Sensors and Actuators B 230 (2016) 581–591

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Sensors and Actuators B: Chemical

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

Experimental and theoretical studies of gold nanoparticle decorated

zinc oxide nanoflakes with exposed {1 0 1̄ 0} facets for butylamine
sensing
Yusuf Valentino Kaneti a,b , Xiao Zhang a , Minsu Liu b , David Yu b , Yuan Yuan c ,
Leigh Aldous c , Xuchuan Jiang b,∗
a
School of Materials Science and Engineering, University of New South Wales, Sydney, NSW 2052, Australia
b
Department of Chemical Engineering, Monash University, Melbourne, VIC 3800, Australia
c
School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia

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

Article history: The exposed surface facets play an important role in determining the gas-sensing performance of nanos-
Received 14 September 2015 tructured materials. This study reports the facile hydrothermal synthesis of zinc oxide nanoflakes with
Received in revised form 17 February 2016 exposed {1 0 1̄ 0} facets, as confirmed by the high resolution transmission electron microscopy (HRTEM)
Accepted 19 February 2016
and the corresponding selected area electron diffraction (SAED) analysis. The gas-sensing properties of
Available online 22 February 2016
the ZnO nanoflake sensor were investigated toward toxic n-butylamine, an important marker compound
in food and medical industries. The pure ZnO nanoflake sensor exhibits a response of 23.9–50 ppm of n-
Keywords:
butylamine at an optimum operating temperature of 300 ◦ C. Density Functional Theory (DFT) simulations
Organic amine
Gas-sensing
were used to study the adsorption behavior of n-butylamine on the ZnO(1 0 1̄ 0) surface. The results show
Density functional theory simulation that n-butylamine chemically adsorb on the ZnO(1 0 1̄ 0) surface through the formation of a bond between
Gold nanoparticles the nitrogen atom of the n-butylamine (C4 H11 N) and the surface Zn atom of ZnO. To further improve
Zinc oxide nanostructures the gas-sensing properties, the as-prepared ZnO nanoflakes were subsequently loaded with three dif-
ferent quantities of Au (1.37, 2.82, and 5.41 wt% Au). The gas-sensing measurements indicate that the
Au nanoparticle-decorated ZnO nanoflakes display superior sensing performance to non-modified ZnO
nanoflakes by exhibiting 4–6 times higher response and an improved selectivity toward n-butylamine
gas, along a decreased optimum operating temperature of 240 ◦ C. Moreover, the response and recovery
properties of the ZnO nanoflake sensor are improved by a factor of 1.5–2.5 depending on the Au loading.
The enhanced sensing performance of the Au nanoparticle-decorated ZnO nanoflakes to n-butylamine
gas can be attributed to the excellent catalytic activity of Au nanoparticles (NPs) which promotes a
greater adsorption of oxygen molecules on the surface of ZnO and the presence of multiple electron
depletion layers, specifically at the surface of ZnO and at the ZnO/Au interface, which greatly increases
their conductivity upon exposure to the gas.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Detection and monitoring of hazardous gases in food, chemical
and manufacturing industries have received increasing atten-
tion recently due to the growing awareness about public health
safety [1]. Many studies have been carried out to develop high-
performance gas sensors with excellent response, selectivity and
stability. Among the various forms of gas sensors, semiconducting
(chemiresistive) gas sensors are particularly attractive for the sens-
∗ Corresponding author.
E-mail address: xuchuan.jiang@monash.edu (X. Jiang).
ing of harmful gases, because of the low manufacturing cost, easy
processing, and reliable performance. Semiconducting gas sensors
usually consist of metal oxide materials, such as zinc oxide (ZnO),
tin dioxide (SnO2 ), iron oxide (Fe2 O3 ), tungsten oxide (WO3 ), and
indium oxide (In2 O3 ) [2].
Among these oxides, ZnO, is an important n-type semiconduc-
tor with a band gap of Eg = 3.3 eV, and has been widely applied for
different applications including gas sensors [3,4], photocatalysts
[5,6] solar cells [7,8], and lithium-ion batteries [9]. ZnO exhibits
excellent thermal and chemical stability and high electrical conduc-
tivity, which makes it highly attractive for gas-sensing application
[10]. However, pure ZnO sensors typically suffer from low selectiv-
ity and high optimum operating temperatures of ≥300 ◦ C, which

http://dx.doi.org/10.1016/j.snb.2016.02.091
0925-4005/© 2016 Elsevier B.V. All rights reserved.
582 Y.V. Kaneti et al. / Sensors and Actuators B 230 (2016) 581–591
may impede their broader applications [11,12]. To reduce such
problems, many efforts have been devoted in this area aiming
to controlling particle size and morphology [13], maximizing the
exposure of active crystal facets [14,15], and introducing transition
metal dopants [11,15–19], metal oxide additives [1,17] or noble
metal sensitizers [11,17,20–23].
Organic amines (e.g., n-butylamine) are important marker com-
pounds for quality control in food industries and medical diagnosis
[24]. n-Butylamine is also frequently used as a vulcanizing accel-
erator and reaction initiator in the polymer industries, a chemical
intermediate in the production of emulsifying agents, rubber chem-
icals, tanning agents and special soaps. Furthermore, it is also
utilized in the manufacture of pharmaceuticals, dyes, insecticides
and textiles. n-Butylamine is toxic and is easily absorbed through
skin. Direct exposure of n-butylamine vapor can cause eye, skin
and upper respiratory tract irritation [25]. Therefore, it is nec-
essary to develop sensor material(s) to detect n-butylamine gas
with excellent response, selectivity, and stability. To date, atmo-
spheric n-butylamine has been quantified by isotachophoresis, and
by high pressure liquid chromatography (HPLC), however, these
techniques require expensive equipments [26]. To date, there were
few limited reports on the use of solid state semiconductor nano-
sensors for detection of n-butylamine, with only sensors based on
WO3 , V2 O5 and AgVx Oy nanostructures have been reported so far
[27–29]. The reported responses of these sensors to n-butylamine,
however, are relatively low and require further improvement.
A clear understanding of the sensing mechanism of ZnO nano-
sensors is crucial for ensuring the successful application of these
sensors in real life monitoring applications. Theoretical simulation
studies have been carried out to investigate the adsorption of oxi-
dizing (e.g., NOx , SOx ) and reducing gases (CO, NH3 , ethanol) on
different ZnO surfaces [30–33]. The DFT study by Breedon et al.
[30,34] found that NO2 and NO interacted weakly with ZnO(1 0 1̄ 0)
and (2 1̄ 1̄ 0) crystal without generating any significant surface dis-
tortions. Prades et al. [32] expanded the study further by examining
the adsorption of NO2 on ZnO(1 0 1̄ 0) and (1 1 2̄ 0) crystal planes
with 12.5% O vacancy and found that NO2 was strongly adsorbed
on the surface Zn atoms, in the presence of oxygen vacancies. More-
over, the DFT investigation by An et al. on the adsorption of several
reducing and oxidizing gases on defect-free, single-walled ZnO
nanotube reveal that O2 and H2 molecules were physisorbed on the
sidewall of the ZnO nanotube while CO, NH3 , and NO2 were molec-
ularly chemisorbed. Despite some successes, theoretical simulation
studies of the adsorption of organic amine (e.g., n-butylamine) on
the ZnO surface were not yet reported. Hence, there exists a lack
of clear understanding of the atomic scale interactions that occur
between organic amine gas molecules and ZnO surface during the
gas-sensing process, particularly in terms of: (i) the effect of the
interaction on the bond length and bond angle of the amine gas
molecules, and (ii) the adsorption mechanism of the amine gas
molecules on the ZnO surface.
This study reports the facile hydrothermal synthesis of ZnO
nanoflakes with {1 0 1̄ 0} facets under mild hydrothermal condi-
tions and the subsequent modification with different Au contents
(1.37, 2.82, and 5.41 wt% Au) for gas-sensing application. The
morphology and composition of the as-prepared ZnO/Au nanocom-
posites were characterized by various analytical techniques,
including transmission electron microscopy (TEM), high resolu-
tion TEM (HRTEM), X-ray diffraction (XRD), X-ray photoelectron
spectroscopy (XPS), and inductively coupled plasma atomic emis-
sion spectroscopy (ICP-AES). The effect of the different Au loading
on the sensing properties of ZnO nanoflakes toward n-butylamine
and other gases and the important parameters such as response,
selectivity and stability were evaluated. Additionally, density func-
tional theory (DFT) simulations were also conducted for achieving
a clear atomic-scale understanding of the interaction between n-
Table 1
Summary of the synthesis conditions used for the preparation of Au-decorated ZnO
samples.
Samples V (HAuCl4 ·3H2 O) (␮L) V (NaBH4 ) (␮L) Au loading (wt %—ICP)
ZnO NF/Au (1) 203 121 1.37
ZnO NF/Au (2) 508 303 2.82
ZnO NF/Au (3) 1016 606 5.41
butylamine gas (along with other gases e.g. ethanol, n-butanol, and
acetone) and ZnO(1 0 1̄ 0) surface of the nanoflakes during the gas-
sensing process.
2. Experimental
2.1. Chemicals
Zinc chloride (ZnCl2 , 99%), sodium hydroxide (NaOH, 99%),
gold(III) chloride trihydrate (HAuCl4 .3H2 O, 99.99%), sodium boro-
hydride (NaBH4 ), n-butylamine (C4 H11 N, 99%) acetone (C3 H6 O,
99.9%), n-butanol (C4 H10 O, 99.8%), ethanol (C2 H6 O, 99.8%),
methanol (CH4 O, 99.9%), and heptane (C7 H14 , 99%) were purchased
from Sigma–Aldrich and used as received without further purifica-
tion. All the chemicals were of analytical grade. Ultra-pure water
was used throughout the experiments.
2.2. Synthesis of porous ZnO nanoflakes
The porous ZnO nanoflakes were prepared according to our pre-
vious report with minor modifications [2]. In a typical procedure,
a mixture solution was first prepared by mixing a 40 mL solu-
tion of 0.15 M sodium hydroxide (NaOH) and a 2 mL solution of
0.3 M ZnCl2 . Next, the white-colored suspension was subsequently
transferred into a 50 mL Teflon-lined stainless-steel autoclave and
heated at 150 ◦ C for 16 h and allowed to cool to room temperature
naturally. The resulting precipitate was collected by centrifugation,
washed thoroughly with deionized water and ethanol several times
and finally dried at 60 ◦ C for 5 h before further use.
2.3. Synthesis of Au nanoparticle-decorated ZnO nanoflakes
Briefly, three steps are involved in the synthesis process. Firstly,
30 mg of ZnO nanoflakes was well-sonicated in 10 mL of deionized
water for 20 min. Secondly, varying quantities of a 0.01 M solu-
tion of HAuCl4 ·3H2 O were added into the ZnO suspension under
magnetic stirring to achieve ZnO/Au nanocomposites with three
different Au loading (labeled as ZnO NF/Au (1), ZnO NF/Au (2), and
ZnO NF/Au (3)). Finally, different amounts (depending on the Au
loading) of freshly made 0.05 M NaBH4 solution (Au3+ :BH4 − = 1:3)
were added into the ZnO suspension and allowed to react for 15 min
under stirring. The purplish products were thoroughly washed with
water and ethanol several times until the supernatant was clear
and then dried in an oven at 60 ◦ C for 5 h. The details regarding the
quantities of HAuCl4 and NaBH4 solutions used during the synthe-
sis process can be found in Table 1. The final Au contents in the
samples of ZnO NF/Au (1), ZnO NF/Au (2), and ZnO NF/Au (3) were
determined by ICP-AES to be 1.37, 2.82, and 5.41 wt%, respectively.
2.4. Characterization
The phase composition and purity of the synthesized ZnO
nanoflakes were examined using Phillips X’pert Multipurpose
X-ray Diffraction System (MPD) equipped with graphite mono-
chromatized Cu-K␣ radiation ( = 1.54 Å) in the 2 range of 20–70◦ .
The particle morphologies were observed on a FEI Nova NanoSEM
230 field emission scanning electron microscope (SEM). TEM
 Y.V. Kaneti et al. / Sensors and Actuators B 230 (2016) 581–591
images were recorded with a Tecnai G2 20 transmission elec-
tron microscope, operated at an accelerating voltage of 200 kV.
HRTEM images were recorded on a Phillips CM200 field emission
gun transmission electron microscope with an accelerating voltage
of 200 kV. X-ray photoelectron spectroscopy (XPS) surface analy-
sis of the samples was carried out using an ESCALAB250Xi X-ray
photoelectron spectrometer, which utilizes Al-K␣ radiation as the
excitation source. ICP-AES measurements were carried out to quan-
tify the amount of Au in the ZnO/Au samples using Optima7300DV-
ICP-OES PerkinElmer, with detection limits of ∼0.05 mg/L.
2.5. Gas sensor fabrication and measurements
The gas sensors were fabricated according to the procedures
reported in our previous studies. Basically, the Au-decorated
ZnO samples were first mixed and ground with the binder
polyvinylidene fluoride (PVDF) in agate mortar. Then, 1-methyl-
2-pyrrolidone was added into the mixture to form white slurry,
which was then coated on a ceramic tube with previously printed
Au electrodes and Pt conducting wires. The ceramic tube was
subsequently sintered at 350 ◦ C for 3 h to remove the polymeric
binder and to improve the stability of the sensor. The gas-sensing
properties of the Au nanoparticle-decorated ZnO nanoflakes were
evaluated using a computer-controlled WS-30A gas-sensing mea-
surement system (Weisheng Electronics Co., Ltd., Henan, China), as
schematically shown in Fig. S1.
Prior to the measurement, a Ni–Cr resistor was inserted into
the ceramic tube as a heater, which enables control of the oper-
ating temperature by adjusting the heating voltage (Vheating ). A
reference resistor was placed in series with the sensor to form a
complete measurement circuit. The probe gas such as n-butylamine
was injected into the testing chamber using a micro-syringe. The
response (S) is defined as the ratio of the resistances measured in
air (Ra ) and in the tested gas atmosphere (Rg ): S = Ra /Rg . The output
voltage was set at 5 V and the gas-sensing measurements were car-
ried out at a relative humidity of 55–65%, with a reference resistor
of 100 k.
2.6. Density functional theory (DFT) simulations
DFT simulations were conducted using the commercial soft-
ware: Materials Studio (Version 4.3, Accelrys Inc., 2007) with the
Dmol3 module. GGA (generalized gradient approximation) was
employed for the exchange-correlation. In this work, PBE (Perdew,
Burke, and Emzerhof) exchange-correlation functional coupled
with the precise numerical basis set DNP (double numerical plus
polarization) and a basis file of 4.4 was used. The core electrons
were treated with DFT semi-core pseudo potentials (DSPPs) with a
global orbital cut off of 4.4 Å. The surface simulations were per-
formed using a slab model under periodic boundary conditions
(Scheme 1). A supercell with a surface thickness of ∼9 Å and a vac-
uum space of 20 Å was created from the ZnO lattice structure in
which the bottom layers (∼5 Å) were fixed and the top layers were
relaxed to simulate the surface properties. Then, the optimized gas
molecules were positioned ∼2.0 Å above the adsorption surface.
The gas molecules investigated include n-butylamine, methanol,
ethanol, n-butanol, acetone and heptane.
The adsorption energy can be used to describe the variation
of total energy of each species before and after adsorption. The
signs and values of adsorption energy can indicate the possibility of
adsorption. In the present work, the adsorption energy (Eads ) was
calculated according to the equation [15]:
E ads = E (A/surface) −(E A + E surface )
583
Fig. 1. XRD patterns of (a) pure ZnO nanoflakes, and ZnO nanoflakes loaded with
(b) 1.37 wt% Au (labeled as ZnO NF/Au (1)), (c) 2.82 wt% Au (labeled as ZnO NF/Au
(2)), and (d) 5.41 wt% Au (labeled as ZnO NF/Au (3)).
where E(A/surface) is the total energy of the gas molecules adsorp-
tion system in the equilibrium state on ZnO(1 0 1̄ 0) surface; EA and
Esurface are the total energies of the free gas molecules and clean
ZnO(1 0 1̄ 0) surface, respectively. With this definition, a negative
value corresponds to the stable adsorption on ZnO(1 0 1̄ 0) surface.
3. Results and discussion
3.1. Morphology and composition
The overall quantity of Au in the three Au-decorated ZnO
nanoflake samples (labeled as ZnO NF/Au (1), ZnO NF/Au (2) and
ZnO NF/Au (3)) were initially determined using ICP-AES. As shown
in Table 1, the Au contents in samples ZnO NF/Au (1), (2), and (3)
are 1.37, 2.82 and 5.41 wt%, respectively. The phase composition of
the ZnO nanoflakes with or without metallic decoration was char-
acterized using XRD. Fig. 1 displays the XRD patterns of the pure
and Au-decorated ZnO products. All of the diffraction peaks can be
well indexed to the diffraction peaks of hexagonal wurtzite ZnO
(JCPDS No. 36-1451). In comparison, all the XRD patterns of the
Au-decorated ZnO products show the presence of diffraction peaks
of ZnO along with additional peaks at 2 = 38.4, 44.0, and 66.4◦ ,
which corresponds well to the (1 1 1), (2 0 0), and (2 2 0) peaks of
cubic gold (JCPDS No. 04-0784). The elemental EDS map of the Au
nanoparticle-decorated ZnO nanoflakes shown in Fig. S2 clearly
highlights the presence of Zn, O, and Au elements. Furthermore,
it also shows the good dispersion of the Au NPs on the surface of
the ZnO nanoflakes.
Fig. 2a displays the SEM image of the pure ZnO nanoflakes, show-
ing diameters of 400–800 nm. The TEM image of an individual ZnO
nanoflake (Fig. 2b) clearly indicates the presence of pores with sizes
ranging from 2–20 nm. Such porous structure may be beneficial for
increasing the accessible surface area and active sites, available for
diffusing gas molecules during the sensing process [13]. BET surface
area measurements of the pure and Au-modified ZnO nanoflakes
are shown in Fig. S3. The specific surface areas (S.S.A) of the pure
ZnO NF, ZnO NF/Au (1), ZnO NF/Au (2), and ZnO NF/Au (3) samples
were measured to be 8.56, 9.39, 9.98, and 7.90 m2 /g, respectively.
Furthermore, the pore sizes of the four samples were found to vary
between 2–20 nm. Additionally, no major change was observed in
the average pore size of the ZnO nanoflakes before and after surface
decoration by Au nanoparticles.
The HRTEM image of a single ZnO nanoflake shows the presence
of distinct lattice fringes with an interplanar spacing of 0.261 nm,
corresponding to the d-spacing of ZnO(0 0 0 1) crystal plane (Fig. 2c)
[2,4]. The selected area electron diffraction (SAED) pattern of the
584 Y.V. Kaneti et al. / Sensors and Actuators B 230 (2016) 581–591

Scheme 1. (a) Side view (top) and (b) top view (bottom) of the ZnO (1 0 1̄ 0) crystal surface (red and blue atoms represent O and Zn, respectively); (c) Schematic illustration
of the crystal faces in ZnO nanoflakes; (d) Free n-butylamine molecule (blue, grey, and white atoms represent N, C and H, respectively). (For interpretation of the references
to color in this figure legend, the reader is referred to the web version of this article.)

Fig. 2. (a) SEM, (b) TEM and (c) HRTEM images of pure ZnO nanoflakes; (c) SEM, (d) TEM and (e) HRTEM images of Au nanoparticle-decorated ZnO nanoflakes.

ZnO nanoflakes is consistent with the diffraction pattern of the
[1 0 1̄ 0] zone axis of ZnO (inset of Fig. 2c). This provides evidence
that the bottom and the top surfaces of the ZnO nanoflakes expose
the ±{1 0 1 0} planes [15,35]. Fig. 2d shows a typical SEM image
of the Au nanoparticle-decorated ZnO nanoflakes (sample ZnO
NF/Au (2)). It can be observed that the surface of the nanoflakes
become rough following the Au modification, indicating the suc-
cessful deposition of Au nanoparticles.
The HRTEM image of a single Au-decorated ZnO nanoflake
(Fig. 2f) taken from the selected area in Fig. 2e shows the crystal
lattices of ZnO(0 0 0 1) along with additional lattice fringes with a
measured d-spacing of ∼0.238 nm, indexed to the Au(1 1 1) plane
 Y.V. Kaneti et al. / Sensors and Actuators B 230 (2016) 581–591
Fig. 3. TEM images of ZnO nanoflakes loaded with (a) 0 wt% Au (ZnO NF), (b) 1.37 wt% Au (ZnO NF/Au (1)), (c) 2.82 wt% Au (ZnO NF/Au (2)), and (d) 5.41 wt% Au (ZnO NF/Au
(3)).
[36]. These results confirm the successful deposition of Au NPs on
the surface of ZnO nanoflakes. Fig. 3 shows the TEM images of ZnO
nanoflakes loaded with three different amounts of Au. It is obvi-
ous that with increasing Au loading, a greater amount of Au NPs is
deposited on the surface of the ZnO nanoflakes. The average size of
the Au NPs in samples ZnO NF/Au (1), ZnO NF/Au (2), and ZnO NF/Au
(3) was measured to be 7.18, 8.08, and 8.68 nm, respectively, from
a measurement of 120 Au NPs (Fig. S4). This suggests that there is a
slight increase in the size of the deposited Au NPs with increasing
Au loading.
XPS technique was employed to identify the surface compo-
sition of Au nanoparticle-decorated ZnO nanoflakes using sample
ZnO NF/Au (2) as an example. As shown in Fig. S5a, the Zn 2p XPS
peak of the pure ZnO nanoflakes at 1021.22 eV can be assigned to
Zn 2p3/2 , while in the ZnO/Au nanoflakes, the position of this Zn
2p3/2 peak shifted by 0.13 eV to 1021.35, suggesting that a charge
transfer occurs between Au and ZnO. In addition, the O 1s spec-
trum shown in Fig. 4c is asymmetric, suggesting the presence of
several oxygen species. Deconvolution of the O 1s peak shows the
existence of two peaks centered at 530.2 eV (OI ) and 531.9 eV (OII ),
attributed to the O2− ions in the wurtzite ZnO and O− and O2− ions
in the oxygen deficient regions mainly caused by oxygen vacancies.
The high binding energy oxygen species, OIII centered at 532.8 eV
belong to the chemisorbed oxygen species caused by the surface
hydroxyl groups (O H bond) [37].
Fig. 4d shows the Au 4f XPS spectrum of the Au nanoparticle-
decorated ZnO nanoflakes. This figure reveals the presence of two
585
peaks at the binding energies of 83.5 eV and 85.4 eV, indexed to Au
4f7/2 and Au 4f5/2 peaks, respectively. The binding energies of the
Au4f peaks in the Au nanoparticle-decorated ZnO nanoflakes are
much lower than those found in bulk metallic Au (84.0 eV for Au
4f7/2 while 87.67 eV for Au 4f5/2 ) [37,38]. The decrease in binding
energies is caused by the larger electronegativity of Au compared
to Zn atoms in ZnO, which promotes a charge transfer from ZnO
to Au. In addition to the two Au 4f peaks, a weak shoulder peak
is also noted at 88.68 eV, corresponding to the Zn 3p3/2 peak from
ZnO; whereas the other shoulder peak at 91.68 eV can be indexed
to the Zn 3p1/2 peak. The surface compositional analysis of the three
ZnO/Au samples is summarized in Table S1. By comparing the ICP
and XPS results in Tables 1 and S1, respectively, it can be deduced
that the majority of the Au NPs were decorated on the surface of
the ZnO nanoflakes.
3.2. Gas-sensing performance
Fig. 5a displays the responses of sensors made from
pure ZnO nanoflakes (ZnO NF) and Au nanoparticle-decorated
ZnO nanoflakes (ZnO NF/Au(1), (2) and (3)) toward 50 ppm
of n-butylamine with increasing operating temperature from
150–330 ◦ C. The pure ZnO NF sensor exhibits an optimum operating
temperature of 300 with S = 23.9 toward 50 ppm of n-butylamine.
In comparison, the three ZnO NF/Au sensors exhibit an identical
optimum operating temperature of 240 ◦ C, which is 60 ◦ C lower
than that of the pure ZnO NF sensor. Interestingly, even at a low
586 Y.V. Kaneti et al. / Sensors and Actuators B 230 (2016) 581–591

Fig. 4. (a) XPS survey spectra and XPS high resolution spectra of (b) Zn2p, (c) O1s and (d) Au4f of the Au nanoparticle-decorated ZnO nanoflakes (sample ZnO NF/Au (2)—with
2.82 wt% Au).

Fig. 5. (a) Response vs. operating temperature curves of pure ZnO nanoflakes (NF) and ZnO NF/Au sensors toward 50 ppm of n-butylamine, (b) dynamic response-recovery
transients of ZnO NF/Au sensors toward different concentration of n-butylamine at 240 ◦ C, (c) response vs. concentration curves of pure ZnO NF and ZnO NF/Au sensors at
240 ◦ C, and (d) selectivity test results of pure ZnO NF and ZnO NF/Au sensors at 240 ◦ C.
 Y.V. Kaneti et al. / Sensors and Actuators B 230 (2016) 581–591 587

Table 2
Comparison of the n-butylamine sensing performance of the as-prepared Au nanoparticle-decorated ZnO nanoflakes against previously reported metal oxide nanosensors.

Morphologies Response (S = Ra /Rg ) Concentration (ppm) Operating temp. (◦ C) Refs.

a
ZnO/Au nanoflakes 73.2 50 240 This work
Ag2 V4 O11 nanobelts 3.5 50 260 [27]
VOx@15% Ag nanobelts 2.3 50 260 [27]
Ag0.35 V2 O5 nanobelts 2.1 50 260 [27]
V2 O5 nanofibers 0.42 10 22 [28]
a
Contains 2.82 wt% Au.

operating temperature of 140 ◦ C, the three ZnO NF/Au sensors Table 3

still exhibit a reasonably high response of 8.2–16 to 50 ppm of n-
butylamine, indicating their potential for low-temperature amine
sensing.
The dynamic response-recovery transients of the pure ZnO NF
and ZnO NF/Au sensors are shown in Figs. S5 and 5 b, respectively. It
is clear that the output voltage of all the sensors increases when the
n-butylamine gas is inserted, and subsequently decreases as the gas
is removed. Fig. 5c displays the responses of pure ZnO NF and ZnO
NF/Au sensors toward different concentrations of n-butylamine at
240 ◦ C. It can be observed that the ZnO NF/Au sensors show 4–6
times higher response toward n-butylamine than pure ZnO NF sen-
sor, with a trend of ZnO NF/Au (2) [2.82 wt% Au] > ZnO NF/Au (1)
[1.37 wt% Au] > ZnO NF/Au (3) [5.41 wt% Au] > ZnO NF [0 wt% Au].
In fact, the Au-decorated ZnO sensor, ZnO NF/Au (2), exhibits a
response as high as 119.3 to 100 ppm of n-butylamine vapor. Fur-
thermore, even at a low concentration of 10 ppm, this particular
ZnO/Au sensor still exhibits a reasonably high response of 18.5,
indicating a possible detection limit in ppb level. From the above
analysis, it is evident that the Au modification greatly enhances the
sensing response of the ZnO nanoflakes toward n-butylamine; and
that different Au contents can lead to different responses.
Selectivity is another critical criterion in gas-sensing which
needs to be evaluated to ensure an accurate detection of a single
gas in a mixer with a higher response. Fig. 5d shows the selectivity
tests of the pure ZnO NF and three ZnO NF/Au sensors to different
gases, including n-butanol, ethanol, acetone, methanol and hep-
tane at 240 ◦ C. It can be noted that under similar conditions, ZnO
NF/Au sensors show excellent selectivity to n-butylamine, with the
response being 11–70 time higher than those to other gases. In com-
parison, the response of the pure ZnO NF sensor to n-butylamine
is only 2–7 time higher than the response to other gases. This indi-
cates that the Au decoration on ZnO nanoflakes can highly improve
the selectivity for accurate detection of n-butylamine.
The response and recovery time values of pure ZnO NF and ZnO
NF/Au sensors are given in Fig. 6a and b, respectively. Here, the
response time ( res ) is defined as the time required for the conduc-
tance variation of the sensor to reach 90% of its equilibrium value,
following exposure to n-butylamine vapor. On the contrary, the
recovery time ( rec ) is defined as the time needed by the sensor to
return to 10% of its original conductance in air, after removal of the
n-butylamine vapor. It can be observed from Fig. 6a that the  res
values of the pure ZnO NF sensor upon exposure to 10–100 ppm
of n-butylamine gas vary from 55–77 s, whereas the  res values
of ZnO NF/Au (1), ZnO NF/Au (2), and ZnO NF/Au (3) sensors are
in the ranges of 23–57, 19–57, and 24–37 s, respectively. These
results indicate the improvement in the response speed of the ZnO
nanoflake sensor by a factor of 1.5–2.5 following the Au modifica-
tions. In comparison, the  rec values of the ZnO NF/Au (2) sensor
upon exposure to 10–100 ppm range from 11–100 s, whereas the
 rec values of ZnO NF/Au (1), ZnO NF/Au (2), and ZnO NF/Au (3)
sensors are in the range of 11–46, 8–76, and 8–47 s, respectively
(Fig. 6b). These results suggest that the decoration of Au NPs also
significantly improves the recovery time of the ZnO NF sensor.
Reproducibility and stability are two important parameters
of a sensor material, crucial for ensuring long-term reliability
Summary of calculated bond distances and adsorption energy for n-butylamine (the
numbering of atoms of the n-butylamine molecule is given in Scheme 1d).
Bond Gas phase ZnO
1 0 1̄ 0
Bond distance/angle N H1 (Å) 1.023 1.046
N H2 (Å) 1.023 1.023
C H (Å) 1.102 1.102
C1 N (Å) 1.472 1.493
C1 C2 (Å) 1.526 1.527
H1 N C1 (◦ ) 106.0 105.9
N C1 C2 (◦ ) 110.8 113.8
NBA ZnZnO (Å) – 2.118
H1 OZnO (Å) – 1.849
Eadsorption (eV) – −7.30
of the sensor. As the Au-decorated ZnO sensor, ZnO NF/Au (2),
exhibit the highest response and best selectivity compared to the
other ZnO NF/Au sensors, its reproducibility and stability were
evaluated toward n-butylamine vapor. As shown in Fig. 6c, the
response/recovery behavior of the ZnO NF/Au (2) sensor toward
40 ppm of n-butylamine is highly reproducible following 8 straight
cycles of testing at 240 ◦ C. Furthermore, the good stability of the
ZnO NF/Au (2) sensor is clearly highlighted in Fig. 6d as the response
values remain very consistent during a 21-day test period. This
indicates its excellent potential as a sensitive, selective and sta-
ble sensor material for the detection of toxic n-butylamine vapor.
Table 2 compares the n-butylamine sensing response of the fab-
ricated ZnO nanoflake/Au sensor (sample ZnO NF/Au (2)) against
previously reported sensors based on metal oxide nanostructures.
It can be seen from Table 2 that the ZnO NF/Au (2) sensor (contains
2.82 wt% Au) show superior sensing performance to n-butylamine
compared to Ag2 V4 O11 [27], Ag0.35 V2 O5 [27], VOx /Ag nanobelts
[27], and V2 O5 nanofibers [28].
3.3. DFT simulation
The HRTEM and SAED analysis in Fig. 2c reveal that the
top/bottom surface of the ZnO nanoflakes expose the ±(1 0 1̄ 0)
plane. DFT simulations were used to simulate the adsorption
behavior of n-butylamine along with other gas molecules such as
methanol, ethanol, acetone, and n-butanol, and heptane on the
ZnO(1 0 1̄ 0) surface. Scheme 1a and b shows the side and top view
of the ZnO(1 0 1̄ 0) surface, respectively. This surface was firstly
optimized, and then the gas molecules were placed on the opti-
mized ZnO(1 0 1̄ 0) surface during the simulations.
Table 3 shows the bond distances between various atoms,
the bond angles of the n-butylamine molecule before and after
adsorption and the adsorption energies on ZnO(1 0 1̄ 0). The DFT
calculation performed for the free n-butylamine molecule shows
that it exhibits bond distances of 1.023, 1.102, 1.526 and 1.472 Å,
corresponding to N H, C H, C C and C N bonds, respectively. The
DFT calculations indicate that the distance between H (C4 H11 N)
and O on the ZnO(1 0 1̄ 0) surface is 1.849 Å (Table 3). Furthermore,
from this table, it can be noted that the N H bond distance of the
588 Y.V. Kaneti et al. / Sensors and Actuators B 230 (2016) 581–591
Fig. 6. (a) Response and (b) recovery time values of pure ZnO NF and ZnO NF/Au sensors for different concentration of n-butylamine at 240 ◦ C. (c) Reproducibility and (d)
stability tests of the ZnO NF/Au (2) sensor (contains 2.82 wt% Au) toward 40 ppm of n-butylamine at 240 ◦ C.
C4 H11 N molecule stretches the furthest (by 0.23 Å) following its
interaction with the surface Zn atom. Hence, as the n-butylamine
molecule approaches ZnO(1 0 1̄ 0) surface during the sensing pro-
cess, the nitrogen atom of n-butylamine (C4 H11 N) forms a chemical
bond with the surface Zn atom.
Alcohol molecules such as ethanol and n-butanol are also chemi-
cally adsorbed on the ZnO(1 0 1 0) surface, however the mechanism
is slightly different to that of n-butylamine. The DFT simulation
results summarized in Table S2 reveal that the O H, C H, C O, and
C C bond distances in free ethanol molecule (prior to adsorption)
were determined to be 0.972, 1.101, 1.440, and 1.517 Å, respec-
tively. In comparison, the O H, C H, C O, and C C bond distances
in free n-butanol molecule were calculated to be 0.972, 1.101, 1.439,
and 1.520 Å, respectively, as shown in Table S3. These results are
in good agreement with previously reported theoretical [15,39,40]
and experimental results [41]. As shown in Fig. 7b and c, the
chemical adsorption of ethanol (C2 H6 O) or n-butanol (C4 H8 O) gas
molecule on the ZnO(1 0 1̄ 0) surface occurs through the formation
of a (covalent) bond between the oxygen atom of ethanol/n-butanol
molecule with the surface Zn atom of ZnO.
Acetone also chemically adsorb on the ZnO(1 0 1̄ 0) surface by
following a similar mechanism to ethanol and n-butanol, with the
oxygen atom of the acetone gas molecule being bonded to the sur-
face Zn atom of ZnO (Fig. 7d). However the adsorption energy of
acetone (−4.9 eV) is less than those of ethanol (−7.15 eV) and n-
butanol (−7.24 eV), indicating a weaker adsorption, thus leading
to a poorer response of the pure ZnO sensor to acetone than to
ethanol or n-butanol. This is in accordance with the results depicted
in Fig. 5d which shows that the response of the ZnO nanoflakes is
in the order of: acetone < ethanol < n-butanol. As for other gases
such as heptane and methanol, they were found to be physisorbed
on the ZnO(1 0 1̄ 0) surface but not chemically adsorbed as in the
cases of n-butylamine, ethanol, acetone, and n-butanol. Hence, the
responses of the pure ZnO sensor toward these two gases are
expected to be the lower than the other four gases. This is sup-
ported by the gas-sensing results shown in Fig. 5d. At present, an
accurate DFT simulation study on the adsorption of these gases on
Au-modified ZnO(1 0 1̄ 0) surface is challenging as the Au NPs are
randomly oriented on the ZnO surface (i.e., they do not follow a spe-
cific orientation). In this study, we have explained the role of Au in
enhancing the gas-sensing performance of the ZnO nanoflakes in
terms of ‘electronic’ and ‘chemical’ sensitizations as described in
Section 3.4.
3.4. Sensing mechanism
The sensing mechanism of an n-type semiconductor gas sensor
such as ZnO is largely based on the resistance change caused by
the adsorption of oxygen or gas molecules [3,15]. When the pure
ZnO sensor is exposed to air, oxygen molecules (O2 ) adsorb on the
surface of ZnO nanoflakes and become ionized to O− or O2− by cap-
turing free electron(s) from the conduction band of ZnO, according
to the following equations [3,37]:
O2 (gas) ↔ O2 (adsorbed) (1)
O2 (adsorbed) + e− ↔ O2 − (adsorbed) (2)
− − −
O2 (adsorbed) + e ↔ 2O (adsorbed) (3)
− − 2−
O (adsorbed) + e ↔ O (adsorbed) (4)
The above reactions lead to the formation of an electron
depletion layer (L), which reduces the electron concentration.
However, as the ZnO nanoflake sensor is exposed to n-butylamine,
the n-butylamine gas molecules react with the chemisorbed
 Y.V. Kaneti et al. / Sensors and Actuators B 230 (2016) 581–591 589

Fig. 7. Slice view of the gas molecules (a) methanol, (b) ethanol, (c) n-butanol, (d) acetone, (e) heptane, (f) n-butylamine adsorbed on the ZnO (1 0 1̄ 0) crystal surface (red,
blue, grey and white atoms represent O, Zn, C and H, respectively). (For interpretation of the references to color in this figure legend, the reader is referred to the web version
of this article.)

oxygen species on the surface of the ZnO nanoflakes. This releases

the trapped electrons back into the conduction band of ZnO, which
increases the electron concentration, and ultimately decreases the
resistance of the ZnO sensor.
The sensing mechanism of the ZnO NF/Au sensor, however, is
quite different. This is because of the presence of Au NPs on the
surface of the ZnO nanoflakes, which can induce both chemical and
electronic sensitization. Chemical sensitization occurs due to the
excellent catalytic activity of Au NPs. Our previous simulation study
on Au-loaded SnO2 nanorods with {1 1 0} facets has shown that
the loading of Au NPs on the metal oxide surface can lower the
diffusivities of oxygen, attract the O O bond in oxygen molecules
and enable easier removal of H2 O (moisture) from the metal oxide
surface at lower temperatures (<250 ◦ C) [36]. These factors enable
O2 molecules to diffuse faster into surface vacancies and capture
electrons from the conduction band of ZnO nanoflakes to become
oxygen ions O− or O2− [1,42]. Consequently, this raises the quantity
of adsorbed oxygen and the oxygen molecule to ion conversion rate,
leading to a faster degree of electron depletion from the ZnO/Au
interface than that at the surface of pure ZnO nanoflakes. The n-
butylamine gas then reacts with the chemisorbed oxygen species
and releases the electrons back to the surface of ZnO/Au nanoflakes,
resulting in a greater change in electrical conductivity and therefore
an enhanced response toward n-butylamine.
Apart from chemical sensitization, the decoration of Au NPs
on the surface the ZnO nanoflakes may also induce electronic
sensitization, because of the differences in their work functions
((Au) = 5.1 eV, (ZnO) = 4.65 eV), as shown in Fig. 8 [1]. As Au has
a greater work function than ZnO (4.65 eV), a greater amount of
electrons will be transferred from the conduction band of ZnO to Au
than to the pure ZnO nanoflakes. This results in a greater band bend-
ing at the ZnO/Au interface with a broad depletion layer (Fig. 8b) Fig. 8. A schematic illustration of the energy band diagram of (a) pure ZnO and (b)
ZnO/Au (H and L in the diagram represent potential barrier and the depletion
[2,43]. The existence of this additional depletion layer at the ZnO/Au
layer, respectively).
590 Y.V. Kaneti et al. / Sensors and Actuators B 230 (2016) 581–591
interface in addition to that at the surface of the ZnO nanoflakes
lead to a greater change in resistance of ZnO/Au sensor following
the exposure to the n-butylamine gas. Ultimately, this promotes
an enhanced response of the ZnO/Au sensor to n-butylamine com-
pared to the pure ZnO sensor
4. Conclusions
This study has demonstrated the facile synthesis of ZnO
nanoflakes with exposed {1 0 1 0} facets through a hydrothermal
method and their subsequent modifications with Au NPs. The
effects of the different Au loading on the crystal structure, surface
properties, and amine sensing performance of the ZnO nanoflakes
have been investigated. Several main findings of this study are sum-
marized below:
• The pure ZnO nanoflakes exhibit pores with sizes of 2–10 nm and
the top/bottom surface of these nanoflakes expose the ±{1 0 1̄ 0}
plane. After loading the ZnO nanoflakes with 1.37, 2.82, and
5.41 wt%, Au NPs with average particle sizes of 7.18, 8.08, and
8.68 nm, respectively, were successfully deposited on the surface
of the ZnO nanoflakes.
• The Au nanoparticle-decorated ZnO nanoflakes exhibit a greatly
enhanced selectivity and 4–6 time higher response to n-
butylamine compared to the pure ZnO nanoflakes, with a faster
response/recovery time by a factor of 1.5–2.5. Meanwhile, the
surface decoration of Au NPs is found to lower the optimum oper-
ating temperature of the ZnO nanoflake sensor from 300 to 240 ◦ C.
Furthermore, even at a low operating temperature of 140 ◦ C, the
ZnO/Au sensors still exhibit a reasonably high response of 8.2–16
to 50 ppm of n-butylamine, indicating their excellent low tem-
perature amine-sensing properties.
• The DFT simulation results provide new physical insights into
the adsorption behaviors of different gases on the ZnO(1 0 1̄ 0)
surface. n-Butylamine is found to chemically adsorb on the
ZnO(1 0 1̄ 0) surface through the formation of a bond between
the nitrogen atom of the n-butylamine (C4 H11 N) and the surface
Zn atom of ZnO. Other gases such as ethanol and n-butanol also
chemically adsorb on the ZnO(1 0 1̄ 0) surface, with the oxygen
atoms being covalently bonded to the surface Zn atom of ZnO dur-
ing the interaction. However, heptane and methanol molecules
are only physically adsorbed on the ZnO(1 0 1̄ 0) surface. Hence
the responses of the ZnO nanoflake sensor toward these two gases
are lower than those to the other tested gases.
• The enhanced response of the Au nanoparticle-decorated ZnO
nanoflakes toward n-butylamine can be attributed to two main
factors: (i) the high catalytic activity of Au NPs which increases
the quantity of adsorbed oxygen and the conversion rate of
oxygen molecules to oxygen ions; and (ii) the existence of an
additional electron depletion layer at the ZnO/Au interface in
addition to that at the surface of the ZnO nanoflakes. The combi-
nation of these two factors promotes a higher change in resistance
and therefore, a significantly improved response of the ZnO/Au
sensors toward n-butylamine.
Overall, the findings of this study will provide a better under-
standing of the atomic-scale interactions which occur between
the ZnO surface and reducing amine/alcohol gases during the gas-
sensing process.
Acknowledgments
We gratefully acknowledge the financial support of the Aus-
tralian Research Council (ARC DP1096185, FT0990942) projects.
The authors also acknowledge access to the UNSW node of the Aus-
tralian Microscopy and Microanalysis Research Facilities (AMMRF).
The authors would like to thank Dr. Rabeya Akter for the ICP anal-
ysis, Dr. Jason Scott for the BET analysis, and Dr. Bill Gong for the
XPS measurements.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.snb.2016.02.091.
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Biographies
Dr. Yusuf Valentino Kaneti has obtained his Ph.D. degree in July 2014 from the
University of New South Wales (UNSW), Australia. He is currently working as a post-
doctoral fellow in the School of Materials Science & Engineering at UNSW, focusing
on the synthesis and characterization of semiconductor metal oxide nanostruc-
tures/nanocomposites for energy and environmental applications. He has published
14 journal articles and 1 book chapter, with a H-index of 8.
Mr. Xiao Zhang received his undergraduate degree in materials science and engi-
neering from the University of New South Wales, Australia. His research interest
is on the synthesis and functional application of metal oxide nanostructures for
gas-sensing applications.
Mr. Minsu Liu is a Ph.D. candidate studying materials science and engineering at
Monash University, Australia. His research interest is on the synthesis of metal
oxide (especially for vanadium oxides) nanostructures for energy and environmen-
tal applications.
Mr. David Yu is an M.Sc. candidate studying materials science and engineering at
Monash University, Australia. His research interest is on the synthesis and applica-
tion of magnetic nanoparticles for environmental and biomedical applications.
Ms. Yuan Yuan is a Ph.D. candidate studying materials science and engineering at the
University of New South Wales, Australia. Her research interest is on the synthesis
of shape-controlled noble metal nanostructures for catalytic applications.
Dr. Leigh Aldous is an ARC DECRA fellow and he works as a lecturer/researcher in
the School of Chemistry at the University of New South Wales. Dr. Aldous’ research
focuses upon electrochemistry in ionic liquids (for biomass conversion, hydro-
gen storage and unique physical characteristics), as well as electroanalysis using
nanocarbons. Dr. Aldous has published more than 67 journal articles and 2 patents
in the past 6 years with SCI citations over 1800 times, leading to a H-index of 26.
Prof. Xuchuan Jiang has fully devoted to the study on synthesis and self-assembly
of nanoparticles for energy and environmental applications since the award of his
Ph.D. in 2001. His research focuses on developing new techniques for the synthesis
of noble metals, metal oxides and their nanocomposites for energy, environmental
and biomedical applications. He has published over 100 papers with SCI citations of
over 4000 times, leading to a H-index of 29.