Tải bản đầy đủ (.pdf) (7 trang)

low-temperature h2s sensors based on ag-doped fe2o3 nanoparticles

Bạn đang xem bản rút gọn của tài liệu. Xem và tải ngay bản đầy đủ của tài liệu tại đây (644.38 KB, 7 trang )

A
vailable online at www.sciencedirect.com
Sensors and Actuators B 131 (2008) 183–189
Low-temperature H
2
S sensors based on Ag-doped
␣-Fe
2
O
3
nanoparticles
Yan Wang, Yanmei Wang, Jianliang Cao, Fanhong Kong, Huijuan Xia,
Jun Zhang, Baolin Zhu, Shurong Wang, Shihua Wu

College of Chemistry, Nankai University, Tianjin 300071, China
Received 29 July 2007; received in revised form 2 November 2007; accepted 2 November 2007
Available online 20 February 2008
Abstract
Ag-doped ␣-Fe
2
O
3
nanoparticles were synthesized by a chemical coprecipitation method and characterized by X-ray powder diffraction (XRD),
transmission electron microscopy (TEM) and high-resolution TEM (HRTEM), thermogravimetry-differential thermal analysis (TG-DTA), X-ray
photoelectron spectroscopy (XPS) and Brunauer–Emmett–Teller specific surface area analysis (BET) techniques. Obtained results indicated that
spherical Ag grains with size of about 5 nm are highly dispersed on the surface of ␣-Fe
2
O
3
nanoparticles. The surface area of the Ag/Fe
2


O
3
nanoparticles is several times as large as that of pure ␣-Fe
2
O
3
. The H
2
S sensing properties of these Ag/Fe
2
O
3
sensors were systematically
investigated. In comparison with pure ␣-Fe
2
O
3
, all of the Ag-doped sensors showed better sensing performance in respect of response, selectivity
and optimum operating temperature. The effects of Ag content, calcination and operation temperature on the sensing characteristics of the Ag/␣-
Fe
2
O
3
sensors were also investigated. The sensor containing 2 wt% Ag and calcined at 400

C exhibited the maximum response to H
2
Sat160

C.

A possible mechanism for the influence of Ag on the H
2
S-sensing properties of Ag/␣-Fe
2
O
3
sensors was proposed.
© 2007 Published by Elsevier B.V.
Keywords: Gas sensor; Ag-doped ␣-Fe
2
O
3
;H
2
S; Low operating temperature
1. Introduction
In recent years, the concern over environmental protection
and increasing demands to monitor hazardous gases in industry
and home has attracted extensive interests in developing gas sen-
sors for various polluting and toxic gases. Due to the advantages
of small size, low cost, simple operation and good reversibil-
ity, the semiconductor sensors have become the most promising
devices among the solid-state chemical sensors. Hence, the
metal oxide gas-sensing materials are widely investigated. Many
semiconductor oxides such as SnO
2
, ZnO, Fe
2
O
3

,In
2
O
3
,WO
3
,
and CuO, have been explored to detect the polluting, toxic and
inflammable gases, such as CO, CO
2
,NO
X
,H
2
S, and ethanol
[1–7].
Hematite (␣-Fe
2
O
3
), the most stable iron oxide, is of sci-
entific and technological importance as catalysts, pigments, ion
exchangers, magnetic materials andlithium-ionbatteries [8–11].

Corresponding author. Tel.: +86 22 23505896; fax: +86 22 23502458.
E-mail address: (S. Wu).
Recently, ␣-Fe
2
O
3

has been proved to be an important solid-
state gas sensor. However, the low sensitivity, poor selectivity
and high operating temperature discourage its extensive appli-
cation. In order to fit the increasing demands of sensors in
more complicated systems and strict conditions, many attempts
have been made to improve the sensing properties of ␣-Fe
2
O
3
.
Based on the sensitization effects of noble metals on metal
oxides through chemical and/or electronic interactions, modi-
fying the base materials with noble metals is an efficient way
to the base materials to promote their response towards various
gases [12–16].
Up to now, ␣-Fe
2
O
3
-based sensors have been investigated
for the detection of some organic gases such as ethanol, ace-
tone, methanol, and LPG [17–21]. However, there are few
reports on the study of the gas sensing properties of ␣-Fe
2
O
3
to H
2
S. In our previous works, the effects of Au, Pd and Pt on
the sensing properties of ␣-Fe

2
O
3
sensors to H
2
S have been
investigated [22–24]. The gas sensing properties of ␣-Fe
2
O
3
were markedly promoted by doping with such noble metals.
However, the high cost discourages their extensive applica-
tion. Hence, it is important to search an alternative component
0925-4005/$ – see front matter © 2007 Published by Elsevier B.V.
doi:10.1016/j.snb.2007.11.002
184 Y. Wang et al. / Sensors and Actuators B 131 (2008) 183–189
to replace Au, Pd and Pt. Silver is probably a suitable
one.
In this paper, we reported for the first time the preparation of
Ag/␣-Fe
2
O
3
sensors by a coprecipitation method. The structural
properties of the prepared Ag/␣-Fe
2
O
3
nanoparticles were char-
acterized by means of XRD, TG-DTA, TEM, HRTEM, BET and

XPS. The effects of Ag content, calcination and operating tem-
perature on the gas sensing properties to H
2
S were investigated
in detail. The sensing mechanism of the Ag/␣-Fe
2
O
3
sensors to
H
2
S was also discussed.
2. Experimental
2.1. Preparation of Ag/α-Fe
2
O
3
All the reagents are ofanalytical grade andused as purchased.
Ag/␣-Fe
2
O
3
nanoparticles were prepared by a coprecipita-
tion method. A small quantity of polyglycol was added to an
aqueous solution of AgNO
3
(0.25, 0.5, 1.0, 1.5, 2.0, 3.0 and
5.0 wt%) and Fe(NO
3
)

3
·9H
2
O. The aqueous mixture was then
added dropwise to an aqueous solution of Na
2
CO
3
under vig-
orous stirring at 80

C. The pH of the solution was adjusted
by a diluted Na
2
CO
3
aqueous solution in the reaction process.
After stirring for 1 h, a solid precipitate Ag/FeOOH was formed.
After digesting the precipitate overnight at room temperature, it
was washed with deionized water, dried at 80

C and calcined at
400

C for 1 h. Finally, a series of Ag-doped ␣-Fe
2
O
3
powders
with 0.25, 0.5, 1.0, 1.5, 2.0, 3.0 and 5.0 wt% Ag were obtained.

2.2. Characterization of Ag/α-Fe
2
O
3
Thermal analyses of the Ag/␣-Fe
2
O
3
powders were carried
out on a ZRY-2P thermal analyzer. Ten milligrams of samples
were heated from room temperature to 600

C in air at a heating
rate of 20

C min
−1
. X-ray diffraction (XRD) analyses were per-
formed on a D/MAX-RAX diffractometer with Cu K␣ radiation
(λ = 0.15418 nm) operating at 40 kV and 100 mA. Diffraction
peaks of crystalline phases were compared with those of stan-
dard compounds reported in the JCPDS Data File. Transmission
electron microscopy (TEM) was carried out on a Philips-T20ST
electron microscope, operating at 200 kV. X-ray photoelec-
tron spectroscopy (XPS) measurements were performed with
a Perkin-Elmer PHI 5600 spectrophotometer with Mg K␣ radi-
ation. The operating conditions were kept constant at 187.85 eV
and 250.0 W. In order to subtract the surface charging effect,
the C 1s peak has been fixed at a binding energy of 284.6 eV.
The specific surface areas (S

BET
) of the samples were calculated
following the multi-point Brunauer–Emmett–Teller (BET) pro-
cedure on a Quantachrome NOVA 2000e sorption analyzer at
liquid nitrogen temperature.
2.3. Fabrication and analysis of gas sensors
The gas sensing behavior was investigated by using a com-
mercial gas sensing measurement system of HW-30A from
Henan Hanwei Electronical Technology Co., Ltd. An alumina
substrate tube of 4 mm in length was used for the heater and
sensing base. A small Ni–Cr alloy coil was placed through the
tube to supply the operating temperatures from 100 to 500

C.
Two platinum wires attaching to each gold electrode were used
as electrical contacts. The schematic diagrams of the typical gas
sensor and the measuring principle were shown in our previ-
ous publications [23,24]. The Ag/␣-Fe
2
O
3
powders were mixed
with terpineol to form apaste. The pastewas then coated onto the
outside surface of an alumina tube. In order to improve their sta-
bility and repeatability, the gas sensors were sintered at 300

C
for 10 days in air. The sensing properties of the sensors were
tested in a chamber with a volume of 0.015 m
3

. The test gases
were injected into the closed chamber by a microinjector. The
sensitivity of the gas sensors was measured under a steady-state
condition. The gas response S is defined as the ratioR
a
/R
g
, where
R
a
and R
g
are the resistances measured in air and in a test gas,
respectively.
3. Results and discussion
3.1. Results of characterization
Fig. 1 shows the TG-DTA curves of as-prepared Ag/FeOOH
powders. A dramatic weight loss occurs around 100

C, accom-
panied with an endothermic peak on the DTA curve, which may
be due to the dehydration process of physically adsorbed water
and the release of attached nitrates in the products. Inthe range of
200–400

C, another weight loss is observed, corresponding to
an obvious exothermic peak around 300

C on the DTA curve.
It can be attributed to the reaction 2FeOOH → Fe

2
O
3
+H
2
O.
There is no obvious weight loss peak above 400

C on the TG
curve, indicating that the hydroxide products have already been
well crystallized. According to the TG-DTA results, we can
safely conclude that perfect Ag/Fe
2
O
3
crystals can be obtained
after calcined at 400

C under air atmosphere.
The typical XRD patterns of Ag/Fe
2
O
3
nanoparticles cal-
cined at 400

C with different Ag content are shown in Fig. 2. The
diffraction patterns of the samples match perfectly with the stan-
dard ␣-Fe
2

O
3
reflections (JCPDS No. 33-664). The sharp peaks
indicate thatthe crystals of␣-Fe
2
O
3
are perfect,which is ingood
agreement with the TG-DTA analysis results. The average size
Fig. 1. TG-DTA curves of as-prepared Ag/FeOOH.
Y. Wang et al. / Sensors and Actuators B 131 (2008) 183–189 185
Fig. 2. XRD patterns of Ag/␣-Fe
2
O
3
with different Ag content calcined at
400

C.
of ␣-Fe
2
O
3
particles, calculated by the Deby–Scherrer formula,
is 20 nm. When Ag content is low, no obvious Ag peaks pre-
sented, which may be due to the high dispersion of Ag particles
on thesurface of ␣-Fe
2
O
3

. Theparticles of Ag are too small to be
identified by the conventional X-ray diffraction method. When
Ag content increased to 5 wt%, the diffraction peaks attributed
to Ag crystal phases appeared at 38.1

and 44.3

, which indi-
cates that Ag particles become bigger with the increase of Ag
content.
TEM and HRTEM images of 2 wt% Ag/␣-Fe
2
O
3
calcined
at 400

C are shown in Fig. 3. It can be seen that the morphol-
ogy of ␣-Fe
2
O
3
particles is almost spherical. The diameter of
the particle is about 30–50 nm, which is larger than the crys-
talline size obtained by XRD. That indicates the presence of
polycrystallites because of the high temperature treatment. As
is shown in Fig. 3b, there are a few small spherical grains on the
␣-Fe
2
O

3
surface with the size about 5 nm, which may be the Ag
nanoparticles.
X-ray photoelectron spectroscopy was performed to illu-
minate the surface composition of the studied Ag/␣-Fe
2
O
3
nanoparticles. The spectra of Fe 2p and Ag 3d of 2 wt% Ag/␣-
Fe
2
O
3
calcined at 400

C are shown in Fig. 4.InFig. 4a, the
Table 1
The specific surface areas (S
BET
)of␣-Fe
2
O
3
and Ag/␣-Fe
2
O
3
Sample S
BET
(m

2
/g)
Undoped 18.31
Ag/Fe
2
O
3
with different Ag content (wt%)
0.25% 44.72
0.5% 57.21
1.0% 61.19
1.5% 62.62
2.0% 69.60
3.0% 57.75
5.0% 40.62
bending energies ofFe 2p
3/2
and Fe 2p
1/2
are 710.7 and 724.3 eV,
respectively, which is in well agreement with the literature val-
ues of Fe
3+
in ␣-Fe
2
O
3
[25].InFig. 4b, the peaks of Ag 3d
5/2
and Ag 3d

3/2
are centered at 368.0 and 374.0 eV, respectively,
which indicates that the state of Ag in the sample is metallic
[26]. Surface elemental analysis reveals that the atomic ratio of
Ag/Fe is 1/30. This value is higher than the theoretical one,which
indicates that the Ag dopant is well dispersed on the surface of
␣-Fe
2
O
3
.
The specific surface areas (S
BET
) of the undoped and Ag-
doped ␣-Fe
2
O
3
with different Ag content were measured by
N
2
-sorption analysis. Asshown in Table 1, theundoped ␣-Fe
2
O
3
has a small surface area (18.31 m
2
/g). After Ag is loaded, the sur-
face area of ␣-Fe
2

O
3
can be promoted remarkably, and reaches
the maximum (69.6 m
2
/g) when the content of Ag is 2 wt%.
When the Ag content is larger than 2 wt%, the surface areas
become to decrease unexpectedly. This should be attributed to
the aggregation of Ag particles, resulting in the decrease of the
surface area of ␣-Fe
2
O
3
. Generally, a large BET surface area
will lead to improvement of the sensing properties of the sensor.
3.2. Gas sensing properties
It is well known that the gas sensitivity is greatly influenced
by the operating temperature and the amounts of additives. In
order to determine the optimum operating temperature and addi-
tive amount, the responses of Ag/␣-Fe
2
O
3
sensors calcined at
400

C with different Ag content to 100 ppm H
2
S gas were mea-
Fig. 3. TEM (a) and HRTEM (b) images of 2 wt% Ag/␣-Fe

2
O
3
.
186 Y. Wang et al. / Sensors and Actuators B 131 (2008) 183–189
Fig. 4. XPS of 2 wt% Ag/␣-Fe
2
O
3
(a) Fe 2p (b) Ag 3d.
sured at different operating temperatures. The response of an
undoped ␣-Fe
2
O
3
sensor to H
2
S was also measured for compar-
ison. The results are shown in Fig. 5. It can be seen obviously
from Fig. 5 that the undoped sensor has a poor response to
H
2
S, while the doped sensors with different amounts of Ag all
exhibit much higher responses than the undoped one. Among all
the Ag-doped ␣-Fe
2
O
3
sensors, the one with 2 wt% Ag shows
the largest response to H

2
S. Whilst, the gas sensing property
change trend is similar to the specific surface area change trend
of the samples. Additionally, the responses of the sensors to
H
2
S are also affected by the operating temperature. Each curve
reveals a maximum response at an optimum operating temper-
ature. The undoped sensor has the maximum gas response at
200

C, whereas all the doped sensors have the maximum gas
response at about 160

C. The operating temperature of all the
Ag-doped sensors is lower than that of the reported H
2
S sen-
sors [27–30]. The lower operating temperature could lead to
lower energy consumption, which is one of current pursuits in
solid-state gas sensors. Based on the above results, we can see
that the Ag/␣-Fe
2
O
3
sensors exhibit much better response and
lower operating temperature than pure ␣-Fe
2
O
3

, and the opti-
mum performance is obtained at 160

C for the sensor of 2 wt%
Fig. 5. Responses of undoped ␣-Fe
2
O
3
and Ag/␣-Fe
2
O
3
with different Ag
content to 100 ppm H
2
S.
Ag/␣-Fe
2
O
3
. Therefore,all further experiments were carried out
using this particular composition (2 wt%) and operating temper-
ature (160

C) to explore the effect of other factors on the sensing
performance of Ag/␣-Fe
2
O
3
to H

2
S. Compared with our previ-
ously reported Au, Pt and Pd-doped ␣-Fe
2
O
3
sensors [22–24],
the gas sensitivity of our present prepared Ag/␣-Fe
2
O
3
sensor
is relatively lower than that of Pt-doped one, but a little higher
than that of Au- and Pd-doped ␣-Fe
2
O
3
. Since Ag is cheaper
than Au, Pt and Pd, the present Ag/␣-Fe
2
O
3
sensor system is
worthy to further investigation.
As generally mentioned earlier, the gas-sensing mechanism
of ␣-Fe
2
O
3
-based sensors belongs to the surface-controlled

type, which is based on the change in conductance of the
semiconductor. The oxygen adsorbed on the surface directly
influences the conductance of the ␣-Fe
2
O
3
-based sensors. The
amount of oxygen adsorbed on sensor surface depends on the
operating temperature, particle size, and specific surface area of
the sensor [31]. The state of oxygen on the surface of Ag/␣-
Fe
2
O
3
sensor undergoes the following reaction [15],
O
2
(gas) → O
2
(ads) (1)
O
2
(ads) + e

→ O
2

(ads) (2)
O
2


(ads) + e

→ 2O

(ads) (3)
O

(ads) + e

→ O
2−
(ads) (4)
The oxygen species capture electrons from the material, which
results in the concentration changes of holes or electrons in
the Ag/␣-Fe
2
O
3
semiconductor. When the sensor is exposed
to H
2
S, the reductive gas reacts with the oxygen adsorbed on
the sensor surface. Then the electrons are released back into the
semiconductor, resulting in the change in electrical conductance
of the Ag/␣-Fe
2
O
3
sensor. It can be expressed in the following

reaction,
H
2
S + 3O
2−
→ H
2
O + SO
2
+ 6e

(5)
For the Ag/␣-Fe
2
O
3
sensors, the low response at low operating
temperature can be attributed to the low thermal energy of the
gas molecules, which is not enough to react with the surface
adsorbed oxygen species. As a result, the reaction rate between
them is essentially low [31,32] and low response is observed.
Y. Wang et al. / Sensors and Actuators B 131 (2008) 183–189 187
On the other hand, the reduction in response after the optimum
operating temperature may be due to the difficulty in exother-
mic gas adsorption at higher temperature [33]. Therefore, the
maximum response can just be observed at the right operating
temperature.
The enhanced response of Ag/␣-Fe
2
O

3
sensors can be
attributed to two factors. First, the higher specific surface areas
of the Ag-doped sensors can lead to an increase in active sur-
face for gas sensing. Secondly, the Ag dopants, as a catalyst,
enhance the adsorption of gas molecules and accelerate the elec-
tron exchange between the sensor and the test gas [34]. The two
factors together contribute to the improvement of gas sensing
properties of the Ag-doped ␣-Fe
2
O
3
sensors. Furthermore, the
maximum response is observed for 2 wt% Ag/␣-Fe
2
O
3
, perhaps
due to the largest amount of active reaction sites formed by the
random dispersion of Ag on the Fe
2
O
3
surface in this compo-
sition, as revealed by above BET analysis. The abrupt decrease
of response for the sensors doped with more than 2 wt% Ag is
probably due to the reduction of active sites correlated with the
agglomeration of Ag grains [35].
In this paper, the effect of calcination temperature on the
response of the as-prepared Ag/␣-Fe

2
O
3
sensors to H
2
S is also
investigated. Fig. 6 shows the variation of the responses of a
series of 2 wt% Ag/␣-Fe
2
O
3
sensors calcined at different tem-
peratures to 100 ppm H
2
S. It can be seen that the calcination
temperature has an obvious influence on the sensor response
to H
2
S gas. The obtained results show that the response of
the sensor to H
2
S is enhanced with the increase of calcination
temperature from 200 to 400

C, and the Ag/␣-Fe
2
O
3
sensor
calcined at 400


C has the highest response, being in good agree-
ment with the TG-DTA results that 400

C is the temperature at
which the perfect ␣-Fe
2
O
3
nanocrystallines can be obtained.
But, the sample is amorphous FeOOH when calcined below
400

C, and the gas sensing property of amorphous FeOOH is
far worse than that of the crystalline ␣-Fe
2
O
3
. The responses
of the sensor decrease gradually when the calcination tempera-
ture is higher than 400

C, which may be due to an increase in
Fig. 6. Responses to 100 ppm H
2
S of 2 wt% Ag-doped ␣-Fe
2
O
3
calcined at

different temperatures.
Fig. 7. Responses of 2 wt% Ag/␣-Fe
2
O
3
to various gases at different operating
temperatures.
the particle size. As a result, the 400

C-calcined sensor which
possesses a high surface area exhibits the highest response to
H
2
S.
Selectivity is another important parameter of a gas sensor.
The sensor must have rather high selectivity for its application.
Because ␣-Fe
2
O
3
-based sensors also respond to other gases,
such as ethanol and acetone, the responses of our 2 wt% Ag/␣-
Fe
2
O
3
sensor to other seven gases of 1000 ppm at different
operating temperatures are also examined and the results are
shown in Fig. 7. From Fig. 7, it can be seen clearly that the
sensor exhibits the largest response to 100 ppm H

2
S, moderate
responses to ethanol and acetone, and negligible responses to
n-hexane, NH
3
,H
2
and CO even at such a high concentration
(1000 ppm). On the other hand, the optimum operating temper-
ature to ethanol and acetone is 200

C, which is higher than that
to H
2
S. The selectivity to H
2
S is good enough to detect H
2
S,
especially when the operating temperature is in the range of
120–160

C. According to the experiment results, it is no prob-
lem to detect low concentration H
2
S at relatively low operating
temperature. Furthermore, if there is no H
2
S in the atmosphere,
the sensor can be used to monitor ethanol or acetone vapor at

200

C.
Response and recovery times are the basic parameters of gas
sensors, which are defined as the time required to reach 90% of
the final resistance. Rapid response and recovery to a target gas
are demanded for practical application. Fig. 8 shows the typi-
cal response-recovery characteristics of the 2 wt% Ag/␣-Fe
2
O
3
sensor to different H
2
S concentrations (from 50 to 500 ppm).
Corresponding response values of the sensor to these H
2
S con-
centrations are shown in the inset picture. As can be seen from
Fig. 8, the response of the 2 wt% Ag/␣-Fe
2
O
3
sensor to H
2
S
sharply increases with an increase in gas concentration. The
response and recovery times to 50, 100, 200 and 500 ppm H
2
S
are 68 and 35 s, 42 and 26 s,31 and 25 s, 25 and 21 s, respectively.

These times are short enough for practical application.
The reversibility of the Ag/␣-Fe
2
O
3
sensors was also inves-
tigated. The sensors exhibited excellent responses to H
2
Seven
188 Y. Wang et al. / Sensors and Actuators B 131 (2008) 183–189
Fig. 8. Response-recovery characteristics of 2 wt% Ag-doped ␣-Fe
2
O
3
to H
2
S
of different concentrations.
after several months. This indicates that the sensors possess
excellent stability and reversibility. The Ag/␣-Fe
2
O
3
sensors
should have a promising application to detect H
2
S and is worthy
of further investigation.
4. Conclusions
In summary, the Ag/␣-Fe

2
O
3
nanoparticles were successfully
synthesized by a convenient chemical coprecipitation method,
and Ag/Fe
2
O
3
sensors were made and tested. The XPS analysis
indicated that Ag existed in metallic form and highly dispersed
on the surface of sensors. The specific surface area (S
BET
)of
␣-Fe
2
O
3
nanopowders was remarkably promoted by the Ag-
doping. Compared with pure ␣-Fe
2
O
3
, the Ag-doped sensors
showed much higher response, better selectivity and ratherlower
optimum operating temperature to H
2
S. Especially, the opti-
mum performance was obtained at an operating temperature of
160


C for the 2 wt% Ag/␣-Fe
2
O
3
sensor calcined at 400

C.
The sensor could be used to detect H
2
S at the temperature range
of 120–160

C and to detect ethanol and acetone at 200

C.
The doped sensor also presented long-term stability and rela-
tively short response/recovery times. The Ag/␣-Fe
2
O
3
sensor
is a promising candidate for application in H
2
S monitoring at
low-temperature.
Acknowledgement
We gratefully appreciate the financial support of the 973
program of China (No. 2005Cb623607).
References

[1] M. Law, H. Kind, F. Kim, B. Messer, P. Yang, Photochemical sensing
of NO
2
with SnO
2
nanoribbon nanosensors at room temperature, Angew.
Chem. Int. Ed. 41 (2002) 2405–2408.
[2] A. Kolmakov, Y.X. Zhang, G.S. Cheng, M. Moskovits, Detection of CO
and O
2
using tin oxide nanowire sensors, Adv. Mater. 15 (2003) 997–1000.
[3] N. Koshizaki, T. Oyama, Sensing characteristics of ZnO-based NO sensor,
Sens. Actuators B 66 (2000) 119–121.
[4] G.S.T. Rao, D.T. Rao, Gas sensitivity of ZnO-based thick film sensor to
NH
3
at room temperature, Sens. Actuators B 55 (1999) 166–169.
[5] J.S. Han, D.E. Davey, D.E. Mulcahy, A.B. Yu, An investigation of gas
response of ␣-Fe
2
O
3
(Sn)-based gas sensor, J. Mater. Sci. Lett. 18 (1999)
975–977.
[6] C. Li, D.H. Zhang, X.L. Liu, S. Han, T. Tang, J. Han, C.W. Zhou, In
2
O
3
nanowires as chemical sensors, Appl. Phys. Lett. 82 (2003) 1613–1615.
[7] X.L. Li, T.J. Lou, X.M. Sun, Y.D. Li, Highly sensitive WO

3
hollow-sphere
gas sensors, Inorg. Chem. 43 (2004) 5442–5449.
[8] T. Cheng, Z.Y. Fang, Q.X. Hu, K.D. Han, X.Z. Yang, Y.J. Zhang, Low-
temperature CO oxidation over CuO/Fe
2
O
3
catalysts, Catal. Commun. 8
(2007) 1167–1171.
[9] F. Bondioli, A.M. Ferrari, C. Leonelli, T. Manfredini, Syntheses of
Fe
2
O
3
/silica red inorganic inclusion pigments for ceramic applications,
Mater. Res. Bull. 33 (1998) 723–729.
[10] S. Mitra, S. Das, K. Mandal, S. Chaudhuri, Synthesis of a ␣-Fe
2
O
3
nanocrystal in its different morphological attributes: growth mechanism,
optical and magnetic properties, Nanotechnology 18 (2007) 275608.
[11] J. Chen, L.N. Xu, W.Y. Li, ␣-Fe
2
O
3
Nanotubes in gas sensor and lithium-
ion battery applications, Adv. Mater. 17 (2005) 582–586.
[12] A. Cabot, J. Arbiol, J.R. Morante, U. Weimar, N. Barsan, W. Gopel, Anal-

ysis of the noble metal catalytic additives introduced by impregnation of
as obtained SnO
2
sol–gel nanocrystals for gas sensors, Sens. Actuators B
70 (2000) 87–100.
[13] N. Funazaki, A. Hemmi, S. Ito, Y. Asano, S. Yamashita, T. Kobayashi, M.
Haruta, Development of carbon monoxide detector using Au fine particles-
doped ␣-Fe
2
O
3
, Sens. Actuators B 14 (1993) 536–538.
[14] J. Mizsei, P. Sipila, V. Lantto, Structural studies of sputtered noble metal
catalysts on oxide surfaces, Sens. Actuators B 47 (1998) 139–144.
[15] Y.L. Liu, H. Wang, Y. Yang, Z.M. Liu, H.F. Yang, G.L. Shen, R.Q. Yu,
Hydrogen sulfide sensing properties of NiFeO
4
nanopowder doped with
noble metal, Sens. Actuators B 102 (2004) 148–154.
[16] G. Neri, A. Bonavita, S. Galvagno, L. Caputi, D. Pacile, R. Marsico, L.
Papagno, HREELS study of Au/Fe
2
O
3
thick film gas sensos, Sens. Actu-
ators B 80 (2001) 222–228.
[17] L.H. Huo, Q. Li, H. Zhao, L.J. Yu, S. Gao, J.G. Zhao, Sol–gel route to pseu-
docubic shaped ␣-Fe
2
O

3
alcohol sensor: preparation and characterization,
Sens. Actuators B 107 (2005) 915–920.
[18] O.K. Tan, W. Cao, W. Zhu, J.W. Chai, J.S. Pan, Ethanol sensors based on
nano-sized ␣-Fe
2
O
3
with SnO
2
, ZrO
2
,TiO
2
solid solutions, Sens. Actua-
tors B 93 (2003) 396–401.
[19] G.R. Dai, A study of the sensing properties of thin film sensor to trimethy-
lamine, Sens. Actuators B 53 (1998) 8–12.
[20] V.V. Malyshev, A.V. Eryshkin, E.A. Koltypin, E.A. Varfolomeev, A.A.
Vasiliev, Gas sensitivity of semiconductor Fe
2
O
3
-based thick-film sensors
to CH
4
,H
2
,NH
3

, Sens. Actuators B 19 (1994) 434–436.
[21] A.S. Poghossian, H.V. Abovian, V.M. Aroutiounian, Selective petrolvapour
sensor based on an Fe
2
O
3
thin film, Sens. Actuators B 18 (1994) 155–157.
[22] Y. Wang, Z.H. Jing, S.H. Wu, W.P. Huang, S.M. Zhang, S.R. Wang, The
effect of Au-doped by different methods on gas-sensing properties of ␣-
Fe
2
O
3
nanopowders, Chin. J. Chem. Phys. 22 (2006) 114–117.
[23] Y. Wang, S.R. Wang, Y.Q. Zhao, B.L. Zhu, F.H. Kong, D. Wang, S.H. Wu,
W.P. Huang, S.M. Zhang, H
2
S sensing characteristics of Pt-doped ␣-Fe
2
O
3
thick film sensors, Sens. Actuators B 125 (2007) 79–84.
[24] Y. Wang, F.H. Kong, B.L. Zhu, S.R. Wang, S.H. Wu, W.P. Huang, Synthesis
and characterization of Pd-doped ␣-Fe
2
O
3
H
2
S sensor with low power

consumption, Mater. Sci. Eng. B 140 (2007) 98–102.
[25] M. Sorescu, R.A. Brand, D. Mihaila-Tarabasanu, L. Diamandescu, The
crucial role of particle morphology in the magnetic properties of haematite,
J. Appl. Phys. 85 (1999) 5546–5548.
[26] R.N. Lamb, B. Ngamsom,D.L. Trimm, B.G.P.L. Silveston, P. Praserthdam,
Surface characterisation of Pd–Ag/Al
2
O
3
catalysts for acetylene hydro-
genation using an improved XPS procedure, Appl. Catal. A 268 (2004)
43–50.
[27] Z.Y. Zhang, H.J. Jiang, Z. Xing, X.R. Zhang, A highly selective chemilu-
minescent H
2
S sensor, Sens. Actuators B 102 (2004) 155–161.
Y. Wang et al. / Sensors and Actuators B 131 (2008) 183–189 189
[28] G.N. Caudhari, D.R. Bambole, A.B. Bodade, P.R. Padole, Characteriza-
tion of nanosized TiO
2
-based H
2
S gas sensor, J. Mater. Sci. 41 (2006)
4860–4864.
[29] G.H. Jian, L.A. Patil, M.S. Wagh, D.R. Patil, S.A. Patil, D.P. Amalnerkar,
Surface modified BaTiO
3
thick film resistors as H
2
S gas sensors, Sens.

Actuators B 117 (2006) 159–165.
[30] J.Q. Xu, X.H. Wang, J.N. Shen, Hydrothermal synthesis of In
2
O
3
for
detecting H
2
S in air, Sens. Actuators B 115 (2006) 642–646.
[31] X.F. Chu, D.L. Jiang, Y. Guo, C.M. Zheng, Ethanol gas sensor based
on CoFe
2
O
4
nano-crystallines prepared by hydrothermal method, Sens.
Actuators B 120 (2006) 177–181.
[32] V.M. Aroutiounian, G.S. Aghababian, To the theory of semiconductor gas
sensors, Sens. Actuators B 50 (1998) 80–84.
[33] J.F. Chang, H.H. Kuo, I.C. Leu, M.H. Hon, The effects of thickness and
operation temperature on ZnO:Al thin film CO gas sensor, Sens. Actuators
B 84 (2002) 258–264.
[34] T. Maosong, G.R. Dai, D.S. Gao, Surface modification of oxide thin-
film and its gas-sensing properties, Appl. Surf. Sci. 171 (2001) 226–
230.
[35] G. Xu, Y.W.Zhang, X. Sun, C.L. Xu,C.H. Yan, Synthesis, structure, texture,
and CO sensing behavior of nanocrystalline tin oxide doped with scandia,
J. Phys. Chem. B 109 (2005) 3269–3278.
Biographies
Yan Wang received her M.S. degree in chemistry from Nankai University in
2006. Now she is a Ph.D. candidate in the College of Chemistry, Nankai Univer-

sity in China. Her research focuses on the synthesis, characterization of metal
oxide nanomaterials and their gas-sensing properties.
Yanmei Wang received her B.S. degree in chemistry from Shenyang Institute
of Gold Technology in 1995. Now she works at Nankai University and is also a
M.S. candidate. Her research is focused on the development and application of
catalysis and gas-sensitive materials.
Jianliang Cao received his M.S. degree in chemistry from Nankai University
in 2006. Now he is a Ph.D. candidate in the College of Chemistry, Nankai
University. His research interests include the synthesis of nanomaterials and
their application in catalysis.
Fanhong Kong received her B.S. degree in chemistry from Qufu Normal Uni-
versity in 2005. Currently, she is a master student in the College of Chemistry in
Nankai University. Her research is focused on the development and application
of gas-sensitive materials.
Huijuan Xia received her B.S. degree in chemistry from Liaocheng Normal
University in 2006. Now she is a master student in the College of Chemistry,
Nankai University. Her interest is devoted to the preparation and application of
gas-sensitive materials.
Jun Zhang received his B.S. degree in chemistry from Qufu Normal University
in 2006. Now he is a master student in the College of Chemistry in Nankai
University. His research interest focuses on nanomaterials gas sensors.
Baolin Zhu received her Ph.D. degree in chemistry from Nankai University in
2006. Now she is a faculty in the College of Chemistry, Nankai University. Her
research is focused on the preparation of nanomaterials.
Shurong Wang received her Ph.D. degree in chemistry from Nankai University
in 2007. Now she is a faculty in the College of Chemistry, Nankai University.
Her research covers nanomaterials, catalysis and gas sensors.
Shihua Wu received his degree in chemistry from Nankai University in
1970. At present, he is a professor in the College of Chemistry, Nankai
University, where he has been working for many years in the field of prepa-

ration, characterization and catalytic and gas-sensing properties of metal oxides
nanomaterials.

×