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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

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

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 stacks.iop.org/Nano/19/145602)). As shown in figures 1(a)
through a positively charged capillary using an electrospinning and (b), nanofibers show a clean surface, have diameters in the
apparatus at 25 kV (NT-PS-35K, NTSEE Co., Korea). The range from 800 to 900 nm, and are linear, long and partially
negative electrode was connected to a drum winder collecting aligned along the winding direction. The air stabilization is
the fiber web. The electrospun fibers were collected as a a critical step for converting organic fibers to carbon fibers
web on an aluminum foil wrapped on the metal drum with without disrupting fiber morphology because this step provides
a rotation speed of 300 rpm. The electrospun fiber web was dimensional stability by the high degree of cross-linking [22].
stabilized in an air atmosphere at 280 ◦ C for 1 h (heating Therefore, by subjecting the electrospun organic nanofiber
rate = 1 ◦ C min−1 ), then thermally treated at 300 and 800 ◦ C to 280 ◦ C for 1 h under a controlled air circulation, we
for 1 h in an argon atmosphere. TGA/DTA (Mettler, STAR obtained the air-stabilized nanofiber, as indicated by the
SW) on electrospun organic nanofibers was carried out with appearance of a dark-brown color (see figure S1(b) (available
a heating rate of 5 ◦ C min−1 in air. The nanofiber surface at stacks.iop.org/Nano/19/145602)) due to the formation of
was analyzed by using a scanning electron microscope (SEM, choromophores (e.g. C=C, C=O and N=N) and the
Hitachi, S-4700, Japan) while energy-dispersive spectroscopy reduced fiber diameters (ca. 70–80%) due to the radically
(EDS) attached to the SEM was obtained to evaluate the occurred polycondensation reaction with the evolution of
chemical composition of the metal particles and supporting volatile molecules (e.g. H2 O). We have to discuss the
materials. The morphological features of the palladium species functions of the entrapped palladium ions for the stabilization
for air-stabilized nanofibers and thermally treated carbon process of the electrospun PAN nanofibers. The step-like
nanofibers at 300 ◦ C were observed using transmission electron weight loss in the region from 100 to 350 ◦ C and the
microscopy (TEM, JEOL 2010FEF). Then, the chemical dominant weight loss around 370–380 ◦ C (see figure 2) could
states of the carbon nanofiber and palladium nanoparticles be explained by the catalytic effect of the palladium ions.
were characterized by x-ray photoelectron spectroscopy on Even though there was no consensus about the reaction
a MultiLab2000 spectrometer with a Mg Kα x-ray source mechanism due to its complex chemical reactions such as
(1253.6 eV). Vacuum during analysis was in the range from dehydrogenation, nitrile polymerization and catalytic effect of
10−10 to 10−9 Pa. Finally, we have carried out x-ray diffraction metallic compounds [22], the finally obtained products are
measurements to study the crystallinity of the thermally treated flame-proof, indicating the endorsed thermosetting properties
nanofibers and palladium particles (Rigaku RINT 2100, Cu Kα when exposed to a low flame. The stabilization reactions
(λ = 1.540 56 Å)). in a PAN-based electrospun nanofiber containing catalytic
metals should be further studied because this step plays an
3. Results and discussion important role in determining the physical properties of the
resultantly obtained carbon nanofibers. Finally, by thermally
By judiciously selected the electrospinning conditions, treating the air-stabilized web at 800 ◦ C in argon, we obtained
the electrospun organic nanofibers are obtained in the a flexible black-colored thin web (ca. 50 μm) (see figure S1(c)
form of a white web (see figure S1(a) (available at (available at stacks.iop.org/Nano/19/145602)) consisting of

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Nanotechnology 19 (2008) 145602 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
Figure 2. Thermogravimetric analysis of the pure and value of the Pd 3d5/2 line. In the case of the electrospun
palladium-chloride-incorporated nanofibers in air nanofibers ((I) in figure 3(b)), the binding energy of the Pd
(heating rate = 10 ◦ C). peak around 337.2 eV is ascribed to the characteristic of Pd2+ .
Also, the appearance of a doublet consisting of two peaks, one
partially aligned long carbon nanofibers with diameters in the at 335.8 eV and the other at 338.3 eV, with an intensity ratio of
range from 500 to 600 nm (figures 1(e) and (f)), in which round 13:2, in the air-stabilized sample ((II) in figure 3(b)) might arise
metal particles with diameters ranging from 100 to 200 nm from metallic and oxidized (e.g. PdO and PdO2 ) palladium,
cover the outer surface of the carbon nanofiber homogeneously respectively. However, the reversed intensity ratio of 4:2 in
(figures 1(g) and (h)). It seems that metal particles with the thermally treated nanofiber ((III) in figure 3(b)) suggests
spherical features are partially embedded on the near-surface of that carbon materials could act as an effective substrate for the
the carbon nanofibers, suggesting that they are strongly bound compositional transformation from oxides to pure palladium.
to carbon materials. To confirm the strong binding properties Figure 4 shows x-ray diffraction patterns of all samples.
of Pd nanoparticles, our samples dispersed in ethanol were One strong peak at 2θ = 17.1◦ corresponding to the (100)
subjected to strong sonication for 30 min (KUBOTA UP50H). plane of the electrospun PAN nanofibers (see (I)) disappears
We found that there is no large loss of Pd particles from the after air stabilization. Instead, we found newly appeared lines
carbon nanofibers, indicating that Pd particles are physically at 2θ = 23.2 and 40◦ , which are ascribed to the (002) and (10)
stuck on the carbon nanofibers. planes from the partially carbonized phases of the air-stabilized

Figure 3. (a) Wide-scan XPS, (b) Pd XPS 3d spectra of the (I) electrospun, (II) air-stabilized and (III) thermally treated nanofibers,
respectively.

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Nanotechnology 19 (2008) 145602 C Kim et al

Figure 4. X-ray diffraction patterns of the (I) electrospun, (II)

air-stabilized and (III) thermally treated nanofibers, respectively.

Figure 5. TEM images of air-stabilized ((a), (b)) and thermally

nanofibers (see (II)). When they are thermally treated at 800 ◦ C treated carbon nanofibers at 300 ◦ C ((c), (d)), respectively.
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 nanofibers and carbon nanotubes, should be removed when
structure, and the broad and low intensity of the (002) line they are used as catalyst supporting materials. Unfortunately,
from highly disordered carbons (the intrinsic non-graphitizable it is very hard to remove metallic impurities completely simply
characteristic of PAN polymers). EDS (see figure S2 (available by chemical processes. More specifically, hydrochloric acid
at stacks.iop.org/Nano/19/145602)) also confirms the presence treatment should be avoided for their uses as Pt supporting
of palladium species and carbon atoms from thermally treated materials in a fuel cell system because chlorine atoms can
nanofibers. be easily attached to the active sites (or the end plane of
To better understand the growth patterns of palladium graphene sheets) of carbon nanotubes or carbon nanofibers
particles on carbon nanofibers, TEM observation was carried (e.g. herringbone- and platelet-type nanofibers). In contrast,
out on the air-stabilized and thermally treated carbon electrospun carbon nanofibers do not have any metallic
nanofibers at 300 ◦ C (see figure 5). In the air-stabilization impurities because they are fabricated from the simple thermal
step, palladium cations entrapped in the electrospun PAN- treatment of polymeric organic nanofibers. (2) We could
based nanofibers surely acted as a stabilization accelerator obtain electrospun-derived carbon nanofibers in a form of thin
and they converted to palladium oxide nanoparticles below web. Therefore, they could be used without further processing.
10 nm (figures 5(a), (b)). In the following thermal treatment Regarding carbon nanotubes, single-and double-walled carbon
at 300 ◦ C in argon, the abrupt reduction of diameters from nanotubes can be prepared in a form of sheet via a simple
800 to 400 nm indicates structural conversion from organic filtering process through a strong physical entanglement.
to carbon materials through the carbon densification and the However, it is very difficult to fabricate multi-walled carbon
removal of foreign atoms. Simultaneously, the palladium nanotubes and carbon nanofibers in a form of sheet. (3) Finally,
oxides embedded on the near-surface of carbon nanofibers Pd particles are strongly bound to the outer surface of carbon
coalesce into large-sized particles and partially transform into nanofibers because Pd particles are embedded on the outer
pure palladium through a transition state of the Pd1−x C x surface of carbon nanofibers.
phase [23] when they are thermally treated at 800 ◦ C. Therefore, we envisage this material to be useful in the
fabrication of novel gas/bio-sensors, nanocomposites, high-
performance filters exhibiting high antimicrobial properties
4. Conclusions and electronic devices. The most fascinating aspects of our
developed tool are that their expected applications include not
We have demonstrated the ability to prepare self-assembled
only physics, chemistry, materials science and engineering, but
palladium nanoparticles partially embedded on the outer
also biology and medicine.
surface of carbon nanofibers by the combination of organic
nanofiber formation using the electrospinning system and the Acknowledgments
following conventional thermal treatments. Electrospun-based
carbon nanofibers have several merits over catalytically grown This work was supported by the CLUSTER (the second stage)
carbon nanotubes as supporting materials: (1) metal catalysts of the Ministry of Education, Culture, Sports, Science and
(Fe, Ni, Co, etc), which are inevitable for growing carbon Technology of Japan and a Grant-in-Aid from the Ministry of

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Nanotechnology 19 (2008) 145602 C Kim et al

Education, Culture, Sports, Science and Technology of Japan [12] Radovic L R and Rodriguez-Reinoso F 1997 Chemistry and
(no. 18710084). Physics of Carbon vol 25, ed P A Thrower
(New York: Dekker)
[13] Roman-Martinez MC, Cazoria-Amoros D, Linares-Solano A,
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