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
Benzene, toluene and xylene (BTX), as the typical volatile
organic compounds (VOCs), are colorless and with characteristic
odors [1,2]. Many industrial productions like oil refining, lacquers,
detergents dyes and coke production will inevitably release cer-
tain amounts of BTX [3,4]. And they are all extremely harmful and
dangerous to our human body because of their toxicity, carcino-
genicity and combustibility [5]. Remarkably, benzene is not only a
strong carcinogen but also hard to be metabolized by our physical
body because of its stable chemical structural properties [6]. Amer-
ican Conference of Governmental Industrial Hygienists suggests
that people shouldn’t contact with 0.5 ppm benzene concentration
∗ Corresponding authors at: State Key Laboratory on Integrated Optoelectronics,
College of Electronic Science & Engineering, Jilin University, Changchun 130012,
China.
E-mail addresses: chenwy@jlu.edu.cn (Y. Chen), ruansp1226@163.com
(S. Ruan).
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-
tivity. Therefore, it is with great significance to detect and identify
BTX gases in practice.
Up to date, various methods such as mass spectrometry, chro-
matography, and spectral analysis etc., have been put forward to
detect and analysis individual BTX gases [8–11]. Nevertheless, some
drawbacks such as complicated equipment, great expense and low
efficiency limit the practical application. Gas sensor based on inor-
ganic semiconducting metal oxide like CuO, Co3 O4 , SnO2 , In2 O3 and
LaFeO3 could be a promising approach to achieve inexpensive, real-
time and practicable BTX testing because of its low-cost, nontoxic,
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
morphologies could greatly influence its gas sensitivity. And three-
dimensional (3D) porous structure has been regard as an ideal
structural material for gas sensing application [17,18]. The 3D
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
The synthetic process of hierarchical ZnO rose-like architectures
was as follows: 7 ml of glycerol, 7 ml of ethanol and 10 ml of deion-
ized water were mixed together to form the transparent mixture
solvent. 1.0 g of Zn(NO3 )2 ·6H2 O was dissolved in the mixture sol-
vent under vigorous stirring. 0.5 g of CO(NH2 )2 and 1.2 g of PVP were
put into the solution. The mixture solution was kept stirring for sev-
eral hours until the solvent get transparent again. The transparent
solution was transferred into a 50 ml Teflon-lined stainless steel
autoclave and sealed hermetically. The autoclave was heated at
85 ◦ C for 12 h and then cooled down to room temperature naturally.
The white precipitate was collected through centrifugation with
warm deionized water and alcohol. After being dried at 70 ◦ C for
one night and calcined at 450 ◦ C for 3 h, hierarchical ZnO rose-like
architectures were prepared.
Firstly, the nanomaterial as-prepared were mixed with deion-
ized water in a weight ratio of 4:1 and ground for 10 min into
paste in a mortar. Then, the paste was directly coated on the
ceramic tube (length = 4 mm, internal diameter = 0.8 mm, external
diameter = 1.2 mm) attached previously to a couple of parallel Au
electrodes. A Ni-Cr heating coil was inserted through the tube to
provide the working temperature. The ceramic tube was welded
onto a pedestal having six probes to form the complete sensor unit
(shown in Fig. 1).
The measurement was carried out in a commercial gas sensing
device of CGS-8 intelligent gas sensing analysis system (Beijing Elite
Tech Co., Ltd., China). Briefly, a desired concentration of the target
gas was injected into a closed chamber and mixed with air. Then the
sensor was put into the chamber to test the change of the resistance.
Normally, the definition of response (S) is S = Ra /Rg (Ra denotes the
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
Fig. 2. XRD patterns of the samples (a) before calcination, (b) after calcination and
(c) Au-ZnO rose-like architectures.
of the sensor in the target gas.) [25]. The timeline for the gas sensor
to attain 90% of the total resistance value change is defined as the
response/recovery time.
3. Results and discussion
3.1. Characterization
The crystal phases of the samples before and after calcination
and the Au-loaded ZnO materials were analyzed by XRD. The analy-
sis results were shown in Fig. 2. The diffraction peaks of the samples
before calcination can be well fitted to the Zn5 (CO3 )2 (OH)6 (JCPDS,
Fig. 3. Low and high magnification SEM images of ZnO rose-like architectures before (a-b) and after calcination (c–d).
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.
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
shown in Fig. 4(a–b) revealed that the nanosheets were porous and
filmy, and massive tiny Au nanoparticles were grown evenly on
the surface of these nanosheets. The diameters of these holes are
ranged from 10 nm to 50 nm. It could be measured out through
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
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.
XPS (Fig. 5) was used to detect the elemental composition and
the chemical states of the obtained Au-ZnO composites. As shown
in Fig. 5(a), only Au, Zn, O and C were observed in the survey spec-
trum, which indicated no impurity elements were introduced into
 Z. Shen et al. / Sensors and Actuators B 262 (2018) 86–94
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
reference [26]. The two peaks of O 1s (530.7 and 532.0 eV), which
were found in Fig. 5(b), could be attributed to lattice oxygen and
surface adsorbed oxygen, respectively. It has been reported that the
adsorbed oxygen which existed on the surface of sensing materials
could be further divided into two parts: chemisorbed oxygen and
lattice oxygen. Both of them could take part in the reactions with
the target gas to cause the change of the sensor resistance [24,27].
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
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
in Fig. 2(d). The peaks of 1045.0 eV and 1022.0 eV could be indexed
to Zn 2p1/2 and Zn 2p3/2 , which were fixed well with those of Zn2+
in ZnO. Besides, the concentration of Au nanoparticles was 1.65 at%.
In order to understand the growth process of hierarchical ZnO
rose-like architectures, we performed the morphological evolu-
tion of SEM images which were traced with hydrothermal time.
And the results were shown in Fig. 6. First, zinc ions would coor-
dinate with carbonate ions and hydroxyl ions in presence of PVP
and glycerol to form Zn5 (CO3 )2 (OH)6 complexes. These complexes
would grow up to form thin nanosheets, which could be observed
in Fig. 6(a). These broken nanoparticles after calcination revealed
that the nanosheets were unstable. Upon extending the time to
8 h, the rose-like architectures began to form by assembling these
thin nanosheets together. Since the nano-sheet structure was pre-
served after calcination process, which could be found in Fig. 6(b),
we could infer that the thickness of nanosheets increased and
these nanosheets got stable. When the time was extended to 12 h,
the rose-like architectures were formed completely by assem-
bling more nanosheets which could be seen in Fig. 6(c). And the
porous rose-like architectures were preserved through calcination
process. By designing more tiny pores on hierarchical rose-like
nanosheet surface, the specific surface area of the samples was
further improved. As time was prolonged to 16 h, the thickness of
89
the nanosheets increased further. This would make the rose-like
architectures to be further agglomerated, which were not favor-
able for gas diffusion. This could be observed in Fig. 6(d). During
the hydrothermal process, urea not only provided the carbonate
source but also increased the pH, and made the solution weakly
alkaline due to its hydrolysis reaction. In addition, the polymeric
chain of glycerol and PVP, as a kind of neutral additive, were used
to modify the growth kinetics during the hydrothermal reaction.
3.2. Gas sensing properties
It’s known that the gas sensing properties of the gas sensor could
be influenced by the optimal working temperature. Accordingly,
the responses of the ZnO and Au-ZnO sensors to 20 ppm individual
benzene, toluene and xylene were tested under different temper-
atures. As shown in Fig. 7, the optimal working temperature of the
Au-ZnO sensor was measured at 206 ◦ C, at which the Au-ZnO sen-
sor appeared the maximum responses of 16.25, 46.43 and 76.47 to
benzene, toluene and xylene, individually. By contrast, the pure ZnO
sensor showed the maximum responses of 3.75, 10.38 and 11.74 to
individual benzene, toluene and xylene at a higher temperature
of 302 ◦ C. The enhancement of the responses and the decreasing
of optimal working temperature could be mainly attributed to the
catalytic effect of Au nanoparticles which were distributed evenly
on the surface of porous ZnO nanosheets. The following tests were
operated at their optimal working temperature, respectively.
The dynamic response and recovery characteristics of pure ZnO
and Au-ZnO sensors were investigated under 20 ppm individual
benzene, toluene and xylene. The results were shown in Fig. 8. The
resistance transitions of the ZnO and the Au-ZnO rose-like architec-
tures were shown in Fig. 8(a). The baseline resistance of the Au-ZnO
sensor was 130 M. And the baseline resistance of the ZnO sen-
sor was 22 M. The response values of Au-ZnO sensor to benzene,
toluene and xylene showed a stepped up trend, which could be
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
In view of the basic design strategies of high-performance gas
sensor noted by Yamazoe et al. [37], the enhanced BTX sensing
characteristics of the Au-ZnO sensor could mainly ascribed to two
aspects. The first one could be attributed to the formation of schot-
tky junctions between Au nanoparticles and ZnO materials. It’s
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
lower position. In order to make the two Fermi levels rebalance, Au
nanoparticles would trap some free electrons from ZnO material.
This resulted in the formation of schottky junctions. The massive
schottky junctions would further extend the electron depletion
layer. Therefore, the resistance of the sensor would increase. The
other aspect for the enhanced sensing performance was the cat-
alytic effect of Au nanoparticles, which was known as the “spillover
effect”. It’s known that oxygen species were more favorable to
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
oxygen species would spill onto the ZnO surface to trap free elec-
trons from ZnO material further [41,42]. Thus, the resistance of
the Au-ZnO sensor increased to 130 M. The catalytic effect of
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,
the sensing performances of Au-ZnO sensor were improved.
The other aspect was the superior architecture of the hierar-
chical rose-like structure, which facilitated the target gas diffusing
in and out of the surfaces of ZnO materials. The SEM and TEM
results verified that the hierarchical rose-like ZnO materials were
assembled by tens of ultra-thin porous nanoflakes. This less-
agglomerated architecture effectively provided large reaction areas
for the gas sensing reaction. According to the depletion layer model,
the Debye length (Ld ) could be expressed by
 compounds (VOCs) by metal oxide nanostructures-based gas sensors: a
εkBT
Ld = (8)
nq2
Where ␧ represents the static dielectric, kB indicates the Bolz-
mann constant, T is the optimal temperature in absolute style
and q means the unit charge value and n is the carriers con-
centration [43,44]. The typical values of these parameters for
ZnO sensors are ␧ = 7.9 × 8.85 × 10−12 Fm−1 , kB = 1.38 × 10−23 J K−1 ,
T = 475 K and q = 1.6 × 10−19 C. The electron density of ZnO is about
1017 –1018 cm−3 . With a suitable value of n = 8 × 1017 cm−3 , the Ld
is approximately 5 nm. It’s known that the sensors could exhibit
ultrahigh response and have potential to detect gases in ppb level
when the size of the nanomaterial is close to the value of Debye
length (2Ld ) [40]. Furthermore, Niyom Hongsith al., revealed that
the response of the sensor could be enhanced prominently when
the size of the ZnO nanomaterial is close to 15 nm [43]. Since the
thickness of the porous ZnO nanoflakes was about 15–20 nm, the
Au-ZnO sensor displayed a sensitive detecting ability.
5. Conclusions
Overall, hierarchical ZnO rose-like architectures were synthe-
sized by a facile hydrothermal method. The gas sensing tests
showed that the ZnO materials showed superior individual ben-
zene, toluene and xylene sensing ability. In order to improve
the sensing properties, highly dispersed Au nanoparticles were
deposited on the surface of ZnO materials successfully through
a precipitation manner. The measurements showed Au-ZnO sen-
sor exhibited high response to individual BTX gases, quick
response/recovery speed and good stability. This work confirmed
that ZnO materials could be made to detect benzene, toluene and
xylene. Au nanoparticles could effectively enhance the selectiv-
93
ity and sensitivity to individual benzene, toluene and xylene. The
more methyl groups in the benzenoid hydrocarbons the easier to
be detected by gas sensors. This work is also significant for adopt-
ing a proper method to promote the gas-sensing characters and
detecting the environmental pollutions.
Acknowledgments
This work was supported by the National Natural Science Foun-
dation of China (Grant No. 11574110), the Project of Science and
Technology Plan of Jilin Province, the Project of Jilin provincial
development and Reform Commission, the Project of Science and
Technology Plan of Tianjin City (16YFXTGX00230), Postdoctoral
Science Foundation of China (Grant No. 2016M600231), and the
Program for JLU Science and Technology Innovative Research Team.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.snb.2018.01.205.
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Biographies
Zheng Shen is an undergraduate in College of Electronic Science and Engineering,
Jilin University, China, and interested in functional nanomaterials, chemical sensors.
Xindong Zhang received the PhD degree of electronic science and engineering from
Jilin University in 2007. Now, he is a full professor in the College of Electronics
Science and Engineering, Jilin University, and mainly devoted to the research of
electronic functional materials and devices.
Xiaohui Ma is an undergraduate in College of Electronic Science and Engineering,
Jilin University, China, and interested in functional nanomaterials, chemical sensors.
Ruoning Mi is a college student in electronic science and technology in Jilin Univer-
sity, China. She is currently interested in nanomaterials and chemical sensors.
Yu Chen received the PhD degree from Institute of Semiconductors, Chinese
Academy of Sciences in 2007. Now he is an associate researcher fellow and mainly
devotes to the research of material synthesis and electronic functional materials.
Chuan Chen is a senior engineer with the Master degree and mainly devotes to the
research of gas sensing materials.
Shengping Ruan received the PhD degree of electronic science and engineering
from Jilin University in 2001. Now, he is a full professor in the College of Electronics
Science and Engineering, Jilin University, and mainly devoted to the research of
electronic functional materials and devices.