Journal Home > Volume 2 , Issue 3
Nano Research 2009, 2(3): 183-191 https://doi.org/10.1007/s12274-009-9016-9
Research Article | Open Access | Issue | Published: 08 March 2009

Separation of Metallic and Semiconducting Single-Walled Carbon Nanotubes Through Fluorous Chemistry

Show Author's Information Sandeep Ghosh1,2,  C. N. R. Rao1,2( )
Chemistry and Physics of Materials UnitDST unit on Nanoscience and CSIR Centre of Excellence in ChemistryJawaharlal Nehru Centre for Advanced Scientific ResearchJakkur P.O.Bangalore560064India
Solid State and Structural Chemistry UnitIndian Institute of ScienceBangalore560012India
Keywords:
Carbon nanotubes, separation, metallic, semiconducting, fluorous
Cite this article:
Ghosh S, Rao CNR. Separation of Metallic and Semiconducting Single-Walled Carbon Nanotubes Through Fluorous Chemistry. Nano Research, 2009, 2(3): 183-191. https://doi.org/10.1007/s12274-009-9016-9
Download citation
EndNote(RIS)
BibTeX

568

Views

8

Downloads

Citations

28

Crossref

N/A

WoS

33

Scopus

0

CSCD

Abstract Full text About this article

Separation of metallic from semiconducting single-walled carbon nanotubes has been a major challenge for some time and some previous efforts have resulted in partial success. We have accomplished the separation effectively by employing fluorous chemistry wherein the diazonium salt of 4-heptadecafluorooctylaniline selectively reacts with the metallic nanotubes present in the mixture of nanotubes. The resulting fluoroderivative was extracted in perfluorohexane leaving the semiconducting nanotubes in the aqueous layer. The products have been characterized by both Raman and electronic absorption spectroscopy. The method avoids the cumbersome centrifugation step required by some other procedures.


menu
Abstract
Full text
Outline
About this article

Separation of Metallic and Semiconducting Single-Walled Carbon Nanotubes Through Fluorous Chemistry

Show Author's information Sandeep Ghosh1,2, C. N. R. Rao1,2( )
Chemistry and Physics of Materials UnitDST unit on Nanoscience and CSIR Centre of Excellence in ChemistryJawaharlal Nehru Centre for Advanced Scientific ResearchJakkur P.O.Bangalore560064India
Solid State and Structural Chemistry UnitIndian Institute of ScienceBangalore560012India

Abstract

Separation of metallic from semiconducting single-walled carbon nanotubes has been a major challenge for some time and some previous efforts have resulted in partial success. We have accomplished the separation effectively by employing fluorous chemistry wherein the diazonium salt of 4-heptadecafluorooctylaniline selectively reacts with the metallic nanotubes present in the mixture of nanotubes. The resulting fluoroderivative was extracted in perfluorohexane leaving the semiconducting nanotubes in the aqueous layer. The products have been characterized by both Raman and electronic absorption spectroscopy. The method avoids the cumbersome centrifugation step required by some other procedures.

Keywords: Carbon nanotubes, separation, metallic, semiconducting, fluorous

References(43)

1

Saito, R.; Dresselhaus, G.; Dresselhaus, M. S. Physical Properties of Carbon Nanotubes; Imperial College Press: London, 1998.
DOI
2

Rao, C. N. R.; Govindaraj, A. Nanotubes and Nanowires; RSC Publishing: Cambridge, 2005.
DOI
3

Kukovecz, A.; Kramberger, C.; Georgakilas, V.; Prato, M.; Kuzmany, H. A. Detailed Raman study on thin single-wall carbon nanotubes prepared by the HiPCO process. Eur. Phys. J. B 2002, 28, 223–230.
DOI Google Scholar
4

Appenzeller, J.; Martel, R.; Derycke, V.; Radosavljevic, M.; Wind, S.; Neumayer, D.; Avouris, P. Carbon nanotubes as potential building blocks for future nanoelectronics. Microelectron. Eng. 2002, 64, 391–397.
DOI Google Scholar
5

Fan, S.; Chapline, M. G.; Franklin, N. R.; Tomber, T. W.; Cassell, A. M.; Dai, H. Self-oriented regular arrays of carbon nanotubes and their field emission properties. Science 1999, 283, 512–514.
DOI Google Scholar
6

Kong, J.; Franklin, N. R.; Zhou, C.; Chapline, M. G.; Peng, S.; Cho, K.; Dai, H. Nanotube molecular wires as chemical sensors. Science 2000, 287, 622–625.
DOI Google Scholar
7

Baughman, R. H.; Cui, C.; Zakhidov, A. A.; Iqbal, Z.; Barisci, J. N.; Spinks, G. M.; Wallace, G. G.; Mazoldi, A.; De Rossi, D.; Rinzler, A. G.; Jaschinski, O.; Roth, S.; Kertesz, M. Carbon nanotube actuators. Science 1999, 284, 1340–344.
DOI Google Scholar
8

Ajayan, P. M. Aligned carbon nanotubes in a thin polymer film. Adv. Mater. 1995, 7, 489–491.
DOI Google Scholar
9

Kamras, K.; Itkis, M. E.; Zhao, H.; Hu, B.; Haddon, R. C. Covalent bond formation to a carbon nanotube metal. Science 2003, 301, 1501.
DOI Google Scholar
10

Strano, M. S.; Dyke, C. A.; Usrey, M. L.; Barone, P. W.; Allen, M. J.; Shan, H.; Kitrell, C.; Hauge, R. H.; Tour, J. M.; Smalley, R. E. Electronic structure control of single-walled carbon nanotube functionalization. Science 2003, 301, 1519–1522.
DOI Google Scholar
11

Wang, Q.; Johnson, J. K. Optimization of carbon nanotube arrays for hydrogen adsorption. J. Phys. Chem. B 1999, 103, 4809–4813.
DOI Google Scholar
12

Gülseren, O.; Ylidirim, T.; Ciraci, S. Effects of hydrogen adsorption on single-wall carbon nanotubes: Metallic hydrogen decoration. Phys. Rev. B 2002, 66, 121401.
DOI Google Scholar
13

An, K. H.; Heo, J. G.; Jeon, K. G.; Bae, D. J.; Chulsu, J.; Yang, C. W.; Park, C. Y.; Lee, Y. H. X-ray photoemission spectroscopy study of fluorinated single-walled carbon nanotubes. Appl. Phys. Lett. 2002, 80, 4235–4237.
DOI Google Scholar
14

Krupke, R.; Hennrich, F.; von Lohneysen, H.; Kappes, M. M. Separation of metallic from semiconducting single-walled carbon nanotubes. Science 2003, 301, 344–347.
DOI Google Scholar
15

Chattopadhyay, D.; Galeska, L.; Papadimitrakopoulos, F. A route for bulk separation of semiconducting from metallic single-wall carbon nanotubes. J. Am. Chem. Soc. 2003, 125, 3370–3375.
DOI Google Scholar
16

Li, H. P.; Zhou, B.; Lin, Y.; Gu, L.; Wang, W.; Fernando, K. A. S.; Kumar, S.; Allard, L. F.; Sun, Y. Selective interactions of porphyrins with semiconducting single-walled carbon nanotubes. J. Am. Chem. Soc. 2004, 126, 1014–1015.
DOI Google Scholar
17

Chen, Z.; Du, X.; Du, M.; Rancken, C.; Cheng, H.; Rinzler, A. Bulk separative enrichment in metallic or semiconducting single-walled carbon nanotubes. Nano Lett. 2003, 3, 1245–1249.
DOI Google Scholar
18

Arnold, M. S.; Green, A. A.; Hulvat, J. F.; Stupp, S. I.; Hersam, M. C. Sorting carbon nanotubes by electronic structure using density differentiation. Nat. Nanotechnol. 2006, 1, 60–65.
DOI Google Scholar
19

Toyoda, S.; Yamaguchi, Y.; Hiwatashi, M.; Tomonari, Y.; Murakami, H.; Nakashima, N. Separation of semiconducting single-walled carbon nanotubes by using a long-alkyl-chain benzenediazonium compound. Chem. Asian J. 2007, 2, 145–149.
DOI Google Scholar
20

Zhang, W. Fluorous synthesis of heterocyclic systems. Chem. Rev. 2004, 104, 2531–2556.
DOI Google Scholar
21

Yoshida, J.; Itami, K. Tag strategy for separation and recovery. Chem. Rev. 2002, 102, 3693–3716.
DOI Google Scholar
22

Campidelli, S.; Menegheti, M.; Prato, M. Separation of metallic and semiconducting single-walled carbon nanotubes via covalent functionalization. Small 2007, 3, 1672–1676.
DOI Google Scholar
23

Bahr, J. L.; Tour, J. M. Covalent chemistry of single-wall carbon nanotubes. J. Mater. Chem. 2002, 12, 1952–1958.
DOI Google Scholar
24

Dyke, C. A.; Tour, J. M. Solvent-free functionalization of carbon nanotubes. J. Am. Chem. Soc. 2003, 125, 1156–1157.
DOI Google Scholar
25

Bahr, J. L.; Yang, J.; Kosynkin, D. V.; Bronikowski, M. J.; Smalley, R. E.; Tour, J. M. Functionalization of carbon nanotubes by electrochemical reduction of aryl diazonium salts: A bucky paper electrode. J. Am. Chem. Soc. 2001, 123, 6536–6542.
DOI Google Scholar
26

Kataura, H.; Kumazawa, Y.; Maniwa, Y.; Umezu, I.; Suzuki, S.; Ohtsuka, Y.; Achiba, Y. Optical properties of single-wall carbon nanotubes. Synth. Met. 1999, 103, 2555–2558.
DOI Google Scholar
27

Rao, A. M.; Richter, E.; Bandow, S.; Chase, B.; Eklund, P. C.; Williams, K. A.; Fang, S.; Subbaswamy, K. R.; Menon, M.; Thess, A.; Smalley, R. E.; Dresselhaus, G.; Dresselhaus, M. S. Diameter-selective Raman scattering from vibrational modes in carbon nanotubes. Science 1997, 275, 187–191.
DOI Google Scholar
28

Brown, S. D. M.; Corio, P.; Marucci, A.; Pimenta, M. A.; Dresselhaus, M. S.; Dresselhaus, G. Second-order resonant Raman spectra of single-walled carbon nanotubes. Phys. Rev. B 2000, 61, 7734–7742.
DOI Google Scholar
29

Brown, S. D. M.; Corio, P.; Marucci, A.; Dresselhaus, M. S.; Pimenta, M. A.; Kneipp, K. Anti-Stokes Raman spectra of single-walled carbon nanotubes. Phys. Rev. B 2000, 61, R5137–R5140.
DOI Google Scholar
30

Das, A.; Sood, A. K.; Govindaraj, A.; Marco Saitta, A.; Lazzeri, M.; Mauri, F.; Rao, C. N. R. Doping in carbon nanotubes probed by Raman and transport measurements. Phys. Rev. Lett. 2007, 99, 136803.
DOI Google Scholar
31

Scolari, M.; Mews, A.; Fu, N.; Myalitsin, A.; Assmus, T.; Balasubramanian, K.; Burghard, M.; Kern, K. Surface enhanced Raman scattering of carbon nanotubes decorated by individual fluorescent gold particles. J. Phys. Chem. C 2008, 112, 391–396.
DOI Google Scholar
32

Vivekchand, S. R. C.; Govindaraj, A.; Sheikh M. M.; Rao C. N. R. New method of purification of carbon nanotubes based on hydrogen treatment. J. Phys. Chem. B 2004, 108, 6935–6937.
DOI Google Scholar
33

O'Connell, M. J.; Bachilo, S. M.; Huffman, C. B.; Moore, V. C.; Strano, M. S.; Haroz, E. H.; Rialon, K. L.; Boul, P. J.; Noon, W. H.; Kittrell, C.; Ma, J.; Hauge, R. H.; Weisman, R. B.; Smalley, R. E. Band gap fluorescence from individual single-walled carbon nanotubes. Science 2002, 297, 593–596.
DOI Google Scholar
34

Yoshino, N.; Kitamura, M.; Seto, T.; Shibata, Y.; Abe, M.; Ogino, K. Synthesis of azobenzene derivatives having fluoroalkyl chain and their monomolecular film formation at the air/water interface. Bull. Chem. Soc. Jpn. 1992, 65, 2141–2144.
DOI Google Scholar
35

Fantini, C.; Jorio, A.; Souza, M.; Strano, M. S.; Dresselhaus, M. S.; Pimenta, M. A. Optical transition energies for carbon nanotubes from resonant Raman spectroscopy: Environment and temperature effects. Phys. Rev. Lett. 2004, 93, 147406.
DOI Google Scholar
36

Anderson, N.; Hartschuh, A.; Cronin, S.; Novotny, L. Nanoscale vibrational analysis of single-walled carbon nanotubes. J. Am. Chem. Soc. 2005, 127, 2533–2537.
DOI Google Scholar
37

Maeda, Y.; Takano, Y.; Sagara, A.; Hashimoto, M.; Kanda, M.; Kimura, S.; Lian, Y.; Nakahodo, T.; Tsuchiya, T.; Wakahara, T.; Akasaka, T.; Hasegawa, T.; Kazaoui, S.; Minami, N.; Lu, J.; Nagase, S. Simple purification and selective enrichment of metallic SWCNTs produced using the arc-discharge method. Carbon 2008, 46, 1563–1569.
DOI Google Scholar
38

Zhu, H. -W.; Jiang, B.; Xu, C. -L; Wu, D. -H. Synthesis of high quality single-walled carbon nanotube silks by the arc discharge technique. J. Phys. Chem. B 2003, 107, 6514–6518.
DOI Google Scholar
39

Tarasov, B. P.; Muradyan, V. E.; Shul'ga, Y. M.; Krinichnaya, E. P.; Kuyunko, N. S.; Efimov, O. N.; Obraztsova, E. D.; Schur, D. V.; Maehlen, J. P.; Yartys, V. A.; Lai, H. -J. Synthesis of carbon nanostructures by arc evaporation of graphite rods with Co–Ni and YNi2 catalysts. Carbon 2003, 41, 1357–1364.
DOI Google Scholar
40

Brown, S. D. M.; Jorio, A.; Corio, P.; Dresselhaus, M. S.; Dresselhaus, G.; Saito, R.; Kneipp, K. Origin of the Breit–Wigner–Fano lineshape of the tangential G-band feature of metallic carbon nanotubes. Phys. Rev. B 2001, 63, 155414.
DOI Google Scholar
41

Blackburn, J. L.; Engtrakul, C.; McDonald, T. J.; Dillon, A. C.; Heben, M. J. Effects of surfactant and boron doping on the BWF feature in the Raman spectrum of single-wall carbon nanotube aqueous dispersions. J. Phys. Chem. B 2006, 110, 25551–25558.
DOI Google Scholar
42

Shin, H. -J.; Kim, S. M.; Yoon, S. -M.; Benayad, A.; Kim, K. K.; Kim, S. J.; Park, H. K.; Choi, J. -Y.; Lee, Y. H. Tailoring electronic structures of carbon nanotubes by solvent with electron-donating and -withdrawing groups. J. Am. Chem. Soc. 2008, 130, 2062–2066.
DOI Google Scholar
43

Voggu, R.; Rout, C. S.; Franklin, A. D.; Fisher, J. S.; Rao, C. N. R. Extraordinary sensitivity of the electronic structure and properties of single-walled carbon nanotubes to molecular charge-transfer. J. Phys. Chem. C 2008, 112, 13053–13056.
DOI Google Scholar
Publication history
Copyright
Acknowledgements
Rights and permissions

Publication history

Received: 04 November 2008
Revised: 18 December 2008
Accepted: 18 December 2008
Published: 08 March 2009
Issue date: March 2009

Copyright

© Tsinghua University Press and Springer-Verlag 2009

Acknowledgements

Acknowledgements

The authors thank Ved Varun Agrawal for assistance with STM measurements.

Rights and permissions

Return