Journal of Electroanalytical Chemistry 656 (2011) 29–33

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Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

Carbon nanotube decorated with silver nanoparticles via noncovalent interaction

for a novel nonenzymatic sensor towards hydrogen peroxide reduction
Yan Shi a,c, Zhelin Liu a,c, Bo Zhao b, Yujing Sun a,c, Fugang Xu a,c, Yue Zhang a,c, Zhiwei Wen a,c, Haibin Yang b,
Zhuang Li a,c,⇑
a
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022, PR China
b
State Key Laboratory of Superhard Materials, Jilin University, Changchun, Jilin 130012, PR China
c
Graduate School of the Chinese Academy of Science, Beijing 100039, PR China

a r t i c l e i n f o a b s t r a c t

Article history: A novel electrochemical sensor based on the silver decorated carbon nanotube is reported here for the
Received 20 August 2010 accurate and rapid determination of hydrogen peroxide. The hybrid nanostructure was synthesized sep-
Received in revised form 28 January 2011 arately and characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy
Accepted 31 January 2011
(EDX) and X-ray photoelectron spectroscopy (XPS). The high focus on the silver-based hydrogen peroxide
Available online 1 March 2011
sensor spurred us to investigate the determination of the electrocatalytic activity towards hydrogen per-
oxide. The as-prepared electrochemical senor exhibited well-defined response to the reduction of hydro-
Keywords:
gen peroxide. The detection limit of hydrogen peroxide was found to be 1.6 lM, which was lower than
Carbon nanotube
Silver nanoparticle
the certain enzyme-based biosensor.
Electrochemical sensor Ó 2011 Elsevier B.V. All rights reserved.
Hydrogen peroxide
Nonenzymatic

1. Introduction electrocatalysis of immobilized enzymes towards H2O2 reduction

In recent years, silver nanoparticles used as electrochemical
sensors have received much attention due to their excellent
biocompatibility, unique electronic and catalytic properties [1,2].
Meanwhile, the exceptional electrical, chemical, and mechanical
characters [3] made carbon nanotube (CNT) widely used in the con-
struction of chemical sensors and biosensors [4], especially in the
field of supporting materials [5]. The high surface area of CNT made
it possible to load silver nanoparticles with high catalytic activity
[6,7]. Fabricating CNT-supported nanomaterials is thereby desir-
able since it combines both the advantages of CNT and nanomate-
rials which may be helpful in widening the applications. Much
efforts have been made to acquire these hybrid nanomaterials
[8,1]. Among them, a common strategy is termed as ‘‘separate
methodology’’, which means functionalizing CNT and synthesizing
nanomaterials individually and assembling them together [9–11].
On the other hand, it is crucial to detect hydrogen peroxide
(H2O2) accurately and rapidly because H2O2 is an essential media-
tor in many fields [12,13], such as food industries, organic com-
pounds, clinical, and environmental analyses. A great number of
biosensors for H2O2 detection have been developed based on the
[14,15]. Many disadvantages were appeared that the enzymes
were of high cost, critical on the environmental condition, and
instable to provide the biosensors with a complete long-term sta-
bility [16,17]. Taking the superiority of catalytic activity, stability,
and convenience of electron transfer, nanomaterial has become
an excellent substitute for peroxidase, and nanomaterial modified
electrode in sensing H2O2 has been receiving increasing attentions
[18–20]. Lately, silver nanomaterials have been used to sense dif-
ferent biomaterials, and CNT–Ag nanocomposites have been pre-
pared using other methods [21,22], but never by separate route.
In this paper, we fabricated CNT–Ag nanocomposites by attach-
ing Ag nanoparticles onto the surface of CNT. Poly(diallyldimethy-
lammonium chloride) (PDDA), a positive charge provider, was used
on the CNT functionalization. Then, negatively charged Ag nano-
particles were successfully attached onto the walls of CNTs nonco-
valently by electrostatic interaction. The nanocomposite was
further studied by electrochemical methods, which exhibited
well-defined electrocatalytic activity towards H2O2 reduction.
2. Experimental section

⇑ Corresponding author at: State Key Laboratory of Electroanalytical Chemistry, 2.1. Materials
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun, Jilin 130022, PR China. Tel./fax: +86 431 85262057. Chemicals like silver nitrate, sodium citrate, sodium borohy-
E-mail address: zli@ciac.jl.cn (Z. Li). dride, sodium chloride, nitric acid, sulfuric acid, PDDA were all of

1572-6657/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2011.01.036
30 Y. Shi et al. / Journal of Electroanalytical Chemistry 656 (2011) 29–33

analytical grade and used as received without any purification.

Nafion (perfluorinated ion-exchange resin, 5 wt.% solution in a
mixture of lower aliphatic alcohols and water) were purchased
from Aldrich and used as received. Multiwalled carbon nanotubes
(CNTs) were purchased from Shenzhen Nanotech. Port. Co., Ltd.
(Shenzhen, China), and were purified and shortened by refluxing
in 3 M HNO3 for 24 h before functionalization. Ultrapure water
with resistivity no less than 18 MX cm was used throughout all
experiments.

2.2. Apparatus

For the determination of the morphology and chemical compo-

sition, SEM and EDX data were obtained on a XL 30 ESEM FEG
scanning electron microscope equipped with an energy-dispersive
X-ray analyzer at an accelerating voltage of 20 kV. XPS measure-
ment for surface analysis was performed on an ESCALAB-MK II
spectrometer (United Kingdom) with Al Ka X-ray radiation as the
X-ray source for excitation.

2.3. Synthesis of silver nanoparticles

Silver nanoparticles were synthesized according to the method

reported in previous article [23] with slight modifications. In brief,
200 lL of 0.1 M AgNO3 aqueous solution was mixed with 630 lL of
0.1 M sodium citrate aqueous solution and diluted to 19.6 mL,
followed by adding 0.4 mL of 0.1 M NaBH4 aqueous solution drop-
wise. The resulted solution was stayed still for 24 h to totally
decompose NaBH4.

2.4. Synthesis of silver nanoparticles decorating carbon nanotubes

Fifty milligram CNT was mixed with 250 mL of 0.5 M NaCl

aqueous solution containing 0.5 wt.% PDDA, followed by sonicating
for 6 h. The solution was then centrifuged and washed with water
in order to remove the excessive PDDA. Then, 1 mL of CNT was
mixed with 1.8 mL of silver nanoparticles, and sonicated for 2 h.
The product was then centrifuged, washed and concentrated.

Fig. 1. Typical SEM images of carbon nanotubes (A), and silver nanoparticle-
2.5. Electrochemical measurements decorated carbon nanotubes (B).

Twenty-five micrograms hybrid nanostructure solution was

dropped onto glassy carbon (GC) electrode and dried in air. Then
10 lL of 0.05 wt.% Nafion was overlayed onto GC electrode. Elec-
trochemical experiments were all performed with a CHI 660A elec-
trochemical analyzer (CH Instruments, Chenhua Co., Shanghai,
China), and conducted in a conventional three-electrode cell,
which includes a Ag/AgCl (saturated KCl) electrode as reference
electrode, a platinum wire as counter electrode, and a modified
GC electrode (3 mm in diameter) as working electrode. Solutions
were all deaerated with high-purity nitrogen for 20 min prior to
and blanketed with nitrogen during electrochemical experiments.
All electrochemical experiments were carried out in 0.2 M phos-
phate buffer solution (PBS, pH 7.0) as supporting electrolyte.
3. Results and discussion
Fig. 1A shows the typical SEM image of carbon nanotubes before
functionalization. It can be seen that CNTs after acid treatment are
relatively smooth with the average diameter in 50 nm homoge-
neously. Since the surfaces of acid-treated CNTs and Ag nanoparti-
cles are both negatively charged due to the carboxylic acid and
carboxylate groups on the surfaces, unfunctionalized CNTs are
not capable of loading Ag nanoparticles. Here CNTs were firstly
functionalized by PDDA via a noncovalent route, so that the sur-
faces of CNTs were positive charged. Therefore the prepared Ag
nanoparticles can be easily assembled onto the surface of the func-
tionalized CNTs via electrostatic interaction. The schematic illus-
tration of the fabrication of the hybrid nanostructure is shown in
Fig. 2. The decoration of silver nanoparticles onto the surface of
CNTs has been investigated in previous reports [24], but the reduc-
tion of AgNO3 was all carried out in the presence of CNT. Unlike the
previous reports, noncovalent route was introduced into the sys-
tem. We believe that this route could be more favorable to attach
nanoparticles with more controllable size and shape. Fig. 1B shows
the typical SEM image of silver nanoparticle-decorated carbon
nanotubes. Though larger silver aggregates still exist, many indi-
vidual nanoparticles are attached onto the CNT surfaces. These
small nanoparticles should be responsible for enhancing the cata-
lytic activity of hybrid nanostructure due to the enlarged surface
area.
EDX was employed to investigate the chemical composition of
the hybrid nanostructure. It can be seen that two peaks (a larger
peak comes from Si substrate) are mainly originated from the hy-
brid nanostructure. The two peaks of Fig. 3A can be assigned to Ag
and C respectively. The surface chemical composition of the hybrid
nanostructure was further investigated by XPS. Fig. 3B and C shows
the Ag 3d and C 1s regions of XPS spectrum of the hybrid nano-
 Y. Shi et al. / Journal of Electroanalytical Chemistry 656 (2011) 29–33 31

Fig. 2. Schematic illustration of fabrication of silver nanoparticle-decorated carbon nanotube.

368.1
B
374.1
Intensity / a.u.

365 370 375 380

Binding Energy / eV

C 284.6
Intensity / a.u.

280 285 290 295

Binding Energy / eV

Fig. 3. EDX (A), and XPS (B, C), data of silver nanoparticle-decorated carbon nanotubes (B: Ag 3d region; C: 1s region).

structure. As shown in Fig. 3B, the peaks at binding energies of
368.1 and 374.1 eV can be ascribed to Ag 3d5/2 and Ag 3d3/2 respec-
tively, which are in accordance with the metallic Ag previously re-
ported [25]. Besides that, the peak shown in Fig. 3C is agreed with
the characteristic of CNT [26]. Combining the data of EDX and XPS,
the chemical composition of the hybrid nanostructure can be iden-
tified as Ag and C.
Recently, silver-based nanoparticles were found to possess the
ability to catalyze hydrogen peroxide in previous reports [1,2]. In
this study, the silver nanoparticle-decorated carbon nanotubes
32 Y. Shi et al. / Journal of Electroanalytical Chemistry 656 (2011) 29–33

was modified on GC electrode and applied as electrochemical sen- 50 µm

sor towards hydrogen peroxide reduction. Fig. 4 shows the CVs of
0
hybrid nanocomposite modified GC electrode in the absence and 500 µm
presence of H2O2 with different concentrations in N2-saturated -50

Current / µ A
0.2 M PBS (pH 7.0) at the scan rate of 50 mV/s. It can be seen that
no characteristic peak was shown when no H2O2 was introduced -100 200
R=0.997

Current / µ A
into the system. When H2O2 was injected into the 0.2 M PBS, the
current was enhanced a lot and reduction peak appeared, indicat- -150 100

ing the hybrid nanocomposite was of good electrocatalytic activity

towards H2O2. It is notable that with the increment of H2O2 con- -200 0

centration (from the top: 0, 1, 2, 3, 4 mM), the reduction current 0 c H2O42 / mM 8

gradually increased. We also examined the electrocatalytic activity

0 400 800 1200 1600
by changing the scan rates. As shown in Fig. 5, the cathodic peak
Time / s
current increases with the increasing scan rates from 20 to
200 mV/s. The inset of Fig. 5 shows that the peak current increases Fig. 6. Typical amperometric response of hybrid nanostructure modified GC
in a linear relationship with the square root of scan rates in the electrode on successive injection of 0.05 mM and 0.5 mM H2O2 into the stirring
range of 20–200 mV/s, indicating the process is diffusion- 0.2 M PBS (pH 7.0). Applied potential: 450 mV. Inset: plot of H2O2 current versus
controlled. its concentration.

The amperometric response of the hybrid nanostructure modi-

fied GC electrode was shown in Fig. 6 on successive injection of
be the contribution of the evenly dispersed silver nanoparticles,
0.05 mM and 0.5 mM H2O2 into the stirring PBS at an applied po-
the high surface area and the 3D structure of carbon nanotubes.
tential of 450 mV. When adding H2O2 into the stirring PBS, the
The inset of Fig. 6 shows the linear response to the H2O2 concentra-
hybrid nanostructure could achieve the maximum steady-state
tion up to 9 mM. The reproducibility of the sensor calculated from
current within 3 s. The detection limit of as-prepared electrochem-
the relative standard deviation (RSD) for H2O2 sensing was less
ical sensor was 1.6 lM estimated at S/N = 3, which is lower than
than 5% for six measurements on the same electrode. Combining
certain enzyme-based biosensors [27,28]. The fast response should
the data obtained from the experiments and calculation, we could
conclude that the silver nanoparticles decorating carbon nanotube
had great properties on hydrogen peroxide reduction and found to
be a good electrochemical sensor.
0
4. Conclusions
Current / µA

-20
In this study, silver nanoparticles were decorated onto the wall
of carbon nanotube which was functionalized by PDDA via a
-40 0mM noncovalent method. The prepared hybrid nanostructure was
determined by several characterizations. The introduction of non-
-60 4mM covalent method made the nanoparticles attached on the surface
of carbon nanotube uniformly. The electrochemical sensor fabri-
cated with silver nanoparticle-decorated carbon nanotubes is
-80
-0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 found to exhibit fast, stable, and well-defined response towards
hydrogen peroxide reduction which should be the contribution of
Potential / V
the evenly dispersed silver nanoparticles and the 3D structure of
Fig. 4. CVs of hybrid nanostructure modified GC electrode in N2-saturated 0.2 M carbon nanotubes.
PBS (pH 7.0) in the absence and presence of H2O2 with different concentrations
(from the top: 0, 1, 2, 3, 4 mM). Scan rate, 50 mV/s. Acknowledgments

Financial support by the National Natural Science Foundation of

China (20775077), the National Basic Research Program of China
20 20 mV/s (973 Program, No. 2020CB933600), and the Chinese Academy of
0
Sciences (KJCX2-YW-H11) is gratefully acknowledged.
200 mV/s
Current / µA

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