Nanotube Peapods: A New Class of Carbon Nanotube Hybrids

Transcription

1 NT June , Nagano, Japan. Nanotube Peapods: A New Class of Carbon Nanotube Hybrids Nori Shinohara Department of of Chemistry, Nagoya University, Nagoya, Japan Japan Outline Synthesis of of Nano-Peapods Carbon Nanotubes Encapsulating Fullerenes Nano-Peapods ; Peapods Encaging Linear Polyyne Molecules: Interstellar Molecules

2 善光寺 Zenkoji Temple It is said that Zenkoji temple was built in 642, which was the year of Emperor Kogyoku ascended. However, it was first burnt down in 1179 and it subsequently caught fire on ten separate occasions.. The present main hall was set to rebuild in 1703 and completed in 1707.

3 In a Japanese adage: If you miss to pay a visit to Zenkoji temple, it s s not worth coming to Nagano city.

4 Superb Saving! But we are still in a very difficult situation Japan vs. Croatia (0 : 0) in Nuremberg, Germany

5 Collaborators Synchrotron X-RayX Prof. M.Sakata (Nagoya) Dr. E. Nishibori (Nagoya) Dr. M. Takata (Riken) HRTEM/EELS Prof. S. Iijima (Meijo U) Dr. K. Suenaga (AIST) Dr. S. Bandow (Meijo U) Dr. K. Hirahara (Nagoya U) FET Measurements Prof. T. Mizutani (Nagoya U) Dr. Y. Ohono (Nagoya U) STM Experiments Prof. Y. Kuk (SNU) Dr. Jhin Hwan Lee (SNU) Peopod Syntheses & Characterization Dr. T. Sugai (Nagoya U) Dr. R. Kitaura (Nagoya U) Dr. T. Tomiyama (Nagoya U) Dr. G. Ning (Nagoya U) Dr. R. Palanisami (Nagoya U) Dr. T. Shimada (Nagoya, Stanford U) Y. Ito (Nagoya U) H. Okimoto (Nagoya U) N. Kishi (Nagoya U) D. Nishide (Nagoya U) H. Yoshida (Nagoya U) N. Fukui (Nagoya U) S. Kuwahara (Nagoya U) K. Kobayashi (Nagoya U)

6 Carbon Nanotubes of Our Interests Double-Wall Carbon Nanotubes (DWNT) Peapod ( ピーポット )

7 Encapsulation into Nanotubes Smith (1998) Li (2005) Hirahara (2000) Bandow (2001) Yanagi (2006) Maniwa (2002) Takenobu (2003) Zhao (2003)

8 Peapod Structure さやえんどう

9 Open-Ended Carbon Nanotubes

10 Gas-Phase Synthesis of Peapods via Low Technology 2 cm Purified Fullerenes High-Purity Carbon Nanotubes Fullerenes Opened Carbon Nanotubes

11 C60 molecules inside SWNTs C 60

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13 C80 (D5d) C-R.Wang et al. Chem.Commun. (2000). elongated spherical elongated

14 Syntheses of and

15 Peapods Preparations Growth, purification and opening of DWNTs Growth of DWNTs Fe/MgO catalysts, CH4 cracking at 900 for 10 min. Open DWNTs by 450 heating in open air for 1 h. Synthesis of nano-peapods DWNTs with excessive C60C 60 were sealed in a glass ample under 5x105-5 Torr and heated at 500 for 2 days.

16 TEM images of 1.7 nm 2.6 nm 5.6 nm

17 High-Yield Synthesis of C60C

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19 Endohedral Metallofullerenes Gd 92

20 Electron Charge Density Y M.Takata et al. Nature (1995)

21 The MEM Charge Densities of 82 E.Nishibori et al. Phys.Rev.B (2004) Gd e/å 3 equi-contour surface

22 peapods Suenaga et al. Phys. Rev. Lett., (2000) Hirahara et al. Science, (2000)

23 HRTEM Image of Peapod Gd atom K.Suenaga et al. Nano Lett. (2003).

24 Escaping of Tb atom from A C92C Fullerene Cage K.Suenaga et al. Nano Letters (2005).

25 Escaping of Tb atom from A C92C Fullerene Cage K.Suenaga et al. Nano Letters (2005).

26 Ti 2 C C Peapod 78 Sato et al. Phys.Rev.B in press

27 The 1st Exohedral Metallofullerene Peapod: (Ce-C 60 ) B.Sun et al. J.Am.Chem.Soc. (2005)

28 30

29 Interstellar Molecules Encapsulated in Carbon Nanotubes HC C C C C C C C C CH C10H2@SWNT

30 Motivation Novel Nanotube-based based Hybrid Materials Novel pi-conjugated system New Electronic Device Property in one-dimensional space "Linear-polyyne" As target molecules C 2n H 2 (n 2) Tsuji et al., CPL (2002)

31 Interstellar Molecules Detected by Radio Telescopes(as of September 2000) 分子イオン CO +, SO +, CH +, HCO +, HCS +, HOCO +, HOC +, HN 2+, HC 3 NH +, H 2 CN +, H 3+, H 2 COH +, H 3 O + 無機化合物 H 2, OH, NO, N 2 O, NH, NH 2, HNO, NS, SO, SiO, SiS, SiN, SiH 4 HCl, NaCl, KCl, AlF, AlCl H 2 O, H 2 S, SO 2, NH 3 アルコール エーテル CH 3 OH, C 2 H 5 OH, (CH 3 ) 2 O アルデヒド ケトン H 2 CO, H 2 CCO, CH 3 CHO, HCCCHO, (CH 3 ) 2 CO, HCO 酸 エステル HCOOH, CH 3 OCHO, CH 3 COOH アミン イミン NH 2 CN, NH 2 CHO, CH 2 NH, CH 3 NH 2 シアン イソシアン CN, HNC, CH 2 CN, CH 3 CN, CH 3 NC, CH 3 CH 2 CN, CH 2 CHCN, CH 3 C 3 N, CH 3 C 5 N, H 2 CN, HNCO, MgNC, MgCN, NaCN 糖 CH 2 OHCHO 含いおう化合物 OCS, HNCS, H 2 CS, CH 3 SH 含りん化合物 CP, PN 環状化合物 C 3 H 2, C 3 H, SiC 2, SiC 3, C 2 H 4 O 直線炭素鎖化合物 HCN, HC 3 N, HC 5 N, HC 7 N, HC 9 N, HC 11 N, CH, C 2 H, C 3 H, C 4 H, C 5 H, C 6 H, C 7 H, C 8 H, C 2, C 3, C 5, C 2 H 2, HCCN, HNCCC, HCCNC, CO, CCO, C 3 O, C 3 N, C 5 N, CS, CCS, C 3 S, CSi, C 4 Si その他の有機化合物 CH 2, H 2 C 3, H 2 C 4, H 2 C 6 CH 4, CH 3 C 2 H, CH 3 C 4 H, C 2 H Molecules and Ions

32 Liquid Laser Ablation of Graphite Laser pulse (532nm, 10Hz, 100mJ/pulse, φ10) graphite / n-hexane (0.3g / 200ml) C 8 H 2 Ice-bath (0 ) Absorption C 10 H 2 C 12 H 2 C 14 H 2 Magnetic stirrer Wavelength / nm

33 1 Liquid Preparation of (C10 R. P. (~4*10( -3 Torr) 2 Polyyne in n-hexane (Frozen) Cap-Opened SWNT 3 Drying under air atmosphere at 80 for overnight Mixing & Standing (80,, 2 Days, in Vacuum)

34 HPLC Separation & Isolation of Linear-Chain Polyyene Molecules Intensity (arb.units) Absorption (arb.units) C 10 H 2 C 8 H 2 C 12 H 2 (a) Ex.@275nm Ex.@254nm Ex.@227nm Retention Time / min Wavelength / nm (b)

35 Raman Intensity (arb.units) RBM G D 2066 G' The first Raman detection of well- defined polyyenes at room temperature! Raman Shift / cm -1

36 C 10 H 2 molecules have been selectively encapsulated into SWNTs!!

37 Key Messages 1. High-yield synthesis of fullerenes/metallofullerenes nano-peapods peapods. 2. Single-,, Double- and Triple Nano-peapods provide nano-templates for TEM-imaging of fullerenes and molecules. 3. Even very unstable linear polyyne molecules can safely be encapsulated in SWNT.