Sensors and Actuators B 155 (2011) 716721

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Sensors and Actuators B: Chemical

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

Ag nanoparticles modied TiO2 spherical heterostructures with enhanced

gas-sensing performance
Xiaoli Cheng, Yingming Xu , Shan Gao, Hui Zhao, Lihua Huo
Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, PR China

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

Article history: Monodispersed TiO2 spherical colloids with diameters of about 250 nm were prepared by a solgel
Received 14 December 2010 method. Heterostructural AgTiO2 spheres were manipulated by surface engineering, in which the Ag
Received in revised form 15 January 2011 nanoparticles with an average size of 10 nm were uniformly distributed on the surface of the TiO2
Accepted 20 January 2011
nanospheres by in situ reduction and growth. The gas-sensing properties of the TiO2 nanospheres and
Available online 31 January 2011
heterostructural AgTiO2 nanospheres to ethanol and acetone were measured at 350 C. The results indi-
cated that Ag nanoparticles greatly enhanced the response, stability and response characteristic of TiO2
Keywords:
nanospheres to the tested gases. Response times of AgTiO2 sensor to 30 ppm acetone and 50 ppm ethanol
AgTiO2 heterostructure
Spherical colloids
were <5 s.
Gas-sensing 2011 Elsevier B.V. All rights reserved.
Ethanol
Acetone

1. Introduction gas-sensing materials; for example, morphologically different, TiO2

It is necessary to monitor colorless organic vapour concentra-
tions in the environment for health and the workplace for safety due
to their toxicity and explosive possibility [1]. Nanometer-scaled
TiO2 , an important multifunctional n-type semiconductor, has
stimulated considerable research efforts in seeking morphology-
dependent physical properties and applications in gas sensors, solar
cells, photocatalysis, etc. [26]. Especially, as an organic vapour
sensing material, TiO2 is nontoxic, highly chemically stable and low
costing in comparison with other common metal oxides such as
SnO2 and ZnO. In fact, a variety of TiO2 nanostructures with dif-
ferent sizes and morphologies, including nanoparticles, nanotubes,
nanobelts, and nanowires, have been examined for ethanol and
acetone sensing and exhibited good sensing characteristics [710].
However, several drawbacks, such as low response, poor selectivity
and stability, and long response and recovery times, limited previ-
ously studied TiO2 materials in the practical application. Recently,
Hayakawa et al. [11] reported the Pt dispersed-TiO2 nanoparticles
with an improved selectivity to trimethylamine and NH3 . Hu et al.
[12] reported that heterostructural AgTiO2 nanobelts exhibited
high sensitivity and rapid response for ethanol vapour detection.
These two results remind us that the deposition of noble metal
nanoparticles onto the surface of oxide nanostructures can improve
the response and selectivity, and reduce response time [1316]. For
exploiting gas sensors, it is desirable to develop high performance,
heterostructures modied by noble metal nanoparticles.
The nanometer-scaled TiO2 spherical colloids have currently
been one of the most active areas of material research due to their
high refractive indices, excellent catalytic activities and chemi-
cal stabilities, along with potential applications widely spreading
from photonic crystals to photocatalysis [17,18]. In particular, noble
metal nanoparticles are easily deposited onto the surface of TiO2
nanospheres through the strong synergistic interactions, which fur-
ther enhance the catalytic activities and photoelectronic properties
of TiO2 nanospheres due to modulation of the energy band struc-
tures and surface-to-volume ratios by surface engineering [1921].
Because of its unique physical and chemical characteristics, the
AgTiO2 spherical heterostructure is a remarkable candidate for
organic vapour detection. However, the application of the AgTiO2
spherical heterostructures in sensors remains unexplored. Here,
we successfully prepared the monodispersed TiO2 spherical col-
loids by a solgel method and AgTiO2 spherical heterostructures
by surface engineering of in situ reduction and growth. The gas-
sensing properties of these two materials to vapour phase ethanol
and acetone were measured. The results indicated that modied
Ag nanoparticles could greatly enhance the response, stability and
response characteristic of TiO2 nanospheres to the tested gases.
2. Experimental
2.1. Synthesis of TiO2 nanospheres

Corresponding authors. Tel.: +86 451 86608426; fax: +86 451 86608426. The TiO2 nanospheres were synthesized following the reported
E-mail addresses: ymxu79@yahoo.com.cn (Y. Xu), lhhuo68@yahoo.com (L. Huo). procedure [17] with modications. Tetraethyl titanate (3.5 mL) was

0925-4005/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2011.01.036
 X. Cheng et al. / Sensors and Actuators B 155 (2011) 716721 717

added to ethylene glycol (50 mL) and magnetically stirred for 10 h

at room temperature. Then, the mixture was poured into a solu-
tion containing 170 mL acetone and 2.7 mL water with vigorously
stirring for 1 h. The white precipitate was harvested by centrifu-
gation, followed by washing with distilled water and ethanol ve
times to remove free ethylene glycol from the surfaces of the gly-
colate particles. Finally, the precursor was dried at 60 C for 2 h. The
precursor was annealed at 500 C for 1 h and ready for gas sensing
applications.

2.2. Preparation of AgTiO2 spherical heterostructures

TiO2 precursor nanospheres (0.1 g) were suspended in 20 mL

distilled water with stirring for 10 min. Then, 20 mL HCl solution
with concentration of 0.02 mol/L containing 0.1 g SnCl2 was added
into the above solution while stirring and the mixture solution was
observed to become yellow quickly. After 10 min, the precipitate
was centrifuged and washed with distilled water ve times. The Fig. 1. XRD patterns of the AgTiO2 powders annealed at 500 C for 1 h.
obtained precipitate was immersed in 4 mL ethanol solution con-
taining 5 mmol/L AgNO3 while stirring, and then irradiated using
UV light (340 nm, 30 mW cm2 ) for 5 h, yielding the pale-yellow can be observed because the low diffraction intensity of ounce
precipitate. After centrifuged and washed with distilled water ve silver is immersed in that of TiO2 . Furthermore, a detail com-
times, the pale-yellow precipitate was dried at 60 C for 12 h and ponent analysis of the AgTiO2 heterostructures was carried out
then annealed at 500 C for 1 h. with XPS measurements. Fig. 2a shows the Ti 2p spectra of the
heterostructural AgTiO2 nanospheres. The shape, binding energy
2.3. Characterization and spinorbit splitting of the Ti 2p photoemission envelope are
characteristics of TiO2 [22]. Fig. 2b exhibits the Ag 3d spectra of
Morphology and structure of the sample was examined with heterostructural AgTiO2 nanospheres. The characteristic Ag 3d5/2
scanning electron microscopy (SEM) (FEI/Philips, XL-30). Phase and
crystalline of the AgTiO2 spherical powder annealed at 500 C
for 1 h were determined with X-ray diffractometer (XRD) (Rigaku,
D/MAX-3B) with Cu K radiation ( = 0.15405 nm). The sample was
also analyzed by X-ray photoelectron spectroscope (XPS) (VG Sci-
entic, ESCALAB 250) with Al K radiation (h = 1486.6 eV) within
0.2 eV deviation in the binding energy position.

2.4. Sensor fabrication and measurement

Commercial Taguchi Gas Sensor (TGS), fabricated onto a cylin-

drical Al2 O3 tube of a 4 mm length with two permanent gold
coatings spaced 1 mm, was coated by three-layer paste, and then
sintered at 350 C for 3 h in air to form a thick sensing lm. The
detailed sensor fabrication procedure was reported previously [22].
The electrical resistance of the sensor in various gas concentrations
was measured with a digital gas-sensitive electrometer (Qingdao,
RQ-2, China) at various temperatures. Ethanol and acetone with
different concentrations were injected into a 1 L vacuum container
by a microsyringe and vapourous with heating. After resistance of
the sensor reached a steady state in air, the sensor was immediately
placed into the container with the desired concentration of the test
gas. The response is dened as: Ra/Rg, where Ra and Rg are the
sensor resistances measured in air and in tested gas, respectively.
The time required for a sensor to reach 90% of the total resistance
change was dened as the response time in case of adsorption, or
the recovery time in case of desorption.

3. Results and discussion

3.1. Structure and morphology

The as-prepared precursor before calcinations is in an amor-

phous phase. The XRD pattern of the AgTiO2 powders annealed
at 500 C for 1 h is shown in Fig. 1. The d-values calculated are in
agreement with those given in the standard data (JCPDS, 21-1272),
suggesting that the as-prepared precursor has crystallized in a pure
anatase phase. No obvious peaks for metallic silver nanoparticles Fig. 2. XPS Ti 2p (a) and Ag 3d (b) spectra of the AgTiO2 powder.
718 X. Cheng et al. / Sensors and Actuators B 155 (2011) 716721

peak with a binding energy of 368.0 eV and a 6.0 eV splitting of the

3d doublet, suggests that the deposited silver nanoparticles exist
in a form of metallic silver on the surface of TiO2 nanostructures
[23,24].
The SEM images of the AgTiO2 and TiO2 samples in Fig. 3
show that the TiO2 precursor spheres with smooth surfaces are
almost monodisperse spherical colloids with diameter of about
250 nm. After the TiO2 spherical colloids were immersed in the
AgNO3 solution and in situ photoreduced for 5 h, the smooth sur-
faces were observed to become rough. This result indicates that
Ag nanoparticles are uniformly distributed on the surface of the
TiO2 spherical colloids with average size of 10 nm. The diameters
of the heterostructural AgTiO2 nanospheres are reduced by 10%
after annealing at 500 C for 1 h. In order to further conrm the
composition of the AgTiO2 nanosphere, EDX analysis was carried
out, which presents the existence of Ag, O and Ti, while Sn is not
detected as shown in the inset of Fig. 3c.

3.2. Process of heterostructural AgTiO2 nanosphere

Fig. 4 schematically depicts the overall preparation proce-

dure for loading Ag nanoparticles onto the surface of the TiO2
nanospheres. This is a four-step process. The rst step is to
prepare the TiO2 nanospheres according to the reported proce-
dure [17] with minor modications. The second step is to obtain
hydroxyl-rich, spherical colloids through the TiO2 nanosphere
powder suspending in distilled water for 10 min. In the third step,
Sn(II) ions are attached to the surface of hydroxyl-rich TiO2 spher-
ical colloids through inorganic grafting after the spherical colloids
are impregnated into SnCl2 solution, and then Ag(I) ions are chemi-
cally in situ reduced to yield Ag seeds by the linked Sn(II) species as
a reducing reagent. In the fourth step, under UV irradiation, pho-
toexcited electrons further reduce Ag(I) ions and control growth
of Ag nanoparticles around the seed sites on the TiO2 spherical
colloids surface. Finally, the heterostructural AgTiO2 nanospheres
form after annealing at 500 C for 1 h.

3.3. Gas-sensing property

The responses of the TiO2 and AgTiO2 thick lm sensors to

ethanol and acetone were measured at 350 C in air. Fig. 5 shows
the response of the thick lm sensors versus the concentration of
the testing gases. The linear relationship in the detection range
indicates that the response increases with the testing gas con-
centration. The TiO2 nanospheres based sensors exhibit a better
response to ethanol than acetone with detection limits of 200 ppm
and 1000 ppm for ethanol and acetone, respectively.
By comparison with the TiO2 nanospheres based sensors,
the heterostructural AgTiO2 nanospheres based sensors exhibit
improved sensing properties. The response increases 35 times
while the detection limit reduced 4 and 33 times for ethanol and
acetone, respectively. The differences of the two kinds of lms
result from the following reasons: (a) the Ag nanoparticles improve
the specic surface area and therefore effective adsorption sites
on the heterostructural AgTiO2 lm surface; (b) the resistance
of AgTiO2 composite material (90 M) is lower than that of
TiO2 sensing material (97 M). The Ag nanoparticles modify the
AgTiO2 heterostructures and enhance the electrons conduction of
the lm. When the sensors are exposed to organic vapour, the -H Fig. 3. SEM images of the TiO2 precursor (a, b) and AgTiO2 spheres (c, d). Inset of
(three hydrogen atoms attached to methyl group) atoms of vapour (c), the EDX pattern of AgTiO2 spheres.
molecules are easily dissociated onto the Ag nanoparticle surface.
Then the dissociated -H atoms transfer to the surface of AgTiO2 AgTiO2 spheres present better gas-sensing properties than those
nanospheres and quickly interact with the pre-adsorbed oxygen with pure TiO2 spheres. In addition, the response of the AgTiO2
ions. Subsequently, the change of electron density on the surface of lms against acetone is higher than that of ethanol, which may be
the AgTiO2 spheres leads to a big change in resistance of the sens- caused by the -H atoms of acetone quickly dissociated onto the
ing material. Therefore, the lms prepared with heterostructural heterostructural surface.
 X. Cheng et al. / Sensors and Actuators B 155 (2011) 716721 719

Fig. 4. Schematic process for the Ag nanoparticles modied onto the surface of TiO2 spheres.

Response and recovery behaviours are important characteristics

for evaluating performance of gas sensors. Fig. 6 shows the response
and recovery curves based on the TiO2 and AgTiO2 thick lms with
acetone concentration changing from 100 to 10000 ppm as well as
Table 1 lists all the response and recovery times. The response and
recovery times for the AgTiO2 sensors are less than 5 s and 50 s,
respectively while the response and recovery times for TiO2 sensors
are relatively slow as 120 s and 350 s, respectively. After loading
the Ag nanoparticles, the response and recovery times of the TiO2
sensors are shortened 24 and 7 times, respectively. This likely rea-
son is that dissociation of the -H atoms in testing molecules is
easier and faster onto the AgTiO2 surface, resulting in a rapid
decrease in the O2 ions concentration on the surface and a sharp
increase in the electron concentration, which exhibits an ultrafast
response.

Fig. 5. Response of the TiO2 and AgTiO2 sensors versus concentrations of ethanol Fig. 6. Transient responserecovery characteristics of the TiO2 and AgTiO2 lm in
and acetone. different concentration of acetone.
720 X. Cheng et al. / Sensors and Actuators B 155 (2011) 716721
Table 1
Response, response and recovery times of the TiO2 and AgTiO2 lm sensors.
Vapour concentration (1000 ppm) Response (Ra/Rg)
AgTiO2 TiO2
Ethanol
0.05 2.0
0.1 3.3
0.3 5.1
0.5 6.5
1 9.5
3 19.5
5 24.1 10.6
10 41.7 15.1
Acetone
0.03 2.1
0.1 3.9
0.3 5.2
0.5 7.2
1 10.6
3 20.0
5 29.1
10 47.7 11.1
The reproducibility experiments were conducted for different
samples. With the same AgTiO2 lm in 100 ppm ethanol and ace-
tone for 10 times, the standard error of measurements is within 5%.
Long-term stability and reproducibility of the AgTiO2 lms were
also studied for ethanol and acetone measurements. The results
show that after one-year storage, the sensors remain the original
response and response time with changes within 25%.
4. Conclusion
The thick lm sensors based on pure TiO2 and heterostructural
AgTiO2 nanospheres have been successfully developed. The gas
(ethanol and acetone) sensing properties were characterized and
the results indicate that the Ag nanoparticles modication signif-
icantly enhances the response and stability of TiO2 nanospheres
with an ultrafast response of less than 5 s to 50 ppm ethanol and
30 ppm acetone, respectively.
Acknowledgements
This work is supported by Program for New Century Excel-
lent Talents in University (NCET-06-0349), Science and Technology
Project of Heilongjiang Province (WB10A204), Innovation Team
of Heilongjiang University (Hdtd2010-04), Youth Foundation of
Harbin (2005AFXJ059) and Heilongjiang Educational Department
(11551337, 11551341).
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Biographies
Xiaoli Cheng was born in 1978. She obtained her MSc degree from School of Chem-
istry and Materials Science, Heilongjiang University, in 2004. Now she is studying for
Ph.D. in the same college with the main interests of inorganic functional materials.
 X. Cheng et al. / Sensors and Actuators B 155 (2011) 716721
Yingming Xu received his PhD in analytical chemistry from Changchun Institute
of Applied Chemistry of Chinese Academy of Sciences, China, in 2010. His research
interests are mainly directed towards the hierarchical oxide materials and their
application as gas sensors.
Shan Gao nished his postdoctoral work in Key Laboratory of Inorganic Synthesis
and Preparative Chemistry, Jilin University, China, in 2000. He is now the professor
of School of Chemistry and Materials Science, Heilongjiang University. His research
interests are mainly directed towards the aspects of functional coordination chem-
istry and nano-materials.
721
Hui Zhao received his PhD from Department of Chemistry, Jilin University, China,
in 1999. He is now the professor of School of Chemistry and Materials Science, Hei-
longjiang University. His working interests are the study of oxide electrolyte and
electrode materials for SOFC and organicinorganic catalytic materials.
Lihua Huo acquired her PhD in physical chemistry from Fuzhou University, China,
in 1997. She is now the professor of School of Chemistry and Materials Science,
Heilongjiang University. Her research interests are mainly directed towards the
development of nano-materials and organicinorganic hybrid materials and their
application as gas sensors.