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Self-assembled palladium nanoparticles on carbon nanofibers

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2008 Nanotechnology 19 145602

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IOP PUBLISHING NANOTECHNOLOGY
Nanotechnology 19 (2008) 145602 (5pp) doi:10.1088/0957-4484/19/14/145602

Self-assembled palladium nanoparticles on

carbon nanofibers
Chan Kim1,3 , Yoong Ahm Kim2,3 , Jin Hee Kim2 ,
Masakazu Kataoka2 and Morinobu Endo2
1
AMOMEDI, Co. Ltd, 597-2 Wonsanri, Hasungmyun, Gimpo, Gyunggido 415-863, Korea
2
Faculty of Engineering, Shinshu University, 4-17-1 Wakasato, Nagano-shi 380-8553, Japan

E-mail: ckim37@hanmail.net and yak@endomoribu.shinshu-u.ac.jp

Received 22 October 2007, in final form 30 January 2008

Published 4 March 2008
Online at stacks.iop.org/Nano/19/145602

Abstract
Carbon nanofibers containing palladium nanoparticles were prepared simply by electrospinning
a polymer solution containing palladium chloride and the subsequent thermal treatment in
argon. It is demonstrated that palladium oxide formed in air stabilization transforms into
nanoparticles through an interaction with carbon materials. Since the palladium nanoparticles
covering the outer surface of nanofibers homogeneously are small enough to have high catalytic
activity, this material could find applications as efficient catalysts and hydrogen sensors.
M Supplementary data are available from stacks.iop.org/Nano/19/145602
(Some figures in this article are in colour only in the electronic version)

1. Introduction the expected high thermal stability of carbon nanofibers

The viability of nanotechnology strongly depends on its
ability to synthesize nanometer-sized building blocks and
to position them precisely at a predefined location. Up
to now, various attempts to prepare metal nanoparticles on
carbon-based materials have been reported due to their size-
dependent catalytic, optical, electronic and magnetic properties
compared to those of bulk metals [1–6]. Among many types
of metals, palladium nanoparticles attracted lots of attention
due to its unique catalytic activity [7, 8] and high hydrogen
sensing and storing ability [9–11]. These previous reports
usually generate a wide size distribution of metal particles
and weak binding strength with supporting materials because
metal particles were attached (or grown) on chemically
active sites based on heterogeneous nucleation and growth
mechanisms [12–15]. Recently, Demir et al [16] have reported
the organic nanofiber formation by electrospinning a polymer
solution containing palladium chloride and the following
reduction of Pd cations in an aqueous hydrazine solution. Here
we report a simple way of preparing palladium nanoparticles
impinged on the outer surface of the carbon nanofibers
through the fiber formation from a polyacrylonitrile solution
containing palladium chloride by electrospinning [16–19] and
the following thermal treatment in argon [20, 21]. Therefore,
3 Authors to whom any correspondence should be addressed.
containing Pd particles would be of great important for gas-
phase applications. Palladium cations within the electrospun
organic nanofibers convert to palladium oxide in the air-
stabilization step and consequently transform into a pure metal
cluster through an interaction with carbon materials on/near the
outer surface of carbon nanofibers. Noticeably, our technique
is easily applicable to all kinds of precious metals (e.g., Au, Ag,
Pt, Ru, Rh, Os, Ir). Therefore, these hybrid structures in the
form of a thin nanofiber-based web could be used as an efficient
electrode (nano-Pt) in an electrochemical oxygen-reduction
system, a crucial component in bio/gas sensing (nano-Au) and
antimicrobial (nano-Ag) devices without further processing.
2. Experimental details
The synthesis of a hybrid metal nanoparticles/carbon nanofiber
structure in the form of a thin web was carried out through
the organic nanofiber formation from a polyacrylonitrile
solution containing metal chloride utilizing the electrospinning
system. More specifically, polyacrylonitrile (PAN, molecular
weight = 160 000, palladium chloride (PdCl2 , 99.995%,
powder, anhydrous) and solvent N,N -dimethylformamide
(DMF) (99.9%)) were obtained from Aldrich Chemical
Co. (USA). PAN (10 wt%) and palladium chloride (1, 3,
5 and 10 wt% with regard to the solvent) were dissolved
in DMF at 60 ◦ C to obtain a polymer solution containing

0957-4484/08/145602+05$30.00 1 © 2008 IOP Publishing Ltd Printed in the UK

Nanotechnology 19 (2008) 145602
Figure 1. SEM images of electrospun ((a), (b)), air-stabilized ((c), (d)) and thermally treated fibers ((e)–(h)) at different resolutions. Note that
spherical palladium particles cover the outer surface of carbon nanofibers homogeneously.
metal chloride. The solution was spun into a fiber web
through a positively charged capillary using an electrospinning
apparatus at 25 kV (NT-PS-35K, NTSEE Co., Korea). The
negative electrode was connected to a drum winder collecting
the fiber web. The electrospun fibers were collected as a
web on an aluminum foil wrapped on the metal drum with
a rotation speed of 300 rpm. The electrospun fiber web was
stabilized in an air atmosphere at 280 ◦ C for 1 h (heating
rate = 1 ◦ C min−1 ), then thermally treated at 300 and 800 ◦ C
for 1 h in an argon atmosphere. TGA/DTA (Mettler, STAR
SW) on electrospun organic nanofibers was carried out with
a heating rate of 5 ◦ C min−1 in air. The nanofiber surface
was analyzed by using a scanning electron microscope (SEM,
Hitachi, S-4700, Japan) while energy-dispersive spectroscopy
(EDS) attached to the SEM was obtained to evaluate the
chemical composition of the metal particles and supporting
materials. The morphological features of the palladium species
for air-stabilized nanofibers and thermally treated carbon
nanofibers at 300 ◦ C were observed using transmission electron
microscopy (TEM, JEOL 2010FEF). Then, the chemical
states of the carbon nanofiber and palladium nanoparticles
were characterized by x-ray photoelectron spectroscopy on
a MultiLab2000 spectrometer with a Mg Kα x-ray source
(1253.6 eV). Vacuum during analysis was in the range from
10−10 to 10−9 Pa. Finally, we have carried out x-ray diffraction
measurements to study the crystallinity of the thermally treated
nanofibers and palladium particles (Rigaku RINT 2100, Cu Kα
(λ = 1.540 56 Å)).
3. Results and discussion
By judiciously selected the electrospinning conditions,
the electrospun organic nanofibers are obtained in the
form of a white web (see figure S1(a) (available at
2
C Kim et al
stacks.iop.org/Nano/19/145602)). As shown in figures 1(a)
and (b), nanofibers show a clean surface, have diameters in the
range from 800 to 900 nm, and are linear, long and partially
aligned along the winding direction. The air stabilization is
a critical step for converting organic fibers to carbon fibers
without disrupting fiber morphology because this step provides
dimensional stability by the high degree of cross-linking [22].
Therefore, by subjecting the electrospun organic nanofiber
to 280 ◦ C for 1 h under a controlled air circulation, we
obtained the air-stabilized nanofiber, as indicated by the
appearance of a dark-brown color (see figure S1(b) (available
at stacks.iop.org/Nano/19/145602)) due to the formation of
choromophores (e.g. C=C, C=O and N=N) and the
reduced fiber diameters (ca. 70–80%) due to the radically
occurred polycondensation reaction with the evolution of
volatile molecules (e.g. H2 O). We have to discuss the
functions of the entrapped palladium ions for the stabilization
process of the electrospun PAN nanofibers. The step-like
weight loss in the region from 100 to 350 ◦ C and the
dominant weight loss around 370–380 ◦ C (see figure 2) could
be explained by the catalytic effect of the palladium ions.
Even though there was no consensus about the reaction
mechanism due to its complex chemical reactions such as
dehydrogenation, nitrile polymerization and catalytic effect of
metallic compounds [22], the finally obtained products are
flame-proof, indicating the endorsed thermosetting properties
when exposed to a low flame. The stabilization reactions
in a PAN-based electrospun nanofiber containing catalytic
metals should be further studied because this step plays an
important role in determining the physical properties of the
resultantly obtained carbon nanofibers. Finally, by thermally
treating the air-stabilized web at 800 ◦ C in argon, we obtained
a flexible black-colored thin web (ca. 50 μm) (see figure S1(c)
(available at stacks.iop.org/Nano/19/145602)) consisting of
Nanotechnology 19 (2008) 145602
Figure 2. Thermogravimetric analysis of the pure and
palladium-chloride-incorporated nanofibers in air
(heating rate = 10 ◦ C).
partially aligned long carbon nanofibers with diameters in the
range from 500 to 600 nm (figures 1(e) and (f)), in which round
metal particles with diameters ranging from 100 to 200 nm
cover the outer surface of the carbon nanofiber homogeneously
(figures 1(g) and (h)). It seems that metal particles with
spherical features are partially embedded on the near-surface of
the carbon nanofibers, suggesting that they are strongly bound
to carbon materials. To confirm the strong binding properties
of Pd nanoparticles, our samples dispersed in ethanol were
subjected to strong sonication for 30 min (KUBOTA UP50H).
We found that there is no large loss of Pd particles from the
carbon nanofibers, indicating that Pd particles are physically
stuck on the carbon nanofibers.
Figure 3. (a) Wide-scan XPS, (b) Pd XPS 3d spectra of the (I) electrospun, (II) air-stabilized and (III) thermally treated nanofibers,
respectively.
3
C Kim et al
To track down the chemical state of the palladium
atoms, x-ray photoelectron spectroscopy measurements on the
electrospun, air-stabilized and thermally treated nanofibers
were carried out. From wide-scan spectra for the electrospun
(I), air-stabilized (II) and thermally treated (III) nanofibers
(figure 3(a)), it is confirmed that the intensified O 1s peak
in the air-stabilized sample (II) results from the incorporated
oxygen molecules as the cross-linking agent while the reduced
N 1s peak in the thermally treated sample (III) is a sign of
the evolution of nitrogen-containing gases during structural
conversion from polymer to carbon materials. To accurately
determine Pd binding energies, curve-fitting for Pd 3d spectra
consisting of the Pd 3d5/2 and Pd 3d3/2 spin–orbital splitting
(figure 3(b)) was carried out using the Gaussian–Lorentzian
sum functions. In this work we used only the binding energy
value of the Pd 3d5/2 line. In the case of the electrospun
nanofibers ((I) in figure 3(b)), the binding energy of the Pd
peak around 337.2 eV is ascribed to the characteristic of Pd2+ .
Also, the appearance of a doublet consisting of two peaks, one
at 335.8 eV and the other at 338.3 eV, with an intensity ratio of
13:2, in the air-stabilized sample ((II) in figure 3(b)) might arise
from metallic and oxidized (e.g. PdO and PdO2 ) palladium,
respectively. However, the reversed intensity ratio of 4:2 in
the thermally treated nanofiber ((III) in figure 3(b)) suggests
that carbon materials could act as an effective substrate for the
compositional transformation from oxides to pure palladium.
Figure 4 shows x-ray diffraction patterns of all samples.
One strong peak at 2θ = 17.1◦ corresponding to the (100)
plane of the electrospun PAN nanofibers (see (I)) disappears
after air stabilization. Instead, we found newly appeared lines
at 2θ = 23.2 and 40◦ , which are ascribed to the (002) and (10)
planes from the partially carbonized phases of the air-stabilized
Nanotechnology 19 (2008) 145602
Figure 4. X-ray diffraction patterns of the (I) electrospun, (II)
air-stabilized and (III) thermally treated nanofibers, respectively.
nanofibers (see (II)). When they are thermally treated at 800 ◦ C
in argon (see (III) in figure 4), it is possible to observe the main
crystallographic planes ((111), (200), (220), (311), (222)) from
the palladium nanoparticles with a face-centered cubic crystal
structure, and the broad and low intensity of the (002) line
from highly disordered carbons (the intrinsic non-graphitizable
characteristic of PAN polymers). EDS (see figure S2 (available
at stacks.iop.org/Nano/19/145602)) also confirms the presence
of palladium species and carbon atoms from thermally treated
nanofibers.
To better understand the growth patterns of palladium
particles on carbon nanofibers, TEM observation was carried
out on the air-stabilized and thermally treated carbon
nanofibers at 300 ◦ C (see figure 5). In the air-stabilization
step, palladium cations entrapped in the electrospun PAN-
based nanofibers surely acted as a stabilization accelerator
and they converted to palladium oxide nanoparticles below
10 nm (figures 5(a), (b)). In the following thermal treatment
at 300 ◦ C in argon, the abrupt reduction of diameters from
800 to 400 nm indicates structural conversion from organic
to carbon materials through the carbon densification and the
removal of foreign atoms. Simultaneously, the palladium
oxides embedded on the near-surface of carbon nanofibers
coalesce into large-sized particles and partially transform into
pure palladium through a transition state of the Pd1−x C x
phase [23] when they are thermally treated at 800 ◦ C.
4. Conclusions
We have demonstrated the ability to prepare self-assembled
palladium nanoparticles partially embedded on the outer
surface of carbon nanofibers by the combination of organic
nanofiber formation using the electrospinning system and the
following conventional thermal treatments. Electrospun-based
carbon nanofibers have several merits over catalytically grown
carbon nanotubes as supporting materials: (1) metal catalysts
(Fe, Ni, Co, etc), which are inevitable for growing carbon
4
C Kim et al
Figure 5. TEM images of air-stabilized ((a), (b)) and thermally
treated carbon nanofibers at 300 ◦ C ((c), (d)), respectively.
nanofibers and carbon nanotubes, should be removed when
they are used as catalyst supporting materials. Unfortunately,
it is very hard to remove metallic impurities completely simply
by chemical processes. More specifically, hydrochloric acid
treatment should be avoided for their uses as Pt supporting
materials in a fuel cell system because chlorine atoms can
be easily attached to the active sites (or the end plane of
graphene sheets) of carbon nanotubes or carbon nanofibers
(e.g. herringbone- and platelet-type nanofibers). In contrast,
electrospun carbon nanofibers do not have any metallic
impurities because they are fabricated from the simple thermal
treatment of polymeric organic nanofibers. (2) We could
obtain electrospun-derived carbon nanofibers in a form of thin
web. Therefore, they could be used without further processing.
Regarding carbon nanotubes, single-and double-walled carbon
nanotubes can be prepared in a form of sheet via a simple
filtering process through a strong physical entanglement.
However, it is very difficult to fabricate multi-walled carbon
nanotubes and carbon nanofibers in a form of sheet. (3) Finally,
Pd particles are strongly bound to the outer surface of carbon
nanofibers because Pd particles are embedded on the outer
surface of carbon nanofibers.
Therefore, we envisage this material to be useful in the
fabrication of novel gas/bio-sensors, nanocomposites, high-
performance filters exhibiting high antimicrobial properties
and electronic devices. The most fascinating aspects of our
developed tool are that their expected applications include not
only physics, chemistry, materials science and engineering, but
also biology and medicine.
Acknowledgments
This work was supported by the CLUSTER (the second stage)
of the Ministry of Education, Culture, Sports, Science and
Technology of Japan and a Grant-in-Aid from the Ministry of
Nanotechnology 19 (2008) 145602
Education, Culture, Sports, Science and Technology of Japan
(no. 18710084).
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