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Sensors and Actuators B 137 (2009) 134–138
Contents lists available at ScienceDirect
Sensors and Actuators B: Chemical
journal homepage: www.elsevier.com/locate/snb
An amperometric glucose biosensor fabricated with Pt nanoparticle-decorated
carbon nanotubes/TiO
2
nanotube arrays composite
Xinyu Pang, Dongmei He, Shenglian Luo, Qingyun Cai
∗
State Key Laboratory of Chemo/Biosensing and Chemometrics, Department of Chemistry, Hunan University, Changsha 410082, People’s Republic of China
article info
Article history:
Received 14 August 2008
Received in revised form
27 September 2008
Accepted 30 September 2008
Available online 15 October 2008
Keywords:
Carbon nanotube
Titania nanotube
Platinum nanoparticles
Glucose biosensor
abstract
Carbon nanotubes (CNTs)-modified titania nanotube (NT) arrays are prepared by vapor-growing CNTs
in the inner of titania NTs. Pt nanoparticles of ∼3 nm in diameter are uniformly decorated on the as
synthesized titania-supported CNTs (TiO
2
/CNTs) electrode, showing remarkably improved catalytic activ-
ities for the oxidation of hydrogen peroxide. The consequent glucose biosensor fabricated by modifying
TiO
2
/CNT/Pt electrode with glucose oxidase (GOx) presents a high sensitivity of 0.24 AmM
−1
cm
−2
to
glucose in the range of 0.006 mM to 1.5 mM with a response time of less than 3 s and a detection limit of
5.7 M at 3 signal/noise ratio.
© 2008 Elsevier B.V. All rights reserved.
1. Introduction
Since the development of the first glucose biosensor, much
attention has been focused on the improvement of the response
performances of enzyme electrodes for biosensor research [1–8].
Wireless glucose biosensors were developed by using a pH-
responding polymer [4] or a glucose-responding mass-changing
polymer [9] as the sensing coating. Significant research and efforts
concerning preparation of glucose sensor for blood glucose mon-
itoring have been reported [2–4] and most of them are based on
the determination of hydrogen peroxide [5–8]. Carbon nanotubes
(CNT) have attracted increasing research interests due to their
unique electrical, geometrical, and mechanical properties [10] that
make them excellent materials for the construction of ultrasensi-
tive electrochemical biosensors which has led more recently to an
upsurge of research on incorporating CNTs into biosensing plat-
forms [7,8]. It has been demonstrated that electrodes based on
the combination of metal nanoparticles and CNT exhibits highly
sensitive and selective responses to hydrogen peroxide generated
by enzymatic reactions [7,8,11]. Wang et al. [11] reported that
multi-wall CNTs dissolved in Nafion could be applied to construct
amperometric sensor for hydrogen peroxide. Electrochemists have
also successfully taken advantage of CNT for accelerating the elec-
∗
Corresponding author. Tel.: +86 731 8822170; fax: +86 731 8821848.
E-mail address: qycai0001@hnu.cn (Q. Cai).
tron transfer reaction involving electrocatalytic activities toward
H
2
O
2
, NADH, cysteine, ascorbic acid, nucleic acids, and homocys-
teine [12,13].
Enzyme immobilization is a key step in fabrication of a sen-
sitive and stable biosensor. Generally in biosensors enzymes are
immobilized to the sensor surface by either cross-linking with, e.g.
glutaraldehyde [14] or being protected with a thin gel or poly-
mer layer of, e.g. Nafion [15,16] to avoid the loss of enzymes. In
particular, new materials and methods were researched for get-
ting more active and stable biosensors in immobilizing enzyme
[17,18]. Nano-architectured TiO
2
has also attracted considerable
interest due to the superior properties such as large specific sur-
face area, high uniformity, and excellent biocompatibility [19–25],
and has been applied in a variety of fields including highly effi-
cient photocatalysis [20,21], fuel cells [22], biosensors [23], and
hydrogen sensor [24,25]. Liu and Chen [23] fabricated a biosen-
sor for measuring H
2
O
2
utilizing a TiO
2
nanotube array on which
horseradish peroxidase and thionine were adsorbed. The high uni-
formity and superior semi-conductivity of the TiO
2
NT array makes
it a sensitive hydrogen gas-responsive material [24,25].TiO
2
film
has also been utilized in the immobilization of proteins for bio-
analytical applications due to its stability and biocompatibility
[26–28]. Topoglidis et al. reported the adsorption of protein on
nanocrystalline TiO
2
films based on the electrostatic interactions
between the negatively and positively charged groups of them [28].
These successful applications indicate that nanocrystalline TiO
2
materials are promising ideal functional materials for biosensor
substrate.
0925-4005/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2008.09.051
X. Pang et al. / Sensors and Actuators B 137 (2009) 134–138 135
Here, an electrocatalytic enzyme biosensor based on Pt
nanoparticles-decorated TiO
2
/CNT composite substrate was devel-
oped. The Electrochemical catalytic activity of the as-prepared
TiO
2
/CNT/Pt electrode in response to H
2
O
2
was investigated. An
amperometric glucose oxidase (GOx) biosensor was fabricated
by modifying GOx on the as-prepared electrode, and a sensitive
response to glucose was achieved.
2. Experimental
2.1. Reagents and apparatus
Titanium foil (99.8%, 0.127 mm thick) was purchased from
Aldrich (Milwaukee, WI). Sodium fluoride, citric acid, hexachloro-
platinic (IV) acid and glucose of analytical reagent grade were
purchased from commercial sources and used as supplied. GOx
(type: X-S, Aspergillus niger, 127 units/mg) were obtained from
Aldrich–Sigma (St. Louis, MO). The supporting electrolyte was
0.067 M pH 7.2 phosphate buffer solutions (PBS). Double distille d
water was used throughout the experiments.
The catalyst topology was characterized using a field-emission
scanning electron microscope (FE–SEM) operating at 5 kV (JSM
6700F; JEOL, Tokyo, Japan). An energy dispersive X-ray (EDX) spec-
trometer fitted to the scanning electron microscope was used
for elemental analysis. Transmission electron microscopy (TEM)
images were obtained using a JEM 3010 (JEOL; Tokyo, Japan)
operating at 300 kV. Cyclic voltammetry (CV) and amperometric
measurements were performed in a standard three-electrode con-
figuration with the modified electrodes as working electrode, a
platinum flake auxiliary electrode, and Ag/AgCl reference electrode
(saturated by KCl) by an electrochemical working station (CHI660B;
CH Instruments, Inc., Austin, TX).
2.2. Preparation of TiO
2
/CNT/Pt/GOx electrode
The construction process of the electrode is schemati-
cally shown in Fig. 1. Prior to anodization, the titanium foil
(3 mm× 15 mm) was degreased by sonication in acetone and then
ethanol. The cleaned titanium ribbon was anodized at anodiza-
tion voltages of 15 V in an electrolyte containing 0.2 M citric acid
and 0.1 M NaF at room temperature for 5 h in a conventional two-
electrode system with a platinum cathode. The titanium sample
was only partially immersed in the electrolyte, with the upper
un-anodized portion used as an electrical contact. The efficient
geometrical area of the anodize d part (both sides) is 0.6 cm
2
. The
resulting nanotube arrays were ∼90 nm in diameter.
CNTs were prepared by chemical vapor deposition (CVD)accord-
ing to paper [29]. Nickel cations were introduced into the TiO
2
nanotubes by capillary action and electric field, and electrochemi-
cally reduced to form Ni nanoparticles as the catalyst for the growth
of CNTs. CNTs were grown from the inner of TiO
2
nanotubes through
catalytic decomposition of acetylene over Ni nanoparticles in a vac-
uum tube furnace for 1 h at 700
◦
C.
On the CNT-modified TiO
2
NTs, Pt nanoparticles were electode-
posited using chronopotentiometry at a current density of 5 mA/s
in astandard three-electrode system with a TiO
2
/CNT working elec-
trode, a platinumwire auxiliary electrode, and an Ag/AgCl reference
electrode. The catalytic activity of TiO
2
/CNT/Pt electrode was deter-
mined by cyclic voltammetry with 1 mM H
2
O
2
as the testing probe
at a scan rate of 100 mV s
−1
in a solution containing 10 mL pH 7.2
(measured with Mettler-Toledo Delta 320 pH meter) phosphate
buffer solution (PBS) and 0.1 M NaCl.
The enzyme solution was prepared by dissolving 36 mg of GOx
in 1 mL of 0.067 M PBS(pH 7.2) containing 0.1 M NaCl. A TiO
2
/CNT/Pt
electrode was loaded with 20 L enzyme solution, and dried at 4
◦
C
overnight. The resultant electrode was rinsed with PBS to remove
free enzymes. When not in use, the enzyme biosensor was stored in
phosphate buffer (pH 7.2) at 4
◦
C in a refrigerator. Amperometry of
glucose were performed in 10 mL phosphate buffer solution under
stirring at ambient temperature.
3. Results and discussion
3.1. Characterization of TiO
2
/CNT/Pt electrode
To investigate the microstructure of the as synthesized
TiO
2
/CNT/Pt electrode, it was characterized by SEM and TEM. Fig. 2
shows the topography of the TiO
2
nanotubes and configuration of
TiO
2
/CNT/Pt electrode. Fig. 2a shows that uniform TiO
2
nanotubes
were formed with a pore size of about 90 nm in diameter and a
length of about 320nm (shown in the inset of Fig. 2a). Fig. 2(b)
shows that long CNTs with an average diameter of about 50 nm are
grownonTiO
2
NTs. The CNTs were grownfrom the inside of the TiO
2
NTs [30] as the Ni catalyst was electrodeposited inside the TiO
2
NTs.
To confirm this speculation the surface CNTs was removed by son-
ication, and a CNTs-embedded porous annealed TiO
2
substrate is
seen as shown inFig. 2(c), where the TiO
2
NTs were collapsed during
the growth process of CNTs. Since the CNTs were forme d at around
650
◦
C [31] before the collapse of TiO
2
NTs at around 680
◦
C [32],
Fig. 1. Schematic showing the construction of the Pt nanoparticle-decorated CNT/TiO
2
NT electrode, step (a): electrodeposition of Ni nanoparticles into TiO
2
NTs; step (b):
CNTs development from the inner of TiO
2
by chemical vapor deposition; and step (c): electrodeposition of Pt nanoparticles on CNTs.
136 X. Pang et al. / Sensors and Actuators B 137 (2009) 134–138
Fig. 2. SEM micrographs showing the morphology of TiO
2
/CNT/Pt electrode: (a) TiO
2
NTs prepared at 15 V with 90 nm in diameter and 300 nm in length (the inset), (b) Pt
nanopaticles-deposited CNTs grown from the inner of TiO
2
NTs; the corresponding TEM image is shown in the inset and the corresponding EDX pattern is shown in (d). (c)
The SEM image of TiO
2
/CNT/Pt electrode after removing the surface CNTs.
CNTs were embedded in TiO
2
substrate which existed in the mix-
ture of rutile and anatase phase based on the former results [19,32].
The CNTs-embedded TiO
2
substrate facilitates the electron trans-
fer due to its enhanced conductivity, and the disorderly distributed
CNTs provide a large surface area for Pt nanoparticles dispersion
and a conductive network for electrons transfer. The TEM imaging
(the inset in Fig. 2b) shows that Pt nanoparticles at an average size
∼3 nm are uniformly dispersed within the CNT network. The corre-
sponding EDX spectrum given in Fig. 2(d) shows the presence of Ti,
Pt, C, and O, with a Ti:O atomic ratio of 1:2. The uniformly dispersed
small Pt nanoparticles are essential to a high catalytic activity.
3.2. Detection of hydrogen peroxide
While the quantification of glucose is based on the electro-
chemical detection of the enzymatically liberated H
2
O
2
, the sensor
sensitivity is dependent on the electrochemical response ofthe sen-
sor to H
2
O
2
; electrodes with high catalytic efficiency to H
2
O
2
would
achieve high sensitivity to glucose. The electrochemical response
of the TiO
2
/CNT/Pt electrode to H
2
O
2
was firstly investigated. Fig. 3
shows the cyclic voltammograms of the TiO
2
/CNT/Pt electrode in
the absence (curve d) and in the presence of increasing H
2
O
2
con-
centration (curves a–c). The response of the TiO
2
/CNT/Pt electrode
in 0.067 M pH 7.2 PBS displays a distinct background current, which
indicates that the incorporation of CNT with TiO
2
NTs facilitates
the electron transfer between electrode and H
2
O
2
. A pair of well-
defined redox peaks (Epa, 0.45 V;Epc, 0.0 V) of H
2
O
2
were observed,
and the H
2
O
2
oxidation peak potential at the TiO
2
/CNT/Pt electrode
is at 0.45 V, which is 230 mV lower than that at the Pt bulk electrode
(0.67 V). This suggests the catalytic activity of Pt nanopartilces to
the oxidation of H
2
O
2
[14] and a faster electron transfer rate at
the TiO
2
/CNT/Pt electrode. Hall et al. [33] investigated the mecha-
nism of electrochemical oxidation of H
2
O
2
at platinum electrodes,
concluding that the oxidation reaction is an adsorption-controlled
Fig. 3. Cyclic voltammograms of TiO
2
/CNT/Pt electrode in 0.067 M pH 7.2 phosphate
buffer containing: (a) 15, (b) 5, (c) 2.5, and (d) 0 mM H
2
O
2
. Scan rate: 100 mV/s.
X. Pang et al. / Sensors and Actuators B 137 (2009) 134–138 137
Fig. 4. Ampermetric responses of TiO
2
/CNT/Pt electrode to continuously injection of
1 mol/L H
2
O
2
(pH 7.2, 0.067 mol/L PBS). Working potential: 400 mV (vs. Ag/AgCl);
the inset shows the calibration curve.
mechanism, which depends on the potential, temperature, phos-
phate buffer, pH value, and chloride concentration. The mechanism
should be applicable to the oxidation of H
2
O
2
at the TiO
2
/CNT/Pt
electrode; the high adsorbability of TiO
2
and CNT to H
2
O
2
facil-
itate the oxidation reaction of H
2
O
2
. Such electrocatalytic action
facilitates low-potential amperometric measurements of hydrogen
peroxide.
The redox currents of H
2
O
2
increase with the increase of H
2
O
2
concentration. The peak potential difference is 0.45V, indicating
an irreversible redox reaction of H
2
O
2
at the TiO
2
/CNT/Pt electrode.
The catalytic activity toward H
2
O
2
of the TiO
2
/CNT/Pt electrode was
assessed by quantitative analysis of the amperometric response to
successive injection of 1 MH
2
O
2
. As shown in Fig. 4, a current
response (i)of0.145A/M was achieved at applied poten-
tial of 400 mV, with a liner response in the range of 0.001 mM
to 2 mM with a slope of 0.134 A/M(R
2
= 0.997) and a limit of
detection (LOD) of 1 M at a signal-to-noise ratio of 3 as shown
in the inset. The achieved LOD is much lower than what was
obtained at a horseradish peroxidase-modified multi-wall carbon
nanotubes/chitosan sensor (10M) [34], and at the mesoporous
Pt microelectrode (4.5M) [35], indicating that the TiO
2
/CNT/Pt
electrode is with a superior electrocatalytic activity toward the
oxidation of H
2
O
2
.
3.3. Detection of glucose
A glucose biosensor was fabricated by modifying GOx onto
the as prepared TiO
2
/CNT/Pt electrode which detects H
2
O
2
gen-
erated by enzymatic reactions. Fig. 5 shows the amperometric
responses of the glucose sensor to the successive additions of 1 mM
glucose at applied potential of 400 mV vs. Ag/AgCl reference elec-
trode. An evident current response (i)of0.138A was achieved.
Successive addition of 1 mM glucose (n = 7) showed a relative stan-
dard deviation (R.S.D.) of 3.2% verifying a good repeatability of
the sensor. As shown in the inset, the nanocomposite biosensor
exhibits a linear response from 0.01 mM to 1.5mM with a response
slope of 0.146 AmM
−1
(R
2
= 0.998). A sensitivity of as high as
0.24 AmM
−1
cm
−2
was achieved. The LOD was 5.7 M at a signal-
to-noise ratio of 3, and the response time was less than 3 s. The
proposed sensor represents a simple and fast approach to the detec-
tion of glucose.
The inter-sensor reproducibility was investigated at a glucose
concentration of 0.01 mM. Three independently made GOx sensors
showed an acceptable reproducibility with a variation coefficient of
Fig. 5. Ampermetric responses of TiO
2
/CNT/Pt/GOx sensor to continuously injec-
tion of 1 mmol/L glucose (pH 7.2, 0.067 mol/L PBS). Working potential: 400 mV (vs.
Ag/AgCl); the inset shows the calibration curve.
4.8% (n = 5) for the current determination at 0.01 mM g lucose. The
sensor response to 0.01 mM glucose was decreased by 18% after one
month mostly due to the decrease in the enzyme activity.
3.4. Performances of biosensors
The functions of the CNT and Pt nanoparticles were inves-
tigated by fabricating GOx sensors with (a) bare TiO
2
NTs, (b)
Pt-deposited TiO
2
NTs (TiO
2
/Pt), (c) Pt-deposited TiO
2
NTs/CNT
composite (TiO
2
/CNT/Pt), and (d) the electrode c but the sur-
face CNT was removed (TiO
2
/(CNT)/Pt) as substrate, respectively.
The Pt loading was 0.126 mg/cm
2
. Fig. 6 shows the amperomet-
ric responses of the four sensors upon subsequent additions of
1 mM glucose. The TiO
2
/CNT/Pt/GOx sensor exhibits the highest
electrocatalytic activity toward glucose (Fig. 6c), while the bare
TiO
2
NT/GOx sensor exhibits negligible response (Fig. 6a), indicat-
ing the catalytic activity of Pt nanoparticles. The current response
(i)atTiO
2
/CNT/Pt/GOx sensor (Fig. 6c) is ten times that at the
TiO
2
/Pt/GOx sensor (Fig. 6b), indicating that the CNT enhances the
catalytic activity of Pt due to the large surface area of the CNT net-
Fig. 6. Amperometric responses of sensors: (a) TiO
2
/GOx, (b) TiO
2
/Pt/GOx, (c)
TiO
2
/CNT/Pt/GOx, and (d) TiO
2
(CNT)/Pt/GOx in 10 mM PBS (pH 7.2) to continu-
ous injection of 1 mM glucose at 400 mV working potential (vs. Ag/AgCl). Scan rate:
100mVs
−1
.
138 X. Pang et al. / Sensors and Actuators B 137 (2009) 134–138
work which increases the Pt loading and facilitates the electron
transfer. In addition, CNT network provides superior adsorption
ability toward glucose. The interesting result is that even the sur-
face CNT has been removed (TiO
2
(CNT)/Pt/GOx sensor), the current
response (Fig. 6d) is still three times that at the TiO
2
/Pt/GOx sen-
sor (Fig. 6b), confirming again that the CNTs were grown from the
inner of TiO
2
NTs, and the CNTs-embedded TiO
2
showed sensitive
responses to glucose. As for practical applications, we can remove
the surface CNTs to obtain a stable electrode structure. There would
be no potential bio-hazards resulted from the lose of CNTs.
4. Conclusions
A Pt nanoparticle-decorated electrode was fabricated by using
the TiO
2
/CNT composite as substrate. The electrode exhibits a high
catalytic efficiency to the oxidation of hydrogen peroxide with a
slop of 0.134 A/mM. The resultant GOx sensor by modifying GOx
on the as-prepared electrode displays a good response to glucose
with a sensitivity of 0.24 AmM
−1
cm
−2
and a LOD of 5.7 M. The
sensor-to-sensor reproducibility was measured on three indepen-
dently made GOx sensors with a variation coefficient of 4.8%. The
high catalytic activity is ascribed to the large surface area and good
conductivity of CNT network, the highly dispersed Pt nanoparticles,
and the excellent biocompatibility of TiO
2
to H
2
O
2
.
Acknowledgment
Funding for this work by the National Science Foundation of
China under Grants No. 20775024, and the Specialized Research
Fund for the Doctoral Program of Higher Education under grant
20050532024 is gratefully acknowledged. Professor Shenglian
Luo gratefully acknowledges partial support of this work by the
National Science Foundation for Distinguished Young Scholars
under Grant No. 50725825.
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Biographies
Xinyu Pang received BS degree in chemistry from Hunan University, PR China in
2006. Now he is pursuing his MS degree in analytical chemistry at Hunan University
in the research group of professor Qingyun Cai.
Dongmei He received BS degree in chemistry from Henyang Normal University, PR
China in 2005 and MS degree in analytical chemistry from Hunan University, PR
China in 2008. She is currently an assistant researcher at Kangde Solar Energy Int.
Co., Dongguan, Guandong, PR, China.
Qingyun Cai received BA degree in 1983 and MS degree in 1986, both in chemistry
from Hunan University, PR China. Since then he has been on the faculty at Hunan
University. He earned the PhD in chemistry in 1996 from Hunan University. He is cur-
rently a full-time professor in the Department of Chemistry at Hunan University, PR
China. His primary research interests concern the chemo/biosensors and functional
(nano) materials.
. www.elsevier.com/locate/snb
An amperometric glucose biosensor fabricated with Pt nanoparticle-decorated
carbon nanotubes/TiO
2
nanotube arrays composite
Xinyu Pang, Dongmei. September 2008
Accepted 30 September 2008
Available online 15 October 2008
Keywords:
Carbon nanotube
Titania nanotube
Platinum nanoparticles
Glucose biosensor
abstract
Carbon
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