1. Hydrogenated Nanostructured Carbons: Fullerenes & SWNTs Jeremy Kintigh and Glen P. Miller Department of Chemistry and Materials Science Program University of New Hampshire American Chemical Society Meeting, Wash. DC Aug 19, 2009

2. Hydrogenation of Fullerenes

3. Proposed Mechanism of Fullerene Hydroamination/ Hydrogenation . . . . . . . .. .. . . . .. .. (a) Kintigh, J., Briggs, J., Letourneau, K., and Miller, G. P., Journal of Materials Chemistry , 2007 , 17 , 4647 – 4651 ; (b) G. P. Miller, Comptes Rendus Chimie , 2006 , 9 , 952

4. Polyamine Hydrogenation of C 60 Gives C 3v Symmetric C 60 H 18 C 60 H 18 First Isolated and Identified by Roger Taylor and co-workers: J. Chem. Soc., Perkin Trans. 2, 1996 , 2051-2054. J. B. Briggs, M. N. Montgomery, L. Silva and G. P. Miller, Organic Letters 2005 , 7 , 5553

5. Spectroscopic Evidence for C 3v C 60 H 18 738 LDI Mass spectrum UV-vis trace J. B. Briggs, M. N. Montgomery, L. Silva and G. P. Miller, Organic Letters 2005 , 7 , 5553

6. Spectroscopic Evidence for C 3v C 60 H 18 1 H NMR Spectrum * * J. B. Briggs, M. N. Montgomery, L. Silva and G. P. Miller, Organic Letters 2005 , 7 , 5553

7. Spectroscopic Evidence for C 3v C 60 H 18 * * * * J. B. Briggs, M. N. Montgomery, L. Silva and G. P. Miller, Organic Letters 2005 , 7 , 5553 A B C D

8. DET Hydrogenations of C 60 are Both High Yielding and Scalable mass C 60 (g) mL DET time (h) mass C 60 H 18 (g) % yield J. B. Briggs, M. N. Montgomery, L. Silva and G. P. Miller, Organic Letters 2005 , 7 , 5553 0.10 7 14 0.083 81 1.0 50 16 0.919 90 5.0 100 20 4.674 91

9. DET Hydrogenation of C 60 Total reaction time is reduced to 5-10 minutes using microwave reactor Kintigh, J., Briggs, J., Letoutneau, K., and Miller, G. P., Journal of Materials Chemistry , 2007 , 17 , 4647 - 4651 .

10. DET Hydrogenation of C 70 Using Standard Conditions: 200 o C, 15 h ~ 26-28 hydrogens per C 70 1 H NMR spectrum Lack of Regioselectivity as compared to reaction with C 60 Mass spectrum Kintigh, J., Briggs, J., Letourneau, K., and Miller, G. P., “Fulleranes produced via efficient polyamine hydrogenation of [60]fullerene, [70]fullerene and giant fullerenes,” J. Mater.Chem . 2007 , 17 , 4647 - 4651.

11. DET Hydrogenation of C 70 Using More Severe Conditions: 300 o C, 15 h ~ 24-28 hydrogens per C 70 1 H NMR spectrum C 70 allowed to react with DET at 300 o C for 15 hours Mass spectrum Kintigh, J., Briggs, J., Letourneau, K., and Miller, G. P., “Fulleranes produced via efficient polyamine hydrogenation of [60]fullerene, [70]fullerene and giant fullerenes,” J. Mater.Chem . 2007 , 17 , 4647 - 4651.

12. DET Hydrogenation of Large Fullerenes LDI-MS of large fullerenes prior to DET hydrogenation 1-phenylnaphthalene extract C 78 m/z=936 C 84 m/z=1008 C 96 m/z=1152 C 200 m/z=2400 Kintigh, J., Briggs, J., Letourneau, K., and Miller, G. P., “Fulleranes produced via efficient polyamine hydrogenation of [60]fullerene, [70]fullerene and giant fullerenes,” J. Mater.Chem . 2007 , 17 , 4647 - 4651.

13. LDI-MS of large fullerenes after DET hydrogenation DET Hydrogenation of Large Fullerenes C 78 H 26-32 C 84 H 22-30 C 96 H 26-32 Kintigh, J., Briggs, J., Letourneau, K., and Miller, G. P., “Fulleranes produced via efficient polyamine hydrogenation of [60]fullerene, [70]fullerene and giant fullerenes,” J. Mater.Chem . 2007 , 17 , 4647 - 4651.

14. Polyamine Hydrogenations of Large Fullerenes Fullerene Approx. no. of H’s added [76] 21-28 [78] 26-32 [80] 24 [82] 28 [84] 22-30 [86] 28 [88] 28 [90] 30 [92] 28 [94] 30 [96] 26-32

15. Polyamine Hydrogenation of SWNTs

16. Before Hydrogenation After Hydrogenation DET Hydrogenation of SWNTs Results in Highly Dispersed Species “ Hydrogenation of Single-Wall Carbon Nanotubes Using Polyamine Reagents: Combined Experimental and Theoretical Study,” J. Amer. Chem. Soc . 2008 , 130 , 2296-2303.

17. Raman Spectrum of H-SWNTs D-band ~1300 cm -1 G-band ~1584 cm -1 Before Hydrogenation After Hydrogenation “ Hydrogenation of Single-Wall Carbon Nanotubes Using Polyamine Reagents: Combined Experimental and Theoretical Study,” J. Amer. Chem. Soc . 2008 , 130 , 2296-2303.

18. 30 Seconds 5 Minutes 1 Hour 2 Days Hydrogenated SWNTs Stay Well Dispersed Without Added Surfactant H-SWNTs SWNTs H-SWNTs SWNTs H-SWNTs SWNTs H-SWNTs SWNTs “ Hydrogenation of Single-Wall Carbon Nanotubes Using Polyamine Reagents: Combined Experimental and Theoretical Study,” J. Amer. Chem. Soc . 2008 , 130 , 2296-2303.

19. Hydrogenation Weakens SWNTs Making Them Prone to Fracture Under TEM Irradiation “ Hydrogenation of Single-Wall Carbon Nanotubes Using Polyamine Reagents: Combined Experimental and Theoretical Study,” J. Amer. Chem. Soc . 2008 , 130 , 2296-2303.

20. Thermal Annealing at 800 o C Restores Original Structure BEFORE AFTER “ Hydrogenation of Single-Wall Carbon Nanotubes Using Polyamine Reagents: Combined Experimental and Theoretical Study,” J. Amer. Chem. Soc . 2008 , 130 , 2296-2303.

21. Acknowledgements National Science Foundation: Nanoscale Science & Engineering Center for High-rate Nanomanufacturing ( Award # NSF-0425826) National Science Foundation: Nanoscale Exploratory Research (Award # NSF-0403954) Army Smart Materiel Command Mikael Jazdzyk Wenling Jia Irvinder Kaur Jeremy Kintigh Jonathan Briggs Ryan Kopreski Chandrani Pramanik Yi Xu Nathan Stein Polina Prushevich Elizabeth Stairs Gillian Liu Yushu Li Shunfu Hu Jianhua Gao The Miller Group at UNH Collaborators Mehmet Dokmeci (NEU) David Tomanek (MSU) Ahmed Busnaina (NEU) Luis Echegoyen (Clemson) Howard Mayne (UNH) Nicholas McGruer (NEU) Joey Mead (UML)