Fabrication of copper/single-Fabrication of copper/single-walled carbon nanohorn hybrid walled carbon nanohorn hybrid material by microwave material by microwave irradiationirradiation

Parichat Thipayang, Kunio Shinohara, Chantamanee Poonjarernsilp, Tawatchai Charinpanitkul

Center of Excellence in Particle TechnologyDepartment of Chemical Engineering, Faculty of Engineering

Chulalongkorn University

Outline

I. Rationale & MotivationII. ObjectiveIII. Experimental procedureIV. Result & discussionV. Conclusion

Rationale & Motivation

Carbon nanoparticl

e

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

Rationale & Motivation

Carbon structures

Carbon nanotubes

Carbon nanohorns

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 3CNHs 4

Metal-CNTs 5

Metal-CNHs 6Copper

High thermal & electric conductivity

Low cost

Rationale & Motivation

CuCu

Cu

CuCu

Cu

Pre-functionalize the surface of CNHs

Pre-functionalize the surface of CNHs

Acid treatment

Microwave irradiation

Highly efficient

Uniform heating

Objectives

To examine a process of CNHs surface modification using microwave irradiation

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

Experimental procedure

1. Synthesis of single-walled carbon nanohorns (SWCNHs)

80A / 40V

N2 supply 5 l/min

Raised up speed 1.5 mm/s

SWCNHs

Cathode graphite rod

Anode graphite rod

Arc zone

N2

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 current 80 A

Type / Flow rate of gas injected

N2 / 5 L.min-1

Electrode materialGraphite 99.9999%

Electrode supplying speed

1.5 mm.s-1

Experimental procedure

2. Microwave-assisted acid treatment for SWCNH surface modification

SWCNHs

HNO3 + H2SO4 Sonicate

Microwave

Filter and wash with DI water

Dry in an oven

Experimental procedure

3. Copper/SWCNH hybrid material preparation

Ethylene glycol

CuSO4۰5H2O

NaOH

Treated-SWCNHs

Sonicate

Microwave

FilterDry 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.

Results & discussion

Morphological and particle size distribution of synthesized SWCNHs

TEM image of agglomerated SWCNHs

Particle size distribution

Results & discussion

Surface polarity of SWCNHs

Zeta-potential of SWCNH samples

With a simple sonication of SWCNH suspension in a mixture of H2SO4 and HNO3 for 3 hr, the treated SWCNHs has surface polarity of -50.77 uv

-60

-50

-40

-30

-20

-10

0

0 50 100 150 200

Time (s)

Zeta

pote

nti

al u

V

Avg

Result & discussion

Surface polarity of SWCNHs

40080012001600200024002800320036004000

Wavenumber(cm-1)

%Tra

nsm

itta

nce

C=O

C=C C-O

(a)

(b)

(c)

(d)

(e)

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

Result & discussion

Hydrophilicity

Pristine CNHsAcid treated CNHs

at 360 W for 45 sec

Better dispersion in water

Conclusion

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

16

AcknowledgemeAcknowledgementsnts

Center of the Excellence in Particle Technology

Department of Chemical Engineering Chulalongkorn

University

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

Gra

phit

eG

rap

hit

e

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 2 0 0 4 ;7 :A9 3 –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.

II. Literature Review (1)

Yu et al. (1998) 9 synthesized Pt deposited on carbon nanotubes. They studied on kinds of oxidant for chemical modification. HNO3 and H2SO4-HNO3 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

HNO3 treated CNTs

H2SO4-HNO3 treated CNTs

H2SO4-HNO3 treated CNTs

HNO3 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.

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

HNO3 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

3 – 5 days 20 – 30 20 – 30 minmin

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 an d hybrid materials with different irradi

ation time

Pristine

1min 3min

5min 7min 9min

-60

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0

0 50 100 150 200

Time (s)

Zeta

pote

nti

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V

Avg

-60

-50

-40

-30

-20

-10

0

0 50 100 150 200

Time (s)

Zeta

pote

nti

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Avg