Sensors and Actuators B 171–172 (2012) 658–665

Contents lists available at SciVerse ScienceDirect

Sensors and Actuators B: Chemical

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

Functionalized nanoporous TiO2 fibers on quartz crystal microbalance platform

for formaldehyde sensor
Xianfeng Wang a , Fuhai Cui b , Jinyou Lin a , Bin Ding c,d,∗ , Jianyong Yu c,∗∗ , Salem S. Al-Deyab e
a
College of Textiles, Donghua University, Shanghai 201620, China
b
Department of Biological and Chemical Engineering, Guangxi University of Technology, Liuzhou 545006, China
c
Nanomaterials Research Center, Research Institute of Donghua University, Shanghai 200051, China
d
College of Materials Science and Engineering, Wuhan Textile University, Wuhan 430073, China
e
Petrochemical Research Chair, Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia

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

Article history: This paper describes the detection of formaldehyde through analyses of the resonance frequency sig-
Received 15 February 2012 nal from quartz crystal microbalance (QCM) sensors coated with a novel organic–inorganic hybrid
Received in revised form 12 May 2012 sensing coating. Nanoporous titanium dioxide (TiO2 ) fibers with high Brunauer–Emmett–Teller (BET)
Accepted 15 May 2012
surface area (68.72 m2 /g) were fabricated by electrospinning a sol–gel titanium tetraisopropoxide
Available online 24 May 2012
(TIP)/polystyrene (PS) composite solution and following calcination process. Ethylene glycol (EG) dis-
persed TiO2 nanofibers were drop casted onto the electrode of QCM, followed by the functionalization
Keywords:
of the sensing polyethyleneimine (PEI) on the fibers. The nanoporous TiO2 fibers covered with PEI layers
Titanium dioxide (TiO2 )
Polyethyleneimine (PEI)
worked as a highly sensitive sensing interface to provide output signal for weight changes during expo-
Electrospinning technology sure to formaldehyde vapor. The developed formaldehyde-selective sensors exhibited rapid response
Nanoporous fibers and low detection limit (1 ppm) at room temperature. This is because the high specific surface area of the
Formaldehyde sensors electrospun nanoporous TiO2 fibers and efficient nucleophilic addition reaction between formaldehyde
Quartz crystal microbalance (QCM) molecules and primary amine groups of PEI. Our new synthetic methodology promises to be a powerful
approach to fabricating hybrid organic–inorganic nanostructures on QCM for gas sensing and chemical
analysis.
Crown Copyright © 2012 Published by Elsevier B.V. All rights reserved.

1. Introduction [12]. Among many available SMOs, due to its chemical stability,
high reactivity, non-toxicity and low cost, titanium dioxide (TiO2 )
Increasing demands for ever more sensitive vapor sensors for is the most popular candidate used in ultrasensitive sensors, espe-
environmental monitoring and control, healthcare, defense and cially in resistive sensors [1,13,14]. For example, Kim et al. [1] have
security, and other applications have led to an upsurge of interest in developed an ultrasensitive chemiresistors for the detection of NO2
one-dimensional (1D) nanostructures (e.g., nanotubes, nanowires, based on electrospun TiO2 nanofiber. The resultant sensor exhib-
nanorods, and nanofibers) [1–5]. Recently, 1D nanostructured ited exceptional sensitivity when exposed to 500 ppb NO2 at 300 ◦ C.
semiconductor metal oxides (SMOs) based vapor sensors have been As mentioned above, TiO2 nanofibers can provide many opportu-
demonstrated excellent sensitivity, fast response and recovery nities for improved sensing behavior of resistive sensors; however,
[2,6–8]. Particularly, the SMOs nanofibers-based gas sensors pre- the often-used higher operation temperature restricts their prac-
pared by electrospinning technique come into the spotlight [9–11]. tical use for detecting gaseous pollutants in the environment [12].
These fibrous materials are known for their advances in facilitating Therefore, it is highly desirable to develop a new sensor platform
rapid mass transfer of the analyte molecules to and from the inter- that can be operated at room temperature.
action region and requiring charge carriers to traverse any barriers Quartz crystal microbalance (QCM) has been widely used as
introduced by molecular recognition events along the entire fiber a room-temperature operated platform for mass sensing by the
deposition with the sensitive coatings [15–18]. Their resonance fre-
quency has been proven to decrease linearly upon the additional
mass loading of adsorbed associated analytes on the surface of
∗ Corresponding author at: Nanomaterials Research Center, Research Institute of
the QCM electrode in a nanogram level [19]. The determination
Donghua University, Shanghai 200051, China. Tel.: +86 21 6237 8202;
of mass changes is directly related to the interactions between
fax: +86 21 6237 8392.
∗∗ Corresponding author. Tel.: +86 21 6237 8202; fax: +86 21 6237 8392. the sensitive coatings and target compounds [16,20]. To date,
E-mail addresses: [email protected] (B. Ding), [email protected] (J. Yu). TiO2 thin films prepared by liquid phase deposition technique as

0925-4005/$ – see front matter. Crown Copyright © 2012 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2012.05.050
 X. Wang et al. / Sensors and Actuators B 171–172 (2012) 658–665 659

sensing materials on QCM for NH3 detection have been reported 2.3. Preparation of PEI–TiO2 fibers on QCM
by Georgieva et al. However, the poor specific surface area of such
thin film is sometimes a limiting factor to the diffusion of analytes Schematic diagram shown in Fig. 1 presents the fabrication pro-
into the sensing materials, and thus leads to less sensitivity (detec- cess of sensing PEI–TiO2 fibers on QCM. A 0.5 wt% TiO2 suspension
tion limit of 100 ppm) [21]. Electrospun nanofibers with a high was prepared by adding TiO2 nanofibers into the EG with magnetic
specific surface area would be an ideal candidate to replace the stirring for 1 h. In this procedure, EG was used as the dispersing
flat films to enhance the sensor performances [22,23]. However, agent due to its lower volatility and higher viscosity than other
on the basis of our current knowledge, no literature about electro- common organic solvents, which could benefit the dispersion of
spun TiO2 nanofiber based QCM sensor has ever been reported until TiO2 . The TiO2 fiber EG dispersed phase was drop casted on the
now. Additionally, the surface of semiconductor nanofibers can be grounded electrode of QCM (Stanford Research Systems, Inc.) by
modified with a monolayer of adsorbed organic molecules [2,24]. a micropipettor (5–50 ␮L, Shanghai Liansheng Instrumental Fac-
Highly efficient dye-sensitized solar cells have been developed by tory), followed by heat treatment at 120 ◦ C for 5 h in vacuum until
attaching dye molecules to multi-core cable-like TiO2 nanofibrous the EG was completely evaporated. The QCM sensors consists of a
membranes [24]. A large surface area of porous TiO2 fibrous mem- disk-shaped AT-cut piezoelectronic quartz crystal deposited with
branes plays an important role in enhancing the light-to-electricity gold electrodes on both sides, and are operated at a frequency of
conversion yield of the photovoltaic systems. In this article, we 5 MHz. The resonance frequencies were measured by a QCM digital
developed a novel nanostructured complex of polyethyleneimine controller (QCM200, Stanford Research Systems). The coating loads
(PEI) functionalized TiO2 nanofiber (PEI–TiO2 ) as sensing coating of TiO2 fibers on QCM were regulated at about 1300 and 4000 Hz.
on QCM for formaldehyde detection. To the best of our knowl- PEI was diluted to 1 wt% with a pure water/ethanol weight ratio
edge, there have no previous reports of organic–inorganic hybrid of 1:2. The ethanol was used to accelerate the diffusion process of
porous fibrous membranes composed of SMOs nanofibers covered PEI into porous TiO2 fibers. PEI (1 wt%) solution was drop casted
with polymer layers for use as the sensing coating on QCM for onto TiO2 fibers by the micropipettor, through which PEI–TiO2
vapor sensing. As-developed QCM sensor showed a good response fibers were prepared. After the solvents completely evaporated at
to formaldehyde vapor at room temperature and it could be used room temperature, the membranes coated on QCM sensors were
to detect formaldehyde with low detection limit (1 ppm) and good dried at 25 ◦ C for 12 h in vacuum. The coating loads of PEI on QCM
selectivity. Furthermore, another important issue of establishing were regulated at about 2700 and 6600 Hz.
good adhesion between the SMOs nanofibers and QCM electrodes
was also properly addressed to enable practical devices.
2.4. Measurement of sensing properties using QCM technique
2. Experimental
The change in resonant frequency of a QCM (f ) can be related
to the change in mass (m) due to the adsorption of gas molecules
2.1. Materials
on the surface of the sensing material using the Sauerbrey equation
as follows [26]:
The starting materials included polyethyleneimine (PEI)
(Mw = 70,000, Alfa Aesar Co., Ltd.), polystyrene (PS) (Mw = 208,000,
Wako), titanium tetraisopropoxide (TIP) (Aldrich), formaldehyde 2fo2 m
f = − (1)
(GCS grade, Aladdin Chemical Co., China), pure water with a A()1/2
resistance of 18.2 M, ethanol (Shanghai Zhenxing Chemical Co.,
Ltd.), ethylene glycol (EG) (Analytical grade, Sinopharm Chemical where f the frequency shift (Hz), fo the fundamental frequency
Reagent Co., Ltd.), tetrahydrofuran (THF), N,N-dimethylformamide of a bare QCM chip (5 MHz), m the mass change per unit
(DMF), and other volatile organic compounds (VOCs) (Analytical area (g/cm2 ), A the electrode area (1.00 cm2 ),  the density of
grade, Shanghai Chemical Reagents Co., Ltd.). All chemicals were quartz (2.648 g/cm3 ), and  the shear modulus of quartz crystal
used as received without any further purification. (2.947 × 1011 dyne/cm2 ). As a result, the change of 1 Hz corre-
sponds to the mass of 17.67 ng of materials adsorbed onto the
2.2. Preparation of TiO2 nanofibers crystal surface of a 5 MHz QCM.
Schematic diagram of a static-type gas testing system is shown
TiO2 nanofibers were prepared by the combination of electro- as in our previous report [22]. The sensor was installed in the test-
spinning and sol–gel process [25]. In a typical procedure, 1.5 g of ing chamber (7.64 L) which kept with the constant temperature at
TIP was dissolved in the mixture of acetic acid (3 mL) and ethanol 22 ◦ C and the RH of 50%, respectively. A Hamilton microliter syringe
(3 mL). After complete dissolution by stirring for 30 min, a 30 wt% (Hamilton Bonaduz AG, Switzerland) was used for analyte injec-
PS solution with solvents of THF/DMF (1/4, wt/wt) was added to tions. The concentration of injected analyte in the chamber was
the solution, followed by magnetic stirring for 1 h. The precursor calculated in ppm according to the following equation:
nanofibers were then electrospun with the electrospinning setup
[20]. The precursor solution was delivered to a needle made of 22.4TVs × 103
C= (2)
stainless steel at a constant flow rate of 4 mL/h controlled by a 273MV
peristaltic pump (LSP10-1B, Baoding Longer Precision Pump Co.,
Ltd.), where the metallic needle was connected to a high voltage where C the analyte concentration in ppm, 1 the density of liquid
power supply (DW-P303-1ACD8, Tianjin Dongwen High Voltage analyte in g/mL, T the temperature in testing chamber in Kelvin,
Co., China). When a high voltage of 20 kV is applied, fibers were Vs the volume of liquid analyte in ␮L, M the molecular weight of
collected on a grounded aluminum foil at an electrode distance analyte in g/mol, and V the chamber volume in liter. The sensing
of 20 cm. The electrospinning chamber was kept with the tem- properties of the sensors to analyte were examined by measuring
perature of 24 ◦ C and relative humidity (RH) of 40%. The as-spun the resonance frequency shifts of QCM which due to the additional
nanofibers were left in air for 24–48 h to allow the hydrolysis of mass loading. The resonance frequencies were measured by the
TIP to go to completion. Finally, TiO2 nanofibers were obtained by frequency counter. The data from the sensors were recorded by a
treating them in air at 450 ◦ C for 5 h. personal computer.
660 X. Wang et al. / Sensors and Actuators B 171–172 (2012) 658–665

Fig. 1. Schematic diagram illustrating the fabrication of sensing layers on QCM.

2.5. Materials characterization attributed to rapid phase separation in the calcination process. The
porous structure of TiO2 fibers was also confirmed by the nitrogen
The morphology of fibrous membranes was characterized by adsorption–desorption isotherm and BET surface area (68.72 m2 /g).
field emission scanning electron microscopy (FE-SEM) (S-4800, The nitrogen adsorption–desorption isotherm of the TiO2 fibers
Hitachi Ltd., Japan). An image analyzer (Adobe Photoshop CS2) exhibits a type IV adsorption branch with a combination of H1 and
was applied to measure fiber diameters. Brunauer–Emmett–Teller H3 hysteresis loops characteristic [29,30] of a predominantly meso-
(BET) surface area, pore volume, and pore width of TiO2 fibers were porous system (Fig. 4). The Barrett–Joynes–Halenda (BJH) plot of
examined by the nitrogen adsorption/desorption test with the help pore size distribution shows a characteristic broad range of pores
of a surface area analyzer (ASAP 2020). (1.7–122 nm) with an average pore diameter of 28 nm (Fig. 4, inset).
In calcination process, the temperature was fixed to 450 ◦ C at which
3. Results and discussion nucleation and growth process readily occurs [31]. Therefore, par-
ticulate TiO2 crystals are evident in the fibers as shown from the
3.1. Structural characterization of TiO2 fibers cross-section of the fibers (Fig. 3b). The FE-SEM images in Fig. 3c
and d show the variation in morphology as the TiO2 fibers dispersed
Fig. 2 presents the FE-SEM images of hybrid TiO2 /PS fibers, by EG. TiO2 nanoparticles embedded in the fibers were transferred
indicating that the resultant nanofibers were randomly oriented onto the fiber surface, which could be attributed to the vortex
as three-dimensional (3D) nonwoven membranes with a uniform caused by the magnetic stirring and thus lead to hollow structure
diameter of several hundred nanometers. The high-magnification of the fibers (Fig. 3d). These observations led us to conclude that the
SEM image (Fig. 2b) clearly shows that the electrospun nanofibers versatile structure creates enhanced surface area and facilitates the
are straight with an average diameter of 625 nm (Fig. 2b, inset). diffusion of analytes into the fibers, which may be potentially useful
These nanofibers have rough and uniform surfaces due to the rapid for applications such as sensing materials.
phase separation in the electrospinning process [27,28]. After PEI modification, the 3D porous fibrous structure was
The TiO2 /PS fibers were subjected to calcination at 450 ◦ C in air still maintained in the PEI–TiO2 composite fibers (Fig. 3e and f).
and TiO2 fibers were obtained. The 3D porous fibrous membranes The sensing PEI was not only adsorbed on the surface of the
with nonwoven structure were still maintained in these mem- TiO2 fibers but also penetrated into the interspaces among the
branes upon calcination process. However, the fracture of fibers fibers and thus formed the conglutination phenomenon, which fur-
and significant reduction in diameter (average diameter of 457 nm) ther enhanced the connection between sensing membranes and
were observed due to the pyrolysis of PS in the hybrid TiO2 /PS fibers. QCM electrode and thus improved the stability of the sensing
By close observation of Fig. 3b, it can be seen that the fibers exhib- layers, making this structure useful in practical electronic device
ited a highly porous structure at interior of fibers, which could be applications [9,22].

Fig. 2. Low and high resolution FE-SEM images of hybrid TiO2 /PS fibers. Inset shows the fiber diameter distributions of the composite fibers.
 X. Wang et al. / Sensors and Actuators B 171–172 (2012) 658–665 661

Fig. 3. FE-SEM images of (a, b) TiO2 fibers, (c, d) EG dispersed TiO2 fibers, and (e, f) PEI–TiO2 composite fibers. Inset of (b) shows the fiber diameter distributions of the TiO2 fibers.

3.2. Formaldehyde sensing properties frequency changes when the fibers were exposed to formalde-
hyde vapors. During the exposure process, the porous fibers on the
The formaldehyde-sensing properties of PEI-modified TiO2 QCM act as sensing layers for target formaldehyde molecules and
porous fibers on QCM were investigated by measuring the the interaction of formaldehyde molecules with the sensing layer
causes the frequency to decrease. The sensor responses (F) for
each concentration were obtained from the frequency differences
between the corresponding QCM frequencies at the beginning and
the end of the exposure process. Fig. 5a shows time courses of
response of QCM-based PEI–TiO2 sensors with different PEI coating
loads upon exposure to increasing formaldehyde concentrations
(1–100 ppm) in a temperature-controlled measurement cell (tem-
perature of 25 ◦ C). The QCM sensor coated with only TiO2 fibers
exhibited only F = 0.2 Hz under exposure to 1 ppm formaldehyde
vapor. The F of the TiO2 fibers coated QCM sensors exposed to 5,
15, 35, 70 and 100 ppm of formaldehyde were 0.3, 0.5, 0.9, 1.2 and
1.6 Hz, respectively. It could be seen that the response amplitude
of the sensors was gradually increased with the increased vapor
concentration. The response caused by the additional mass loading
may be attributed to the moisture absorbed on TiO2 fibers that can
absorb formaldehyde molecules.
In contrast, QCM-based PEI–TiO2 sensors with PEI coating loads
of 2700 and 6600 Hz responded rapidly and reached higher F
(0.4 and 0.8 Hz) within 120 s upon exposure 1 ppm formaldehyde.
Fig. 4. Nitrogen adsorption–desorption isotherm of TiO2 fibers. The inset image Additionally, QCM-based PEI–TiO2 sensors with PEI coating load of
shows the pore size distribution. 6600 Hz exhibited the fastest response speed among three samples.
662 X. Wang et al. / Sensors and Actuators B 171–172 (2012) 658–665

Fig. 6. Response of QCM-based PEI–TiO2 sensors with different TiO2 coating loads
(i.e. 1300, 4000 Hz) upon exposure to increasing formaldehyde concentrations from
1 to 100 ppm at ambient temperature of 25 ◦ C. The coating load of PEI was 2700 Hz.

[36], CdO–In2 O3 [37], and Ga-doped ZnO [38] sensors that can
detect formaldehyde (1.2–32 ppm) only at higher operating tem-
perature (95–400 ◦ C).
Fig. 6 shows the effects of the TiO2 fibers coating load on the
sensor performance. On this occasion, the TiO2 substrates were
functionalized with the same coating load of PEI (2700 Hz). It can
be found that the QCM-based PEI–TiO2 sensor with higher coat-
ing load of TiO2 (4000 Hz) exhibits the higher response amplitudes
toward each concentration, in contrast to our previous study that
the sensitivity of fibrous PEI–PS membranes coated QCM sensors
for formaldehyde decreased with increasing the coating load of PS
substrates. We attributed the difference to the nature of fibrous
template materials. In the case of fibrous PEI–PS membranes, the
Fig. 5. Response of QCM-based PEI–TiO2 sensors with different PEI coating loads fluffy texture of soft PS fibers increased the energy dissipation dur-
(i.e. 0, 2700, 6600 Hz) upon exposure to increasing formaldehyde concentrations ing vibration transfer on the QCM, and thus leaded to the decreased
(1–100 ppm) at ambient temperature of 25 ◦ C. (b) The frequency shift versus
formaldehyde concentration. The coating load of TiO2 was 1300 Hz.
sensitivity with increasing the coating load of PS substrates. How-
ever, for the PEI–TiO2 fibers, the large rigidity and stacking density
of inorganic TiO2 was conducive to the vibration transfer on the
When exposed to 100 ppm of formaldehyde, the F of the QCM QCM. As a result, the nature of fibrous template materials was one
sensors coated with PEI–TiO2 sensors with different PEI coating of the key factors to affect the QCM sensor sensitivity.
loads (0, 2700, and 6600 Hz) were 1.6, 4.3, and 13.7 Hz, respectively. The change in environment condition such as temperature and
Evidently, QCM-based PEI–TiO2 sensors with PEI coating load of humidity usually influences a QCM sensor response. For example,
6600 Hz has achieved the best sensing performance toward the Fig. 7 shows the sensor responses of the QCM-based PEI–TiO2 sen-
accumulated formaldehyde concentrations, approximately eight sors to the formaldehyde at different ambient temperature but
times as much as TiO2 fibers coated sensor. The large and rapid same humidity. When exposed to 100 ppm of formaldehyde, the
responses can be attributed to the nucleophilic addition interaction F of the QCM sensors at ambient temperature of 30 and 25 ◦ C
between the formaldehyde molecules and the amine groups of PEI, were 5.1 and 14.1 Hz, respectively. It could be seen that the sensitiv-
as well as the porous structure of TiO2 fibers. Fig. 5b shows the F ity to the formaldehyde exhibited negative Arrhenius temperature
values of QCM-based PEI–TiO2 sensors with different PEI coating dependence [39], with responses increasing by factor of about 2.8
loads (0, 2700, and 6600 Hz) in sensing formaldehyde with various on going from 30 to 25 ◦ C. The changes in sensor responses with
concentrations of 1–100 ppm. The QCM isotherm to formaldehyde temperature agreed well with the report by Zellers et al. [40] based
shows a Henry-type sorption [16] at the concentration range. This on polymer-coated QCM sensor responses to vapors, where they
sorption behavior was also observed in the QCM response of fibrous demonstrated that the sensitivities to the seven organic vapors
PEI/poly(vinyl alcohol) (PVA) membranes [20]. examined all exhibited negative Arrhenius temperature dependen-
We have made comparison the performance of our QCM sen- cies, with responses increasing by factors of 1.5–4.4 on going from
sor to various kind of the sensors recently reported as summarized 38 to 18 ◦ C. This phenomenon is possibly due to the following two
in Table 1. It can be seen that the present QCM-based PEI–TiO2 aspects: (1) the frequency–temperature characteristic of an AT-Cut
sensor has not only the lowest detection limit (1 ppm) but also crystal unit has excellent frequency stability at room temperature
the fastest time response (<120 s) compared with all presented (∼25 ◦ C) since the temperature coefficients go to zero in this range
QCM-based formaldehyde sensors [28,32,33]. Moreover, the per- [41]; (2) the variation of Brownian motion at different temperature
formance of our sensors is comparable to commercially available leads to different response of QCM sensors. As a result, we con-
metal oxide semiconductor sensors and can be operated at room cluded that the optimal operation temperature of our QCM sensors
temperature, unlike NiO [34], ZnO/ZnSnO3 [35], SnO2 –In2 O3 –CdO was in the range of 20–25 ◦ C.
 X. Wang et al. / Sensors and Actuators B 171–172 (2012) 658–665 663

Table 1
Brief summary of results reported on the response of formaldehyde sensors.

Sensor types Sensing structures Operating temperature (◦ C) Detection limit (ppm) Response time (s) Reference

Resistive NiO film 280 1.2 13 [34]

ZnO/ZnSnO3 , ceramic tube structure 300 2 15 [35]
SnO2 –In2 O3 –CdO, ceramic tube structure 133 10 60 [36]
CdO–In2 O3 , ceramic tube structure 95 10 120 [37]
Ga-doped ZnO film 400 32 360 [38]

QCM Polyaniline–TiO2 nanocomposite film Room temperature 150 – [32]

Molecularly imprinted polymers film Room temperature 49 ∼270 [33]
PEI/PVA fibers Room temperature 10 ∼800 [20]
PEI–PS nanoporous fibers Room temperature 3 ∼1000 [28]
PEI–TiO2 nanoporous fibers Room temperature 1 <120 This work

Fig. 7. Effects of ambient temperature on the performance of the QCM-based

PEI–TiO2 sensors. The coating loads of PEI and TiO2 were 6600 and 1300 Hz, respec- Fig. 8. Responses of QCM-based PEI–TiO2 sensors upon exposure to 20 ppm
tively. formaldehyde at ambient temperature of 25 ◦ C. Inset shows the frequency shift of
the sensor versus 20 ppm of various VOCs.

Typical response profiles of QCM-based PEI–TiO2 sensors response to formaldehyde with a F up to 4 Hz, while for other
exposed to 20 ppm of formaldehyde is depicted in Fig. 8. On injec- vapors the response is less than 0.3 Hz, implying a high selectivity
tion of formaldehyde into the chamber, the response undergoes a to formaldehyde and can be considered as an excellent candidate
dramatical drop and reaches a steady value after several minutes. for gas sensing applications.
The response time, which was defined as the time required for the
sensor signal to reach 90% of the saturation and original values, was 3.3. Discussion on sensing mechanism
less than 70 s. Selectivity is a key property for sensors in practical
use. In this section, the selectivity of QCM sensors to formaldehyde Previous investigations on electrospun fibers-based sensors
were investigated in consideration of possible interfering conven- put their attention on the fact that the unique structure and
tional VOCs, such as ethanol, acetone, DMF, dichloromethane, and high porous configuration are advantageous to achieve high and
THF. As shown in the inset of Fig. 8, the sensor shows the highest rapid response via effective and quick diffusion of analyte vapor

Fig. 9. Schematic representation of formaldehyde vapor detecting mechanism based on PEI–TiO2 fibers.
664 X. Wang et al. / Sensors and Actuators B 171–172 (2012) 658–665

into the sensing membranes [1,20,42]. Here, the present work References
are in well agreement with these statements and confirm the
key role of the nanostructure of the electrospun fibers on their [1] I.D. Kim, A. Rothschild, B.H. Lee, D.Y. Kim, S.M. Jo, H.L. Tuller, Ultrasensi-
tive chemiresistors based on electrospun TiO2 nanofibers, Nano Lett. 6 (2006)
sensing performances. The highly porous sensitive PEI–TiO2 layer 2009–2013.
can supply high-diffusivity paths for the formaldehyde molecules, [2] X.F. Wang, B. Ding, J.Y. Yu, M.R. Wang, Engineering biomimetic superhydropho-
enhancing vapor diffusion and mass transportation in sensing bic surfaces of electrospun nanomaterials, Nano Today 6 (2011) 510–530.
[3] J. Du, Y.L. Hsieh, Nanofibrous membranes from aqueous electrospinning of
material providing faster response time. Additionally, the large carboxymethyl chitosan, Nanotechnology 19 (2008) 125707.
rigidity and stacking density of inorganic TiO2 fibers also largely [4] Y.P. Li, W. Xiao, K. Xiao, L. Berti, J. Luo, H.P. Tseng, G. Fung, K.S. Lam,
facilitate the oscillation transmission, resulting in much faster Well-Defined, reversible boronate crosslinked nanocarriers for targeted drug
delivery in response to acidic pH values and cis-diols, Angew. Chem. Int. Ed. 51
response. (2012) 2864–2869.
The decrease in QCM frequency due to the additional mass load- [5] B. Li, B. Jiang, B.M. Boyce, B.A. Lindsey, Multilayer polypeptide nanoscale coat-
ing of adsorbed formaldehyde molecules on QCM is attributed to ings incorporating IL-12 for the prevention of biomedical device-associated
infections, Biomaterials 30 (2009) 2552–2558.
the reversible nucleophilic addition reaction between formalde-
[6] V.V. Sysoev, J. Goschnick, T. Schneider, E. Strelcov, A. Kolmakov, A gradient
hyde molecules and primary amine groups of PEI (Fig. 9). Therefore, microarray electronic nose based on percolating SnO2 nanowire sensing ele-
the number of primary amine groups plays an key role in deter- ments, Nano Lett. 7 (2007) 3182–3188.
mining the sensing performance of QCM sensors [28], which was [7] J. Huang, Q. Wan, Gas sensors based on semiconducting metal oxide one-
dimensional nanostructures, Sensors 9 (2009) 9903–9924.
also demonstrated in this contribution that increasing the coating [8] B.J. Li, H.Q. Cao, ZnO@graphene composite with enhanced performance for the
load of PEI deposited on the QCM leads to the improvement of the removal of dye from water, J. Mater. Chem. 21 (2011) 3346–3349.
sensitivity. Moreover, the reversible reaction guarantees the repro- [9] Y. Zhang, J. Li, G. An, X. He, Highly porous SnO2 fibers by electrospinning and
oxygen plasma etching and its ethanol-sensing properties, Sens. Actuators B
ducibility of the resultant sensor. Furthermore, QCM have been 144 (2010) 43–48.
widely used as the platform for mass sensing by the deposition [10] B. Ding, M. Wang, J. Yu, G. Sun, Gas sensors based on electrospun nanofibers,
with the sensing materials. Their resonance frequency has been Sensors 9 (2009) 1609–1624.
[11] W.S. Kim, B.S. Lee, D.H. Kim, H.C. Kim, W.R. Yu, S.H. Hong, SnO2 nanotubes fab-
proven to decrease linearly upon the increase of weight on the QCM ricated using electrospinning and atomic layer deposition and their gas sensing
electrode in a nanogram level, according to the Sauerbrey equation performance, Nanotechnology 21 (2010) 245605.
as shown in the Experimental part. According to the relationship [12] B. Ding, M.R. Wang, X.F. Wang, J.Y. Yu, G. Sun, Electrospun nanomaterials for
ultrasensitive sensors, Mater. Today 13 (2010) 16–27.
between the frequency shift and mass loading (1 Hz = 17.67 ng) for [13] Z. Li, H. Zhang, W. Zheng, W. Wang, H. Huang, C. Wang, A.G. MacDiarmid, Y.
a 5 MHz QCM, the formaldehyde mass loads for the QCM-based Wei, Highly sensitive and stable humidity nanosensors based on LiCl doped
PEI–TiO2 sensors upon exposure to 20 ppm formaldehyde was esti- TiO2 electrospun nanofibers, J. Am. Chem. Soc. 130 (2008) 5036–5037.
[14] Y. Ding, Y. Wang, L. Zhang, H. Zhang, C.M. Li, Y. Lei, Preparation of TiO2 –Pt hybrid
mated to be 70.68 ng.
nanofibers and their application for sensitive hydrazine detection, Nanoscale
3 (2011) 1149–1157.
[15] X. Wang, B. Ding, J. Yu, M. Wang, F. Pan, A highly sensitive humidity sensor
4. Conclusion based on a nanofibrous membrane coated quartz crystal microbalance, Nano-
technology 21 (2010) 055502.
[16] M. Kimura, R. Sakai, S. Sato, T. Fukawa, T. Ikehara, R. Maeda, T. Mihara, Sensing of
To summarize, we have demonstrated that a highly sensitive vaporous organic compounds by TiO2 porous films covered with polythiophene
QCM sensor comprising nanoporous TiO2 fibers with a large surface layers, Adv. Funct. Mater. 22 (2012) 469–476.
[17] X.F. Wang, B. Ding, J.Y. Yu, Y. Si, S.B. Yang, G. Sun, Electro-netting. Fabrication
area and functionalized with PEI layers can detect formaldehyde of two-dimensional nano-nets for highly sensitive trimethylamine sensing,
through analyses of frequency changes in their sensing layer. The Nanoscale 3 (2011) 911–915.
large BET surface area (68.72 m2 /g) and porosity of the fibers [18] X. Wang, B. Ding, J. Yu, M. Wang, Highly sensitive humidity sensors
based on electro-spinning/netting a polyamide 6 nano-fiber/net modified by
enhanced their sensitivity to formaldehyde due to the internal polyethyleneimine, J. Mater. Chem. 21 (2011) 16231–16238.
surface area accessible in them. Enhancing the coating load of [19] J. Krim, QCM tribology studies of thin adsorbed films, Nano Today 2 (2007)
TiO2 improved the sensitivity for the formaldehyde sensing. As- 38–43.
[20] X.F. Wang, B. Ding, M. Sun, J.Y. Yu, G. Sun, Nanofibrous polyethyleneimine
developed QCM sensor showed a good response to formaldehyde membranes as sensitive coatings for quartz crystal microbalance-based
vapor at room temperature and it could be used to detect formalde- formaldehyde sensors, Sens. Actuators B 144 (2010) 11–17.
hyde with low-level concentration (1 ppm). The sensitivity to the [21] V. Georgieva, P. Stevchev, P. Vitanov, L. Spassov, Quartz resonator with thin
TiO2 for NH3 detection, Vacuum 76 (2004) 203–206.
formaldehyde exhibited negative Arrhenius temperature depen-
[22] B. Ding, X. Wang, J. Yu, M. Wang, Polyamide 6 composite nano-fiber/net func-
dence, with responses increasing by factor of about 2.8 on going tionalized by polyethyleneimine on quartz crystal microbalance for highly
from 30 to 25 ◦ C. Additionally, the sensor has a good selectivity to sensitive formaldehyde sensors, J. Mater. Chem. 21 (2011) 12784–12792.
formaldehyde over various vapors such as ethanol acetone, DMF, [23] R. Nirmala, R. Navamathavan, H.S. Kang, M.H. El-Newehy, H.Y. Kim, Preparation
of polyamide-6/chitosan composite nanofibers by a single solvent system via
dichloromethane, and THF. The simplicity of the preparation tech- electrospinning for biomedical applications, Colloids Surf. B 83 (2011) 173–178.
nique reported here may offer a new means for preparing similar [24] H. Kokubo, B. Ding, T. Naka, H. Tsuchihira, S. Shiratori, Multi-core cable-like
functionalized metal-oxide nanomaterials with attractive applica- TiO2 nanofibrous membranes for dye-sensitized solar cells, Nanotechnology
18 (2007) 165604.
tions in real-time monitoring gas sensors with ultra-fast response [25] D. Li, Y. Xia, Fabrication of titania nanofibers by electrospinning, Nano Lett. 3
speed. (2003) 555–560.
[26] G. Sauerbrey, The use of quartz oscillators for weighing thin layers and for
microweighing, Z. Phys. 155 (1959) 206–222.
[27] J. Lin, Y. Cai, X. Wang, B. Ding, J. Yu, M. Wang, Fabrication of biomimetic super-
Acknowledgments hydrophobic surfaces inspired by lotus leaf and silver ragwort leaf, Nanoscale
3 (2011) 1258–1262.
[28] C.Y. Zhang, X.F. Wang, J.Y. Lin, B. Ding, J.Y. Yu, N. Pan, Nanoporous polystyrene
This work is supported by the Shanghai Nano Special Projects
fibers functionalized by polyethyleneimine for enhanced formaldehyde sens-
(11nm0502900), the National Basic Research Program of China (973 ing, Sens. Actuators B 152 (2011) 316–323.
Program, 2012CB525005), the National Natural Science Foundation [29] S. Bag, I.U. Arachchige, M.G. Kanatzidis, Aerogels from metal chalcogenides and
their emerging unique properties, J. Mater. Chem. 18 (2008) 3628–3632.
of China (No. 51173022), the “Dawn” Program of Shanghai Educa-
[30] R. Liang, H. Cao, D. Qian, MoO3 nanowires as electrochemical pseudocapacitor
tion Commission (10SG32), the Scientific Research Foundation for materials, Chem. Commun. 47 (2011) 10305–10307.
the Returned Overseas Chinese Scholars, Ministry of Education of [31] N. Horzum, D. Tascioglu, S. Okur, M.M. Demir, Humidity sensing properties of
China, the Program for New Century Talents of the University in ZnO-based fibers by electrospinning, Talanta 85 (2011) 1105–1111.
[32] J.B. Zheng, G. Li, X.F. Ma, Y.M. Wang, G. Wu, Y.N. Cheng, Polyaniline–TiO2 nano-
China, and the Fundamental Research Funds for the Central Uni- composite-based trimethylamine QCM sensor and its thermal behavior studies,
versities. Sens. Actuators B 133 (2008) 374–380.
 X. Wang et al. / Sensors and Actuators B 171–172 (2012) 658–665 665

[33] L. Feng, Y.J. Liu, X.D. Zhou, J.M. Hu, The fabrication and characterization of a Jinyou Lin received his BE degree from Zhongyuan Uni-
formaldehyde odor sensor using molecularly imprinted polymers, J. Colloid versity of Technology of China in 2007. He is currently
Interface Sci. 284 (2005) 378–382. pursuing his doctorate degree at Donghua University. His
[34] C.Y. Lee, P.R. Hsieh, C.H. Lin, P.C. Chou, L.M. Fu, C.M. Chiang, MEMS-based research interests include nanoporous fibers and its appli-
formaldehyde gas sensor integrated with a micro-hotplate, Microsyst. Technol. cation in filters and solar cells.
12 (2006) 893–898.
[35] J. Xu, X. Jia, X. Lou, G. Xi, J. Han, Q. Gao, Selective detection of HCHO gas using
mixed oxides of ZnO/ZnSnO3 , Sens. Actuators B 120 (2007) 694–699.
[36] T. Chen, Q. Liu, Z. Zhou, Y. Wang, A high sensitivity gas sensor for formalde-
hyde based on CdO and In2 O3 doped nanocrystalline SnO2 , Nanotechnology 19
(2008) 095506.
[37] T. Chen, Q. Liu, Z. Zhou, Y. Wang, The fabrication and gas-sensing characteristics
of the formaldehyde gas sensors with high sensitivity, Sens. Actuators B 131
(2008) 301–305.
[38] N. Han, Y.J. Tian, X.F. Wu, Y.F. Chen, Improving humidity selectivity in formalde- Bin Ding received his BS degree from the Department
hyde gas sensing by a two-sensor array made of Ga-doped ZnO, Sens. Actuators of Applied Chemistry of Northeast Normal University
B 138 (2009) 228–235. (China) in 1998. From 1998 to 2000 he was appointed an
[39] A.B. Littlewood, Gas Chromatography, Academic Press, New York, 1970. Instructor at the same university. In 2003, he received his
[40] E.T. Zellers, M. Han, Effects of temperature and humidity on the performance ME degree in Polymer Engineering from Chonbuk National
of polymer-coated surface acoustic wave vapor sensor arrays, Anal. Chem. 68 University in South Korea. In 2005, he received his PhD
(1996) 2409–2418. degree from Keio University in Japan. He was a visit-
[41] K. Yamamura, S. Shimada, Y. Mori, Damage-free improvement of thickness uni- ing scientist at the Keio University (2005–2007) and the
formity of quartz crystal wafer by plasma chemical vaporization machining, University of California at Davis (2007–2008). He is now
CIRP Ann.-Manuf. Technol. 57 (2008) 567–570. a Professor at Donghua University, China. His primary
[42] J.S. Lee, O.S. Kwon, S.J. Park, E.Y. Park, S.A. You, H. Yoon, J. Jang, Fabrication of research interests include fabrication of nanostructured
ultra-fine metal oxide decorated carbon nanofibers for DMMP sensor applica- materials, design and fabrication of bio-inspired surfaces
tion, ACS Nano 5 (2011) 7992–8001. with special wettability, gas sensors, bio-sensors, cata-
lysts, solar cells, and filters. He serves on the editorial boards of the Recent Patents
on Nanotechnology, Journal of Modern Textile Science and Engineering, The Internet
Biographies Journal of Nanotechnology, and The Open Surface Science Journal.

Jianyong Yu received his BE, ME, and PhD degrees from

Xianfeng Wang received his BE and ME degrees from Donghua University of China in 1985, 1988, and 1991,
Qingdao University of China in 2005 and 2008, respec- respectively. From 1997 to 1999, he was a visiting scientist
tively. He is currently pursuing his doctorate degree at at the Tokyo Institute of Technology in Japan. He is cur-
Donghua University. His research interests include the rently a Professor at Donghua University and responsible
fabrication and structure regulation of functional nano- for National Key Discipline of Textile Science & Engi-
materials and their applications in gas sensors, filtration, neering. He is engaged in research on basic theory, key
and self-cleaning materials. technology and application of textile materials.

Fuhai Cui received his BE from Heilongjiang Institute Salem Al-Deyab is a professor of King Saud University. He
of Science and Technology of China in 2009. He is cur- received his MS degree and PhD from university of Cincin-
rently pursuing his master degree at Guangxi University nati in USA in 1981 and 1982, respectively. From 2008
of Technology. His research interests include electrospun till now he was appointed as a Supervisor of Petrochem-
nanofibrous membranes and gas sensors. ical Research Chair and Coordinator of Master Program
in Polymer Science at King Saud University. His research
focuses polymer synthesis and characterization, industrial
catalysis and fabrication of nanostructured materials for
applications in biomedical and energy fields.