Metal Nanoparticle/Carbon

Nanotube Catalysts

Brian Morrow

School of Chemical, Biological and Materials Engineering

University of Oklahoma
 Introduction
Armchair Zigzag Chiral
Carbon nanotubes have many properties
which make them ideal supports for catalytic
metal nanoparticles.

However, the surfaces of nanotubes are

relatively inert, and they tend to form bundles
which reduces their surface areas.

Metal nanoparticle/carbon nanotube materials

are being investigated for use in catalytic and
electrocatalytic applications such as fuel cells.

Baughman et al., Science 297 (2002) 787

A. Kongkanand, K. Vinodgopal, S. Kuwabata, P. V. Kamat, J, Phys.

Chem. B 110 (2006) 16185-16188
 Example

Anode (methanol oxidation):

CH3OH + H2O → CO2 + 6H+ + 6e-

Cathode (oxygen reduction):

(3/2)O2 + 6H+ + 6e- → 3H2O

Overall:
CH3OH + (3/2)O2 → CO2 + 2H2O
K. Kleiner, Nature 441 (2006) 1046-1047

Possibility for powering devices such as cell phones and computers:

- Potentially 3-10 times as much power as a battery
- Methanol cheaper and easier to store than hydrogen

Problems:
- Methanol crossover
- Requires catalysts, usually platinum – expensive!
 Example

Methanol oxidation - anode

of direct methanol fuel cells

A. Kongkanand et al., J. Phys. Chem. B 110 (2006)

16185-16188

Oxygen reduction - cathode

of direct methanol fuel cells

Langmuir 22 (2006) 2392-2396

 Other Examples

Selective hydrogenation

Oxidation of formic acid and

formaldehyde

Hydrogen peroxide oxidation

Environmental catalysis

Synthesis of 1,2-diphenylethane Wildgoose et al., Small 2 (2006) 182-193

 Synthesis
Metal particles can be grown directly on the carbon nanotubes

- Precursor metal salts (H2PtCl6,

H2PdCl6, etc.) heated and reduced

- Particle size can be controlled by

temperature and reducing
conditions

- Particles can be anchored by

oxidizing nanotubes (via acid
treatment or microwave irradiation), Georgakilas et al., J. Mater. Chem. 17 (2007) 2679-2694

but this can also damage the

nanotubes
Other techniques include chemical vapor deposition, electrodeposition, laser ablation,
thermal decomposition, substrate enhanced electroless deposition
 Synthesis
Already-grown metal particles can be connect to the carbon nanotubes

Hydrophobic interactions and hydrogen bonds

Covalent Linkage

Han et al. Langmuir 20 (2004) 6019

π-stacking

Coleman et al., J. Am. Chem. Soc. 125 (2003) 8722

Ou and Huang, J. Phys. Chem. B 110 (2006) 2031

 Characterization
TEM/SEM XRD

Bittencourt et al., Surf. Sci. 601 (2007) 2800-2804

AFM

D.-J. Guo and H.-L. Li, Journal of Power Sources 160 (2006) 44-49

Hrapovic et al., Analytical Chemistry 78 (2006) 1177-1183

 Characterization
XPS Raman spectroscopy

Lee et al., Chem. Phys. Lett. 440 (2007) 249-252

Lee et al., Langmuir 22 (2006) 1817-1821

 Future Directions

- Minimizing use of expensive metals

- Synthesis techniques that yield nearly monodisperse

nanoparticle size distributions

- Synthesis techniques that can control final structure of

nanoparticles

- Better understanding of metal-carbon nanotube interactions

Questions?
 Characterization
“X-ray photoelectron
spectroscopy
was employed to investigate the
binding energy of d-band
electrons of Pt. As shown in
Figure 6, a shift of 0.4 eV to a
higher binding energy was found
in both 4d and 4f electrons of Pt
deposited on PW-SWCNT,
proving the role of SWCNTs in
modifying the electronic
properties of Pt.”
A. Kongkanand et al., J. Phys. Chem. B 110 (2006) 16185-16188