1. Fabrication of copper/single-walled carbon nanohorn hybrid material by microwave irradiation Parichat Thipayang, Kunio Shinohara, Chantamanee Poonjarernsilp, Tawatchai Charinpanitkul Center of Excellence in Particle Technology Department of Chemical Engineering, Faculty of Engineering Chulalongkorn University

2. Outline I. Rationale & Motivation II. Objective III. Experimental procedure IV. Result & discussion V. Conclusion

3. Rationale & Motivation Carbon nanoparticle Nanospace Nanosize High surface area Good adsorbent Superm thermal & electrical conductivity 1. Zhu, S. and G. Xu, Single-walled carbon nanohorns and their applications. Nanoscale, 2010. 2(12): p. 2538-49. 2. Paradise, Melissa, and Tarun Goswami. "Carbon Nanotubes – Production and Industrial Applications." Materials & Design 28, no. 5 (2007): 1477-1489. 1 2

4. Surface treatment Plasma treatment Acid treatment Rationale & Motivation Carbon structures Carbon nanotubes Carbon nanohorns Synthesize of carbon nanohorns CO 2 laser ablation Arc discharge Microwave heating High efficient Uniform heating 3. Paradise, M. and T. Goswami (2007). "Carbon nanotubes – Production and industrial applications." Materials & Design 28(5): 1477-1489. 4. Iijima, S., M. Yudasaka, et al. (1999). "Nano-aggregates of single-walled graphitic carbon nano-horns." Chemical Physics Letters 309(3-4): 165-170. 5. Yu, Y., L.-L. Ma, et al. (2005). "Coating MWNTs with Cu2O of different morphology by a polyol process." Journal of Solid State Chemistry 178(5): 1488-1494 6. K. Murata, M. Yudasaka, S. Iijima: Hydrogen production from methane and water at low temperature using EuPt supported on single-wall carbon nanohorns, Carbon 44, 818 (2006) CNTs 3 CNHs 4 Metal-CNTs 5 Metal-CNHs 6 Copper High thermal & electric conductivity Low cost

5. Rationale & Motivation Cu Pre-functionalize the surface of CNHs Acid treatment Microwave irradiation Highly efficient Uniform heating

6. Objectives To examine a process of CNHs surface modification using microwave irradiation

7. Experimental procedure Synthesis of single-walled carbon nanohorns SWCNH surface modification using microwave-assisted acid treatment Preparation of Copper/SWCNH hybrid material SWCNHs Treated-SWCNHs Cu/SWCNH hybrid

8. Experimental procedure 1. Synthesis of single-walled carbon nanohorns (SWCNHs) 80A / 40V N 2 supply 5 l/min Raised up speed 1.5 mm/s SWCNHs Cathode graphite rod Anode graphite rod Arc zone N2N2 7. Poonjarernsilp, C., et al., Single-step synthesis and characterization of single-walled carbon nanohorns hybridized with Pd nanoparticles using N2 gas-injected arc-in-water method. Carbon, 2011. 49(14): p. 4920-4927. Arc current80 A Type / Flow rate of gas injected N 2 / 5 L.min -1 Electrode material Graphite 99.9999% Electrode supplying speed 1.5 mm.s -1

9. Experimental procedure 2. Microwave-assisted acid treatment for SWCNH surface modification SWCNHs HNO 3 + H 2 SO 4 Sonicate Microwave Filter and wash with DI water Dry in an oven Effect of microwave irradiation power 90 – 800 W Effect of microwave irradiation time 30 – 540 sec Effect of solution Acid, DI water

10. Experimental procedure 3. Copper/SWCNH hybrid material preparation Ethylene glycol CuSO 4 ۰5H 2 O NaOH Treated-SWCNHs Sonicate Microwave Filter Dry in an oven 8. Leelaviwat, N., et al., Microwave-induced fabrication of copper nanoparticle/carbon nanotubes hybrid material. Current Applied Physics, 2012. 12(6): p. 1575-1579.

11. Results & discussion Morphological and particle size distribution of synthesized SWCNHs TEM image of agglomerated SWCNHs Particle size distribution

12. Results & discussion Surface polarity of SWCNHs Zeta-potential of SWCNH samples With a simple sonication of SWCNH suspension in a mixture of H 2 SO 4 and HNO 3 for 3 hr, the treated SWCNHs has surface polarity of -50.77 uv

13. Result & discussion Surface polarity of SWCNHs FT-IR spectra Pristine SWCNHs Acid treated SWCNHs at 360 W for 30 sec Acid treated SWCNHs at 360 W for 45 sec Acid treated SWCNHs at 360 W for 60 sec Acid treated SWCNHs at 360 W for 180 sec

14. Result & discussion Hydrophilicity Pristine CNHs Acid treated CNHs at 360 W for 45 sec Better dispersion in water

15. Conclusion The processing time for SWCNH surface modification using microwave irradiation is in the order of second The microwave irradiation power of 360 W and the microwave irradiation time of 45 sec. could lead to the equilibrated polarity of SWCNH surface The presence of functional groups on the surface of the acid treated SWCNHs would be beneficial to the hybridization of SWCNHs with copper nanoparticles

16. 16 Acknowledgements Center of the Excellence in Particle Technology Department of Chemical Engineering Chulalongkorn University

19. I. Rationale & Motivation (3) Li alloy (Si) 1,2 Higher theoretical specific capacity Low electrical conductivity High volume expansion/contraction CNTs 3 Higher capacity than graphite Graphite Cu 4 High capacity (2x CNTs) Large hysteresis in charge-discharge curve Anode material 1. Obrovac MN, Christensen L. Structural changes in silicon anodes during lithium insertion/extraction. Electrochem Solid State Lett 2004;7:A93–6. 2. Hatchard TD, Dahn JR. In-situ XRD and electrochemical study of the reaction of lithium with amorphous silicon. J Electrochem Soc 2004;151:A838–42. 3. Ishihara T, Kawahara A, Nishiguchi H, Yoshio M, Takita Y. Effect of synthesis condition of graphitic nanocarbon tube on anodic property of Li-ion rechargeable battery. J Power Sources 2001;97–98:129–32. 4. Poizot P, Laruelli S, Grugeon S, Dupont L, Tarascon JM. Nano-sized transitionmetal oxides as negative electrode materials for lithium-ion batteries. Nature 2000;407:496–9.

20. II. Literature Review (1) Yu et al. (1998) 9 synthesized Pt deposited on carbon nanotubes. They studied on kinds of oxidant for chemical modification. HNO 3 and H 2 SO 4 -HNO 3 mixture were investigated. Carbon nanotubes was refluxed in acid solution 5 hours.  XPS spectra of oxygen-containing species on the surface of carbon nanotubes Raw CNTs HNO 3 treated CNTs H 2 SO 4 -HNO 3 treated CNTs HNO 3 treated  TEM image of deposition of Pt clusters on fuctional carbon nanotubes 9. Yu, R.Q., et al., Platinum deposition on carbon nanotubes via chemical modification. Chemistry of Materials, 1998. 10(3): p. 718-722.

21. II. Literature Review (2) Wang et al. (2005) 10 studied about using of microwave to rapid functionalize single-walled carbon nanotubes.  Model microwave induced reaction as amidation of SWCNTs  FTIR spectra from the amidation reaction of SWNTs Pristine SWNTs HNO 3 trated SWNTs 2,6-dinitroaniline functionalized SWNTs 10. Wang, Y., Z. Iqbal, and S. Mitra, Microwave-induced rapid chemical functionalization of single-walled carbon nanotubes. Carbon, 2005. 43(5): p. 1015-1020. Total processing time 20 – 30 min 3 – 5 days  20 – 30 min

22. II. Literature Review (3) Leelaviwat et al. (2012) 11 studied about effect of microwave irradiation time to fabricate copper/multi-walled carbon nanotubes hybrid material. 11. Leelaviwat, N., et al., Microwave-induced fabrication of copper nanoparticle/carbon nanotubes hybrid material. Current Applied Physics, 2012. 12(6): p. 1575-1579.  TEM images of pristine MWCNTs and hybrid materials with different irradiation time Pristine1min3min 5min7min9min