Covalent Sidewall Functionalization of SWNTs by Nucleophilic Addition of Lithium Amides
Zois Syrgiannis
Department of Chemistry and Pharmacy and Central Institute of Advanced Materials and Processes (ZMP), University of Erlangen-Nürnberg, 91054 Erlangen, Germany, Fax: + 49-9131-8526864
Search for more papers by this authorFrank Hauke
Department of Chemistry and Pharmacy and Central Institute of Advanced Materials and Processes (ZMP), University of Erlangen-Nürnberg, 91054 Erlangen, Germany, Fax: + 49-9131-8526864
Search for more papers by this authorJonas Röhrl
Technische Physik, University of Erlangen-Nürnberg, 91058 Erlangen, Germany
Search for more papers by this authorMartin Hundhausen
Technische Physik, University of Erlangen-Nürnberg, 91058 Erlangen, Germany
Search for more papers by this authorRalf Graupner
Technische Physik, University of Erlangen-Nürnberg, 91058 Erlangen, Germany
Search for more papers by this authorYiannis Elemes
Department of Chemistry, University of Ioannina, Dourouti, 45110 Ioannina, Greece
Search for more papers by this authorAndreas Hirsch
Department of Chemistry and Pharmacy and Central Institute of Advanced Materials and Processes (ZMP), University of Erlangen-Nürnberg, 91054 Erlangen, Germany, Fax: + 49-9131-8526864
Search for more papers by this authorZois Syrgiannis
Department of Chemistry and Pharmacy and Central Institute of Advanced Materials and Processes (ZMP), University of Erlangen-Nürnberg, 91054 Erlangen, Germany, Fax: + 49-9131-8526864
Search for more papers by this authorFrank Hauke
Department of Chemistry and Pharmacy and Central Institute of Advanced Materials and Processes (ZMP), University of Erlangen-Nürnberg, 91054 Erlangen, Germany, Fax: + 49-9131-8526864
Search for more papers by this authorJonas Röhrl
Technische Physik, University of Erlangen-Nürnberg, 91058 Erlangen, Germany
Search for more papers by this authorMartin Hundhausen
Technische Physik, University of Erlangen-Nürnberg, 91058 Erlangen, Germany
Search for more papers by this authorRalf Graupner
Technische Physik, University of Erlangen-Nürnberg, 91058 Erlangen, Germany
Search for more papers by this authorYiannis Elemes
Department of Chemistry, University of Ioannina, Dourouti, 45110 Ioannina, Greece
Search for more papers by this authorAndreas Hirsch
Department of Chemistry and Pharmacy and Central Institute of Advanced Materials and Processes (ZMP), University of Erlangen-Nürnberg, 91054 Erlangen, Germany, Fax: + 49-9131-8526864
Search for more papers by this authorGraphical Abstract
The synthesis and characterization of sidewall amino-functionalized single-walled carbon nanotube derivatives (nPrNH)n-SWNTs is reported. The nucleophilic addition of in situ generated lithium n-propylamide to the sidewall of SWNTs and the subsequent reoxidation of charged intermediates of the type (nPrNH)n-SWNTn– leads to carbon nanotube derivatives with covalently attached amino groups.
Abstract
The synthesis and characterization of sidewall-functionalized SWNT derivatives (nPrNH)n-SWNTs containing n-propylamine addends is reported. The nucleophilic addition of in situ generated lithium n-propylamide to the sidewall of SWNTs and the subsequent reoxidation of charged intermediates of the type (nPrNH)n-SWNTn– leads to carbon nanotube derivatives with covalently attached amino groups. Based on the reaction sequence, a homogeneous dispersion of the carbon nanotube material is achieved as a result of the electrostatic repulsion of negatively charged intermediates. The solubility of the resulting propylamine-functionalized (nPrNH)n-SWNT material in organic solvents is drastically increased. The functionalized tubes were characterized in detail by Raman spectroscopy, thermogravimetric analysis (TGA/MS), X-ray photoelectron spectroscopy (XPS) and UV/Vis/NIR spectroscopy. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
References
- 1
- 1a S. Iijima , T. Ichihashi , Nature 1993 , 363 , 603 –605 .
- 1b D. S. Bethune , C. H. Kiang , M. S. de Vries , G. Gorman , R. Savoy , J. Vazquez , R. Beyers , Nature 1993 , 363 , 605 –607 .
- 2
- 2a C. Journet , W. K. Maser , P. Bernier , A. Loiseau , M. Lamy de la Chapells , S. Lefrant , P. Deniard , R. Lee , J. E. Fischer , Nature 1997 , 388 , 756 –758 .
- 2b P. Nikolaev , M. J. Bronikowski , R. K. Bradley , F. Rohmund , D. T. Colbert , K. A. Smith , R. E. Smalley , Chem. Phys. Lett. 1999 , 313 , 91 –97 .
- 3
- 3a W. A. de Heer , A. Chatelain , D. Ugarte , Science 1995 , 270 , 1179 –1180 .
- 3b M. M. J. Treacy, T. W. Ebbesen , J. M. Gibson , Nature 1996 , 381 , 678 –680 .
- 3c E. W. Wong , P. E. Sheehan , C. M. Lieber , Science 1997 , 277 , 1971 –1975 .
- 3d S. Frank , P. Poncharal , Z. L. Wang , W. A. de Heer , Science 1998 , 280 , 1744 –1746 .
- 3e J. Hu , T. W. Odom , C. M. Lieber , Acc. Chem. Res. 1999 , 32 , 435 –445 .
- 3f M.-F. Yu , B. S. Files , S. Arepalli , R. S. Ruoff , Phys. Rev. Lett. 2000 , 84 , 5552 –5555 .
- 3g S. Reich , C. Thomsen , J. Maultzsch , Carbon Nanotubes, Wiley-VCH, Weinheim, 2004 .
- 4
- 4a P. Avouris , Acc. Chem. Res. 2002 , 35 , 1026 –1034 .
- 4b R. H. Baughman , A. A. Zakhidov , W. A. de Heer , Science 2002 , 297 , 787 –792 .
- 4c M. Ouyang , J.-L. Huang , C. M. Lieber , Acc. Chem. Res. 2002 , 35 , 1018 –1025 .
- 4d
K. Tanaka
, T. Yamabe
, K. Fukui (Eds.), The Science and Technology of Carbon Nanotubes, Elsevier, Oxford, 1999
.
10.1016/B978-008042696-9/50005-7 Google Scholar
- 4e
M. S. Dresselhaus
, G. Dresselhaus
, P. Avouris (Eds.), Carbon Nanotubes: Synthesis, Structure, Properties, and Applications, Springer, Berlin, 2001
.
10.1007/3-540-39947-X Google Scholar
- 4f
S. V. Rotkin
, S. Subramoney (Eds.), Applied Physics of Carbon Nanotubes: Fundamentals of Theory, Optics and Transport Devices, Springer, Berlin, 2005
.
10.1007/3-540-28075-8 Google Scholar
- 5 J. Chen , M. A. Hamon , H. Hu , Y. Chen , A. M. Rao , P. C. Eklund , R. C. Haddon , Science 1998 , 282 , 95 –98 .
- 6
- 6a C. A. Dyke , J. M. Tour , Chem. Eur. J. 2004 , 10 , 812 –817 .
- 6b C. A. Dyke , J. M. Tour , J. Phys. Chem. A 2004 , 108 , 11151 –11159 .
- 7
- 7a A. Hirsch , O. Vostrowsky in Functional Organic Materials (Eds.: T. J. J. Müller , U. H. F. Bunz) , Wiley-VCH, Weinheim, 2007 , pp. 1–57.
- 7b D. Tasis , N. Tagmatarchis , A. Bianco , M. Prato , Chem. Rev. 2006 , 106 , 1105 –1136 .
- 7c A. Hirsch , O. Vostrowsky , Top. Curr. Chem. 2005 , 245 , 193 –237 .
- 7d S. Banerjee , T. Hemraj-Benny , S. S. Wong , Adv. Mater. 2005 , 17 , 17 –29 .
- 7e S. Banerjee , G. C. Kahn Michael , S. S. Wong , Chem. Eur. J. 2003 , 9 , 1898 –1908 . S. Banerjee , G. C. Kahn Michael , S. S. Wong , Chem. Eur. J. 2003 , 9 , 1898 –1908 .
- 7f T. Lin , V. Bajpai , T. Ji , L. Dai , Aust. J. Chem. 2003 , 56 , 635 –651 .
- 7g S. Niyogi , M. A. Hamon , H. Hu , B. Zhao , P. Bhowmik , R. Sen , M. E. Itkis , R. C. Haddon , Acc. Chem. Res. 2002 , 35 , 1105 –1113 .
- 7h
A. Hirsch
, Angew. Chem. Int. Ed.
2002
, 41
, 1853
–1859
.
10.1002/1521-3773(20020603)41:11<1853::AID-ANIE1853>3.0.CO;2-N CASPubMedWeb of Science®Google Scholar
- 7i J. L. Bahr , J. M. Tour , J. Mater. Chem. 2002 , 12 , 1952 –1958 .
- 7j Y.-P. Sun , K. Fu , Y. Lin , W. Huang , Acc. Chem. Res. 2002 , 35 , 1096 –1104 .
- 8
- 8a Z. Chen , W. Thiel , A. Hirsch , ChemPhysChem 2003 , 4 , 93 –97 .
- 8b E. Joselevich , ChemPhysChem 2004 , 5 , 619 –624 .
- 9
- 9a A. Hamwi , H. Alvergnat , S. Bonnamy , F. Beguin , Carbon 1997 , 35 , 723 –728 .
- 9b E. T. Mickelson , C. B. Huffman , A. G. Rinzler , R. E. Smalley , R. H. Hauge , J. L. Margrave , Chem. Phys. Lett. 1998 , 296 , 188 –194 .
- 9c H. Touhara , F. Okino , Carbon 2000 , 38 , 241 –267 .
- 10
- 10a V. Georgakilas , K. Kordatos , M. Prato , D. M. Guldi , M. Holzinger , A. Hirsch , J. Am. Chem. Soc. 2002 , 124 , 760 –761 .
- 10b M. Melle-Franco , M. Marcaccio , D. Paolucci , F. Paolucci , V. Georgakilas , D. M. Guldi , M. Prato , F. Zerbetto , J. Am. Chem. Soc. 2004 , 126 , 1646 –1647 .
- 10c N. Tagmatarchis , M. Prato , J. Mater. Chem. 2004 , 14 , 437 –439 .
- 11
- 11a J. L. Bahr , J. Yang , D. V. Kosynkin , M. J. Bronikowski , R. E. Smalley , J. M. Tour , J. Am. Chem. Soc. 2001 , 123 , 6536 –6542 .
- 11b J. L. Bahr , J. M. Tour , Chem. Mater. 2001 , 13 , 3823 –3824 .
- 11c M. S. Strano , C. A. Dyke , M. L. Usrey , P. W. Barone , M. J. Allen , H. Shan , C. Kittrell , R. H. Hauge , J. M. Tour , R. E. Smalley , Science 2003 , 301 , 1519 –1522 .
- 11d J. J. Stephenson , J. L. Hudson , S. Azad , J. M. Tour , Chem. Mater. 2006 , 18 , 374 –377 .
- 12
- 12a
M. Holzinger
, O. Vostrowsky
, A. Hirsch
, F. Hennrich
, M. Kappes
, R. Weiss
, F. Jellen
, Angew. Chem. Int. Ed.
2001
, 40
, 4002
–4005
.
10.1002/1521-3773(20011105)40:21<4002::AID-ANIE4002>3.0.CO;2-8 CASPubMedWeb of Science®Google Scholar
- 12b H. Peng , P. Reverdy , V. N. Khabashesku , J. L. Margrave , Chem. Commun. 2003 , 362 –363 .
- 12c P. Umek , J. W. Seo , K. Hernadi , A. Mrzel , P. Pechy , D. D. Mihailovic , L. Forro , Chem. Mater. 2003 , 15 , 4751 –4755 .
- 12d Y. Ying , R. K. Saini , F. Liang , A. K. Sadana , W. E. Billups , Org. Lett. 2003 , 5 , 1471 –1473 .
- 12e H. Peng , L. B. Alemany , J. L. Margrave , V. N. Khabashesku , J. Am. Chem. Soc. 2003 , 125 , 15174 –15182 .
- 12f T. Nakamura , M. Ishihara , T. Ohana , A. Tanaka , Y. Koga , Chem. Commun. 2004 , 1336 –1337 .
- 13
- 13a Y. Chen , R. C. Haddon , S. Fang , A. M. Rao , P. C. Eklund , W. H. Lee , E. C. Dickey , E. A. Grulke , J. C. Pendergrass , A. Chavan , B. E. Haley , R. E. Smalley , J. Mater. Res. 1998 , 13 , 2423 –2431 .
- 13b J. Chen , M. A. Hamon , H. Hu , Y. Chen , A. M. Rao , P. C. Eklund , R. C. Haddon , Science 1998 , 282 , 95 –98 .
- 13c H. Hu , B. Zhao , M. A. Hamon , K. Kamaras , M. E. Itkis , R. C. Haddon , J. Am. Chem. Soc. 2003 , 125 , 14893 –14900 .
- 13d K. Kamaras , M. E. Itkis , H. Hu , B. Zhao , R. C. Haddon , Science 2003 , 301 , 1501 .
- 14
- 14a M. Holzinger , J. Abraham , P. Whelan , R. Graupner , L. Ley , F. Hennrich , M. Kappes , A. Hirsch , J. Am. Chem. Soc. 2003 , 125 , 8566 –8580 .
- 14b Z. Yinghuai , A. T. Peng , K. Carpenter , J. A. Maguire , N. S. Hosmane , M. Takagaki , J. Am. Chem. Soc. 2005 , 127 , 9875 –9880 .
- 15
- 15a F. Liang , A. K. Sadana , A. Peera , J. Chattopadhyay , Z. Gu , R. H. Hauge , W. E. Billups , Nano Lett. 2004 , 4 , 1257 –1260 .
- 15b F. Liang , L. B. Alemany , J. M. Beach , W. E. Billups , J. Am. Chem. Soc. 2005 , 127 , 13941 –13948 .
- 15c J. J. Stephenson , A. K. Sadana , A. L. Higginbotham , J. M. Tour , Chem. Mater. 2006 , 18 , 4658 –4661 .
- 15d J. Chattopadhyay , F. de Cortez , S. Chakraborty , N. K. H. Slater , W. E. Billups , Chem. Mater. 2006 , 18 , 5864 –5868 .
- 15e
W. E. Billups
, F. Liang
, J. Chattopadhyay
, J. M. Beach
, ECS Trans.
2007
, 2
, 65
–76
.
10.1149/1.2408953 Google Scholar
- 15f D. Wunderlich, F. Hauke, A. Hirsch, J. Mater. Chem. 2008, DOI: 10.1039/b716732f.
- 16
- 16a G. Viswanathan , N. Chakrapani , H. Yang , B. Wei , H. Chung , K. Cho , Y. Ryu Chang , M. Ajayan Pulickel , J. Am. Chem. Soc. 2003 , 125 , 9258 –9259 .
- 16b R. Blake , Y. K. Gun'ko , J. Coleman , M. Cadek , A. Fonseca , J. B. Nagy , W. J. Blau , J. Am. Chem. Soc. 2004 , 126 , 10226 –10227 .
- 16c S. Chen , W. Shen , G. Wu , D. Chen , M. Jiang , Chem. Phys. Lett. 2005 , 402 , 312 –317 .
- 16d R. Graupner , J. Abraham , D. Wunderlich , A. Vencelova , P. Lauffer , J. Roehrl , M. Hundhausen , L. Ley , A. Hirsch , J. Am. Chem. Soc. 2006 , 128 , 6683 –6689 .
- 16e D. Wunderlich, F. Hauke, A. Hirsch, Chem. Eur. J., DOI: 10.1002/chem.200701038.
- 17
- 17a M. A. Hamon , J. Chen , H. Hu , Y. Chen , M. E. Itkis , A. M. Rao , P. C. Eklund , R. C. Haddon , Adv. Mater. 1999 , 11 , 834 –840 .
- 17b E. V. Basiuk , V. A. Basiuk , J.-G. Banuelos , J.-M. Saniger-Blesa , V. A. Pokrovskiy , T. Y. Gromovoy , A. V. Mischanchuk , B. G. Mischanchuk , J. Phys. Chem. B 2002 , 106 , 1588 –1597 .
- 17c G. Gabriel , G. Sauthier , J. Fraxedas , M. Moreno-Manas , M. T. Martinez , C. Miravitlles , J. Casabo , Carbon 2006 , 44 , 1891 –1897 .
- 18
- 18a D. Chattopadhyay , I. Galeska , F. Papadimitrakopoulos , J. Am. Chem. Soc. 2003 , 125 , 3370 –3375 .
- 18b Y. Maeda , S. Kimura , M. Kanda , Y. Hirashima , T. Hasegawa , T. Wakahara , Y. Lian , T. Nakahodo , T. Tsuchiya , T. Akasaka , J. Lu , X. Zhang , Z. Gao , Y. Yu , S. Nagase , S. Kazaoui , N. Minami , T. Shimizu , H. Tokumoto , R. Saito , J. Am. Chem. Soc. 2005 , 127 , 10287 –10290 .
- 18c Y. Maeda , M. Kanda , M. Hashimoto , T. Hasegawa , S.-I. Kimura , Y. Lian , T. Wakahara , T. Akasaka , S. Kazaoui , N. Minami , T. Okazaki , Y. Hayamizu , K. Hata , J. Lu , S. Nagase , J. Am. Chem. Soc. 2006 , 128 , 12239 –12242 .
- 18d J. Chen , A. M. Rao , S. Lyuksyutov , M. E. Itkis , M. A. Hamon , H. Hu , R. W. Cohn , P. C. Eklund , D. T. Colbert , R. E. Smalley , R. C. Haddon , J. Phys. Chem. B 2001 , 105 , 2525 –2528 .
- 19 J. L. Stevens , A. Y. Huang , H. Peng , I. W. Chiang , V. N. Khabashesku , J. L. Margrave , Nano Lett. 2003 , 3 , 331 –336 .
- 20 E. V. Basiuk , M. Monroy-Pelaez , I. Puente-Lee , V. A. Basiuk , Nano Lett. 2004 , 4 , 863 –866 .
- 21 A. Thess , R. Lee , P. Nikolaev , H. Dai , P. Petit , J. Robert , C. Xu , Y. H. Lee , S. G. Kim , A. G. Rinzler , D. T. Colbert , G. E. Scuseria , D. Tománek , J. E. Fischer , R. E. Smalley , Science 1996 , 273 , 483 –487 .
- 22
- 22a M. J. O'Connell , S. M. Bachilo , C. B. Huffman , V. C. Moore , M. S. Strano , E. H. Haroz , K. L. Rialon , P. J. Boul , W. H. Noon , C. Kittrell , J. Ma , R. H. Hauge , R. B. Weisman , R. E. Smalley , Science 2002 , 297 , 593 –596 .
- 22b C. A. Dyke , J. M. Tour , Nano Lett. 2003 , 3 , 1215 –1218 .
- 22c V. C. Moore , M. S. Strano , E. H. Haroz , R. H. Hauge , R. E. Smalley , J. Schmidt , Y. Talmon , Nano Lett. 2003 , 3 , 1379 –1382 .
- 23 G. Beamson , D. Briggs (Eds.), High resolution XPS on organic polymers, Wiley, Chichester, 1992 .
- 24 R. J. J. Jansen , H. van Bekkum , Carbon 1995 , 33 , 1021 –1027 .
- 25
- 25a M. S. Dresselhaus , G. Dresselhaus , A. Jorio , A. G. Souza Filho , M. A. Pimenta , R. Saito , Acc. Chem. Res. 2002 , 35 , 1070 –1078 .
- 25b M. S. Dresselhaus , G. Dresselhaus , R. Saito , A. Jorio , Phys. Rep. 2005 , 409 , 47 –99 .
- 25c R. Graupner , J. Raman Spectrosc. 2007 , 38 , 673 –683 .
- 25d M. Müller , J. Maultzsch , D. Wunderlich , A. Hirsch , C. Thomsen , Phys. Stat. Sol B 2007 , 244 , 4056 –4059 .
- 25e M. Müller , J. Maultzsch , D. Wunderlich , A. Hirsch , C. Thomsen , Phys. Stat. Sol. (RRS) 2007 , 1 , 144 –146 .
- 26
- 26a T. Umeyama , N. Tezuka , M. Fujita , Y. Matano , N. Takeda , K. Murakoshi , K. Yoshida , S. Isoda , H. Imahori , J. Phys. Chem. C 2007 , 111 , 9734 –9741 .
- 26b T. Nakamura , T. Ohana , M. Ishihara , M. Hasegawa , Y. Koga , Diamond Relat. Mater. 2007 , 16 , 1091 –1094 .