CARBON 4 6 (2 0 0 8) 7 4 7–75 2

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Controllable deposition of Ag nanoparticles on carbon

nanotubes as a catalyst for hydrazine oxidation

Guang-Wu Yang, Guo-Yu Gao, Ce Wang, Cai-Ling Xu, Hu-Lin Li*

College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, PR China

A R T I C L E I N F O A B S T R A C T

Article history:
Received 24 November 2007
Accepted 26 January 2008
Available online 2 February 2008
A simple method is devised to deposit highly monodispersed Ag nanoparticles (about 5 nm)
on multi-walled carbon nanotubes (CNTs), which started from an initial modification of Ag
nanoparticles with benzyl mercaptan molecules. By simply tuning the relative ratio of Ag
catalyst to CNTs in solution, Ag/CNT composite with different Ag content can be achieved.
The as-prepared Ag/CNT composite materials showed high electrocatalytic activity
towards hydrazine oxidation, which was ascribed to the high dispersion of Ag nanoparti-
cles on CNT surface.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction ing to their large surface-to-volume ratio [16]. To get better

Recently, a great deal of attention has been given to fuel cells,
which are promising as clean, renewable sources of energy.
[1–4]. Since now, a lot of work has been done to improve the
efficiency of fuel cells in aspects of catalytic material, electro-
lyte, water management and innovative cell design [5–7].
Among these factors, new catalytic materials play a key role
[8–11]. Noble metals such as Pt, Pd, Ru and Au have been re-
ported to be efficient catalysts for most fuel cell anodes [12].
However, the cost associated to these materials is still a great
drawback for full commercial application of fuel cells. To date,
some studies have been done trying to search for an
abundant, inexpensive, stable and efficient electrocatalytic
material as a substitute for noble metal catalysts [13,14].
Recently, we found that Ag supported on CNTs showed high
electrocatalytic activity towards hydrazine oxidation. This
finding indicates that relatively cheap Ag catalyst may be able
to replace noble metal catalysts in fuel cells [15].
On the other hand, the specific activity of metal catalysts
is strongly related to their size and distribution. Highly dis-
tributed catalyst nanoparticles with small size and narrow
size distribution are ideal for high electrocatalyst activity ow-
catalyst size and size distribution on supports, for example,
CNTs, the most widely used catalyst support, many research-
ers have done a lot of work. Modifying CNT surface with de-
sired functional groups by chemical treatments is a
common strategy to get well-dispersed catalyst nanoparticles
on CNTs [17–23]. Although these strategies are effective, the
controllability has not been fully realized. The other ap-
proaches, such as physical evaporation, electroless deposition
and electrodeposition were also reported recently [24–27].
Close examination of the existing methods reveals that they
involved either a tedious pretreatment procedure to modify
CNT walls or complex equipment to achieve high dispersion
of metal nanoparticles on CNTs. Guo et al. reported the poten-
tial application of electrocrystallized Ag nanoparticles on
CNTs for as a catalyst in fuel cells [11]. In a similar attempt
by Gao et al., the electrocatalytic properties of the Ag/CNT
electrode for hydrazine oxidation were also investigated
[15]. We noted that although Ag nanoparticles were success-
fully deposited on CNT surface, they were randomly dis-
persed, which massed together, thus limited their overall
electrocatalytic activity towards hydrazine oxidation. There-
fore, it is desirable to develop a simple and effective synthesis

* Corresponding author: Fax: +86 931 891 2582.

E-mail address: lihl@lzu.edu.cn (H.-L. Li).
0008-6223/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2008.01.026
748 CARBON 4 6 ( 2 0 0 8 ) 7 4 7 –7 5 2

route that provides homogeneously dispersed catalyst nano-
particles while maintaining some degree of control of particle
size and size distribution on CNTs.
In this paper, we report a novel process to prepare highly
monodispersed Ag nanoparticles on multi-walled CNTs. More
importantly, the content of Ag catalyst supported on CNTs
can be well controlled by simply tuning the relative ratio of
Ag to CNTs. Different from the methods reported before,
which produce metal/CNT composite by modifying CNTs to
achieve high metal dispersion, the method we adopted was
to modify Ag nanoparticles with benzyl mercaptan molecules
(C6H5–CH2–SH). In contrast to CNTs, the functionalization of
Ag nanoparticles was easy and effective under much more
benign conditions, such as no harsh acid and room tempera-
ture. Ag nanoparticles prepared in ethanol solution kept their
small particle size and narrow size distribution after being
modified with benzyl mercaptan and deposited on the surface
of CNTs. The structure and nature of Ag/CNT composite were
characterized by transmission electron microscopy (TEM), X-
ray diffraction (XRD) and Brunauer–Emmet–Teller (BET) sur-
face area analysis.
The electrocatalytic activity of as-prepared Ag/CNT com-
posite for hydrazine oxidation was investigated in detail.
2. Experimental
2.1. Ag nanoparticle synthesis
Ag nanoparticles were synthesized by reducing AgNO3 under
ultrasound irradiation in the presence of benzyl mercaptan.
In a typical synthesis circuit, 5 mL of benzyl mercaptan in
ethanol (0.1 mol L 1) and 5 mL of AgNO3 in ethanol
(0.02 mol L 1) with initial molar ratio 5:1 of benzyl mercaptan
to Ag were mixed together all at once. This makes a transpar-
ent yellow solution. The solution was ultrasonicated at
200 kHz in ambient environment continuously for 2 h. The
color of the solution changed to dark red, implying that ben-
zyl mercaptan modified Ag nanoparticles were synthesized.
The BET specific surface area analysis was measured on a
Sorptomatic 1990 using the N2 adsorption/desorption
method.
To study the electrocatalytic characteristics of our Ag/CNT
composite, a conventional three-electrode system was used
at room temperature throughout this work. A glassy carbon
(GC) electrode (3 mm in diameter; electrode active area:
7 mm2) was employed as the working electrode, on which a
thin layer of nafion impregnated electrocatalyst was cast. A
platinum sheet and a saturated calomel electrode (SCE) were
used as the counter electrode and the reference electrode
respectively. The electrolyte was 10 mM hydrazine in 0.1 M
K2SO4 solution which had been purged with N2 for at least
30 min prior to the experiment. Cyclic voltammetry (CV)
scans were recorded using BAS100B electrochemical analyzer
(USA).
3. Results and discussion
3.1. Ag nanoparticle synthesis
The morphologies of Ag nanoparticles were investigated by
TEM. The thiol stabilizes the growing colloids by binding to
Ag nanocrystal surface and helps to maintain a relatively nar-
row particle size distribution. Fig. 1 presents the as-prepared
Ag nanoparticles. It can be seen that Ag nanoparticles are
homogeneously dispersed and do not aggregate with each
other even with a quite high density, indicating that the
phenyl rings of benzyl mercaptan can effectively isolate
adjacent Ag nanoparticles.
3.2. Preparation of Ag/CNT
The phenyl rings of benzyl mercaptan correlate with the
sidewall of CNTs, and the free thiol groups at the end of the
molecules interact with Ag nanoparticles to form strong S–
Ag bond. There are three main functions of benzyl mercap-
tan. Firstly, it prevents Ag nanoparticles from aggregating

2.2. Deposition of Ag nanoparticles to CNTs

4 mg multi-walled CNTs was dispersed in 15 ml ethanol and

ultrtasonicated for 30 min to completely separate the nano-
tube bundles. Then as-prepared Ag/ethanol solution was
added to the CNT/ethanol solution and the mixture was ultr-
asonicated for 10 h at 200 kHz until all Ag nanoparticles were
deposited on CNTs. The ethanol solution became colorless,
suggesting that the benzyl mercaptan modified Ag nanoparti-
cles were completely deposited on CNTs. The Ag/CNT com-
posite was separated from the solution by filtration and
washed by ethanol three times.

2.3. Measurements

The structure and morphology of the synthesized Ag/CNT

samples were observed by XRD and TEM (TEM; Hitachi 600,
Japan). XRD data were collected using a Rigaku D/MAX 2400 Fig. 1 – TEM image of Ag nanoparticles protected by benzyl
diffractmeter with Cu Ka radiation. For TEM observation, the mercaptan (inset: an enlarged image of diluted Ag
samples were dispersed in ethanol by ultrasonic treatment. nanopatticle colloid).
 CARBON 4 6 (2 0 0 8) 7 4 7–75 2
with each other. Secondly, it interacts with CNTs via p–p inter-
action, which will not destroy the electronic network of CNTs
like covalent modification strategies, and thirdly, it links Ag
nanoparticles with CNTs and leads to the uniform dispersion
of Ag nanoparticles on CNTs.
3.3. TEM analysis of Ag/CNT composite
The morphologies of the Ag/CNT composite were investigated
by TEM. Fig. 2 presents the Ag/CNT composite of different Ag
content. It can be seen that Ag nanoparticles are homoge-
neously dispersed and strongly adhered on CNT surface.
The average Ag nanoparticle size is 5 nm. Aggregation does
not come out seriously even with a quite high Ag content
(60%), because the thiol groups of benzyl mercaptan
effectively isolate adjacent Ag nanoparticles. Obviously, the
content of Ag catalyst on CNTs was well controlled by simply
Fig. 2 – TEM images of Ag/CNT composite with different Ag content: 10% (a), 20% (b) (inset: enlarged image of panel b), 40% (c),
and 60% (d).
749
tuning the ratio of Ag to CNTs, which is crucial to their
industrial applications as catalyst.
3.4. XRD analysis of Ag/CNT composite
Crystallinity of the benzyl mercaptan modified Ag nanoparti-
cles on MWCNTs was assessed from their XRD patterns. The
diffractogram shown in Fig. 3 reveals the phase purity of the
material. Despite the small size of Ag (0) particles, they are
well crystallized. The diffraction peaks at 39.1°, 45.2°, 65.2°
and 78.3°, corresponding to Ag (1 1 1), (2 0 0), (2 2 0) and (3 1 1)
reflections, indicate the formation of Ag nanocrystals with
cubic face centered structure [28]. Ag nanoparticles are com-
posed of pure crystalline Ag, since no other impurity peaks
are observed in the XRD patterns. The spherical size of the
crystalline is calculated from the major diffraction peak
(1 1 1) using Scherrer’s formula [29]. It is found that the Ag
750 CARBON 4 6 ( 2 0 0 8 ) 7 4 7 –7 5 2

3.6. Electrocatalytic characteristics of Ag/CNT composite

Ag (200)
600
In our research on the electrochemical properties of Ag/
CNT composite, we found that the Ag nanoparticles exhibit
high catalytic activity for the oxidation of hydrazine. It is
CNTs (002)
Intensity

400 known that the electrochemical behaviour of hydrazine is

Ag (111)
poor at ordinary graphite electrode [33]. As is shown in
Fig. 5a, no well defined peak of hydrazine oxidation could be

200
20
Fig. 3 – XRD pattern of Ag/CNT composite.
nanoparticles on CNTs have an average particle size of
4.9 nm, which accords well with the average particle size
(5 nm) estimated from TEM images, indicating a good crystal-
Ag (311)
Ag (220)
observed in the potential range of 0–0.6 V at bare GC electrode.
However, a typical peak appears around at 0.42 V in the same
solution at Ag/CNT modified GC electrode, which is in good
agreement with literature reports [15,34], indicating that the
electrooxidation of hydrazine is greatly improved by Ag/
40 60 80
CNT. Compared with the relation between the peak current
2θ (degree)
(Ip) obtained from the CV scan and Ag catalyst content in
same electrode active area, a nice straight line is obtained.
Noted that when the Ag catalyst content is up to 60%, the
peak current is a little lower than expected, which may be
a 1000 1200

1000

linity and dispersion of supported Ag catalyst on CNTs [30]. 800

I (μA)
800 600

400 F
3.5. BET analysis 200
600
I (μA)

10 20 30 40 50 60

The N2 adsorption/desorption isotherms of MWCNTs and Content (%)

E
Ag/CNT composite with Ag content of 40% are presented in 400
Fig. 4. As can be seen, both N2 adsorption isotherms are quite
similar with a hysteresis loop, which is ascribed to the capil-
D
200
lary condensation and the intertubular structure amongst C
samples [31]. The specific surface area of pristine MWCNTs B
0 A
calculated by the BET equation is found to be 122.6 m2g 1,
and the BET surface areas of Ag/CNT composite with Ag con- -200 0 200 400 600
tents of 10%, 20%, 40% and 60% are 101.3, 87.5, 72.9 and E (mV vs. SCE)
52.6 m2g 1, respectively, which clearly indicates that the
specific surface areas of Ag/CNT decrease on increasing the b 800
800
content of Ag nanoparticles. This decrease can be largely 700
600
ascribed to an increase in density of the composite after Ag
I (μA)

500

nanoparticle deposition [32]. 600 400 F

300
200 E
100
I (μA)

3 4 5 6 7 8 9 10 11
400 ν (mV s ) D
C
B
Volume adsorbed (cm (STP)g )

400
-1

200
A
300
3

0
-200 0 200 400 600
200
E (mV vs. SCE)

Fig. 5 – CV curves of 10 mM hydrazine in 0.1 M K2SO4

100
a solution. (a) At different electrode: (A) bare GC electrode, (B)
pristine MWCNTs modified GC electrode and Ag/CNT
b modified GC electrode with different Ag catalyst content: (C)
0
0.0 0.2 0.4 0.6 0.8 1.0 10%, (D) 20%, (E) 40%, and (F) 60%. Inset: plots of peak current
Relative pressure (P/P0) (Ip) against Ag catalyst content in Ag/CNT composite. Scan
rate: 100 mVs 1. (b) At Ag/CNT modified GC electrode with
Fig. 4 – N2 adsorption/desorption isotherms of pristine various scan rate: (A) 10, (B) 30, (C) 50, (D) 70, (E) 90 and (F)
MWCNTs (a) and Ag/CNT composite with Ag content of 40% 110 mVs 1. Inset: plots of peak current (Ip) against square
(b). root of the scan rates (m1/2).
 CARBON 4 6 (2 0 0 8) 7 4 7–75 2
caused by the slight aggregation of Ag nanoparticles, as can
be seen from its TEM image (Fig. 2d). Preliminary tests indi-
cated that as-prepared Ag/CNT composite exhibit a high cat-
alytic activity to the electrooxidation of hydrazine.
It has recently been shown the catalyst iron impurities
trapped in single-walled CNTs will dominate the electro-
chemical response for the electrochemical oxidation of
hydrazine [35,36]. It is probable that other CNTs, containing
metallic impurities, also have an influence on the electro-
chemical response of CNTs for the electrochemical oxidation
of hydrazine. To avoid any potential misinterpretations, we
subsequently examined the electrochemical activity of pris-
tine MWCNTs for hydrazine oxidation via CV. As can be seen
in Fig. 5a, there is no electrochemical oxidation wave is ob-
served on pristine MWCNTs modified GC electrode, indicating
the absence of electrocatalytic activity. This clearly demon-
strates that in the electrochemical oxidation of hydrazine,
the origin of the electrochemical activity, in our experiment,
is due to the Ag nanoparticles deposited on CNTs, not the
MWCNTs we adopted. While CNTs occur in various types,
and the amount and type of catalyst residue vary from type
to type as well as sample to sample, it is reasonable to under-
take careful characterization before use.
The nature of the oxidation process was found to be diffu-
sion controlled, as evidenced by the linear plots of the peak
current (Ip) versus square root of the scan rate (m1/2) for hydra-
zine. Fig. 5b shows the CV curves of Ag/CNT modified electrode
in 10 mM hydrazine in 0.1 M K2SO4 solution at various scan
rates. It can be seen that the anodic currents increase and
the peak potential shift positively with the rising of scan rate.
When Ip values were plotted against m1/2, a nice linear relation-
ship was obtained. This behavior suggests that the oxidation
process is controlled by diffusion. The kinetic parameters were
discussed in detail in [37]. All of this indicates that Ag/CNT
composites exhibit a high catalytic activity to the electrooxida-
tion of hydrazine in potential application for fuel cells.
4. Conclusions
Ag nanoparticles prepared in ethanol solution kept their
small particle size and narrow size distribution after being
modified with benzyl mercaptan and deposited on CNT sur-
face. The content of Ag supported on CNTs was well con-
trolled by simply tuning the relative ratio of Ag to CNTs.
The as-prepared Ag/CNT composite showed very high electro-
catalytic activity towards hydrazine oxidation. Such a promis-
ing synthesis procedure may be a versatile approach that can
be extended to the fabrication of some CNTs-supported metal
catalysts or as a simple, rapid, and highly sensitive method
for hydrazine determination.
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