Vous êtes sur la page 1sur 9

Sensors and Actuators B 262 (2018) 86–94

Contents lists available at ScienceDirect

Sensors and Actuators B: Chemical


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

The significant improvement for BTX (benzene, toluene and xylene)


sensing performance based on Au-decorated hierarchical ZnO porous
rose-like architectures
Zheng Shen a , Xindong Zhang a , Xiaohui Ma a , Ruoning Mi a , Yu Chen a,b,∗ ,
Shengping Ruan a,∗
a
State Key Laboratory on Integrated Optoelectronics, College of Electronic Science & Engineering, Jilin University, Changchun 130012, China
b
Institute of Semiconductors, Chinese Academy of Sciences, No. A35 QingHua East Road, Beijing 100083, China

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

Article history: A novel hierarchical ZnO rose-like architecture assembled by porous nanosheets was synthesized through
Received 1 July 2017 a facile hydrothermal method combined with calcination process and used to fabricate gas sensors. The
Received in revised form 18 January 2018 gas sensing measurements showed that the samples exhibited superior individual BTX (benzene, toluene
Accepted 25 January 2018
and xylene) sensing properties. By designing more tiny pores on hierarchical rose petal-like nanosheet
Available online 31 January 2018
surface, the specific surface area of the samples was further extended. Besides, highly dispersed Au
nanoparticles were grown on the ZnO rose-like architectures to enhance the gas sensing performance
Keywords:
via a precipitation manner. Transmission electron microscopy (TEM) analyses indicated the average grain
ZnO
Porous rose-like architecture
size of these Au nanoparticles was about 3 nm. The gas sensing results showed that the responses of the
Au decoration Au-ZnO sensor to 20 ppm individual benzene, toluene and xylene were 16.25 46.43 and 76.47, which were
BTX sensor 4.33, 4.47 and 6.51 times higher than those of the pure specimens. Besides, the optimal working tempera-
ture was also decreased from 302 ◦ C to 206 ◦ C. The Au-ZnO sensor also exhibited short response/recovery
times, low-concentration detection capability and good stability. The schottky contact between Au and
ZnO, catalytic activity of Au nanoparticles and the specific ZnO porous rose-like architectures could be
three pivotal factors for the superior BTX sensing properties.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction for more than 8 h [7]. Besides, due to their similar characteristics,
it’s still a challenge to devise gas sensor with favorable BTX selec-
Benzene, toluene and xylene (BTX), as the typical volatile tivity. Therefore, it is with great significance to detect and identify
organic compounds (VOCs), are colorless and with characteristic BTX gases in practice.
odors [1,2]. Many industrial productions like oil refining, lacquers, Up to date, various methods such as mass spectrometry, chro-
detergents dyes and coke production will inevitably release cer- matography, and spectral analysis etc., have been put forward to
tain amounts of BTX [3,4]. And they are all extremely harmful and detect and analysis individual BTX gases [8–11]. Nevertheless, some
dangerous to our human body because of their toxicity, carcino- drawbacks such as complicated equipment, great expense and low
genicity and combustibility [5]. Remarkably, benzene is not only a efficiency limit the practical application. Gas sensor based on inor-
strong carcinogen but also hard to be metabolized by our physical ganic semiconducting metal oxide like CuO, Co3 O4 , SnO2 , In2 O3 and
body because of its stable chemical structural properties [6]. Amer- LaFeO3 could be a promising approach to achieve inexpensive, real-
ican Conference of Governmental Industrial Hygienists suggests time and practicable BTX testing because of its low-cost, nontoxic,
that people shouldn’t contact with 0.5 ppm benzene concentration stable and superior gas sensing properties [12–16]. As a kind of
n-type semiconductor metal oxide, ZnO has been widely studied
and applied in the field of gas sensor for its stable physicochem-
ical characteristics. It’s believed that nanomaterial with different
∗ Corresponding authors at: State Key Laboratory on Integrated Optoelectronics, morphologies could greatly influence its gas sensitivity. And three-
College of Electronic Science & Engineering, Jilin University, Changchun 130012, dimensional (3D) porous structure has been regard as an ideal
China. structural material for gas sensing application [17,18]. The 3D
E-mail addresses: chenwy@jlu.edu.cn (Y. Chen), ruansp1226@163.com
(S. Ruan).
porous morphology not only provides large surface-to-volume

https://doi.org/10.1016/j.snb.2018.01.205
0925-4005/© 2018 Elsevier B.V. All rights reserved.
Z. Shen et al. / Sensors and Actuators B 262 (2018) 86–94 87

ratio but also avoids the agglomeration among nanoparticles.


Therefore, gas sensors fabricated by 3D porous morphology usu-
ally exhibited high response and fast response/recovery rate.
For example, Jing Liu et al. prepared 3D interconnected macro-
mesoporous ZnO nanomaterial via a template-based filtration
deposition method, and the nanomaterial displayed excellent ace-
tone and methanol sensing performance [19]. Ling-min Yu et al.
synthesized 3D porous ZnO films via a seed layer solution, which
showed good ethanol sensing [20]. However, in spite of the complex
synthesis process, adopting of templates as well as low production
make it hard to produce on a large scale. Moreover, it’s known that
noble metals are extensively used to improve the sensing proper-
ties by chemical sensitized effects [21–23]. Au nanoparticles are
frequently used due to their thermal stability and relatively low
cost [24]. Although there have been some researches on gas sen-
sors which could detect one or two kinds of BTX gases, as far as we
know, investigations on gas sensors, especially about pure ZnO 3D
architectures and Au-ZnO 3D architectures, which could simulta-
neously detect and distinguish BTX gases with superior selectivity
and sensitivity have seldom been reported. Fig. 1. The schematic illustration of gas sensor.
In this paper, a novel hierarchical ZnO rose-like architecture
composed by hundreds of porous nanosheets have been produced
2.3. Preparation of Au nanoparticles grown on hierarchical ZnO
for the first time by a facile solvothermal method combined with
rose-like architectures
calcination. Au nanoparticles with average diameters of 3 nm are
decorated on the surface of the pure samples through a precip-
0.20 mmol of the as-synthesized pure ZnO samples was dis-
itation method. The gas sensing properties of the pure ZnO and
persed into 18 ml deionized water. The suspension was under
the Au-ZnO materials are investigated. The results showed that the
stirring and ultrasonic operations alternatively for several minutes
Au-ZnO sensor exhibited better sensitivity and selectivity towards
to make the samples well dispersed. Then, 1.5 ml of HAuCl4 (0.01 M)
benzene, toluene and xylene individually. The synergistic effect
aqueous solution were dropped into the above suspension. The sus-
between ZnO material and Au nanoparticles as well as the struc-
pension was stirred for 1 h to make the negative auric chloride ions
tural property of the obtained samples is discussed in terms of the
diffuse and adsorb on the surface of the samples evenly. Next, 0.5 ml
gas sensing enhancement to BTX gases.
of aqueous ammonia (25 wt%) were dropped slowly into the sus-
pension and stirred for another 1 h. After stirring, the suspension
was centrifuged twice with ethanol. Last, after being dried at 60 ◦ C
for 6 h and calcined at 350 ◦ C for 1 h, purple products were obtained.
2. Experimental
2.4. Characterization
2.1. Chemical reagent
The crystal properties were analyzed by X-ray diffraction (XRD,
Zinc nitrate hexahydrate (Zn(NO3 )2 ·6H2 O) and urea (CO(NH2 )2 ) TTRIII, Japan) with CuK␣1 (␭ = 1.5406 Å) in the range of 20–80◦ . The
were obtained from Xilong Chemical Co., Ltd. Aqueous ammo- element chemical states and morphological features were charac-
nia (25 wt%), glycerol (C3 H8 O3 ) and ethyl alcohol (C2 H5 OH) terized by X-ray photoelectron spectroscopy (XPS, PHI Quantera II,
were purchased from Beijing Chemical Works. Chloroauric acid Perkin Elmer), scanning electron microscopy (SEM, SU8010, Japan)
(HAuCl4 ·6H2 O) and polyvinyl pyrrolidone (PVP, MW 30,000) were with an accelerated voltage of 10 kV and transmission electron
purchased from Aladdin Chem. Co., Ltd. All the chemicals (AR grade) microscope (TEM, JEM-2100, Japan).
were used as received.

2.5. Fabrication and measurements of gas sensors

The fabricating process was described in detail as follows:


2.2. Preparation of hierarchical ZnO rose-like architectures Firstly, the nanomaterial as-prepared were mixed with deion-
ized water in a weight ratio of 4:1 and ground for 10 min into
The synthetic process of hierarchical ZnO rose-like architectures paste in a mortar. Then, the paste was directly coated on the
was as follows: 7 ml of glycerol, 7 ml of ethanol and 10 ml of deion- ceramic tube (length = 4 mm, internal diameter = 0.8 mm, external
ized water were mixed together to form the transparent mixture diameter = 1.2 mm) attached previously to a couple of parallel Au
solvent. 1.0 g of Zn(NO3 )2 ·6H2 O was dissolved in the mixture sol- electrodes. A Ni-Cr heating coil was inserted through the tube to
vent under vigorous stirring. 0.5 g of CO(NH2 )2 and 1.2 g of PVP were provide the working temperature. The ceramic tube was welded
put into the solution. The mixture solution was kept stirring for sev- onto a pedestal having six probes to form the complete sensor unit
eral hours until the solvent get transparent again. The transparent (shown in Fig. 1).
solution was transferred into a 50 ml Teflon-lined stainless steel The measurement was carried out in a commercial gas sensing
autoclave and sealed hermetically. The autoclave was heated at device of CGS-8 intelligent gas sensing analysis system (Beijing Elite
85 ◦ C for 12 h and then cooled down to room temperature naturally. Tech Co., Ltd., China). Briefly, a desired concentration of the target
The white precipitate was collected through centrifugation with gas was injected into a closed chamber and mixed with air. Then the
warm deionized water and alcohol. After being dried at 70 ◦ C for sensor was put into the chamber to test the change of the resistance.
one night and calcined at 450 ◦ C for 3 h, hierarchical ZnO rose-like Normally, the definition of response (S) is S = Ra /Rg (Ra denotes the
architectures were prepared. resistance value of the gas sensor in air, and Rg means the resistance
88 Z. Shen et al. / Sensors and Actuators B 262 (2018) 86–94

19-1458). The diffraction peaks of the samples after calcination can


be indexed accurately to the hexagonal ZnO architecture (JCPDS,
36-1451), which indicated the as-prepared ZnO was pure and well
crystallized. Three extra peaks of Au (111), (200) and (220) planes
could be found in the XRD spectrum of the Au loaded hierarchi-
cal ZnO rose-like samples, which confirmed that Au nanoparticles
were successfully decorated on the surface of ZnO.
The morphological structures of as-prepared pure ZnO samples
before and after calcination were shown in Fig. 3(a–d). The pure ZnO
products displayed clear hierarchical 3D rose-like shape gathered
with tens of extremely thin nanosheets. The average diameter of the
hierarchical 3D rose-like architecture was 2–3 ␮m. It was clear that
the smooth nanosheets turned into porous structure after being
calcined. This could be attributed to the loss of the water and car-
bon dioxide in the process of changing Zn5 (CO3 )2 (OH)6 into ZnO by
calcination. The thickness of these porous nanosheets was approx-
imately 15–20 nm. This kind of hierarchical 3D porous rose-like
architecture possesses of large specific surface area and is facili-
tated for gas diffusion.
Fig. 2. XRD patterns of the samples (a) before calcination, (b) after calcination and
(c) Au-ZnO rose-like architectures. The refined structures of the hierarchical ZnO rose-like architec-
tures decorated with Au nanoparticles were investigated by TEM.
The results were shown in Fig. 4. The low-resolution TEM images
of the sensor in the target gas.) [25]. The timeline for the gas sensor shown in Fig. 4(a–b) revealed that the nanosheets were porous and
to attain 90% of the total resistance value change is defined as the filmy, and massive tiny Au nanoparticles were grown evenly on
response/recovery time. the surface of these nanosheets. The diameters of these holes are
ranged from 10 nm to 50 nm. It could be measured out through
3. Results and discussion the high-resolution TEM images in Fig. 4(c–d) that the average
size of these Au nanoparticles was about 3 nm. The lattice pitch of
3.1. Characterization 0.236 nm was matched with the (111) plane of Au. And the lattice
pitch of 0.148 nm could be fit with the (103) plane of ZnO.
The crystal phases of the samples before and after calcination XPS (Fig. 5) was used to detect the elemental composition and
and the Au-loaded ZnO materials were analyzed by XRD. The analy- the chemical states of the obtained Au-ZnO composites. As shown
sis results were shown in Fig. 2. The diffraction peaks of the samples in Fig. 5(a), only Au, Zn, O and C were observed in the survey spec-
before calcination can be well fitted to the Zn5 (CO3 )2 (OH)6 (JCPDS, trum, which indicated no impurity elements were introduced into

Fig. 3. Low and high magnification SEM images of ZnO rose-like architectures before (a-b) and after calcination (c–d).
Z. Shen et al. / Sensors and Actuators B 262 (2018) 86–94 89

Fig. 4. Low and high magnification TEM images of Au-ZnO rose-like architectures.

the samples. In addition, the C 1s peak (284.0 eV) was treated as a the nanosheets increased further. This would make the rose-like
reference [26]. The two peaks of O 1s (530.7 and 532.0 eV), which architectures to be further agglomerated, which were not favor-
were found in Fig. 5(b), could be attributed to lattice oxygen and able for gas diffusion. This could be observed in Fig. 6(d). During
surface adsorbed oxygen, respectively. It has been reported that the the hydrothermal process, urea not only provided the carbonate
adsorbed oxygen which existed on the surface of sensing materials source but also increased the pH, and made the solution weakly
could be further divided into two parts: chemisorbed oxygen and alkaline due to its hydrolysis reaction. In addition, the polymeric
lattice oxygen. Both of them could take part in the reactions with chain of glycerol and PVP, as a kind of neutral additive, were used
the target gas to cause the change of the sensor resistance [24,27]. to modify the growth kinetics during the hydrothermal reaction.
Our XPS results also confirmed the existence of lattice oxygen. In
Fig. 5(c), it could be found that Au 4f5/2 was located at 89.1 eV and 3.2. Gas sensing properties
Au 4f7/2 at 83.9 eV, indicating that Au nanoparticles were loaded on
the surface of ZnO microspheres. The scan of Zn 2p was displayed It’s known that the gas sensing properties of the gas sensor could
in Fig. 2(d). The peaks of 1045.0 eV and 1022.0 eV could be indexed be influenced by the optimal working temperature. Accordingly,
to Zn 2p1/2 and Zn 2p3/2 , which were fixed well with those of Zn2+ the responses of the ZnO and Au-ZnO sensors to 20 ppm individual
in ZnO. Besides, the concentration of Au nanoparticles was 1.65 at%. benzene, toluene and xylene were tested under different temper-
In order to understand the growth process of hierarchical ZnO atures. As shown in Fig. 7, the optimal working temperature of the
rose-like architectures, we performed the morphological evolu- Au-ZnO sensor was measured at 206 ◦ C, at which the Au-ZnO sen-
tion of SEM images which were traced with hydrothermal time. sor appeared the maximum responses of 16.25, 46.43 and 76.47 to
And the results were shown in Fig. 6. First, zinc ions would coor- benzene, toluene and xylene, individually. By contrast, the pure ZnO
dinate with carbonate ions and hydroxyl ions in presence of PVP sensor showed the maximum responses of 3.75, 10.38 and 11.74 to
and glycerol to form Zn5 (CO3 )2 (OH)6 complexes. These complexes individual benzene, toluene and xylene at a higher temperature
would grow up to form thin nanosheets, which could be observed of 302 ◦ C. The enhancement of the responses and the decreasing
in Fig. 6(a). These broken nanoparticles after calcination revealed of optimal working temperature could be mainly attributed to the
that the nanosheets were unstable. Upon extending the time to catalytic effect of Au nanoparticles which were distributed evenly
8 h, the rose-like architectures began to form by assembling these on the surface of porous ZnO nanosheets. The following tests were
thin nanosheets together. Since the nano-sheet structure was pre- operated at their optimal working temperature, respectively.
served after calcination process, which could be found in Fig. 6(b), The dynamic response and recovery characteristics of pure ZnO
we could infer that the thickness of nanosheets increased and and Au-ZnO sensors were investigated under 20 ppm individual
these nanosheets got stable. When the time was extended to 12 h, benzene, toluene and xylene. The results were shown in Fig. 8. The
the rose-like architectures were formed completely by assem- resistance transitions of the ZnO and the Au-ZnO rose-like architec-
bling more nanosheets which could be seen in Fig. 6(c). And the tures were shown in Fig. 8(a). The baseline resistance of the Au-ZnO
porous rose-like architectures were preserved through calcination sensor was 130 M. And the baseline resistance of the ZnO sen-
process. By designing more tiny pores on hierarchical rose-like sor was 22 M. The response values of Au-ZnO sensor to benzene,
nanosheet surface, the specific surface area of the samples was toluene and xylene showed a stepped up trend, which could be
further improved. As time was prolonged to 16 h, the thickness of seen clearly in Fig. 8(b). The two sensors performed relatively fast
90 Z. Shen et al. / Sensors and Actuators B 262 (2018) 86–94

Fig. 5. XPS patterns of Au-ZnO rose-like architectures: (a) XPS survey of scan spectrum; (b) O 1s of Au-ZnO rose-like architectures; (c) Au 4f of Au-ZnO rose-like architectures;
(d) Zn 2p of Au-ZnO rose-like architectures.

Fig. 6. The SEM images for evolution of hierarchical ZnO samples with different hydrothermal time.
Z. Shen et al. / Sensors and Actuators B 262 (2018) 86–94 91

Fig. 7. Response of ZnO and Au-ZnO rose-like architectures to 20 ppm individual Fig. 9. Responses of sensors based on ZnO and Au-ZnO rose-like architectures versus
benzene, toluene and xylene at different temperatures. different concentrations of individual benzene, toluene and xylene.

reaction rate. The response of the Au-ZnO sensor could be finished


within 5 s and the recovery process could be done within 50 s. Due
to the acceleration of reaction rate caused by the increase of optimal
working temperature, The ZnO sensor displayed relatively faster
response and recovery ability. And its response and recovery time
could be finished within 3 s and 10 s.
Fig. 9 showed the responses of pure ZnO and Au-ZnO sensors to
different concentrations of individual benzene, toluene and xylene.
All of the saturation curves exhibited similar tendency of increasing
rapidly at lower gas concentration conditions and then gradu-
ally becoming saturated. Compared with toluene and xylene, the
responses of the two sensors to benzene reached saturation earlier
at the concentration of 100 ppm. It was worth mentioning that the
Au-ZnO sensor could reach the response values of 3.6, 4.3 and 5.2
to 1 ppm benzene, toluene and xylene, individually. However, the
response values of the ZnO sensor to BTX gases at 1 ppm were below
2.0. In addition, the responses of the Au-ZnO sensor to 0.1 ppm indi- Fig. 10. Selectivity measurements of ZnO and Au-ZnO microspheres exposed in
different target gases at the concentration of 20 ppm.
vidual benzene, toluene and xylene were 1.5 1.7 and 2.0 (shown in
Fig. S1).
Selectivity is another essential feature for gas sensor. Hence, were all promoted to some extent. Especially, the responses of
the two sensors were measured to various gases, such as carbon Au-ZnO sensor to individual benzene, toluene and xylene were sig-
monoxide (CO), hydrogen (H2 ), methane (CH4 ), ethylene (C2 H4 ) nificantly improved about 4.33, 4.47 and 6.51 times higher than
and formaldehyde (HCHO). The response results were shown in those of the pure one. The responses of Au-ZnO sensor to carbon
Fig. 10. Compared with pure ZnO sensor, the responses of Au-ZnO monoxide, hydrogen, formaldehyde, methane and ethylene were

Fig. 8. Transient characteristics of the ZnO and the Au-ZnO rose-like architectures to 20 ppm individual benzene, toluene and xylene in resistance values (a) and response
values (b).
92 Z. Shen et al. / Sensors and Actuators B 262 (2018) 86–94

2.55, 1.36, 2.18, 1.32 and 1.43, which were less than 3.0 at 20 ppm
concentration. The selectivity measurements of ZnO and Au-ZnO
microspheres exposed in different target gases at the concentration
of 1 ppm were provided in Fig. S2. On the one hand, the superior
selectivity of ZnO sensor to BTX gases might be attributed to the
differences in reactivity among the target gases which are rooted
form the diversity in bond energies as well as chemical molecular
structures. On the other hand, some literatures reported that the Au
nanoparticles were preferred to catalyze and decompose this kind
of benzenoid hydrocarbon [28,29]. Therefore, the appropriate coor-
dination between Au nanoparticles and the benzene rings might be
a factor for the enhanced selectivity of the Au-ZnO sensor to BTX
gases. The stepped up response values of the Au-ZnO sensor to ben-
zene, toluene and xylene, as a distinguishing feature, were likely
attributed to the more active chemical properties of toluene and
xylene compared with that of benzene. It’s known that the methyl
group, as a kind of electron withdrawing group, would increase
electron cloud density on the benzene ring and make the benzene
rings activated [30]. Thus, xylene displayed the most active chem-
Fig. 11. Stability measurements of ZnO and Au-ZnO sensors to 20 ppm individual
ical property among the BTX gases. And benzene performed the
benzene, toluene and xylene within 30 days.
least active chemical property. This resulted in the three ladder-like
distribution features of the Au-ZnO sensor responses to benzene,
gen anions (Eqs. (1)–(4)). When the continuous adsorption process
toluene and xylene.
reached certain equilibrium, electron depletion layer was formed
In order to test their stability, the response data based on these
at the superficial zone of ZnO materials. Eventually, the resistance
two sensors to 20 ppm individual benzene, toluene and xylene over
of the sensor increased (Our experimental results showed that the
30 days were collected. As shown in Fig. 11, the responses only had
resistance of the sensor reached 22 M). When the ZnO sensor
a slight decrease after a month of measurement. Table 1 lists some
was exposed to one kind of the BTX gases, some gas molecules
reports published recently upon gas sensing performance of vari-
which were diffusing to the surface of the ZnO materials would
ous gas sensors based on ZnO materials and our work [28,31–35].
be oxidized by these adsorbed oxygen anions (Eqs. (5)–(7)). Ben-
Significantly, the Au-ZnO sensor fabricated in this research exhib-
efiting from the reduction reaction process, the desorbed oxygen
ited higher response and more obvious discriminating capacity to
would release some free electrons back to the ZnO materials to nar-
BTX gases, which implied that it is promising for practical detection
row the thickness of the electron depletion layer. This increased
of BTX gases.
the electron concentration of the conduction band and decreased
the sensor resistance (The resistance of ZnO sensor was decreased
3.3. Gas sensing mechanism from 22 M to 5.87 M, 2.12 M and 1.87 M when exposed into
20 ppm of benzene, toluene and xylene, individually).
The sensing mechanism of pure ZnO sensor could be explained
with the modulation of the conductivity of the semiconducting O2 (gas) → O2 (ads) (1)
sensing materials caused by the reactions between the adsorbed O2 (ads) + e- → O2 − ◦
(ads) (T < 100 C) (2)
oxygen anions and the individual BTX gases [36]. Accurately,
− − ◦ ◦
the reactions could be subdivided into surface reactions between O2 (ads) + e- → 2O (ads) (100 C < T < 300 C) (3)
adsorbed oxygen and one of the BTX gases and the bulk reactions −
O (ads) + e- → O 2−
(ads) (T > 300 C) ◦
(4)
between lattice oxygen and the individual BTX gases [24], which

could be seen in XPS results. Firstly, the ZnO sensor could adsorb C6 H6 + 15O → 6CO2 + 3H2 O (5)
oxygen molecules from air to the surface of ZnO materials. These −
C6 H5 CH3 + 18O → 7CO2 + 4H2 O (6)
adsorbed oxygen molecules could trap a certain amount of free

electrons from the conduction band of ZnO materials to form oxy- C6 H4 (CH3 )2 + 21O → 8CO2 + 5H2 O (7)

Table 1
Performance comparison of various gas sensors based on ZnO materials.

Material Optimum temperature Gas Concentration S = Rair /Rgas Res. Time/Rec. time (s) Ref.

Au-ZnO rose-like architecture 206 ◦ C Benzene 20 ppm 16.25 5 s/36 s Our work
Toluene 46.43 2 s/50 s
Xylene 76.47 2 s /24 s
ZnO nanoflower 200 ◦ C Benzene 200 ppm 1.79 15 s/58 s [28]
Toluene 1.85 10 s/50 s
Xylene 1.87 9 s/38 s
TiO2 -ZnO thick film 370 ◦ C Benzene 100 ppm 24 10 s/5 s [31]
Toluene 35 –
Xylene 50 –
Au-ZnO nanowire 340 ◦ C Benzene 100 ppm 5.71 64 s/43 s [32]
Toluene 8.63 36 s/45 s
Co-ZnO nanowire 400 ◦ C Toluene 5 ppm 8.5 – [33]
Xylene 19.55 –
ZnO/ZnCo2 O4 nanocages 320 ◦ C Xylene 100 ppm 34.26 – [34]
ZnO/ZnNi0.9 Zn0.1 O DSNCs 240 ◦ C Xylene 100 ppm 54.7 – [35]

The short line denotes that the data is not spelled out in the literature.
Z. Shen et al. / Sensors and Actuators B 262 (2018) 86–94 93

In view of the basic design strategies of high-performance gas ity and sensitivity to individual benzene, toluene and xylene. The
sensor noted by Yamazoe et al. [37], the enhanced BTX sensing more methyl groups in the benzenoid hydrocarbons the easier to
characteristics of the Au-ZnO sensor could mainly ascribed to two be detected by gas sensors. This work is also significant for adopt-
aspects. The first one could be attributed to the formation of schot- ing a proper method to promote the gas-sensing characters and
tky junctions between Au nanoparticles and ZnO materials. It’s detecting the environmental pollutions.
known that the work function of Au (5.1 eV) was higher than that
of ZnO (4.45 eV) [38,39]. This caused the Fermi level of Au at a
Acknowledgments
lower position. In order to make the two Fermi levels rebalance, Au
nanoparticles would trap some free electrons from ZnO material.
This work was supported by the National Natural Science Foun-
This resulted in the formation of schottky junctions. The massive
dation of China (Grant No. 11574110), the Project of Science and
schottky junctions would further extend the electron depletion
Technology Plan of Jilin Province, the Project of Jilin provincial
layer. Therefore, the resistance of the sensor would increase. The
development and Reform Commission, the Project of Science and
other aspect for the enhanced sensing performance was the cat-
Technology Plan of Tianjin City (16YFXTGX00230), Postdoctoral
alytic effect of Au nanoparticles, which was known as the “spillover
Science Foundation of China (Grant No. 2016M600231), and the
effect”. It’s known that oxygen species were more favorable to
Program for JLU Science and Technology Innovative Research Team.
be adsorbed on the surface of noble metals [40]. Therefore, the
Au nanoparticles played the role of improved adsorption sites to
adsorb more activated oxygen species. And some of the activated Appendix A. Supplementary data
oxygen species would spill onto the ZnO surface to trap free elec-
trons from ZnO material further [41,42]. Thus, the resistance of Supplementary data associated with this article can be found, in
the Au-ZnO sensor increased to 130 M. The catalytic effect of the online version, at https://doi.org/10.1016/j.snb.2018.01.205.
Au nanoparticles would decrease the required activation energy to
make the catalytic reactions easier, which made the optimal work-
ing temperature decreased from 302 ◦ C to 206 ◦ C. Consequently, References
the sensing performances of Au-ZnO sensor were improved.
[1] A. Szczurek, M. Maziejuk, M. Maciejewska, T. Pietrucha, T. Sikora, BTX
The other aspect was the superior architecture of the hierar- compounds recognition in humid air using differential ion mobility
chical rose-like structure, which facilitated the target gas diffusing spectrometry combined with a classifier, Sens. Actuators B 240 (2017)
in and out of the surfaces of ZnO materials. The SEM and TEM 1237–1244.
[2] K.H. Kim, S.K. Pandey, R. Pal, Analytical bias among different gas
results verified that the hierarchical rose-like ZnO materials were chromatographic approaches using standard BTX gases and exhaust samples,
assembled by tens of ultra-thin porous nanoflakes. This less- J. Sep. Sci. 32 (2009) 549–558.
agglomerated architecture effectively provided large reaction areas [3] E. Gallego, F.X. Roca, X. Guardino, M.G. Rosell, Indoor and outdoor BTX levels
in Barcelona City metropolitan area and Catalan rural areas, J. Environ. Sci. 20
for the gas sensing reaction. According to the depletion layer model, (2008) 1063–1069.
the Debye length (Ld ) could be expressed by [4] A. Mirzaei, S.G. Leonardi, G. Neri, Detection of hazardous volatile organic
 compounds (VOCs) by metal oxide nanostructures-based gas sensors: a
εkBT review, Ceram. Int. 42 (2016) 15119–15141.
Ld = (8) [5] A. Robert Schnatter, P.J. Kerzic, Y. Zhou, M. Chen, M.J. Nicolich, K. Lavelle,
nq2 et al., Peripheral blood effects in benzene-exposed workers, Chem. Biol.
Interact. 184 (2010) 174–181.
Where ␧ represents the static dielectric, kB indicates the Bolz- [6] A. Andrejeva, A.M. Gardner, W.D. Tuttle, T.G. Wright, Consistent assignment
mann constant, T is the optimal temperature in absolute style of the vibrations of symmetric and asymmetric para–disubstituted benzene
molecules, J. Mol. Spectrosc. 321 (2016) 28–49.
and q means the unit charge value and n is the carriers con- [7] S.-Y. Jeong, J.-W. Yoon, T.-H. Kim, H.-M. Jeong, C.-S. Lee, Y. Chan Kang, et al.,
centration [43,44]. The typical values of these parameters for Ultra-selective detection of sub-ppm-level benzene using Pd–SnO2 yolk–shell
ZnO sensors are ␧ = 7.9 × 8.85 × 10−12 Fm−1 , kB = 1.38 × 10−23 J K−1 , micro-reactors with a catalytic Co3 O4 overlayer for monitoring air quality, J.
Mater. Chem. A 5 (2017) 1446–1454.
T = 475 K and q = 1.6 × 10−19 C. The electron density of ZnO is about [8] F.-m. Peng, P.-h. Xie, H.-y. Li, Y.-h. Zhang, W.-q. Liu, Effect of atmospheric
1017 –1018 cm−3 . With a suitable value of n = 8 × 1017 cm−3 , the Ld interfering absorption on measurement of BTX by DOAS, Chin. J. Chem. Phys.
is approximately 5 nm. It’s known that the sensors could exhibit 21 (2008) 202.
[9] H. Oser, M.J. Coggiola, S.E. Young, D.R. Crosley, V. Hafer, G. Grist, Membrane
ultrahigh response and have potential to detect gases in ppb level introduction/laser photoionization time-of-flight mass spectrometry,
when the size of the nanomaterial is close to the value of Debye Chemosphere 67 (2007) 1701–1708.
length (2Ld ) [40]. Furthermore, Niyom Hongsith al., revealed that [10] M.Y. Bottein, J.M. Fuquay, R. Munday, A.I. Selwood, R. van Ginkel, C.O. Miles,
et al., Bioassay methods for detection of N-palmitoylbrevetoxin-B2 (BTX-B4),
the response of the sensor could be enhanced prominently when
Toxicon 55 (2010) 497–506.
the size of the ZnO nanomaterial is close to 15 nm [43]. Since the [11] K. Hamdi, M. Hébrant, P. Martin, B. Galland, M. Etienne, Mesoporous silica
thickness of the porous ZnO nanoflakes was about 15–20 nm, the nanoparticle film as sorbent for in situ and real-time monitoring of volatile
Au-ZnO sensor displayed a sensitive detecting ability. BTX (benzene, toluene and xylenes), Sens. Actuators B 223 (2016) 904–913.
[12] A. Urbutis, S. Kitrys, Dual function adsorbent-catalyst CuO-CeO2 /NaX for
temperature swing oxidation of benzene, toluene and xylene, Open Chem. 12
(2014) 492–501.
5. Conclusions
[13] Y. Liu, H. Dai, J. Deng, S. Xie, H. Yang, W. Tan, et al., Mesoporous
Co3 O4 -supported gold nanocatalysts: highly active for the oxidation of carbon
Overall, hierarchical ZnO rose-like architectures were synthe- monoxide, benzene, toluene, and o-xylene, J. Catal. 309 (2014) 408–418.
sized by a facile hydrothermal method. The gas sensing tests [14] S.-Y. Jeong, J.-W. Yoon, T.-H. Kim, H.-M. Jeong, C.-S. Lee, Y.C. Kang, et al.,
Ultra-selective detection of sub-ppm-level benzene using Pd–SnO2 yolk–shell
showed that the ZnO materials showed superior individual ben- micro-reactors with a catalytic Co3 O4 overlayer for monitoring air quality, J.
zene, toluene and xylene sensing ability. In order to improve Mater. Chem. A 5 (2017) 1446–1454.
the sensing properties, highly dispersed Au nanoparticles were [15] V.R. Choudhary, S.K. Jana, Benzoylation of benzene and substituted benzenes
by benzoyl chloride over In2 O3 /Si-MCM-41 catalyst, J. Mol. Catal. A: Chem.
deposited on the surface of ZnO materials successfully through 184 (2002) 247–255.
a precipitation manner. The measurements showed Au-ZnO sen- [16] B. Gao, J. Deng, Y. Liu, Z. Zhao, X. Li, Y. Wang, et al., Mesoporous LaFeO3
sor exhibited high response to individual BTX gases, quick catalysts for the oxidation of toluene and carbon monoxide, Chin. J. Catal. 34
(2013) 2223–2229.
response/recovery speed and good stability. This work confirmed [17] R.C. Pawar, J.-W. Lee, V.B. Patil, C.S. Lee, Synthesis of multi-dimensional ZnO
that ZnO materials could be made to detect benzene, toluene and nanostructures in aqueous medium for the application of gas sensor, Sens.
xylene. Au nanoparticles could effectively enhance the selectiv- Actuators B 187 (2013) 323–330.
94 Z. Shen et al. / Sensors and Actuators B 262 (2018) 86–94

[18] X. Wang, W. Liu, J. Liu, F. Wang, J. Kong, S. Qiu, et al., Synthesis of nestlike ZnO sensing material for selective detection of xylene, Sens. Actuators B 252
hierarchically porous structures and analysis of their gas sensing properties, (2017) 649–656.
ACS Appl. Mater. Interfaces 4 (2012) 817–825. [36] H. Chen, S.Y. Ma, H.Y. Jiao, G.J. Yang, X.L. Xu, T.T. Wang, et al., The effect
[19] J. Liu, H. Huang, H. Zhao, X. Yan, S. Wu, Y. Li, et al., Enhanced gas sensitivity and microstructure on the gas properties of Ag doped zinc oxide sensors: spheres
selectivity on aperture-controllable 3D interconnected macro-mesoporous and sea-urchin-like nanostructures, J. Alloys Compd. 687 (2016) 342–351.
ZnO nanostructures, ACS Appl. Mater. Interfaces 8 (2016) 8583–8590. [37] N. Yamazoe, G. Sakai, K. Shimanoe, Oxide semiconductor gas sensors, Catal.
[20] L.-m. Yu, F. Guo, Z.-y. Liu, S. Liu, B. Yang, M.L. Yin, et al., Facile synthesis of Surv. Asia 7 (2003) 63–75.
three dimensional porous ZnO films with mesoporous walls and gas sensing [38] U.T. Nakate, R.N. Bulakhe, C.D. Lokhande, S.N. Kale, Au sensitized ZnO
properties, Mater. Charact. 112 (2016) 224–228. nanorods for enhanced liquefied petroleum gas sensing properties, Appl. Surf.
[21] J. Tian, J. Wang, Y. Hao, H. Du, X. Li, Toluene sensing properties of porous Sci. 371 (2016) 224–230.
Pd-loaded flower-like SnO2 microspheres, Sens. Actuators B 202 (2014) [39] Y.J. Fang, J. Sha, Z.L. Wang, Y.T. Wan, W.W. Xia, Y.W. Wang, Behind the change
795–802. of the photoluminescence property of metal-coated ZnO nanowire arrays,
[22] J. Ding, J. Zhu, P. Yao, J. Li, X. Wang, Synthesis of ZnO–Ag hybrids and their Appl. Phys. Lett. 98 (2011) 033103.
gas-sensing performance toward ethanol, Ind. Eng. Chem. Res. 54 (2015) [40] H.-J. Kim, J.-H. Lee, Highly sensitive and selective gas sensors using p-type
8947–8953. oxide semiconductors: overview, Sens. Actuators B 192 (2014) 607–627.
[23] C.R. Michel, A.H. Martínez-Preciado, E.R. López-Mena, A. Elías-Zuñiga, N. [41] J. Zhang, X. Liu, S. Wu, M. Xu, X. Guo, S. Wang, Au nanoparticle-decorated
Cayetano-Castro, O. Ceballos-Sanchez, Improvement of the gas sensing porous SnO2 hollow spheres: a new model for a chemical sensor, J. Mater.
response of nanostructured LaCoO3 by the addition of Ag nanoparticles, Sens. Chem. 20 (2010) 6453–6459.
Actuators B 246 (2017) 181–189. [42] L. Wang, S. Wang, M. Xu, X. Hu, H. Zhang, Y. Wang, et al., A Au-functionalized
[24] L. Sui, X. Zhang, X. Cheng, P. Wang, Y. Xu, S. Gao, et al., Au-loaded hierarchical ZnO nanowire gas sensor for detection of benzene and toluene, Phys. Chem.
MoO3 hollow spheres with enhanced gas-sensing performance for the Chem. Phys. 15 (2013) 17179–17186.
detection of BTX (benzene, toluene, and xylene) and the sensing mechanism, [43] N. Hongsith, E. Wongrat, T. Kerdcharoen, S. Choopun, Sensor response formula
ACS Appl. Mater. Interfaces 9 (2017) 1661–1670. for sensor based on ZnO nanostructures, Sens. Actuators B 144 (2010) 67–72.
[25] S.-W. Choi, J. Zhang, K. Akash, S.S. Kim, H2S sensing performance of [44] K. Zhang, X. Yang, Y. Wang, Y. Bing, L. Qiao, Z. Liang, et al., Pd-loaded SnO2
electrospun CuO-loaded SnO2 nanofibers, Sens. Actuators B 169 (2012) 54–60. ultrathin nanorod-assembled hollow microspheres with the significant
[26] F. Qu, Y. Wang, J. Liu, S. Wen, Y. Chen, S. Ruan, Fe3 O4 –NiO core–shell improvement for toluene detection, Sens. Actuators B 243 (2017) 465–474.
composites: hydrothermal synthesis and toluene sensing properties, Mater.
Lett. 132 (2014) 167–170.
[27] X.-L. Cheng, Z. Rong, X.-F. Zhang, Y.-M. Xu, S. Gao, H. Zhao, et al., In situ Biographies
assembled ZnO flower sensors based on porous nanofibers for rapid ethanol
sensing, Sens. Actuators B 188 (2013) 425–432.
[28] L. Wang, S. Wang, M. Xu, X. Hu, H. Zhang, Y. Wang, et al., A Au-functionalized Zheng Shen is an undergraduate in College of Electronic Science and Engineering,
ZnO nanowire gas sensor for detection of benzene and toluene, Phys. Chem. Jilin University, China, and interested in functional nanomaterials, chemical sensors.
Chem. Phys. 15 (2013) 17179–17186.
Xindong Zhang received the PhD degree of electronic science and engineering from
[29] L. Wang, S. Wang, H. Zhang, Y. Wang, J. Yang, W. Huang, Au-functionalized
Jilin University in 2007. Now, he is a full professor in the College of Electronics
porous ZnO microsheets and their enhanced gas sensing properties, New J.
Science and Engineering, Jilin University, and mainly devoted to the research of
Chem. 38 (2014) 2530.
electronic functional materials and devices.
[30] C. Zhang, J. Hu, X. Li, Y. Wu, J. Han, Hydrogen-bonding interactions in hard
segments of shape memory polyurethane: toluene diisocyanates and 1, Xiaohui Ma is an undergraduate in College of Electronic Science and Engineering,
6-hexamethylene diisocyanate. A theoretical and comparative study, J. Phys. Jilin University, China, and interested in functional nanomaterials, chemical sensors.
Chem. A 118 (2014) 12241–12255.
[31] D. Acharyya, P. Bhattacharyya, An efficient BTX sensor based on ZnO Ruoning Mi is a college student in electronic science and technology in Jilin Univer-
nanoflowers grown by CBD method, Solid-State Electron. 106 (2015) 18–26. sity, China. She is currently interested in nanomaterials and chemical sensors.
[32] B.L. Zhu, C.S. Xie, W.Y. Wang, K.J. Huang, J.H. Hu, Improvement in gas
sensitivity of ZnO thick film to volatile organic compounds (VOCs) by adding Yu Chen received the PhD degree from Institute of Semiconductors, Chinese
TiO2 , Mater. Lett. 58 (2004) 624–629. Academy of Sciences in 2007. Now he is an associate researcher fellow and mainly
[33] H.S. Woo, C.H. Kwak, J.H. Chung, J.H. Lee, Co-doped branched ZnO nanowires devotes to the research of material synthesis and electronic functional materials.
for ultraselective and sensitive detection of xylene, ACS Appl. Mater. Chuan Chen is a senior engineer with the Master degree and mainly devotes to the
Interfaces 6 (2014) 22553–22560. research of gas sensing materials.
[34] F. Qu, H. Jiang, M. Yang, Designed formation through a metal organic
Shengping Ruan received the PhD degree of electronic science and engineering
framework route of ZnO/ZnCo2 O4 hollow core-shell nanocages with
from Jilin University in 2001. Now, he is a full professor in the College of Electronics
enhanced gas sensing properties, Nanoscale 8 (2016) 16349–16356.
Science and Engineering, Jilin University, and mainly devoted to the research of
[35] F. Qu, B. Zhang, X. Zhou, H. Jiang, C. Wang, X. Feng, et al., Metal-organic
electronic functional materials and devices.
frameworks-derived porous ZnO/Ni0.9 Zn0.1 O double-shelled nanocages as gas