Towards an ultrasensitive method for the determination of metal impurities in carbon nanotubes.

Residual catalyst metal nanoparticles remain one of the major obstructions in the utilization of carbon nanotubes (CNTs) in many areas owing to their ability to participate in redox chemistry of biomarkers. Presented here is a comparative study of several techniques for quality control of carbon nanotubes in terms of metallic impurities, namely magnetic susceptibility, electron paramagnetic resonance, energy-dispersive X-ray spectrometry, X-ray photoelectron spectroscopy, and thermogravimetric analysis. It is found that the dc magnetic susceptibility is the most sensitive method such that the difference between two CNT samples that underwent slightly different treatments can be detected, whereas the two samples are indistinguishable by other techniques. Therefore, it is suggested that the most accurate statistical method for quality control of carbon nanotubes is dc magnetic susceptibility, which allows the detection of traces of magnetic metal impurities embedded in purified carbon nanotubes, whereas other methods may provide false "impurity-free" information.

[1]  Martin Pumera,et al.  Micro- and nanotechnology in electrochemical detection science. , 2007, Talanta.

[2]  T. Ichihashi,et al.  Single-shell carbon nanotubes of 1-nm diameter , 1993, Nature.

[3]  Darren J. Martin,et al.  THE BIOCOMPATIBILITY OF CARBON NANOTUBES , 2006 .

[4]  J. Fischer,et al.  Structure and electronic properties of potassium-doped single-wall carbon nanotubes , 2000 .

[5]  Hiroshi Ajiki,et al.  Magnetic Properties of Carbon Nanotubes , 1993 .

[6]  M. Itkis,et al.  SOLUTION-PHASE EPR STUDIES OF SINGLE-WALLED CARBON NANOTUBES , 1999 .

[7]  K. Stevenson,et al.  Influence of nitrogen doping on oxygen reduction electrocatalysis at carbon nanofiber electrodes. , 2005, The journal of physical chemistry. B.

[8]  H. Dai,et al.  Individual single-wall carbon nanotubes as quantum wires , 1997, Nature.

[9]  M. Monthioux,et al.  Carbon nanotube superconducting quantum interference device , 2006, Nature nanotechnology.

[10]  P. Li,et al.  Electron spin resonance studies of hydrogen adsorption on defect-induced carbon nanotubes , 2007 .

[11]  C N R Rao,et al.  The problem of purifying single-walled carbon nanotubes. , 2005, Small.

[12]  S. Iijima,et al.  Correlation between diamagnetic susceptibility and electron spin resonance feature for various multiwalled carbon nanotubes , 2007 .

[13]  R. Smalley,et al.  Magnetic Susceptibility of Molecular Carbon: Nanotubes and Fullerite , 1994, Science.

[14]  C. Banks,et al.  New electrodes for old: from carbon nanotubes to edge plane pyrolytic graphite. , 2006, The Analyst.

[15]  S. Iijima Helical microtubules of graphitic carbon , 1991, Nature.

[16]  Richard G Compton,et al.  Iron oxide particles are the active sites for hydrogen peroxide sensing at multiwalled carbon nanotube modified electrodes. , 2006, Nano letters.

[17]  Lu Novel magnetic properties of carbon nanotubes. , 1994, Physical review letters.

[18]  Charles M. Lieber,et al.  Nanowire-based biosensors. , 2006, Analytical chemistry.

[19]  M. Pumera,et al.  New materials for electrochemical sensing VI: Carbon nanotubes , 2005 .

[20]  K. Stevenson,et al.  Anomalous electrochemical dissolution and passivation of iron growth catalysts in carbon nanotubes. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[21]  P. Nikolaev,et al.  Protocol for the characterization of single-wall carbon nanotube material quality , 2004 .

[22]  F. Alvarez,et al.  Single chamber PVD/PECVD process for in situ control of the catalyst activity on carbon nanotubes growth , 2005 .

[23]  Liming Dai,et al.  DNA damage induced by multiwalled carbon nanotubes in mouse embryonic stem cells. , 2007, Nano letters.

[24]  C. Banks,et al.  Use of high-purity metal-catalyst-free multiwalled carbon nanotubes to avoid potential experimental misinterpretations. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[25]  D. Golberg,et al.  Paramagnetic defects in boron nitride nanostructures , 2005 .

[26]  H. Krug,et al.  Oops they did it again! Carbon nanotubes hoax scientists in viability assays. , 2006, Nano letters.

[27]  K. Shen,et al.  Electron spin resonance of carbon nanotubes under hydrogen adsorption , 2003 .

[28]  R. F. Jardim,et al.  Superparamagnetism and magnetic properties of Ni nanoparticles embedded in SiO 2 , 2002 .

[29]  S. Curran,et al.  Electron spin resonance and raman scattering spectroscopy of multi-walled carbon nanotubes: a function of acid treatment. , 2006, Journal of nanoscience and nanotechnology.

[30]  Joseph Wang,et al.  Comparison of the Electrochemical Reactivity of Electrodes Modified with Carbon Nanotubes from Different Sources , 2005 .

[31]  G. Rivas,et al.  Carbon nanotubes for electrochemical biosensing. , 2007, Talanta.

[32]  S. Garaj,et al.  Electronic properties of carbon nanohorns studied by ESR , 2000 .

[33]  Martin Pumera,et al.  Carbon nanotubes contain residual metal catalyst nanoparticles even after washing with nitric acid at elevated temperature because these metal nanoparticles are sheathed by several graphene sheets. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[34]  François Huaux,et al.  Respiratory toxicity of carbon nanotubes: How worried should we be? , 2006 .

[35]  J. Suh,et al.  Catalyst free synthesis of high-purity carbon nanotubes by thermal plasma jet , 2005 .

[36]  F. Papadimitrakopoulos,et al.  Complete elimination of metal catalysts from single wall carbon nanotubes , 2002 .

[37]  J. Ketterson,et al.  Magnetic susceptibility of buckytubes , 1994 .

[38]  M. S. de Vries,et al.  Cobalt-catalysed growth of carbon nanotubes with single-atomic-layer walls , 1993, Nature.

[39]  K. Morokuma,et al.  Theory and experiment agree: single-walled carbon nanotube caps grow catalyst-free with chirality preference on a SiC surface. , 2006, The Journal of chemical physics.

[40]  R. Compton,et al.  Apparent 'electrocatalytic' activity of multiwalled carbon nanotubes in the detection of the anaesthetic halothane: occluded copper nanoparticles. , 2006, The Analyst.

[41]  P. Hendriksen,et al.  Magnetization and Mössbauer studies of ultrafine Fe-C particles , 1993 .

[42]  Sandip Niyogi,et al.  Comparison of analytical techniques for purity evaluation of single-walled carbon nanotubes. , 2005, Journal of the American Chemical Society.

[43]  J. Salvetat,et al.  MODIFICATION OF MULTIWALL CARBON NANOTUBES BY ELECTRON IRRADIATION : AN ESR STUDY , 1999 .

[44]  T. Xia,et al.  Toxic Potential of Materials at the Nanolevel , 2006, Science.

[45]  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.

[46]  H. Lezec,et al.  Electrical conductivity of individual carbon nanotubes , 1996, Nature.

[47]  J. C. Tsang,et al.  Electrically Induced Optical Emission from a Carbon Nanotube FET , 2003, Science.

[48]  K. Dinse,et al.  EPR characterization of catalyst‐free SWNT and N@C60‐based peapods , 2006 .

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