international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

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

Facile synthesis of AleMg co-doped ZnO

nanoparticles and their high hydrogen sensing
performances

S. Jaballah a, H. Dahman a, I. Ghiloufi a,b, G. Neri c, L. El Mir a,b,*

a
Laboratory of Physics of Materials and Nanomaterials Applied at Environment (LaPhyMNE), Faculty of Sciences in
Gabes, Gabes University, 6072, Gabes, Tunisia
b
Al Imam Mohammad Ibn Saud Islamic University (IMSIU), College of Sciences, Department of Physics, Riyadh,
11623, Saudi Arabia
c
Department of Engineering, University of Messina, 98166, Messina, Italy

highlights graphical abstract

AleMg co-doped ZnO nano-

particles were synthesized by sol
egel process.

Morphological and structural
characterizations were
investigated.

AMZO nanoparticles have demon-
strated promising performances
for hydrogen sensing.

Between 100 and 30,000 ppm at
250  C the 5A1MZO presents the
best results.

Very good selectivity was noted by
5A1MZO towards some interfering
gases.

article info abstract

Article history: Recently hydrogen has received a great attention as a renewable, clean and high-efficiency
Received 7 August 2020 source of energy. However, its high explosiveness and leakage increased demand for
Received in revised form sensors to monitor hydrogen during production, transport, storage and use. This paper
4 September 2020 presents a new nanostructured material for hydrogen monitoring. Indeed, to our knowl-
Accepted 7 September 2020 edge, the aluminum/magnesium co-doped ZnO nanoparticles are used in the first time for
Available online xxx hydrogen sensing. Al(5%)-Mg(1,3,5%) co-doped ZnO nanoparticles were effectively synthe-
sized by facile sol-gel method in supercritical conditions. The structural, morphological
Keywords: and optical properties have been examined by different techniques. X-ray diffraction data
Nanoparticles confirmed the hexagonal wurtzite structure and showed a good enhancement of crystal-
ZnO linity with introduction of Al and Mg dopants. Transmission electron microscopy

* Corresponding author. Laboratory of Physics of Materials and Nanomaterials Applied at Environment (LaPhyMNE), Faculty of Sciences
in Gabes, Gabes University, 6072, Gabes, Tunisia.
E-mail address: Lassaad.ElMir@fsg.rnu.tn (L. El Mir).
https://doi.org/10.1016/j.ijhydene.2020.09.053
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Jaballah S et al., Facile synthesis of AleMg co-doped ZnO nanoparticles and their high hydrogen sensing
performances, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.053
2 international journal of hydrogen energy xxx (xxxx) xxx

Aluminum observations showed the nanometric size of the nanoparticles (15e25 nm) and the pris-
Magnesium matic like shape of the crystallites. The TGA study proves the stability of the samples and
Sol-gel the BET analysis illustrate that the isotherm of the 5A1MZO sample is belong to type II.
Hydrogen gas sensor UltravioleteVisible spectroscopy measurements evidenced the narrowing of the band gap
energy for the co-doped samples which range between 3.14 and 3.19 eV. Photo-
luminescence spectra of all samples consist of two major components: a narrow ultraviolet
emission band and a broad visible emission band (above 500 nm). Electrical properties were
also studied. The synthesized samples have been screen printed and investigated as active
layer for conductometric gas sensor devices. Their sensing characteristics towards wide
range of hydrogen concentrations (100e30,000 ppm) were tested at various temperatures
ranging from 200 to 400  C in dry air. The Al(5%)-Mg(1%) co-doped ZnO sensor displayed the
best sensing performances, showing a fast (3 s) and high (larger than 70) response towards
2000 ppm hydrogen at 250  C. In addition, it showed low detection limit, good repeatability
and high selectivity against various interfering gases. Compared to others recent works,
the sensor showed competitive performances and by considering the facile, fast and low
cost synthesized method of nanoparticles, it represents a promising material for the se-
lective detection of hydrogen.
© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

new systems or devices with potential applications in a vari-

Introduction
Hydrogen (H2) is predicted to be a green and renewable energy
source and it is expected to contribute to mitigating today’s
serious environmental problems [1,2]. Hydrogen can be pro-
duced from different process like water electrolysis [3], steam
methane reforming [4], biomass gasification [5], microbial fuel
cell [6] and photo-electrochemical water splitting [7].
Hydrogen is a colorless gas, odorless, very light and its pres-
ence easily goes unnoticed. So, the main risks are its
extremely high flammability and large explosive limits (be-
tween 4 and 75% by volume) [8]. Also, high hydrogen con-
centrations create an oxygen-depleted environment that can
leads to suffocation. In this context, hydrogen monitoring
during use, production, storage and transport plays an
important role for health and safety reasons. Different
hydrogen sensors including conductometric, electrochemical
and catalytic were investigated [9e11]. Among the main types
of conductometric sensors, those based on semiconductor
metal oxides such as ZnO [12], TiO2 [13], and SnO2 [14] have
been widely used. They have several advantages such as
simple integration into the detection system, low production
and maintenance costs as well as good sensitivity to variety of
gases [14,15].
Zinc oxide (ZnO) has attracted relevant attention as
sensing material from long time [16]. It is an n-type semi-
conductor very abundant in nature, low cost, non-toxic, and
nor ignitable nor explosive in case of fire. It has a specific
properties which basically dwell in its wide direct forbidden
band (3.37 eV), the important excitonic energy (60 meV), the
good transparency in the visible region, the high piezoelectric
coefficient, the high thermal stability and the suitability to
doping [17e21]. On the other hand, the field of materials has
been closely interwoven with that of “nano-technology”. The
main interest of nanomaterials lies in their properties which
differ from those of solid materials and allows the creation of
ety of disciplines [22e30]. In this context, zinc oxide has been
used as sensing material in diverse nanostructures like
nanorods [31], thin films [32] and nanoparticles [33,34].
Numerous reports have shown that the synthesis of zinc
oxide with different morphologies greatly improves the
detection properties [35,36].
Zinc oxide based gas sensors still suffer from some deficit
like low selectivity. Doping with suitable elements [37] and UV
illumination [38] are among the main method used to improve
ZnO gas sensor performances. Many researchers have focused
their attention on ZnO doping with elements from IIIA (Al, Ga,
In …) and IIA column (Ca, Mg, …). Doping ZnO with elements
from IIIA column induces the reduction of the electrical
resistance of the material and adjusts its optical, electrical and
catalytic performances. In addition, doping ZnO with trivalent
cations (In3þ, Al3þ …) generates an excess of positive charge
thus promoting the properties of n-type semiconductors.
Among the IIIA column elements, Al is the most interesting
thanks to its high stability, high abundance, low cost and non-
toxicity. It has been widely used as doping for nanostructured
metal oxides materials. It has strong effect to improve the gas
detection properties by increasing the surface-volume ratio.
Indeed, the main reason of changes in surface to volume ratio
and crystallite size is the mismatch created between the ionic
radius Al3þ ion (rAl3þ ¼ 0.054 nm) and the host cations [39,40].
For the IIA column, magnesium is considered as a very
attractive element. It is the 8th most abundant element in the
Earth’s crust and it is relatively nontoxic. Several studies have
shown the prominent role of magnesium because of its
controllable band gap and good crystallinity. On other hand, it
attracts researchers thanks to its high solubility in ZnO crystal
lattice. Indeed, the ionic radius of magnesium
(rMg2þ ¼ 0.066 nm) is similar as that of Zn (rZn2þ ¼ 0.074 nm)
which increases the probability of incorporation of Mg2þ ions
in the ZnO lattice. Also, Magnesium was characterized by its

Please cite this article as: Jaballah S et al., Facile synthesis of AleMg co-doped ZnO nanoparticles and their high hydrogen sensing
performances, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.053
 international journal of hydrogen energy xxx (xxxx) xxx
low electronegativity (c ¼ 1.31) compared to majority of other
ions which may increase its combination with oxygen in order
to form stable crystalline structure [41e44].
In this context, the binary AleZnO and MgeZnO compos-
ites have been proposed as hydrogen sensor. The applicability
of AleZnO sensor for hydrogen monitoring was found how-
ever very limited [45,46]. More promising are instead data
concerning MgeZnO sensors. Liu et al. [47] have prepared Mg-
doped ZnO thin film based sensor using PLD method, showing
an improvement of sensor response compared to ZnO in a
wide ranges of H2 concentration and temperature intervals.
The sensor can detect 5000 ppm of H2 gas with an optimum
response about 50 at temperature around 300  C. Karthick
et al. [48] have synthesized Mg doped ZnO films on c-cut
sapphire substrate using rf-sputtering method. The sensor
exhibited desirable responses at room temperature and over
wide H2 concentration (100e700 ppm).
Studies on AleMg co-doped ZnO have been performed by
various groups in order to improve the electrical and the op-
tical properties of ZnO [12,49,50]. However, until now, no pa-
pers have been reported regarding co-doping of these two
elements for developing AleMg co-doped ZnO nanostructures
for hydrogen sensing. Therefore, in this study, we report the
successfully synthesis of AleMg co-doped ZnO nanoparticles
by a facile sol-gel method, their characterization by different
techniques for investigating their morphological, micro-
structural, optical and electrical properties and a wide inves-
tigation of their hydrogen sensing characteristics.
The miniaturization in the size of the sensor device, the
low cost production, and the simultaneously improvement of
sensor performances for high sensitivity, selectivity, stability,
and fast response have gained outstanding interests in the
field of gas sensor technology [51,52]. In this context, we have
compared our work to other literature results as it is
mentioned in the following. The sensor developed by Lin et al.
[53] showed high response, and low detection limit to
hydrogen. However, this sensor has certain disadvantages,
such as the high operating temperature (400  C) and long re-
covery times. Wu et al. [54] have recently developed a prom-
ising room temperature Pd/MWO3 hydrogen gas sensor.
While, this sensor exhibits low response and long response
time as well as very high detection limit (1000 ppm). On other
hand, Huang et al. [55] have elaborated TFMG/UNCD/ZnO
nanorods based sensor for hydrogen detection. Even though
the sensor showed low working temperature, fast response,
good stability, but it suffers from unstable baseline and rela-
tively low selectivity.
The main objective of this work, is that we have tried to
enhance different performances of gas sensor in the same
time. Indeed, we have succeed to detect hydrogen in wide
concentration range, relatively low temperature, high and fast
response, excellent selectivity to variety of gases, high base-
line stability, good repeatability and low detection limit. On
other hand we have used a fast, simple and low cost modified
sol-gel method to synthesize our samples and the electrical
and sensing experiments were carried with small size and
very easy functioning sensor device.
Please cite this article as: Jaballah S et al., Facile synthesis of AleMg co-doped ZnO nanoparticles and their high hydrogen sensing
performances, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.053
3
Experimental
Synthesis
The preparation of the ZnO sample, has been followed the
protocol reported by L. El Mir et al. [56e58]. First, 16 g of zinc
acetate dehydrate (Zn(CH3COO)2  2H2O,99%) were dissolved
in 112 mL of methanol, under magnetic stirring for 15 min.
After that, the resulting solution was introduced into an
autoclave with 112 mL of ethyl alcohol for drying at a tem-
perature of 250  C, in the supercritical conditions of ethanol
(Tc ¼ 243  C and Pc ¼ 63.6 bars) with a heating speed of 50  C/h.
For the preparation of the 5Al doped ZnO sample, we have
followed the same protocol. We just added the appropriate
quantity (5 at.%) of aluminum isoproxide (C9H21AlO3, 99%) in
the solution in the first step. The mixture remained under
magnetic stirring until the total dissolution of the precursor.
After that, the whole solution was introduced into an auto-
clave with 220 mL of ethyl alcohol for drying in the super-
critical conditions of ethanol. The prepared sample was
named 5AZO. The MgeAl co-doped ZnO nanopowders were
prepared also by the same adopted modified sol-gel route.
After dissolving the zinc acetate dehydrate in the solvent
(methanol), we added at the same time the appropriate
quantities of magnesium chloride hexahydrate (MgCl26H2O,
99,9%) (1,3 and 5 at %) and aluminum isoproxide (C9H21AlO3,
99%) (5 at %). Next, the resulting solution was placed in an
autoclave and was dried in the supercritical conditions of
ethanol. The samples codes are named as 5A1MZO, 5A3MZO
and 5A5MZO, according the nominal Al and Mg loading of
each sample.
When the supercritical conditions are reached, we imme-
diately and rapidly extract the solvents which are in the form of
gas. We finished by a nitrogen injection in order to remove the
last drops of the solvent. After natural cooling, we obtained
aerogels nanoparticles with good chemical homogeneity. Then
all the obtained aerogels are heat treated in air at 400  C for 2 h.
This step was carried out using a muffle furnace of the Naber-
them GmbH type. The experimental procedure for the synthe-
sis of AleMg co-doped ZnO aerogels is illustrated in Fig. 1.
Characterization
The crystalline phases of the as-prepared samples were
identified by X-ray diffraction (XRD) using a Philips PW1710 X-
ray diffractometer. The surface morphologies were recorded
with a transmission electron microscopy (TEM) (Tecnai G2-
200 kV). The Thermal gravimetric study (TGA) was investi-
gated using a TGA apparatus (PerkinElmer). The specific sur-
face characteristics and pore size of the nanoparticles were
performed at 77 K by N2 adsorption-desorption isotherms
using Micromeritics ASAP 2020 apparatus. The optical prop-
erties were examined using a UVeViseNIR spectrophotom-
eter (ShimadzuUV-3101PC) and the photoluminescence (PL)
measurements were carried out with a NanoLog modular
spectrofluorometer Horiba.
4 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 1 e Experimental procedure for the synthesis of AleMg co-doped ZnO.

Sensing tests

Sensor devices were fabricated as following: first, we mixed

the prepared nanopowders with distilled water until obtaining
a paste. Then, the obtained paste has been printed on alumina
substrates supplied with interdigitated Pt electrodes and
heating element. Then, the sensor was placed in a stainless
steel test chamber to perform the detection tests. The sensing
tests were carried out in the temperature range 200e400  C
under a synthetic dry air (20% O2 e 80% N2) stream of 100
sccm. The concentrations of target gas were varied from 100 to
30,000 ppm by using certified bottles. The control of the elec-
trical resistance of the detection layers was performed by a
multimeter data acquisition unit (Agilent 34,970 A). A double
channel power supply instrument (Agilent E3632A) is used for
Fig. 2 e XRDpatterns of ZnO, 5AZO and 5AxMZO with x ¼ 1,
sensor heating. The sensor response, R, is determined as
3 and 5.
R ¼ Ra/Rg, where Ra and Rg correspond to the resistance of the
gas sensor in dry synthetic air and injecting gas, respectively.
The dynamic of the sensors was defined by response time and
recovery time, i.e. the time required reaching 90% of the final planes (100), (002), (101), (102), (110), (103), (200), (112) and (201)
change of resistance after exposing to H2 and dry air, of ZnO in the hexagonal wurtzite structure, according to the
respectively. JCPDS card file 36e1451 [59]. Secondary phases related to Al2O3
and MgeAleO start to appear in the 5A3MZO sample and they
are more intense for the 5A5MZO one. The associated JCPDS
Results and discussion cards are respectively no.008e0013 and 010e0238.The
enlarged zone of XRD pattern comprising the three main
Samples characterization peaks is represented in Fig. 3. XRD spectra of the binary and
ternary samples exhibit significant enhancement of peaks
X-ray diffraction analysis has been performed to characterize intensity compared to pure ZnO. Thus, the crystallinity of
the crystalline structure of the pure and doped samples. XRD samples appears to be improved after co-doping. Also, we can
patterns of the ZnO, A5ZO, 5A1MZO, 5A3MZO and 5A5MZO see a slight shift towards lower diffraction angles of the XRD
prepared samples, are reported in Fig. 2. On all samples, the peaks of the doped and co-doped samples. Similar observa-
presence of well pronounced diffraction peaks demonstrates tions of peaks shift were reported by Abed et al. [60]. They
their crystalline structure. The peaks are correlated to the have attributed the shift to lower angles to the elongation in

Please cite this article as: Jaballah S et al., Facile synthesis of AleMg co-doped ZnO nanoparticles and their high hydrogen sensing
performances, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.053
 international journal of hydrogen energy xxx (xxxx) xxx 5

0:9 l
D ¼ (3)
B cosq
where D is the average crystallite size, l ¼ 1.541874
A is the X-
ray wavelength, B is the full width at half maximum peak
(FWHM), and q is the Bragg diffraction angle. The average
crystallite size was estimated to be 36 nm for undoped ZnO. It
was almost similar for binary 5AZO (35 nm). However, it de-
creases for ternary AMZO to reach 27, 25 and 23 nm for
5A1MZO, 5A3MZO and 5A5MZO respectively. The decrease of
crystallite size is likely due to the small ionic radius of Al3þ
(0.053 nm) and Mg2þ (0.066 nm) in comparison with Zn2þ
(0.074 nm). Several studies [67,68] have shown a progressive
decrease in the crystallites size with the incorporation of
some dopants like Al, Mg and Fe in ZnO lattice. The decrease
in crystallites size was attributed to some reasons among
Fig. 3 e Shift of three main peaks (100), (002) and (101). which the compression stress provoked by the difference of
the ionic radii of the dopant and Zn, the generation of defects
in the crystals and also to the high the number of nucleation
the crystal structure and to the formation of secondary phases
sites and the obstruction of growth process.
ZnMgO which may increases defects and disorder in the ZnO
Typical TEM images of 5A1MZO sample is shown in Fig. 4.
lattice. In our case, this shift can be related to the change of
The 5A1MZO sample shows particles with prismatic like
the lattice parameters, the presence of secondary phases and
shape and nanometric size. There is a good agreement be-
to the stress built in the lattice [61,62]. The Stress could be
tween the grain sizes and the d(101), given by TEM and XRD.
generated from many factors such as crystallites size, inter-
The estimated particle sizes varied between 15 and 25 nm and
planar spacing, structural changes, stacking fault (planar
they are comparable with those mentioned in XRD results
imperfection), elastic and inelastic deformation as well as
(27 nm). The HRTEM image of above sample (Fig. 3b) indicates
lattice strain which can be calculated based to the
that the distance between the planes of the fringes is of about
Williamson-hall plot method [63,64].
0.24 nm, which corresponds to the (101) plane of the hexago-
The lattice parameters “a” and “c” of the ZnO hexagonal
nal structure of ZnO.
structure were determined from the (100) and (002) peaks
The thermal behavior of the different AMZO samples have
respectively using the relations given by Eqs. (1) and (2) [33].
been investigated by thermal gravimetric analysis (TGA). Fig. 5
" #
1 4 h2 þ hk þ k2 l2 depicts the TGA results of the 5A1MZO as an example. It can
2
¼ 2
þ 2 (1) be denoted that the weight of the sample decreases continu-
dhkl 3 a c
ously with increasing the temperature before coming to a
stable value up to 450  C. The TGA curve shows mainly four
2dhkl sinq ¼ nl (2)
weight loss regions. The first one, between room temperature
The values of lattice parameters of all samples are sum- and 150  C, is due to the dehydration phenomenon. The sec-
marized in Table 1. The calculated values showed an increase ond one, from 150 to 220  C, is correlated to the decomposition
for Al doped and AleMg co-doped samples in comparison to of chemically bound groups. The third one from 220 to 350  C
undoped ZnO. This increase is probably due to the replace- is attributed to the decomposition of the organic groups. The
ment of Al and Mg atoms in the interstitial site of ZnO lattice last weight-loss from 350 to 450  C is attributed to the
[65]. Crystallite sizes (D) were estimated from the Scherrer’s decomposition of the impurity ions from ZnO lattice. The TGA
equation (Eq. (3)) [66]. study proves the stability of the AMZO nanopowders.
The adsorption-desorption isotherm shape is essential to
specify the nanomaterials surface texture, that can be
appointed as microporous, mesoporous or macroporous. Fig. 6
presented the isotherm of the 5A1MZO sample, it is belong to
Table 1 e Structural parameters of ZnO, 5AZO and type II, according to IUPAC and Brunauer-Emmet-Teller (BET).
5AXMZO with x ¼ 1, 3 and 5. The estimated SBET is about 30 m2 g1; in addition, the pore
Sample Average Lattice SA diameter and pore volume are found of about 248
A and
crystallite size parameters 0.15 cm3 g1 respectively. The obtained results are very close
(

A) to those obtained by L. El Mir et al. using the same protocol for
(D) (nm) a c m2/g other doping elements [69,70].
ZnO 36 3.245 5.200 29.73 Fig. 7.a illustrates the UVeViseNIR absorption spectra in
5AZO 35 3.251 5.207 30.57 the wavelength of 200e2400 nm of pure ZnO, 5AZO, 5A1MZO,
5A1MZO 27 3.250 5.204 39.64 5A3MZO and 5A5MZO nanoparticles. An intense absorption in
5A3MZO 25 3.252 5.209 42.81 the UV range can be observed for all samples. The intensity of
5A5MZO 23 3.254 5.211 46.53
the absorbance bands in the UV region increases, probably

Please cite this article as: Jaballah S et al., Facile synthesis of AleMg co-doped ZnO nanoparticles and their high hydrogen sensing
performances, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.053
6 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 4 e TEM images of 5A1MZO nanoparticles.

Fig. 5 e a)Absorbance spectra and b),c),d),e) and f) Plots of (ahn)2 versus photon energy hn of all samples.

because of an increase in the concentration of free carriers
[71].Moreover, the absorption curve of Al doped and AleMg co-
doped ZnO samples slightly shifts to higher wavelength
compared to undoped ZnO. This red shift is attributed to the
decrease of gap energy. Fig. 7bef shows the spectra of (ahn)2 as
a function of the photon energy (hn) for all prepared samples.
The optical energy gap (Eg) was determined by extrapolating
the curve’s tangent to the x-axis. The optical band gap energy
(Eg) of all samples is given by the following equation (Eq. (4))
[72].

Please cite this article as: Jaballah S et al., Facile synthesis of AleMg co-doped ZnO nanoparticles and their high hydrogen sensing
performances, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.053
 international journal of hydrogen energy xxx (xxxx) xxx 7

100 decrease has been reported in some studies. Aranovich et al.

5A1MZO [72] have attributed this red shift to the merging of an impurity
band into the conduction band. However, Mohanty et al. [73]
have interpreted it in terms of the stress relaxation mecha-
75 nism. In our work, we can attribute the band gap shrinkage to
Weight (%)

the formation of additional energy levels, named Urbach tails,

caused by lattice disorder [74,75].
Fig. 8 shows PL spectra of AMZO samples. All samples
50 exhibit two major peaks. The UV emission peak corresponds
to the near band edge (NBE). It is ascribed to the band to band
recombination [38]. The second broad peak is located in the
visible region above 500 nm; it corresponds to the deep level
100 200 300 400 500 600 700
emission (DLE) [76]. This intense emission is assigned to
Temperature oC
different intrinsic defects. The green emission is typically
Fig. 6 e TGA curve of 5A1MZO nanopowder sample. ascribed to oxygen vacancies (VO). The yellow emission is
ascribed to oxygen interstitial (Oi). The orange-red emission is
related to oxygen interstitials (Oi) and oxygen anti-site (OZn)
100
[77,78]. Further, a new peak, centered at about 430 nm,
90 appeared only in the PL spectra of AleMg co-doped samples.
Quantity Adsorbed, cm /g STP

80 5A1MZO This blue emission might arise from the recombination be-
70 tween zinc interstitials (Zni) and valence band (VB) [79]. The
3

DLE/NBE ratio shows the considerable improvement of the

60
crystal quality for Al doped and AleMg co-doped ZnO sam-
50
ples. This behavior is totally in agreement with XRD results.
40 Moreover, compared with pure ZnO, the near band edge (NBE)
30 emission of 5AZO and AMZO nanoparticles reveal a slight
20 shift toward higher wavelength. This red shift in NBE emis-
sion is in good accord with the absorption results.
10

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
Hydrogen sensing tests
Relative Pressure, P/P0
In order to evaluate the characteristics of the developed sen-
Fig. 7 e Adsorption-desorption isotherms of N2 at 77 K of sors, first we tested their response to hydrogen at different
5A1MZO sample. temperatures. Fig. 9 summarizes the result obtained for ZnO,
Al doped ZnO and AleMg co-doped ZnO, reporting the sensors
responses to 2000 ppm of H2 versus the testing temperature,
 n from 200  C to 400  C. The optimal temperature recorded for
ðahnÞ ¼ A hn  Eg (4)
pure ZnO is 250  C. It increases to 300  C for 5A1MZO and
where a is the absorption coefficient, hn the photon energy, A 5A3MZO sensors and reaches higher values for 5A5MZO and
is a constant, n ¼ 1/2 for direct transition, and Eg is the energy 5AZO sensors (350 and 400  C respectively).These data seems
band gap. The estimated band gap values are 3.24, 3.17, 3.19,
3.17 and 3.14 eV for ZnO, 5AZO, 5A1MZO, 5A3MZO
and5A5MZO nanoparticles, respectively. Such band gap

Fig. 9 e ZnO, 5AZO and 5AxMZO nanoparticles to 2000 ppm

Fig. 8 e PL spectra of ZnO, 5AZO and 5AxMZO. hydrogen at different operating temperatures.

Please cite this article as: Jaballah S et al., Facile synthesis of AleMg co-doped ZnO nanoparticles and their high hydrogen sensing
performances, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.053
8 international journal of hydrogen energy xxx (xxxx) xxx

to suggest that magnesium induces an increase of operating

temperature. However, the response increases too and this is
an advantage. For example, at the temperature of 300  C, the
response of 5A1MZO and 5AM3ZO widely increased and was
about 2 times larger than on pure ZnO. The maximum
response (~86) was recorded for the 5A1MZO nanoparticles
based sensor.
Recently, many efforts are devoted to detect gases at room
temperature (RT) in standard environmental conditions for
low power consumption with high selectivity and sensibility.
For example, Simo.et al. have synthesized RT sensors based
on VO2 nanobelts and nanorods respectively for H2 and VOC
detection. The prepared sensors showed good performances
with low power detection [80e82]. On other hand, Kadhim
et al. [83] have successfully synthesized SnO2 thin film based
gas sensor for hydrogen detection. The sensor exhibits
promising characteristics in terms of sensitivity and stability
at room temperature. Hence, in future work we will look to
shift the H2 sensitivity to room temperature by optimizing the
composition of sensing materials and light activation.
On the basis of sensor performances displayed, in the
following, we focus our attention only on5A1MZO sensor. The
electrical properties of this sensor, compared with the pure
ZnO one, are reported in Fig. 10. For both sensing layers, the
decrease of resistance with the temperature is attributed to
the thermal excitation of electrons into the conduction band.
The resistance of the 5Al1Mg ZnO layer in air is lower than
that of pure ZnO at all temperatures. This improvement of the
conductivity could be related to the aluminum doping, in
agreement with literature data on binary ZnO samples
reporting that group III elements such as Al, In and Ga induce
an excess of carriers [84,85].This is more evident at lower
temperatures where a larger difference is noted.
Hydrogen sensing tests have been performed at 250  C.
Fig. 11a shows the dynamic response of 5A1MZO film over a
wide range of H2 gas concentrations (100e30000 ppm).It can be
seen the fully reversible behavior when hydrogen was injected
over the sensor. Fig. 11b illustrates the corresponding cali-
bration curve of the investigated sensor at 250  C. The
response to H2 increases with the increase of hydrogen con-
centration. By the log-log calibration curves a low detection
limit of few ppm towards hydrogen, at S/N ¼ 3, can be
Fig. 11 e a) Transient response of 5A1MZO film over a wide
range of H2 gas concentrations (100e30000 ppm); b)
calibration curve. Inset shows calibration curve in log-log
5
10 scale; c) response/recovery time of 5A1MZO and pure ZnO
sensors, exposed to 2000 ppm of H2 gas, at the temperature
10
4 of 250  C.
Resistance kΩ

3
10 extrapolated, demonstrating the good performances of the
sensor. Fig. 11c compare the response/recovery time of
2
10 5A1MZO and pure ZnO sensors, exposed to 2000 ppm of H2
ZnO
5A1MZO gas, at the temperature of 250  C. The5A1MZO sensor exhibits
1
a short response time of about ~3 s, and a recovery time of
10
200 300 400 about 70 s. The comparison with the ZnO sensor confirms also
the better dynamics characteristics of the sensor based on the
Temperature (°C)
co-doped ZnO nanoparticles.
Fig. 10 e Electrical resistance in dry air vs. temperature of Baseline drift, response stability and selectivity are other
5A1MZO composite samples, compared to pure ZnO. important features for the practical applications of gas

Please cite this article as: Jaballah S et al., Facile synthesis of AleMg co-doped ZnO nanoparticles and their high hydrogen sensing
performances, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.053
 international journal of hydrogen energy xxx (xxxx) xxx 9

4 5A1MZO, H2, 250°C Table 2 e Comparison of hydrogen sensing properties of

10
sensor prepared with different materials.
Material Temp. Response Conc. Ref
( C) (ppm)
Resistance k:

10
3 Au/SnO2 400 50 * 5000 [44]
RhO2 200 12.5# 10 [45]
Pd/M-WO3 RT 11.7* 5000 [46]
rGO-decorated Ni 150 63.8# 100 [47]
eZnO
2
10 ZnO NL-buds 180 178 # 80 [48]
2000 ppm 2000 ppm 2000 ppm 2000 ppm ZnO film 400 23# 1200 [49]
ZnO nanorods RT 49.6 # 100 [50]
Pd doped In2O3 250 94* 150 [51]
16500 17000 17500 18000 Mg doped ZnO RT 35* 200 [26]
Time (s) Pd/BN/ZnO NWs 200 12.2* 50 [52]
ZnO-nanofibers 350 150* 10 [43]
Fig. 12 e Repeatability test toward 2000 ppm of the SnO2 coating 250 80# 500 [53]
5A1MZO sensor. dumbbell ZnO 300 20* 2000 [54]
5A1MZO 250 70* 2000 This work
nanoparticles
sensors. Fig. 12 shows the short-term stability in the baseline    
Ra Rg Ra  Rg Rg  Ra
and response of the sensor at 2000 ppm of H2.The 5A1MZO * means or and # means *100 or *100
Rg Ra Ra Ra
sensor exhibits good stability of the baseline after repeated where Ra and Rg represent the values of sensor resistance in
cycling. Further, the investigated sensor characterized by its presence of air and target gas respectively.
reliable and reproducible responses during the change of
signal between air and hydrogen. Cross sensitivity tests
(Fig. 13) were performed by testing the 5A1MZO sensor at the
operating temperature of 250  C with the following interfering Hydrogen sensing mechanism and relationships with
gases NH3, NO2, H2, CO2, CH4, NO, ethanol and CO. It is clear microstructure
from the cross sensing analysis, the higher response of the
5A1MZO sensor compared to other investigated gases. This Hydrogen sensing mechanism has been investigated by
result indicates a very good selectivity of the 5A1MZO sample numerous researchers [86,96,97]. In agreement with the most
towards the interfering gases tested. accepted mechanism, when the Al, Mg co-doped ZnO sensor is
The sensing performances of the sensor were compared in air oxygen molecules will be adsorbed on the sensor’s layer
with recently reported hydrogen gas sensors based of semi- surface. Then, these adsorbed molecules will capture elec-
conductors oxide [48,53,54,86e95]. The different gas sensors trons from the conduction band of sensing layer to generate
performances are summarized in Table 2. The presented chemisorbed oxygen species, which alter the depletion layer
5A1MZO nanoparticles exhibited comparatively competitive width and markedly impact the sensor resistivity. The above
gas sensor performances, suggesting that the ternary, co- mentioned phenomena occurred for our sensor at tempera-
doped 5A1MZO nanoparticles can be used as a novel mate- ture between 200 and 400  C, thus producing O and O2 ions
rial for the selective hydrogen detection. [98]. The reactions are followed in Eqs. (5)e(7) [99]:

O2ðgasÞ % O2ðadsÞ (5)

O  
2ðadsÞ þ e % 2OðadsÞ (6)

O
ðadsÞ þ e

% O2
ðadsÞ (7)

Exposing the sensitive layer to H2, these molecules interact

with the adsorbed oxygen species. This induces the release of
the electrons trapped in the sensing layer conduction band
and reduces the depletion layer. Consequently, the resistance
decreases. The following reaction (Eq. (8)) explain better the
whole phenomenon [100].

H2 þ O ðadÞ%H2 O þ e (8)

To explain the effect of Al and Mg on the sensor response to

Fig. 13 e Gas responses of the 5A1MZO based sensor
toward common reducing and oxidizing gases in dry air,
operating at 250  C.
hydrogen, we compared the sensor response with the char-
acterization data. XRD analysis showed a big decrease of
crystallites size for the co-doped samples. It is well known
that the decrease of grains size offers more surface area.

Please cite this article as: Jaballah S et al., Facile synthesis of AleMg co-doped ZnO nanoparticles and their high hydrogen sensing
performances, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.053
10 international journal of hydrogen energy xxx (xxxx) xxx
Consequently, the improved sensor response can be corre-
lated to the higher surface area (SA). The surface area was
theoretically calculated based to the following equation (Eq.
(9)) [98]:
6
SA ¼ (9)
d*r
where d is the particle size and r represent the theoretical
density of ZnO (5.606 g/cm3). The calculated SA values are
29.7, 39.6, 42.8 and 46.5 m2/g for ZnO, 5AZO, 5A1MZO and
5A3MZO and 5A5MZO respectively. The ternary AMZO sam-
ples present the higher surface area compared to 5AZO and
ZnO samples. Although 5A5MZO sample possess the highest
SA, it shows lower response than other co-doped samples. So,
we cannot just rely on the size of nanoparticles. On other
hand, the secondary phases revealed in this sample may have
a negative effect, inhibit the interaction between oxygen
species and target gas and then decreases the sensitivity of
the sensor.
Afterwards, we have tried to correlate the sensing results
with PL measurements. It is known that more donor defects
like oxygen vacancy (VO) and zinc interstitial (Zni) result in
more oxygen adsorption. Then, adsorbed oxygen will further
reacts with target gas and produces larger sensing signal.
However, Han et al. [76] indicated that high donor defects
levels should be accompanied with less acceptor defects in
order to improve gas sensing. Phan and Chung [101] have also
supported this idea. They have attributed the enhancement of
CO sensitivity of Ga doped ZnO sensor to the less interstitial
oxygen. They assumed that the interstitial oxygen inhibited
the free oxygen from being chemisorbed onto the ZnO surface
and decrease the sensitivity of the sensor. Also, they
mentioned that the low interstitial oxygen is proved by the
decrease of visible to ultra-violet luminescence ratio (Ivis/IUV)
in PL spectra. In our case, PL spectra of the 5AZO and AMZO
samples show similar behavior. With the insertion of Al3þ and
Mg2þ ions, the intensity of visible peak was considerably
decreased compared to pure ZnO. We can rely on the same
adopted hypothesis. Thus, the decrease of interstitial oxygen
defect, induce improvement of hydrogen detection. Finally,
surface area, secondary phases and interstitials oxygen are all
important factors which influence the sensitivity of the sensor
toward hydrogen.
Conclusion
AleMg co-doped ZnO nanoparticles were synthesized by a
modified sol-gel process and their hydrogen sensing perfor-
mances were investigated for the first time. The morpholog-
ical analysis highlighted the nanometric size of the prismatic
like shape AMZO nanoparticles synthesized. Microstructural
analysis of co-doped samples evidenced the formation of
well-structured material, which maintains the hexagonal
wurtzite structure of pristine ZnO. The incorporation of
aluminum and magnesium dopants resulted instead in a
decrease of gap energy. When investigated as active layer for
fabricating conductometric hydrogen sensors, AMZO nano-
particles demonstrated better performances with respect to
pristine ZnO. A fast, high, reproducible and selective response
Please cite this article as: Jaballah S et al., Facile synthesis of AleMg co-doped ZnO nanoparticles and their high hydrogen sensing
performances, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.053
towards hydrogen in the concentration range between 100
and 30,000 ppm at 250  C was noticed using the optimized
5A1MZO nanoparticles. These excellent characteristics are
promising for the practical applications of the sensor in the
hydrogen detection.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This work was funded by the National Plan for Sciences,
Technology and innovation (MAARIFAH) e King Abdulaziz
City for Sciences and Technology e Kingdom of Saudi Arabia,
award number: 13-NAN517-08.
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