www.elsevier.com/locate/elecom
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
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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
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
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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].
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
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4. Conclusion
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