbert,et al.  Parameters important in tuning the response of monolayer enzyme electrodes fabricated using self-assembled monolayers of alkanethiols. , 2000, Biosensors & bioelectronics.

[36]  Tianshu Zhou,et al.  Study of carbon nanotubes-HRP modified electrode and its application for novel on-line biosensors. , 2003, The Analyst.

[37]  Robert H. Hauge,et al.  Purification and Characterization of Single-Wall Carbon Nanotubes (SWNTs) Obtained from the Gas-Phase Decomposition of CO (HiPco Process) , 2001 .

[38]  Jun Li,et al.  The fabrication and electrochemical characterization of carbon nanotube nanoelectrode arrays , 2004 .

[39]  A. Rinzler,et al.  Carbon nanotube actuators , 1999, Science.

[40]  Federica Valentini,et al.  Carbon nanotube purification: preparation and characterization of carbon nanotube paste electrodes. , 2003, Analytical chemistry.

[41]  N. Chaniotakis,et al.  Carbon nanotube array-based biosensor , 2003, Analytical and bioanalytical chemistry.

[42]  R. Smalley,et al.  Oxygen-containing functional groups on single-wall carbon nanotubes: NEXAFS and vibrational spectroscopic studies. , 2001, Journal of the American Chemical Society.

[43]  Mei Gao,et al.  Aligned Coaxial Nanowires of Carbon Nanotubes Sheathed with Conducting Polymers , 2000 .

[44]  R. Murray,et al.  Chemically modified electrodes: Part XXII. Solvent effects on the electrochemistry of thin films of plasma polymerized vinylferrocene , 1979 .