Published on Web 07/19/2005

Substrate-Enhanced Electroless Deposition of Metal Nanoparticles on Carbon

Nanotubes
Liangti Qu and Liming Dai*
Department of Chemical and Materials Engineering, School of Engineering, The UniVersity of Dayton,
300 College Park, Dayton, Ohio 45469-0240
Received May 27, 2005; E-mail: [email protected]

Carbon nanotubes have been demonstrated to possess excellent

electronic properties, a good chemical stability, and a large surface
area.1 These unique properties make carbon nanotubes very useful
for supporting metal nanoparticles in many potential applications,
ranging from advanced catalytic systems through very sensitive
electrochemical sensors to highly efficient fuel cells.2 Consequently,
functionalization of carbon nanotubes with metal nanoparticles has Figure 1. Schematic illustration of metal nanoparticle deposition on carbon
nanotubes via the SEED process.
received ever-increasing interest in recent years, and a few
interesting routes have now been devised for either covalently or
noncovalently attaching certain metal nanoparticles onto carbon
nanotubes.3-7 Examples include chemical binding through DNA
double-helix linkages,3 electrochemical deposition,4 electroless
deposition with and without the aid of reducing agents,5,6 and
physical/chemical deposition on carbon nanotubes with and without
surface activation.2a,7 Among them, the electroless deposition is of
particular interest because its simplicity could facilitate a large-
scale production of the nanotube-nanoparticle hybrids. General
applications of the electroless deposition, however, are limited by
the fact that only metal ions of a redox potential higher than that
of a reducing agent or carbon nanotube can be reduced into
nanoparticles on the nanotube support. Given that a single-walled
carbon nanotube (SWNT) has a redox potential of +0.5 V vs SHE
(standard hydrogen electrode),6 it is impossible to reduce Cu2+ (Cu-
(NO3)2/Cu, +0.340 V vs SHE) or Ag+ (Ag(NH3)2+/Ag, +0.373 V
vs SHE)8 into metal nanoparticles by SWNTs via a galvanic
displacement reaction without the aid of a reducing agent,6 though
Au (AuCl4-/Au, +1.002 V vs SHE) and Pt (PtCl42-/Pt, +0.775 vs
SHE) nanoparticles have been successfully deposited on nanotubes
through spontaneous reduction of the metal ions by SWNTs.6 By
simply supporting carbon nanotubes with a metal substrate of a
redox potential lower than that of the metal ions to be reduced into
nanoparticles, we demonstrated for the first time that metal ions
even with a redox potential lower than that of a carbon nanotube
can be readily reduced into metal nanoparticles onto the nanotube Figure 2. SEM images of MWNTs supported by a copper foil after being
supportsa process that we designated as Substrate-Enhanced immersed into an aqueous solution of HAuCl4 (3.8 mM) for different periods
Electroless Deposition (SEED). Here, we report this facile yet of time: (a) 0 s, (b)10 s, (c) same as for (b) under a higher magnification,
versatile and effective SEED method for electroless deposition of (d) 30 s. (e) A transmission electron microscopic (TEM) image of Au
a large variety of metal nanoparticles, including Cu and Ag nanoparticle-coated MWNTs, (f) the Cu-supported MWNTs after being
immersed into an aqueous solutions of K2PtCl4 (4.8 mM) for 10 s, and (g)
nanoparticles, on both SWNTs and multiwalled carbon nanotubes the Cu-supported MWNTs after being immersed into an aqueous solution
(MWNTs) in the absence of any additional reducing agent. of (NH4)2PdCl4 (7.0 mM) for 10 s. (h) EDX spectra for the Au, Pt, and Pd
Figure 1 schematically shows the galvanic displacement reaction nanoparticle-coated MWNTs on Cu foils.
governing the SEED process. As can be seen, the deposition of
metal nanoparticles is achieved via the redox reaction of a galvanic the metal ions (Mm+/M) in solution, indicating a great potential
cell, in which the nanotube acts as a cathode for metal deposition for functionalization of carbon nanotubes with various metal
(M) from the reduction of metal ions (Mm+) in solution, while the nanoparticles by the SEED process that is as yet almost unrecog-
metal substrate serves as an anode where metal atoms (Sub0) are nized.
oxidized into (Subn+) followed by dissolution.9 Therefore, the SEED To demonstrate the SEED process, we started with MWNTs
process should allow electroless deposition of any metal nanopar- prepared by pyrolysis of iron(II) phthalocyanine (FePc).10 Figure
ticles (M) on conducting carbon nanotubes as long as the redox 2a represents a typical scanning electron microscopic (SEM, Philips
potential of the substrate metal (Subn+/Sub0) is lower than that of XL30 FEG) image of the FePc-generated MWNTs randomly
10806 9 J. AM. CHEM. SOC. 2005, 127, 10806-10807 10.1021/ja053479+ CCC: $30.25 © 2005 American Chemical Society
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dispersed on a copper foil (EMS US), showing that the pristine

nanotubes possess a smooth surface and almost free from pyrolytic
impurities on the nanotube surface (e.g., amorphous carbon and
residual catalyst nanoparticles). Upon immersion of the Cu-
supported MWNTs into an aqueous solution of HAuCl4 (3.8 mM),
we found that Au nanoparticles spontaneously formed on the
nanotube sidewalls. The SEM images taken at different stages
during the SEED process reveal that the nucleation of Au
nanoparticles started within seconds. Au clusters with a diameter
around 100 nm are clearly evident along the nanotube sidewalls
after about 10 s of exposure to the HAuCl4 solution (Figure 2b,c).
Longer reaction times caused no obvious change in the particle
size but a significant increase in the density of particles along the
nanotube length (Figure 2d). These observations indicate that
particle nucleation on nanotubes is fast (<10 s) and not correlated
with any defect site of the nanotube structure, as, at least, partially
evidenced by the rather homogeneous distribution of nanoparticles
along the high quality nanotubes shown in Figure 2e (TEM image,
Figure 3. SEM images of (a) the pristine SWNTs and the Cu-supported
Hitachi H-7600). Furthermore, the nanoparticle growth process is SWNTs after being immersed in an aqueous solution of (b) HAuCl4 (3.8
most likely controlled by diffusion of the AuCl4- from the bulk mM), (c) K2PtCl4 (4.8 mM), and (d) (NH4)2PdCl4 (7.0 mM) for 5 s. SEM
solution to the nanotube/solution interface. Under the diffusion images of (e, f) SWNTs and (g, h) MWNTs supported by a zinc foil after
control, smaller particles often gain a faster growth than larger being immersed in an aqueous solution of Cu(NO3)2 (3.8 mM) and Ag-
(NH3)2+ (3.8 mM), respectively, for 5 s.
particles due to relatively more surface-receiving sites for the metal
ions intrinsically associated with their higher surface-to-volume metal nanoparticles, in the absence of any additional reducing agent,
ratios. This could eventually lead to the formation of nanoparticles by simply supporting the nanotubes with a metal substrate of a
with a rather uniform size and effectively avoid the formation of redox potential lower than that of the metal ions to be reduced into
abnormally large particles. Similar galvanic displacement reactions nanoparticles. Judicious selection of the metal substrates allowed
were observed for the carbon nanotubes with aqueous solutions of the SEED process for electroless deposition of various metal
K2PtCl4 (4.8 mM, Figure 2f) and (NH4)2PdCl4 (7.0 mM, Figure nanoparticles, including those otherwise impossible by more
2g). Energy-dispersive X-ray analyses (EDX) on the Au, Pt, and conventional electroless deposition methods, on both the outer- and
Pd nanoparticle-coated carbon nanotubes corresponding to Figure inner-walls of carbon nanotubes. These nanotube-supported metal
2b,f,g clearly show peaks of Au, Pt, and Pd, respectively (Figure nanoparticles are electrochemically active. Therefore, the SEED
2 h), along with peaks for Cu, C, and Fe arising from the copper process can be regarded as a general approach to effective
substrate and traces of Fe catalyst possibly end-encapsulated within functionalization of carbon nanotubes with various metal nanopar-
the nanotube structure.10b As expected, no similar particle deposition ticles for a wide range of potential applications, including in
occurred when a metal substrate (e.g., Au) with a higher redox advanced sensing and catalytic systems.
potential than that of metal ions (e.g., Cu(NO3)2, Ag(NH3)2+) was
used. Acknowledgment. We thank NSF (CCF-0403130), NEDO
In our further investigation on the functionalization of carbon (04IT4), AFRL/ML, WBI, Dayton Development Colations, Uni-
nanotubes, we found that a large variety of metal nanoparticles could versity of Dayton, and NEST for support.
also be electrolessly deposited onto Cu-supported SWNTs (Figure Supporting Information Available: A TEM image and cyclic
3a) by the SEED process, as exemplified by Figure 3b-d for the voltammograms of MWNTs with their inner- and outer-walls coated
Au, Pt, and Pd nanoparticle-coated SWNTs, respectively. By simply by Au and Pt nanoparticles, respectively. This material is available
changing the copper foil (Cu2+/Cu, 0.34 V vs SHE)8 to metal free of charge via the Internet at http://pubs.acs.org.
substrates of a lower redox potential (e.g., Zn2+/Zn, -0.76 V vs
SHE),8 we can further extend the capacity of the SEED process References
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J. AM. CHEM. SOC. 9 VOL. 127, NO. 31, 2005 10807