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, Sensingmechanismof hydrogensensors basedonpalladium-loadedtungstenoxide (PdWO

3
),
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Contents lists available at SciVerse ScienceDirect
Sensors and Actuators B: Chemical
j our nal homepage: www. el sevi er . com/ l ocat e/ snb
Sensing mechanism of hydrogen sensors based on palladium-loaded tungsten
oxide (PdWO
3
)
Abdelhamid Boudiba
a,
, Pascal Roussel
d
, Chao Zhang
a
, Marie-Georges Olivier
a
,
Rony Snyders
b,c
, Marc Debliquy
a
a
Department of Materials Science, Faculty of Engineering, University of Mons, 7000 Mons, Belgium
b
Laboratory of PlasmaSurface Interaction Chemistry, University of Mons, 7000 Mons, Belgium
c
Materia Nova Research Centre, 7000 Mons, Belgium
d
Ecole Nationale Suprieure de Chimie de Lille, Unit de Catalyse et Chimie du Solide UMR CNRS 8181, Villeneuve dAscq, France
a r t i c l e i n f o
Article history:
Available online xxx
Keywords:
Pd-loaded WO
3
H
2
sensing mechanism
XRD
UVvisNIR
a b s t r a c t
This paper presents a study on hydrogen sensing mechanism of Pd-loaded tungsten oxide (PdWO
3
).
WO
3
nanoparticles (sphere-like) were prepared and characterized by transmission electron microscopy
(TEM), scanning electron microscope (SEM) and X-ray diffraction (XRD) analysis. The synthesized WO
3
nanoparticles was loaded with palladium (Pd) catalyst at 1at% and annealed in air at 400

C. The chemical
composition of the elements and their spatial distribution on the surface were determined by X-ray photo-
electronspectroscopy (XPS) and time-of-ight secondary ion mass spectrometry (ToF-SIMS) respectively.
PdWO
3
thick lm was prepared by screen-printing on alumina substrates tted with gold electrodes
and a platinum heater. The responses to 25200 ppm hydrogen (diluted in air) were measured at oper-
ating temperatures ranging from 200 to 280

C in dry air and with 50% relative humidity. The changes

in the optical properties (on the surface) and crystal phases (in bulk) of PdWO
3
in contact with hydro-
gen were investigated by UVvisNIR and XRD respectively. The in situ characterizations were carried
out in different conditions, 3% H
2
diluted in synthetic air/nitrogen at temperatures ranging from 25 to
200

C. The changes in the crystal phases, formation of hydrogen tungsten bronze, on the surface or bulk
were correlated with the electrical responses. A sensing mechanism of PdWO
3
for H
2
is proposed and
discussed.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Because of its interesting chemical, optical and electrical prop-
erties, tungsten oxide (WO
3
), which is n-type semiconductor, has
been the object of extensive research. It was studied in numerous
elds such as electrochromism [15], photoelectrochemical [6,7]
and particularly in gas sensor [813]. Pure WO
3
has good sensing
properties to oxidizing gases such as NO and NO
2
[9,12,14,15], O
3
[16,17] and Cl
2
[18]. However for reducing gases (CO, NH
3
, ethanol,
methanol, etc.), the surface modication of WO
3
by noble catalyst
(Pt, Au, and Pd) is required. The sensing mechanismof gas sensors
basedonmodiedmetal oxides by noble metals (NM-MO) has been
reported in the literature by several authors [19,20]. It is accepted
that the sensing mechanismis associated to the change of the resis-
tance in contact with the chemisorbed oxygen and gas species
on the surface of the metal oxide. For NM-MO such as PdSnO
2
,

Corresponding author. Tel.: +32 6537 4515; fax: +32 6537 4416.
E-mail addresses: Abdelhamid.Boudiba@umons.ac.be,
abdelhamid.boudiba@gmail.com (A. Boudiba).
PtWO
3
and PdWO
3
, the catalyst on the surface of the metal
oxides favours the presence of oxygenspecies (O

, O
2

andO
2
) on
the surface which depends strongly on the temperature [2124].
The ionization of oxygen molecules by the capture of electrons
from the conduction band of oxides results in an electron deple-
tion region on the surface of the sensor material. When the surface
of the gas sensors is exposed to reducing gases, the oxygen species
react with the gases and electrons are given back to the semicon-
ductor, whichincreases the sensor conductivity. For hydrogen(H
2
),
inadditiontothereactiononthesurfaceof thesensor betweenoxy-
gen species and hydrogen, the catalyst dissociates H
2
to H-adatoms
which react with WO
3
itself to form a blue tungsten bronze [20].
The formation of the tungsten bronze can be limited at the sur-
face of the sensitive materials or in the bulk depending on the
atmospheric conditions, temperature and doping elements. The
purpose of this work is to understand the competition between
these two mechanisms. First, PdWO
3
nanocomposites were pre-
pared and characterized and then, the effects of the temperature,
the catalyst (pure WO
3
and Pd-loaded WO
3
), the water vapour
and the oxygen (in air or in nitrogen atmospheres) on the elec-
trical, optical and crystal phase of tungsten oxide are studied. The
0925-4005/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2012.09.063
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),
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Fig. 1. Representative scheme of the in situ characterization (PdWO
3
/H
2
) by UVvisNIR spectrometer.
changes in the optical properties (diffuse reectance) and crystal
phases of Pd-loaded WO
3
in contact with hydrogen were demon-
stratedat the surface andinthe bulk depending onthe atmospheric
conditions.
2. Experimental
2.1. Preparation of WO
3
nanoparticles
The synthesis of WO
3
nanopowder is reported in a previous
article [11]. Briey, a solution of Na
2
WO
4
(0.5M) was prepared
and heated at 80

C in a reux. Hydrochloric acid (3M) was added

drop wise to the Na
2
WO
4
solution until precipitation. The resulting
product was washed several times with deionized water, dried and
annealed in air at 400

C for 4h.
2.2. Preparation of PdWO
3
nanocomposites and PdWO
3
coating (sensor)
To prepare PdWO
3
nanocomposites as a powder, palladium
chloride salt (PdCl
2
) was dissolved and dispersed in terpineol with
WO
3
nanopowder using sonication probe (UP50H, Hielscher Ultra-
sonic GmbH), the resultant dispersion with 1at% Pd loading was
dried at 100

C for 24h and then annealed in air at 400

C for 12h.
PdWO
3
coatings (sensors) were prepared by screen-printing of
PdWO
3
inks on alumina substrates tted with gold electrodes and
a platinum heater (C-MAC Micro Technology Company, Belgium).
The PdWO
3
sensor was annealed in air at 400

C for 12h. For

gas sensing tests, the PdWO
3
coatings are heated at 200

C for
24h in ambient air before their exposure to hydrogen in a Teon
chamber. The setup for gas sensing measurements is reported
in Ref. [8].
2.3. Characterization
The morphology of WO
3
was observed by TEM (TEM, Philips
CM200, 120kV) and SEM (SEM, Philips XL20, 20kV). The crys-
tal structure of the prepared WO
3
nanopowder and PdWO
3
nanocomposites was dened by X-ray diffraction (XRD, Siemens
D5000) using CuK

radiation with 2 scanning rate of 1

/min.
The chemical composition of the samples was investigated
using X-ray photoelectron spectroscopy (XPS), VERSAPROBE PHI
5000 from Physical Electronics, equipped with a Monochromatic
Al K

X-ray. To analyse the Pd distribution of PdWO

3
lm,
the experiments were conducted on a ToF-SIMS IV instrument
from ION-ToF GmbH (Mnster, Germany). The ToF-SIMS chem-
ical micrographs on the surface were obtained with a 25keV
Ga+ beam at a 45

incidence pulsed with a 70s period. The

pulsed ion current was typically 0.5pA (positive mode), the sur-
face of the analysed area was 199m199m. The reectance
measurements of PdWO
3
lm were made using an integrat-
ing sphere (Labsphere model RSA-PE-19 reectance spectroscopy
accessory) attached to a PerkinElmer Lambda 19 UV/VIS/NIR
spectrophotometer. The measurements were carried out at 200

C
in the wavelength range 2000400nm in air and in contact
with hydrogen (0.4% diluted in air); the scheme illustrating the
in situ characterization by UVvisNIR spectrometer is shown in
Fig. 1.
2.4. H
2
measurements
The resistivity changes of PdWO
3
sensor in air and in function
of hydrogen concentrations (25200ppm hydrogen) were mea-
sured at different working temperatures ranged from200 to 280

C
at relative humidity of 50% (measured at 22

C). UVvisNIR spec-

tra in diffuse reection were recorded on PdWO
3
lm at 200

C
in air and in contact with 0.4% of hydrogen diluted in synthetic
air.
In order to study the change in the crystal phase of WO
3
in
contact with hydrogen versus temperature, the HTXRD were car-
ried out on pure WO
3
and PdWO
3
powders (annealed in air at
400

C for 12h) from 27 to 200

C in contact with hydrogen fol-

lowing two conditions: (I) 3% hydrogen diluted in nitrogen and
(II) 3% hydrogen diluted in synthetic air. The HTXRD was per-
formed on a Bruker axs D8 Advance diffractometer equipped with
a high-temperature Anton Paar HTK 1200N chamber and a one-
dimensional X-raydetector (VNTEC-1) usingCuK

radiation. Data
were collected over the range 2060

C in 2, with a 0.015

step
and a time of 0.2s per step from room temperature to 200

C.
The samples were deposited on platinum sheets to avoid any
contamination.
Please cite this article inpress as: A. Boudiba, et al., Sensingmechanismof hydrogensensors basedonpalladium-loadedtungstenoxide (PdWO
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),
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Fig. 2. SEMmicrographs at different magnications (a) and TEM(b) images recorded on WO
3
nanopowder as synthesized and annealed in air at 400

C for 4h.
3. Results and discussion
3.1. Morphology and crystal structure characterization of WO
3
Fig. 2(a) shows the SEM images of WO
3
powder annealed in
air for 4h. The powder looks consisting in agglomerated spheri-
cal particles. The agglomerates were dispersed in methanol and
observed by TEM(Fig. 2(b)). The image shows that the nanopowder
has a monodisperse population with average size is approximately
100nm. The crystal structure was determined by XRD analysis. As
well known, WO
3
can exist under different forms and its crystal
phase changes are reversible with temperature (Table 1). At room
temperature (27

C), the synthesised WO

3
presents a monoclinic
phase as discussed in Section 3.5.
3.2. Characterization of the chemical composition of PdWO
3
nanocomposites
Thechemical compositionof PdWO
3
nanocomposites was ana-
lysed by XPS, the concentration of Pd as estimated was about 1at%.
The typical XPS survey recorded on PdWO
3
nanopowder after
annealing in air at 400

C is presented in Fig. 3. The C1s peak

(285eV) was usedas a binding energy reference. XPS survey of W4f
core level spectrum shows the two compounds associated with
W4f
5/2
and 4f
7/2
spin orbit doublet at 37.23 and 35.30eV respec-
tively (Fig. 3(b)). These energy values are reported to be generated
by photoelectrons emittedby tungstenatoms inthe oxidationstate
Table 1
Different crystallographic phases of WO
3
depending on the temperature.
Phase Symmetry temperature
-WO
3
Tetragonal 720

C
-WO
3
Orthorhombic From320

C to 720

C
-WO
3
Monoclinic From17

C to 320

C
-WO
3
Triclinic From40

C to 17

C
-WO
3
Monoclinic 40

C
+6 [25] which means that the lms are close to the chemical stoi-
chiometry of WO
3
. The survey spectrum of O1s and Pd3d peaks
recordedare showninFig. 3(c) and(d) respectively. The energy val-
ues generated by photoelectrons emitted by Pd atoms showthat Pd
is oxidized on the surface (PdO
2
). The XRD patterns of PdWO
3
do
not reveal any presence of Pd due to the small amount of Pd load-
inginthenanocomposites (1at%). Thecrystal phaseof PdWO
3
was
similar to pure WO
3
(monoclinic WO
3
). The patterns are presented
in the Section 3.5.
3.3. ToF-SIMS characterization
An effective dispersion of the catalyst on the surface of semi-
conductor grains is the key to reach a good response to hydrogen.
The dissociation of hydrogen is controlled by the catalyst and its
dispersion [29]. In order to analyse the distribution of Pd at the sur-
face of PdWO
3
lms, ToF-SIMS measurements in imaging mode
were performed on the surface. The most characteristic ions pro-
duced are O
+
, W
+
and
186
W
+
(m/z =186, isotope of tungsten) from
the WO
3
matrix, Pd
+
and
108
Pd
+
(m/z =108, isotope of Pd) fromPd.
As observed from the ToF-SIMS micrograph represented in Fig. 4,
the spatial distribution on the surface of Pd
+
and
108
Pd
+
ions is
rather uniform as well as the spatial distribution of W
+
and O
+
.
This homogeneous dispersion obtained by sonication makes the
PdWO
3
sensors very sensitive to hydrogen.
3.4. Response to hydrogen
H
2
sensing measurements of PdWO
3
coatings (sensors) were
carried out at working temperature ranged from 200 to 280

C at
50% relative humidity which obtained by owing the air through a
water bubbler maintained at 22

C. The concentrations of hydrogen

(diluted in air) were varied from50 to 200ppm. The response was
dened as (R
0
R
g
)/R
0
=R/R, where R
0
is the resistance in air and
R
g
is theresistanceincontact withhydrogenat agiventemperature.
A typical response of PdWO
3
sensor to 50200ppm hydrogen at
Please cite this article inpress as: A. Boudiba, et al., Sensingmechanismof hydrogensensors basedonpalladium-loadedtungstenoxide (PdWO
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Fig. 3. XPS spectra of PdWO
3
nanopowder annealed in air at 400

C for 12h: (a) typical XPS spectra; (b) W4f energy region; (c) O1s energy region; (d) Pd4d region.
200 and 280

C is presented in Fig. 5. As observed, the sensor shows

a good response and a short response time. The resistance of WO
3
(n-typesemiconductor) decreases rapidlyinhydrogenwhichreacts
as a reducing gas. As seenfromthe curve presenting the response at
200and280

C, thekinetic of theresponse(andrecovery) is acceler-

atedbyelevatingtheoperatingtemperature. Theresponseat 280

C
reaches very fast its maximum and then decreases to reach the
equilibrium. The two steps for reaching the equilibrium at 280

C
compared to 200

C can be explained by the effect of water vapour

(seeSection3.5). Theevolutionof theresistanceof thesensor versus
working temperature inair andincontact with50200ppmhydro-
gen is shown in Fig. 6. As can be seen, the curve Ln(R) versus 1/T
is linear at operating temperature in the range of 200280

C. In
fact, the transfer of electrons between adsorbed molecules (O
2

,
O
2
and O

) and WO
3
modies the energy barrier (eV
s
) at the grain
boundaries which given by G=G
0
exp(qVs/k
b
T), where G
0
, is the
conductance of the grain itself, k
b
is the Boltzmanns constant. The
deduced energy barriers (eV
s
) from curve presenting Ln(R) versus
1/T are presented in Table 2. The energy barrier (eV
s
) is reduced
from 0.45eV (in air) to 0.12eV in contact with 200ppm H
2
. As
seen on Fig. 6(b), the eV
s
are reduced in hydrogen compared to air
for all concentrations (50200ppm) because the concentration of
adsorbed oxygen species is reduced by reacting with hydrogen and
then, the number of carriers (electrons) is increased. Fig. 7(a) and
(b) shows the sensitivity of the sensor versus working temperature
Table 2
The deducedbarrier energy (eVs) fromcurve plottedLn(R) versus 1/T showninFig. 6.
Atmosphere Energy barrier (eVs)
Air 0.45eV
50ppmH
2
0.20eV
100ppmH
2
0.21eV
150ppmH
2
0.15eV
200ppmH
2
0.12eV
(from 200 to 280

C) and hydrogen concentrations (from 50 to

200ppm) respectively. The sensors showed a high sensitivity even
at low temperature. At 200

C, the response to 50 and 200ppm

of hydrogen was about 7 and 20 respectively. From Fig. 7(b), it is
shown that the evolution of the sensitivity versus hydrogen con-
centrations (50200ppm) is linear at operating temperature in the
range of 200280

C which makes it a suitable sensor for hydrogen

detection.
3.5. H
2
sensing mechanism
The sensing mechanism of semiconductor gas sensors is asso-
ciated to the change of the electrical resistance which depends
on the gas molecules or ions and chemisorbed oxygen species
on the surface of semiconductor. From the curve presenting the
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Fig. 4. ToF-SIMS micrograph recorded on PdWO
3
sensor annealed in air at 400

C
for 12h showing the homogenous distribution of Pd on the surface of the lm.
electrical response of PdWO
3
sensor (n-type semiconductor) to
25200ppmhydrogen shown in Fig. 5, it is well illustrated that the
resistance of the sensor decreases once in contact with hydrogen.
This change in the resistance in contact with hydrogen which is a
reducing gas can be attributed to two phenomena:
(I) The oxygenspecies chemisorbedonthe surface of WO
3
reacts
with hydrogen to formwater vapour as following:
H
2
(gas)
Pd
2H

(H-adatoms) (1)
2H

(ads) + O

(ads) H
2
O + e

(2)
These reactions (1) and (2) do not happen in the case of pure WO
3
.
The variation of the resistance of pure WO
3
sensor in contact with
hydrogen (50200ppm) remains unchanged even at 200

C [11].
(II) The dissociated hydrogen on the catalyst (Pd) reacts with
WO
3
to formhydrogen tungsten bronze following the reaction:
xH

(ads) + WO
3
H
x
WO
3
(3)
Both mechanisms (I) and (II) result in an increase of the conductiv-
ity. The dispersion of Pd on the surface of the WO
3
grains (Fig. 8)
increases the global electrical resistance of the sensor compared
to pure WO
3
[11]. This is due to the changes in the number of
carriers (electrons) in the conducting band because the catalyst,
Fig. 5. Response of PdWO
3
sensor to 50200ppmH
2
at 200 and 280

C (RH=50%
measured at 22

C).
Fig. 6. Evolution of the resistance of PdWO
3
sensor (Ln(R) versus 1/T) in air and in
contact with 50200ppmhydrogen (RH=50% measured at 22

C).
which is dispersed as small clusters, enhances the concentrations
of the oxygen ions (O

, O
2
and O
2

) on the surface of WO
3
. These
ions trap electrons from the conducting band of semiconductor
results in an electron depletion region schemed in Fig. 8(a). When
PdWO
3
sensor is exposed to H
2
, the oxygen ions react with the
latter according to reaction (2). The electrons resulting from this
reaction are given back to WO
3
inducing a change in the resistivity
of the sensor. In addition to reaction (2), the Pd catalyst dissociates
H
2
to H-adatoms which react with WO
3
to form a blue tungsten
Fig. 7. Response of PdWO
3
sensor versus (a) operating temperature and (b) hydro-
gen concentration (CH
2
= 50200ppm, RH=50% measured at 22

C, T =20080

C).
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Fig. 8. Representative scheme of the energy barrier (eVs) caused by (a) the catalyst in air and (b) the hydrogen at the surface grains of the sensor.
bronze. H-adatoms react as electrons donors to WO
3
and conse-
quently, the sensor resistance decreases because of an increase in
the number of carriers.
To understand the effect of the water vapour on the kinetic
reactions between Pd-loaded WO
3
and hydrogen, the sensor was
exposed to 200ppmH
2
(21% or 1% oxygen) diluted in dried air and
moist air with 0% and 50% relative humidity respectively. As can
be seen in Fig. 9(a) and (b), the kinetic response of the sensor at
280

C follows different steps from(a) to (d). The different mecha-

nisms related to the reaction Steps (a)(d) can be described by the
following reactions:

Step (a): The resistance of the sensor incontact withhydrogen(in

moist/or dried) decreases following the upper reactions (1)(3).

Step (b): The resistance (in moist/or dried air) increases to reach
the equilibriumfollowing the reactions:
H
x
WO
3
+O
2
(air) WO
3
+H
2
O (4)
O
2
(air) + 2e

2O

(ads) (5)

Step (c): When the hydrogen is replaced by air, the resistance

increases following the reactions:
H
x
WO
3
+1/2O
2
(air) WO
3
+H
2
O (6)
O
2
(air) + 2e

2O

(ads) (7)

Step (d): The resistance in moist air decreases because of the

presence of hydroxyl groups on the surface resulted from the
dissociation of water molecules following the reaction:
H
2
O OH

+H
+
(8)
OH

and H
+
serve as conductive species. On the other
hand, free electrons can also be released to the metal
oxide inducing a decreased in the resistance following the
reactions proposed by Heiland and Kohl [26]:
H
2
O(gas) 2OH + V
O

+2e` (9)
V
O

+ 2e

(10)
As seen in Fig. 9(b), the resistance of the sensor in dried
air (RH=0%), reach its equilibrium after the Step (c) and stays
stable contrary to the resistance measured at 50%relative humidity
(Fig. 9(c)). In fact, above 200

C the molecular water disappears at

the surface of the sensor [21]. Hydroxyl groups canappear andreact
as a donor to the metal oxides [21,26]. Contrary to the mechanism
proposed by Heiland and Kohl. Morrison, as well as Henrich and
Cox [27,28], consider an indirect effect more probable. This effect
could be the interaction between either the hydroxyl group or the
hydrogen atom originating from the water molecule with an acid
(metallic sites) or basic group (lattice oxygen) or with the adsorbed
oxygen on the surface. Both mechanisms lead in an increased of
the sensor conductivity. Therefore, the diminution of the resis-
tance during the Step (d) presented in Fig. 9(c) can be attributed
to the higher vapour concentration. In fact, the dissociation of
water molecules (reaction (8)) is more effective at high temper-
ature (280

C) explaining once more the different behaviours of the

sensor response presented in Fig. 5.
Furthermore, the concentration of the dissociated hydrogen
is controlled by the catalyst and its dispersion on the surface
of WO
3
[29], the formation of the hydrogen tungsten bronze
described by the reactions (1) and (3) respectively [30,31] can hap-
pen on the surface or in the bulk. These reactions on the surface
and in the bulk are put in evidence using in situ characteriza-
tion by (a) UVvisNIR spectrometry and (b) X-ray diffraction
respectively.
3.5.1. In situ characterization (PdWO
3
in contact with 0.4% H
2
)
by UVvisNIR spectrometry
The reectance measurements were carried out on PdWO
3
sensor in contact with 0.4% H
2
diluted in synthetic air at 200

C.
The colour change of PdWO
3
from yellow to dark blue when the
sensor is exposed to hydrogen (change of WO
3
to H
x
WO
3
, Eq. (3))
is shown in Fig. 10. The colour change is due to the formation of
hydrogen tungsten bronze on the surface because of the reduction
of W
6+
to W
5+
or W
4+
. The reectance decreased in contact with
hydrogen (30min) from45% to 30% around 2000nm. After 60min
of contact with hydrogen, the sensor was exposed to synthetic air
for 60min; the reectance comes back to the base line showing
that the reaction Eq. (3) is reversible (oxidation of H
x
WO
3
to form
WO
3
).
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Fig. 9. (a) Response of PdWO
3
sensor to 200ppm H
2
at 200

C: (i) 200ppm H
2
diluted in dried air (RH=0%, 1% oxygen), (ii) 200ppm H
2
diluted in dried air (RH=0%, 21%
oxygen) and (iii) 200ppmhydrogen diluted in moist air (RH=50%, 21% oxygen); (b and c) response of the sensor to 200ppmH
2
in dried and moist air respectively showing
the different steps of the evolution of the resistance.
3.5.2. In situ characterization (PdWO
3
in contact with 3% H
2
) by
XRD analysis
In situ characterization using XRD analysis were carried out
on PdWO
3
and pure WO
3
nanopowders depending on the
Fig. 10. Evolution of the reectance of PdWO
3
sensor in air and contact with 0.4%
H
2
diluted in air at 200

C.
temperature (27200

C) and the atmosphere conditions. The two

conditions are (I) 3% hydrogen diluted in nitrogen and (II) 3%
hydrogen diluted in synthetic air. The XRD patterns of PdWO
3
are shown in Fig. 11(a) and (b); the data showed that the diffu-
sion of hydrogen and its insertion into WO
3
lattice is governed
essentially by the presence of oxygen. The XRD data presented in
Fig. 11(a) showed that WO
3
is transformed to H
x
WO
3y
after
60min of contact with 3%hydrogen (diluted in in nitrogen), while
in the presence of oxygen (3% H
2
diluted in air), no change in
the crystal phase is observed. The monoclinic WO
3
phase remains
unchanged even after 16h at 200

C (Fig. 11(b)). To understand the

effect of Pd on the kinetic reactions of WO
3
with hydrogen (reac-
tions (1)(3)), XRD analyses were carried out on pure WO
3
under
conditions (I) and (II). As seen in Fig. 12(a) and (b), no change is
observed if Pd is not added. The crystal phase of pure WO
3
was
not changed to tetragonal hydrogen tungsten bronze even after
16h of contact with hydrogen diluted in nitrogen (Fig. 12(b)). This
means that the reactions are essentially governed by the catalyst
whichis necessary to dissociate hydrogenbefore its insertioninthe
lattice of WO
3
to formhydrogen tungsten bronze. Table 3 summa-
rizes the change in the crystal phase of WO
3
for different operating
conditions. The tetragonal hydrogen tungsten bronze phase was
observedonly for PdWO
3
incondition(I): temperature range from
Please cite this article inpress as: A. Boudiba, et al., Sensingmechanismof hydrogensensors basedonpalladium-loadedtungstenoxide (PdWO
3
),
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Fig. 11. XRD patterns of PdWO
3
versus working temperature showing the (a)
formation of tetragonal hydrogen tungsten bronze (t 60min) in contact with 3%
diluted hydrogen in N
2
; (b) the crystal phase remains monoclinic in contact with 3%
hydrogen diluted in air (t 16hours).
Table 3
Summary of the change in the crystal phases obtained by XRD analysis of pure WO
3
and Pd-loaded WO
3
in contact with hydrogen (3% diluted hydrogen in synthetic
air/or diluted in nitrogen).
Temperature Sample Atmospheres Crystal phase
200

C Pure WO
3
3% of H
2
in air Monoclinic WO
3
200

C Pure WO
3
3% of H
2
in N
2
Monoclinic WO
3
27200

C PdWO
3
3% of H
2
in air Monoclinic WO
3
27200

C PdWO
3
3% of H
2
in N
2
Tetragonal hydrogen
tungsten bronze
Fig. 12. XRD patterns of pure WO
3
versus working temperature of (a) in contact
with 3% hydrogen diluted in air and (b) in contact with 3% hydrogen diluted in N
2
.
27

C to 200

C in contact with 3% hydrogen diluted in nitrogen

atmosphere. The fact that XRD does not reveal any phase change
while optical spectra do, means that the formation of the bronze is
limited to the surface when oxygen is present.
4. Conclusions
Pd-loaded WO
3
nanocomposites were prepared and charac-
terized. Their sensing properties to hydrogen in the ppm level
were measured. In situ characterizations (in contact with air and
hydrogen) of the changes in the crystal phases and the surface
coloration (formation of bronze) for different operating conditions
Please cite this article inpress as: A. Boudiba, et al., Sensingmechanismof hydrogensensors basedonpalladium-loadedtungstenoxide (PdWO
3
),
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were performed. We put in evidence the formation of a hydrogen
tungsten bronze on the surface but not in the bulk in presence of
oxygen due to competitions between bronze formation and oxida-
tion.
Acknowledgements
This work was carried out in the framework of the Cold-Plasma
Project of the University of Mons, nancially supported by the
Communaut Franc aise de Belgique and also in the framework of
the Opti
2
mat Programme Excellence supported by the Walloon
Region of Belgium. Rony Snyders acknowledges the Belgian Gov-
ernment through the Ple dAttraction Interuniversitaire (PAI,
P6/08, PlasmaSurface Interaction, ).
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Biographies
Abdelhamid Boudiba received his master degree in nanotechnology and
nanomaterials in 2007 from University of Claude Bernard Lyon 1 (France).
He has worked for 18months between Nanocyl SA (Belgium) and Techni-
cal University of Eindhoven (Nederland) as a Research-Engineer on Carbon
Nanotube-Polymer Composites. Since October 2008, he entered in Material Sci-
ence Department of Faculty of Engineering of University of Mons as Assistant
Researcher, Ph.D. student. He is working on gas sensors based on metal oxide
nanostructures.
Pascal Roussel 41 is Research Director at CNRS in the eld of both solid-state
chemistry and crystallography. After a Ph.D. at Lab. CRISMAT (Pr Bernard Raveau),
Caen, France, and a post-doctoral position at the Institute of Crystallography
of the University of Aachen, Germany (Pr Gernot Heger), he was hired as CNRS
Research scientist at Catalysis and Solid State Chemistry Unit. He defended his
Habilitation in 2008 on the subject Order-disorder phenomena in solids: on the
use of X-rays and neutron diffractions at the University of Lille, France (Pr Francis
Abraham) and in 2012 he was promoted as Research Director. His main research
areas are the structural studies by mean of X-rays and/or neutrons diffraction, the
Anharmonicity, the Maximum Entropy Method, the orderdisorder in structures,
the twinned structures, pseudo-symmetry, etc. and his current research projects
are dealing with oxide ionic conductivity in solids, new mixed valence transi-
tion metal oxides compounds and new approaches of the structural studies. He
is responsible of the X-ray diffraction facilities of Lille 1 University (10 diffrac-
tometers), Deputy President of the French Crystallographic Association (in charge
of chemistry) and Co-editor of Acta Crystallographica. Finally, he is co-author of
more than 150 publications and 114 Communications in national or international
congresses.
Chao Zhang received a B.S. degree from the Chongqing University (China) in
2003 and a joint Ph.D. degree from Technology University of Belfort-Montbliard
(France) and Xian Jiaotong University (China) in June 2008. From September
2007 to January 2009, he worked as a teaching-research assistant in Technol-
ogy University of Belfort-Montbliard. Since February 2009, he is a postdoctoral
researcher in Material Science Department of Faculty of Engineering of Univer-
sity of Mons (Belgium). His research interests include thermal-sprayed coatings
and sputtered lms, especially for the application of solid oxide fuel cells and gas
sensors.
Marie-Georges Olivier received her Ph.D. degree in Applied Science in 1996
at Faculty of Engineering in Mons (Belgium). She was responsible of indus-
trial relationships in the eld of the activities of the Materia Nova Research
Center between 1997 and 2003. She is chief of the Department of Materials
Science of Faculty of Engineering of University of Mons since 2007. The main
research axes of the department are corrosion and surface treatments, sensors
and ceramic materials. She published numerous papers in corrosion science and
coatings.
Rony Snyders graduated in Chemistry in 1998 fromthe University of Mons-Hainaut
(UMH, Mons) where he received his Ph.D. in 2004. The same year, he started a
post-doc fellowship in the Department of Engineering Physics of the Polytechnic
School of Montreal. In 2006, he moved to the Materials Chemistry group of the
RWTH Aachen University for a second post-doc. In 2007, he got a permanent posi-
tion as a Professor at the University of Mons where he leads the PlasmaSurface
Interactions Laboratory (ChIPS). His interests are on the understanding of the
plasmasurface interactions during cold plasmas-based treatment of materials
(thin lms synthesis, surface modication, etc.) with a special interest on plasma
chemistry.
Please cite this article inpress as: A. Boudiba, et al., Sensingmechanismof hydrogensensors basedonpalladium-loadedtungstenoxide (PdWO
3
),
Sens. Actuators B: Chem. (2012), http://dx.doi.org/10.1016/j.snb.2012.09.063
ARTICLE IN PRESS
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10 A. Boudiba et al. / Sensors and Actuators B xxx (2012) xxxxxx
Marc Debliquy received his Ph.D. at Faculty of Engineering in Mons (Belgium) in
1999 inthe eld of organic semiconductors for re detection. He joined the Sochinor
Company in 2000. He left in 2003 for joining Materia Nova (Research Center in the
eld of Materials in Mons). He was responsible for the research activities in the
eld of gas sensors. Since October 2008, he joined in Material Science Department
of Faculty of Engineering of University of Mons and worked as a team leader of
semiconductor and sensor group. His main research interest is smart coatings for
chemical detection.