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Electrochemistry Communications 9 (2007) 15821586

www.elsevier.com/locate/elecom

Electrocrystallized Ag nanoparticle on functional multi-walled


carbon nanotube surfaces for hydrazine oxidation
Guoyu Gao, Daojun Guo, Ce Wang, Hulin Li

College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, PR China
Received 11 January 2007; received in revised form 28 February 2007; accepted 28 February 2007
Available online 6 March 2007

Abstract
4-Aminobenzoic acid was covalently grafted on multi-walled carbon nanotubes (MWNTs) by amine cation radical formation in the
electrooxidation process of the amino-containing compound. Then, silver (Ag) nanoparticles were electrocrystallized on 4-aminobenzoic
acid monolayer-grafted MWNTs by a potential-step method. The structure and nature of the resulting Ag/MWNT composites were
characterized by transmission electron microscopy and X-ray diraction. The electrocatalytic properties of the Ag/MWNT electrode
for hydrazine oxidation have been investigated by cyclic voltammetry, high electrocatalytic activity of the Ag/MWNT electrode can
be observed. This may be attributed to the small particle size of the silver particles. The results imply that the Ag/MWNT composites
have a good application potential in fuel cells.
2007 Elsevier B.V. All rights reserved.
Keywords: 4-Aminobenzoic acid; MWNTs; Ag nanoparticles; Hydrazine

1. Introduction
Since the discovery of the carbon nanotubes (CNTs) in
1991, there are tremendous interesting aspects on their
characterization and potential application in various elds
[19], at the same time, due to a large specic surface area
and good electronic properties, it can be used as a new support for catalysts [10,11]. Many attempts have been conducted to deposit various metal particles onto the surface
of CNTs, some metals and their compounds, such as platinum, palladium, copper, nickel, ruthenium and so on,
have been deposited on the CNTs successfully [1216].
Chemical treatments are common methods to generate
acid groups on CNTs. However, previous attempts to prepare metal nanoparticles on CNT surface have not often
obtained size-similar and highly dispersed nanoparticles.
One of the reasons is that metal nanoparticles are spontaneously formed at the defect sites on the surface of CNTs.
*

Corresponding author. Tel.: +86 931 891 2517; fax: +86 931 891 2582.
E-mail address: lihl@lzu.edu.cn (H. Li).

1388-2481/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2007.02.026

Therefore, to obtain a good highly dispersed nanoparticles,


the spontaneous deposition of metal nanoparticles on
CNTs must be suppressed. Recently, free radical grafting
methods, which forming covalent bond on carbon electrodes by electrochemical reduction and oxidation of diazonim salts, and amino-containing compounds operated
in nonaqueous solution [1726]. Considering the recent
interest in the use of CNTs from both an electrochemical
point of view and as metal nanoparticle catalyst supports,
we can nd some examples of electrochemically controlled
metal nanoparticle deposition on CNTs in the literature
[2735]. Dong et al. synthesized the Pt nanoparticles by
adsorbing [PtCl6]2 onto the CoTMPyP-modied CNTs
through electrostatic interaction [30]. He et al. reported
the high purity of electrochemically deposited nanoparticles to decorate CNTs with bimetallic PtRu nanoparticles
[34]. But very few papers reported the Ag nanoparticles on
CNT surface as a catalyst.
In our previous work, we have deposited several noble
metals onto CNT surface successfully through electrochemical methods [28,29]. Here, a simple, direct syn-

G. Gao et al. / Electrochemistry Communications 9 (2007) 15821586

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Fig. 1. Schematic procedure for the preparation of Ag nanoparticles on MWNT surface.

thetic method of Ag nanoparticles is described in Fig. 1.


An ordered 4-aminobenzoic acid was rst grafted onto
MWNT surface according to other work [24], then,

AgNH3 2 was adsorbed onto the grafted MWNT surface by electrostatic interaction. Finally, Ag nanoparticles could be obtained through pulsed potentiostatic
reduction. Dong et al. ever reported the LBL assembly
method of Pd nanoparticle multi-layer lms. Here we
try to develop a simple way to prepare Ag nanoparticles.
It has several advantages: (1) the 4-aminobenzoic acid
monolayer is modied on MWNT surface via a CN
covalent bond which is strong and stable for next deposition, (2) the modication condition in aqueous solution
instead of organic anhydrous solution can much simplify
the operating process, (3) the electrostatic interaction
between substrate and metal can make distribution better on the surface and (4) electrochemistry is a powerful
technique being both rapid and facile, and thus allowing
to easily controlling the nucleation and growth of metal
nanoparticles on the CNT substrate.
The electrocatalytic activity of an Ag/MWNT electrode
for hydrazine oxidation was also investigated in detail.
2. Experimental
2.1. Preparation of carbon nanotube paste (CNTP)
electrode
MWNTs were purchased from Nanotech Port Ltd., Co.
(Shenzhen, China). The samples were puried by procedures already reported in the literature [36]. Carbon nanotube paste electrode was prepared by mixing MWNTs and
mineral oil in a ratio 60.0% W/W carbon nanotubes and
40.0% W/W mineral oil. The paste was carefully handmixed in a mortar and then packed into a cavity (3-mm
diameter, 2-mm depth) at the end of a Teon tube. The
electrode was provided by a copper wire connected to the
paste in the inner hole of the tube. The paste was kept at
room temperature in a desiccator until used.
2.2. Preparation of Ag nanoparticles on MWNT surface
The electrochemical synthesis of Ag nanoparticles on
the MWNT surface, shown in Fig. 1, is a three-step process
analogous to the procedure employed to synthesis Ag
nanoparticles on carbon nanotubes: (1) the as-produced
carbon nanotube paste electrode was rstly immersed into

an 0.1 M KCl solution containing 7.0 mM 4-aminobenzoic


acid (4-ABA) at a scan rate of 10 mv/s in a potential from
0.5 to 1.4 V (vs. SCE), (2) the 4-ABA monolayer-grafted
MWNT electrode was then immersed into 1 mM

AgNH3 2 solution for 3 min and (3) after rinsing thoroughly with KNO3 solution, the AgNH3
2 adsorbed
MWNT electrode was transferred into 0.1 M KNO3 solution and Ag nanoparticles were grown on the 4-ABA
monolayer-grafted MWNT electrode by a chronoamperometry method. The potential was stepped from 0.0 to
0.5 V (vs. SCE) for 120 ms.
2.3. Measurements
A conventional cell with a three-electrode conguration
was used throughout this work. A MWNT paste electrode
was employed as working electrode. A platinum foil served
as the counter electrode and a saturated calomel electrode
(SCE) was used as the reference electrode. Electrochemical
measurements were performed with BAS100B electrochemical analyzer (USA), and the potentials were measured and
reported with respect to the SCE.
The morphology of synthesized Ag nanoparticles was
observed on a Hitachi600 transmission electron microscopy (TEM). The samples were prepared by dropping the
Ag nanoparticles modied carbon nanotube ethanol suspension on the carbon-coated Cu grids and observed at
100 kV.
X-ray diraction (XRD) data of the samples were collected using a Rigaku D/MAX 24000 diractometer with
Cu Ka radiation.
3. Results and discussion
3.1. Covalent modication of MWNT with 4-ABA
Fig. 2 shows cyclic voltammograms of 7.0 mM 4-ABA
in 0.1 M KCl solution on a MWNT paste electrode at
10 mV/s. Then 4-ABA was found to oxidize at about
0.92 V. This oxidation wave is attributed to one-electron
oxidation of the amino group to its cation radical [37
40]. When the potential is repeatedly scanned, the peak
diminishes. This indicates the formation of a 4-ABA mono3
layer on the electrode surface. The Fe3 CN6 redox probes
was chosed to investigate the eects of the 4-ABA lm on
their electrochemical behavior. Inset in Fig. 2 shows the
cyclic voltammograms of Fe3 CN3
in neutral aqueous
6

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G. Gao et al. / Electrochemistry Communications 9 (2007) 15821586

Fig. 2. Cyclic voltammograms on a CNTP electrode in 0.1 M KCl with


7.0 mM 4-ABA for 5 cycles. Scan rate: 10 mV/s. Inset: cyclic voltammograms on bare MWNTs (A) and 4-ABA modied MWNTs (B) in
5 mM Fe3 CN3
6 solutions buered by 0.1 M PBS (pH 7.0). Scan rate:
100 mV/s.

solution. It clearly shows the peak current on MWNT (A)


is much higher than 4-ABA-MWNTs (B). This indicates
that the electron transfer of Fe3 CN3
6 is blocked on the
4-ABA-MWNTs. We can conclude that a negative potential is established at the lm surface as a result of high negative charge density of the COO group. Thus,
3
the electrostatic repulsion resists access of Fe3 CN6 to
the electrode surface and blocks its electron transfer on
the 4-ABA/MWNT.

Fig. 3. Typical currenttime transient of (A) with (B) without Ag NH3


2
cations grafted onto the 4-ABA monolayer-modied MWNTs in 0.1 M
KNO3.

fully covered on MWNTs. Most Ag nanoparticles distribute almost uniformly on the walls and ends of the
nanotubes with a diameter of 37 nm. Through the clearer
morphology of single tube attached with Ag nanoparticles
(Fig. 4b), we can see that Ag nanoparticles appeared to
have attached selectively to MWNT surfaces [43].

3.2. Preparation of Ag nanoparticles on the 4-ABA


monolayer-grafted MWNT surface
After grafting the 4-ABA monolayer, the modied

MWNT electrode was immersed in a 1 mM AgNH3 2


solution for 3 min and rinsed thoroughly with 0.1 M

KNO3 solution. The AgNH3 2 modied MWNT electrode was then placed in an AgNH3
2 free solution
(0.1 M KNO3) for potential pulse deposition. The potentiostatic deposition was carried out at a potential pulse
from +0.0 to 0.5 V for a duration of 120 ms. A typical

currenttime transient seen for AgNH3 2 cations on a


4-ABA -modied MWNT electrode is shown in Fig. 3, curve
A. Curve B represents the transient of 4-ABA monolayer
grafted MWNTs without AgNH3 2 cations pre-adsorption. Compared with the two curves, curve A exhibits a
much larger current, which clearly shows that AgNH3
2
has been coordinated and reduced on the 4-ABA monolayer-grafted MWNT surfaces [41,42].
3.3. TEM analysis of Ag/MWNT composites
The direct evidence of the formation of Ag nanoparticles on the surface of MWNTs was given by TEM
(Fig. 4). From Fig. 4a, The Ag nanoparticles were success-

Fig. 4. Transmission electron micrograph (TEM) image of Ag/MWNT


composites.

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3.5. Electrochemical properties of Ag/MWNT composites

Fig. 5. X-ray Powder diraction (XRD) pattern of Ag/MWNT


composites.

In our research on the electrochemistry properties of


Ag/MWNT composites, we found that the Ag nanoparticles exhibit excellent catalytic activity for the oxidation of
hydrazine. From Fig. 6, we can see that hydrazine is found
to be electrooxidized at 0.4 V in the cyclic voltammogram,
which is in good agreement with literature reports [44,45],
whereas hydrazine cannot be electrooxidized on a bare
MWNT electrode. Compared with the relation between
the peaks current obtained from the CV scan and v1/2 of
CV, which is shown in inset of Fig. 6, a linear relationship
is also observed. It can be concluded that the oxidation of
hydrazine may be controlled by a diusion process. The
kinetic parameters were discussed in detail in Ref. [29].
All of this indicates that Ag/MWNT composites exhibit a
high catalytic activity to the electrooxidation of hydrazine
in potential application as a simple, rapid, cheap method
for its determination.

3.4. XRD analysis of Ag/MWNT composites

4. Conclusion

The XRD spectrum of Ag nanoparticles is shown in


Fig. 5. The major diraction peaks of Ag nanoparticles
are observed. All peaks can be indexed as the Ag facecentered cubic (fcc) phase base on the data of the JCPDS le.
While the MWNTs showing a typical peak of (0 0 2) reection of MWNTs or graphite at 22.1. The peaks at 38.9,
45.1, 65.1 and 78.2 can be assigned to (1 1 1), (2 0 0),
(2 2 0), (3 1 1) reection of fcc phase of Ag. The average size
of the Ag particles is 4.3 nm calculated using the Scherrer
formula, which is in good agreement with the result by
the TEM image.

In the present work, Ag nanoparticles were electrocrystallized on 4-aminobenzoic acid monolayer-grafted


MWNTs by a potential-step method. TEM studies show
that well-dispersed particles were anchored onto MWNTs.
And the size range of these particles was about
37 nm.Additionally, Ag/MWNT composites exhibit a high
catalytic activity for the oxidation of hydrazine. The application of carbon nanotubes functionalized with metal, also
alloy, metal oxide, compound semiconductor, and other
nanoparticles, is likely to expand greatly in the future.
Acknowledgement
This work is supported by the National Natural Science
Foundation of China (NNSFC60471014).
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Fig. 6. Cyclic voltammograms of 10 mM N2H4 H2O in 0.1 M K2SO4


solution at the Ag/MWNT electrode (A) and bare MWNT electrode (B).
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