Materials Letters 143 (2015) 55–59

Contents lists available at ScienceDirect

Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Facile synthesis of SnO2 mesoporous tubular nanostructure with high

sensitivity to ethanol
X.L. Xu a, Y. Chen b, S.Y. Ma a,n, W.Q. Li a, Y.Z. Mao a, S.H. Yan a, T. Wang a
a
Key Laboratory of Atomic and Molecular Physics & Functional Materials of Gansu Province, College of Physics and Electronic Engineering, Northwest Normal
University, Lanzhou 730070, China
b
Key Laboratory for Electronic Materials of the State National Affairs Commission, Northwest University for Nationalities, Lanzhou, Gansu 730030, China

art ic l e i nf o a b s t r a c t

Article history: Lanthanum (La)-doped SnO2 was facilely prepared by electrospinning technique. The La-doped SnO2 was
Received 4 November 2014 characterized by SEM, XRD, XPS and TEM. The XRD pattern indicates the polycrystalline nature of the La-
Accepted 11 December 2014 doped SnO2 nanostructure. It has been found that the La-doped SnO2 nanofibers with a rough surface are
Available online 19 December 2014
actually mesoporous tubular nanostructure. The mesoporous tubes with a diameter of
200 nm possess
Keywords: a pore size distribution centered at about 23 nm. The La-doped SnO2 sensor shows a high response to
La-doped SnO2 5 ppm ethanol. Compared to pure SnO2, the La-doped SnO2 exhibits high sensitivity and good selectivity
Semiconductors to ethanol at a relatively low optimum operating temperature of 200 1C, in addition to a short response/
Sensors recovery time. The La-doped SnO2 mesoporous tubular nanostructure could be useful in fabricating
Ethanol detection
semiconducting sensors for ethanol.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction [5]. To the best of our knowledge, there are few reports on
synthesis of La-doped SnO2 mesoporous tubular nanostructure
Tin dioxide (SnO2) has been widely used as sensing material for with high sensitivity to ethanol.
monitoring air quality and detecting flammable or toxic gases due In this paper, we present an excellent ethanol sensor based on
to their low cost, high sensitivity and excellent stability [1,2]. lanthanum doped SnO2. The sensing mechanism is also discussed.
Detection of alcohol vapor is one of the most popular demands in
our daily life. The common application of an alcohol sensor is as a
breath checker to test alcohol levels of drivers [3]. Additionally, as
2. Experimental
a common reagent widely used in industries and labs, controlling
and monitoring alcohol vapor in air is also very important. Gas
La-doped SnO2 nanostructure was synthesized as follows. 0.3 g
sensors with one-dimensional (1D) nanostructure exhibit larger
PVP was dissolved in 2 mL ethanol. Meanwhile, 0.72 g SnCl2  2H2O
response due to their large length-to-diameter ratio and high
and 0.035 g La(NO3)3  6H2O were fully dissolved in 2.5 mL DMF.
surface-to-volume ratio [4]. SnO2 possesses significant surface
Subsequently, the two solutions were mixed together followed by
reactivity with reducing gases (CO, C2H2, CH4, etc.). 1D SnO2
magnetically stirring for 2 h before being transferred into a glass
nanostructures, including nanorods, nanofibers, and nanobelts
syringe as the precursor for electrospinning. After electrospinning,
have been successfully synthesized. However, the gas-sensing
specimens were collected and put into a tube furnace for calcining
performances of SnO2 sensor have not been adequate in sensitiv-
at 600 1C for 4 h. For comparison, pure SnO2 nanofibers were
ity, operating temperature and response/recovery rates. Therefore,
prepared under the similar conditions except for the addition of La
there is still of great significance to develop SnO2-based sensors
(NO3)3  6H2O. The as-calcined powders were slightly grinded and
with excellent gas sensing properties. Modifying sensing materials
mixed with deionized water on glass slide to form a paste,
by rare earth elements (La, Y, Ce, etc.) is one kind of doping
subsequently the formed paste was coated on a ceramic tube
strategies to improve the sensing properties of SnO2-based gas
equipped with a pair of gold electrodes and Pt wires, then the
sensors. Specifically, chemical compounds of La (e.g. La2O3) can
sensor was fabricated.
offer new opportunities for enhancing gas-sensing performances
The microstructure and morphology of the La-doped SnO2 were
characterized by X-ray diffraction (D/Max-2400), scanning electron
n
Corresponding author. Tel./fax: þ 86 9317971503. microscope (SEM, S-4800) and transmission electron microscopy
E-mail address: 381585537@qq.com (S.Y. Ma). (TEM, USA FEI Tecnai G2 TF20). The chemical compositions were

http://dx.doi.org/10.1016/j.matlet.2014.12.064
0167-577X/& 2014 Elsevier B.V. All rights reserved.
56
(101)
(110)
Intensity (a.u.)
(200)
20 30 40
2 Theta (degrees)
Fig. 1. (a) SEM image of the La-doped SnO2, (b) XRD pattern and (c) XPS survey spectrum of the La-doped SnO2 nanofibers.
analyzed by using X-ray photoelectron spectroscopy (XPS, ESLA LAB
220-XL). The specific surface area was determined by BET method
( JW-004). The gas sensing measurements were conducted by using a
WS-60A static gas sensor testing system (Wei Sheng Electronics
Science and Technology Co., China). The response (SR) was defined as
Ra/Rg, where Ra and Rg were the resistance of sensors in air and test
gas, respectively. The response/recovery times were defined as the
time required reaching 90% of the final equilibrium value.
3. Results and discussion
Fig. 1(a) presents SEM image of La-doped SnO2. The nanofibers
with diameters of about 200 nm and several tens of microns in
length are straight and uniform, indicating a large length-to-
diameter ratio. Polycrystalline nature of the sample is confirmed
from the XRD pattern (Fig. 1(b)). All the diffraction peaks coincide
well with standard data profile of tetragonal rutile SnO2 (JCPDS
Card no. 41-1445). No characteristic diffraction peaks of La2O3 or
other impurities are detected. Fig. 1(c) shows XPS survey spectrum
of La-doped SnO2, indicating that La are successfully doped into
SnO2 crystal lattice.
TEM have been carried out to further investigate microstructure
of the La-doped SnO2 nanofibers (Fig. 2(a) and (b)). It can be seen
that surface of La-doped SnO2 nanofibers is rough, which could
increase the contact area between analytes and nanostructure. We
can see clearly that the La-doped SnO2 nanofibers are actually
tubular nanostructure, the inside diameter (ID) of the fibers is

160 nm. Each tube is agglomerated with small particles, the
average crystalline size is
20 nm. It should be noted that the
tubular nanostructure with a rough surface is very useful to the gas
sensing performances for their high surface-to-volume ratio [3,4]
The surface-to-volume ratio of hollow nanostructures almost
X.L. Xu et al. / Materials Letters 143 (2015) 55–59
O 1s
(211)
Intensity (a.u.)
Sn 3d3/2
La 3d3/2
La 3d5/2
Sn 3p3/2
Sn 3p1/2
Sn 3d5/2
C 1s
(112)
(301)
Sn 4s
(310)
(220)
(202)
(321)
(002)
Sn 4p
Sn 4d
50 60 70 80 80 0 60 0 40 0 20 0 0
Binding energy (eV)
doubles compared with normal solid nanofibers. The HRTEM
micrograph in Fig. 2(c) shows well-developed lattice fringes. Inter-
planar distances of the hollow nanostructure are 0.333, 0.265 and
0.235 nm, which corresponds to the (110), (101) and (200) planes of
rutile SnO2, respectively. The inset in Fig. 2(c) gives the selected area
electron diffraction (SAED) pattern, which indicates the polycrystal-
line nature of the tubular nanostructure. Furthermore, EDX ele-
mental mapping was employed to verify the distribution of La in
SnO2 phase, as shown in Fig. 3(d). Clearly, La is doped uniformly
throughout the nanostructure within the spatial resolution of the
EDX. Formation of tubular nanostructure in our work can be
attributed to solvent evaporation rate and phase separation [6,7].
Fig. 3(a) shows the response of La-doped SnO2 to 100 ppm
ethanol at different operating temperatures. It seems that the
response increases with the temperature increase from 160 1C to
200 1C, then decreases with further increase in the operating
temperature, with maximum response values of 66 being attained
for ethanol gas. Therefore, the optimum operating temperature
(Topt) to ethanol is 200 1C. Fig. 3(b) exhibits the curves of response
vs ethanol concentration of pure SnO2 and La-doped SnO2. The
results indicate that La dopant improves the response to ethanol
significantly. The responses of La-doped SnO2 are about 8.2, 17.8,
41.5, 64.5, 111, 274, and 419 for 5, 20, 50, 100, 200, 500 and
1000 ppm ethanol, respectively. It is worth noting that the sensor
shows a high response to 5 ppm ethanol. Fig. 3(c) gives the
dynamic resistance change of La-doped SnO2 sensor to 5 ppm
ethanol. The response time and recovery time are 14 s and 6 s,
respectively. The results reveal that high response and short
recovery time can be achieved in detecting low concentration
ethanol by using La-doped SnO2.
The gas-sensing selectivity of the La-doped SnO2 was tested by
exposing it to 100 ppm various gases (Fig. 3(d)). Response of the
sensor to ethanol is about 65, which is about 3.3, 13 times larger
 X.L. Xu et al. / Materials Letters 143 (2015) 55–59 57

dSnO2(110)=0.333 nm

5 1/nm
0.5 µm
dSnO2 (200)=0.235 nm

dSnO2 (110)=0.333 nm
dSnO2 (101)=0.265 nm

100 nm 5 nm

O-K Sn-L La-L

Fig. 2. (a and b) TEM images, (c) HRTEM image, SAED pattern (inset) and (d) EDS mapping images of the La-doped SnO2.

than that to acetone and ammonia, respectively. The results
indicate that the sensor has a satisfactory selectivity for ethanol.
The inset in Fig. 3(d) indicates the reproducibility of La-doped
SnO2 to 5 ppm ethanol at 200 1C. Fig. 3(e) presents the measure-
ment on the stability of La-doped SnO2 to 200 ppm ethanol at
200 1C. The results indicate the long-term stability of La-doped
SnO2 nanostructure.
Response of the SnO2 gas sensor depends on morphology, grain
size, porosity, active surface states, oxygen adsorption quantity,
lattice defects and so on [8–10]. 1D nanofibers could greatly facilitate
gas diffusion and electron transport within sensing material, which
means that the gas-sensing reactions between nanofibers and
ethanol become easily, and the electrons could be efficiently released
to sensing materials, resulting in fast and significant changes of the
sensor resistance. As shown in Fig. 2(b), the tubular nanostructure
with rough surface show porous features. The porous structure
provides a quite large surface including massive active sites for gas
diffusion and gas-sensing reaction. As shown in Fig. 4(a), the BET
analysis shows that the SSA of La-doped SnO2 is 42.89 m2/g. The
tubular nanostructure possesses a pore size distribution centered at
about 23 nm. The large surface-to-volume ratio makes the surface of
the La-doped SnO2 nanostructure be sufficiently utilized, which
should play a key role in gas-sensing improvement. The nanoparti-
cles (NP) size distribution of the mesoporous tubular nanostructure
was researched. Crystallite dimensions were measured by TEM
investigation. Fig. 4(b) indicates that diameter sizes of the nanocrys-
tals show normally distribution ranging from 10 to 32 nm. Broad-
ening of the size distribution is caused by calcination. Calcination is
needed to induce the highly crystalline structures, high temperature
annealing often induces coalescence and coarsening of the nanopar-
ticles, thus broadening the size distribution.
SnO2 prepared in our work is a n-type semiconductive oxide
and the sensing mechanism can be explained by the modulation
model of depletion layer. The electrical conductance of mesopor-
ous tubular nanostructure is determined by the amount of
electrons in conduction band. For gas-sensor applications, the
larger the variation in the resistance is, the higher the sensitivity
can be achieved.
Change of the carriers mobility during the process (chemical
reactions between the adsorbed surface oxygen species and
ethanol) have relationship with phonon scattering. Phonon is the
quantum of lattice vibrational energy. The collisions between
phonons and electrons induce the electron–phonon scattering.
The scattering tends to reduce mobility and leads to the decrease
of gas sensitivity. The higher the operating temperature is, the
stronger the electron–phonon scattering will be. Fortunately, the
relatively low optimum operating temperature (200 1C) of La-
doped SnO2 is helpful to the high sensitivity of ethanol sensor.
As reported by Hulser et al. [11], Debye size of SnO2 is LD ¼3 nm.
Particle size and thickness of the tubular nanostructure in our
work are much larger than the Debye size of SnO2. Therefore,
quantum effects are weak.
Additionally, the catalytic activity of La might also contribute to
the increased ethanol response, since they can accelerate the
dehydrogenation and consecutive oxidation of hydrocarbons
[12]. La can serve as excellent sensitizer and increase the amount
of active sites on surface of semiconducting oxides and then
enhance their catalytic properties [13]. After La doping, incre-
mental oxygen molecules can be chemisorbed and then ionized on
SnO2 surface, resulting in high response.
4. Conclusions
In summary, lanthanum (La)-doped SnO2 was facilely prepared by
electrospinning technique. The La-doped SnO2 crystallizes in tetra-
gonal rutile-type structure. The polycrystalline sample with rough
surface possesses a mesoporous tubular nanostructure. Specific sur-
face area of the nanostructure is 42.89 m2/g. The mesoporous tubes
with a diameter of
200 nm possess a pore size distribution
centered at about 23 nm, and it can be adapted for large-scale
production. The sensor was confirmed to show a high response to
5 ppm ethanol, showing ultrahigh sensitivity and good selectivity to
ethanol at 200 1C. The excellent ethanol sensitive property was
attributed to large surface-to-volume ratio of the mesoporous tubular
nanostructure and the catalytic activity of La. We envisage that the
58 X.L. Xu et al. / Materials Letters 143 (2015) 55–59

70
100 ppm ethanol 420 pure SnO2
60 360 La-doped SnO2

50 300

Response (Sr)
Response (Sr)
240
40
180
30
120
20 60

10 0
150 200 250 300 350 0 200 400 600 800 1000
Temperature (°C) Concentration (ppm)

1500 70
9
60 8
1200 7
50 6
Resistance (KO)

Response (Sr)

Response
5
900
40 4
3
Gas "In" Gas "Off"
600 30 2
1
20 0 600 1200 1800 2400
300 5 ppm working times (s)
10
0 0

ia
l

id
ne
no

G
F

on

ac
M
100 200 300 400 500 600 700

PE
to
ha

m
e

tic
et

am
ac

e
Times (s)

ac
120

100
Response (Sr)

80

60

40

20
0 2 4 6 8 88 90 92 94 96 98 100
Time (day)

Fig. 3. (a) Temperature optimization of the La-doped SnO2. (b) Concentration modulation of pure SnO2 and La-doped SnO2 tubular nanostructure. (c) Dynamic resistance
variation of La-doped SnO2 to 5 ppm ethanol at 200 1C. (d) Responses of La-doped SnO2 sensor to different tested gases (the inset shows the reproducibility of La-doped SnO2
to 5 ppm ethanol at 200 1C). (e) The long-term stability of La-doped SnO2 to 200 ppm ethanol at 200 1C.

Fig. 4. (a) N2 adsorption–desorption isotherm and BJH pore size distribution curve (inset) of La-doped SnO2 nanostructure. (b) The crystallites' grain size distribution (20 nm
is the average crystallite size diameter).
 X.L. Xu et al. / Materials Letters 143 (2015) 55–59 59

research results in our work might provide new possibilities for the References
better design of ethanol sensors.
[1] Xu K, Zeng DW, Tian SQ, Zhang SP, Xie CS. Sens Actuators B 2014;190:585–92.
[2] Korotcenkov G. Mater Sci Eng B 2007;139:1–23.
[3] Rao BB. Mater Chem Phys 2000;64:62–5.
[4] Yang ZX, Huang Y, Chen GN, Guo ZP, Cheng SY, Huang SZ. Sens Actuators B
Acknowledgments 2009;140:549–56.
[5] Zhang GZ, Zhang SP, Yang L, Zou ZJ, Zeng DW. Sens Actuators B
2013;188:137–46.
This work was supported by the Natural Science Foundation of [6] Dayal P, Kyua T. J Appl Phys 2006;100:0435121–6.
Gansu Province (Grant no. 1308RJZA258), the Key Laboratory [7] Wei SH, Zhou MH, Du WP. Sens Actuators B 2011;160:753–9.
[8] Hemmati S, Firooz AA, Khodadadi AA, Mortazavi Y. Sens Actuators B
Foundation of Atomic and Molecular Physics & Functional Materi-
2011;160:1298–303.
als of Gansu Province, the Fundamental Research Funds for the [9] Zhang WH, Zhang WD. Sens Actuators B 2008;134:403–8.
Higher Education Institutions of Gansu Province, Graduate Advisor [10] Rai P, Raj S, Ko KJ, Park KK, Yu YT. Sens Actuators B 2013;178:107–12.
Scientific Research Project of Gansu Province Education Depart- [11] Hulser TP, Wiggers H, Kruis FE, Lorke A. Sens Actuators B 2005;109:13–8.
[12] Jinkawa T, Sakai G, Tamaki J, Miura N, Yamazoe N. J Mol Catal A
ment (1001-07) and the Foundations of Northwest Normal Uni- 2000;155:193–200.
versity (NWNU-LKQN-13-18). [13] Hieu NV, Kim HR, Ju BK, Lee JH. Sens Actuators B 2008;113:228–34.