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Sensors and Actuators B: Chemical

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Sensing mechanism of hydrogen sensors based on palladium-loaded tungsten oxide (PdWO3 )

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 Laboratory of PlasmaSurface Interaction Chemistry, University of Mons, 7000 Mons, Belgium 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
b c

a r t i c l e
Article history: Available online xxx

i n f o

a b s t r a c t
This paper presents a study on hydrogen sensing mechanism of Pd-loaded tungsten oxide (PdWO3 ). WO3 nanoparticles (sphere-like) were prepared and characterized by transmission electron microscopy (TEM), scanning electron microscope (SEM) and X-ray diffraction (XRD) analysis. The synthesized WO3 nanoparticles was loaded with palladium (Pd) catalyst at 1 at% 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 photoelectron spectroscopy (XPS) and time-of-ight secondary ion mass spectrometry (ToF-SIMS) respectively. PdWO3 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 operating 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 PdWO3 in contact with hydrogen were investigated by UVvisNIR and XRD respectively. The in situ characterizations were carried out in different conditions, 3% H2 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 PdWO3 for H2 is proposed and discussed. 2012 Elsevier B.V. All rights reserved.

Keywords: Pd-loaded WO3 H2 sensing mechanism XRD UVvisNIR

1. Introduction Because of its interesting chemical, optical and electrical properties, tungsten oxide (WO3 ), 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 WO3 has good sensing properties to oxidizing gases such as NO and NO2 [9,12,14,15], O3 [16,17] and Cl2 [18]. However for reducing gases (CO, NH3 , ethanol, methanol, etc.), the surface modication of WO3 by noble catalyst (Pt, Au, and Pd) is required. The sensing mechanism of gas sensors based on modied metal oxides by noble metals (NM-MO) has been reported in the literature by several authors [19,20]. It is accepted that the sensing mechanism is associated to the change of the resistance in contact with the chemisorbed oxygen and gas species on the surface of the metal oxide. For NM-MO such as PdSnO2 ,

Corresponding author. Tel.: +32 6537 4515; fax: +32 6537 4416. E-mail addresses: Abdelhamid.Boudiba@umons.ac.be, abdelhamid.boudiba@gmail.com (A. Boudiba). 0925-4005/$ see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.snb.2012.09.063

PtWO3 and PdWO3 , the catalyst on the surface of the metal oxides favours the presence of oxygen species (O , O2 and O2 ) 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 depletion 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 semiconductor, which increases the sensor conductivity. For hydrogen (H2 ), in addition to the reaction on the surface of the sensor between oxygen species and hydrogen, the catalyst dissociates H2 to H-adatoms which react with WO3 itself to form a blue tungsten bronze [20]. The formation of the tungsten bronze can be limited at the surface 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, PdWO3 nanocomposites were prepared and characterized and then, the effects of the temperature, the catalyst (pure WO3 and Pd-loaded WO3 ), the water vapour and the oxygen (in air or in nitrogen atmospheres) on the electrical, optical and crystal phase of tungsten oxide are studied. The

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Fig. 1. Representative scheme of the in situ characterization (PdWO3 /H2 ) by UVvisNIR spectrometer.

changes in the optical properties (diffuse reectance) and crystal phases of Pd-loaded WO3 in contact with hydrogen were demonstrated at the surface and in the bulk depending on the atmospheric conditions. 2. Experimental 2.1. Preparation of WO3 nanoparticles The synthesis of WO3 nanopowder is reported in a previous article [11]. Briey, a solution of Na2 WO4 (0.5 M) was prepared and heated at 80 C in a reux. Hydrochloric acid (3 M) was added drop wise to the Na2 WO4 solution until precipitation. The resulting product was washed several times with deionized water, dried and annealed in air at 400 C for 4 h. 2.2. Preparation of PdWO3 nanocomposites and PdWO3 coating (sensor) To prepare PdWO3 nanocomposites as a powder, palladium chloride salt (PdCl2 ) was dissolved and dispersed in terpineol with WO3 nanopowder using sonication probe (UP50H, Hielscher Ultrasonic GmbH), the resultant dispersion with 1 at% Pd loading was dried at 100 C for 24 h and then annealed in air at 400 C for 12 h. PdWO3 coatings (sensors) were prepared by screen-printing of PdWO3 inks on alumina substrates tted with gold electrodes and a platinum heater (C-MAC Micro Technology Company, Belgium). The PdWO3 sensor was annealed in air at 400 C for 12 h. For gas sensing tests, the PdWO3 coatings are heated at 200 C for 24 h 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 WO3 was observed by TEM (TEM, Philips CM200, 120 kV) and SEM (SEM, Philips XL20, 20 kV). The crystal structure of the prepared WO3 nanopowder and PdWO3 nanocomposites was dened by X-ray diffraction (XRD, Siemens D5000) using Cu K 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 PdWO3 lm, the experiments were conducted on a ToF-SIMS IV instrument from ION-ToF GmbH (Mnster, Germany). The ToF-SIMS chemical micrographs on the surface were obtained with a 25 keV Ga+ beam at a 45 incidence pulsed with a 70 s period. The pulsed ion current was typically 0.5 pA (positive mode), the surface of the analysed area was 199 m 199 m. The reectance measurements of PdWO3 lm were made using an integrating 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 2000400 nm 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. H2 measurements The resistivity changes of PdWO3 sensor in air and in function of hydrogen concentrations (25200 ppm hydrogen) were measured at different working temperatures ranged from 200 to 280 C at relative humidity of 50% (measured at 22 C). UVvisNIR spectra in diffuse reection were recorded on PdWO3 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 WO3 in contact with hydrogen versus temperature, the HTXRD were carried out on pure WO3 and PdWO3 powders (annealed in air at 400 C for 12 h) from 27 to 200 C in contact with hydrogen following two conditions: (I) 3% hydrogen diluted in nitrogen and (II) 3% hydrogen diluted in synthetic air. The HTXRD was performed on a Bruker axs D8 Advance diffractometer equipped with a high-temperature Anton Paar HTK 1200 N chamber and a onedimensional X-ray detector (VNTEC-1) using Cu K radiation. Data were collected over the range 2060 C in 2 , with a 0.015 step and a time of 0.2 s per step from room temperature to 200 C. The samples were deposited on platinum sheets to avoid any contamination.

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Fig. 2. SEM micrographs at different magnications (a) and TEM (b) images recorded on WO3 nanopowder as synthesized and annealed in air at 400 C for 4 h.

3. Results and discussion 3.1. Morphology and crystal structure characterization of WO3 Fig. 2(a) shows the SEM images of WO3 powder annealed in air for 4 h. The powder looks consisting in agglomerated spherical 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 100 nm. The crystal structure was determined by XRD analysis. As well known, WO3 can exist under different forms and its crystal phase changes are reversible with temperature (Table 1). At room temperature (27 C), the synthesised WO3 presents a monoclinic phase as discussed in Section 3.5. 3.2. Characterization of the chemical composition of PdWO3 nanocomposites The chemical composition of PdWO3 nanocomposites was analysed by XPS, the concentration of Pd as estimated was about 1 at%. The typical XPS survey recorded on PdWO3 nanopowder after annealing in air at 400 C is presented in Fig. 3. The C 1s peak (285 eV) was used as a binding energy reference. XPS survey of W 4f core level spectrum shows the two compounds associated with W 4f5/2 and 4f7/2 spin orbit doublet at 37.23 and 35.30 eV respectively (Fig. 3(b)). These energy values are reported to be generated by photoelectrons emitted by tungsten atoms in the oxidation state
Table 1 Different crystallographic phases of WO3 depending on the temperature. Phase -WO3 -WO3 -WO3 -WO3 -WO3 Symmetry Tetragonal Orthorhombic Monoclinic Triclinic Monoclinic temperature 720 C From 320 C to 720 C From 17 C to 320 C From 40 C to 17 C 40 C

+6 [25] which means that the lms are close to the chemical stoichiometry of WO3 . The survey spectrum of O 1s and Pd 3d peaks recorded are shown in Fig. 3(c) and (d) respectively. The energy values generated by photoelectrons emitted by Pd atoms show that Pd is oxidized on the surface (PdO2 ). The XRD patterns of PdWO3 do not reveal any presence of Pd due to the small amount of Pd loading in the nanocomposites (1 at%). The crystal phase of PdWO3 was similar to pure WO3 (monoclinic WO3 ). The patterns are presented in the Section 3.5. 3.3. ToF-SIMS characterization An effective dispersion of the catalyst on the surface of semiconductor 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 surface of PdWO3 lms, ToF-SIMS measurements in imaging mode were performed on the surface. The most characteristic ions produced are O+ , W+ and 186 W+ (m/z = 186, isotope of tungsten) from the WO3 matrix, Pd+ and 108 Pd+ (m/z = 108, isotope of Pd) from Pd. 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 PdWO3 sensors very sensitive to hydrogen. 3.4. Response to hydrogen H2 sensing measurements of PdWO3 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 from 50 to 200 ppm. The response was dened as (R0 Rg )/R0 = R/R, where R0 is the resistance in air and Rg is the resistance in contact with hydrogen at a given temperature. A typical response of PdWO3 sensor to 50200 ppm hydrogen at

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Fig. 3. XPS spectra of PdWO3 nanopowder annealed in air at 400 C for 12 h: (a) typical XPS spectra; (b) W 4f energy region; (c) O 1s energy region; (d) Pd 4d 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 WO3 (n-type semiconductor) decreases rapidly in hydrogen which reacts as a reducing gas. As seen from the curve presenting the response at 200 and 280 C, the kinetic of the response (and recovery) is accelerated by elevating the operating temperature. The response at 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 (see Section 3.5). The evolution of the resistance of the sensor versus working temperature in air and in contact with 50200 ppm hydrogen 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 (O2 , O2 and O ) and WO3 modies the energy barrier (eVs ) at the grain boundaries which given by G = G0 exp(qVs/kb T), where G0 , is the conductance of the grain itself, kb is the Boltzmanns constant. The deduced energy barriers (eVs ) from curve presenting Ln(R) versus 1/T are presented in Table 2. The energy barrier (eVs ) is reduced from 0.45 eV (in air) to 0.12 eV in contact with 200 ppm H2 . As seen on Fig. 6(b), the eVs are reduced in hydrogen compared to air for all concentrations (50200 ppm) 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 deduced barrier energy (eVs ) from curve plotted Ln(R) versus 1/T shown in Fig. 6. Atmosphere Air 50 ppm H2 100 ppm H2 150 ppm H2 200 ppm H2 Energy barrier (eVs ) 0.45 eV 0.20 eV 0.21 eV 0.15 eV 0.12 eV

(from 200 to 280 C) and hydrogen concentrations (from 50 to 200 ppm) respectively. The sensors showed a high sensitivity even at low temperature. At 200 C, the response to 50 and 200 ppm of hydrogen was about 7 and 20 respectively. From Fig. 7(b), it is shown that the evolution of the sensitivity versus hydrogen concentrations (50200 ppm) is linear at operating temperature in the range of 200280 C which makes it a suitable sensor for hydrogen detection. 3.5. H2 sensing mechanism The sensing mechanism of semiconductor gas sensors is associated 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. 6. Evolution of the resistance of PdWO3 sensor (Ln(R) versus 1/T) in air and in contact with 50200 ppm hydrogen (RH = 50% measured at 22 C). Fig. 4. ToF-SIMS micrograph recorded on PdWO3 sensor annealed in air at 400 C for 12 h showing the homogenous distribution of Pd on the surface of the lm.

electrical response of PdWO3 sensor (n-type semiconductor) to 25200 ppm hydrogen 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 oxygen species chemisorbed on the surface of WO3 reacts with hydrogen to form water vapour as following: H2 (gas)2H (H-adatoms) 2H (ads) + O (ads) H2 O + e
Pd

which is dispersed as small clusters, enhances the concentrations of the oxygen ions (O , O2 and O2 ) on the surface of WO3 . These ions trap electrons from the conducting band of semiconductor results in an electron depletion region schemed in Fig. 8(a). When PdWO3 sensor is exposed to H2 , the oxygen ions react with the latter according to reaction (2). The electrons resulting from this reaction are given back to WO3 inducing a change in the resistivity of the sensor. In addition to reaction (2), the Pd catalyst dissociates H2 to H-adatoms which react with WO3 to form a blue tungsten

(1) (2)

These reactions (1) and (2) do not happen in the case of pure WO3 . The variation of the resistance of pure WO3 sensor in contact with hydrogen (50200 ppm) remains unchanged even at 200 C [11]. (II) The dissociated hydrogen on the catalyst (Pd) reacts with WO3 to form hydrogen tungsten bronze following the reaction: xH (ads) + WO3 Hx WO3 (3)

Both mechanisms (I) and (II) result in an increase of the conductivity. The dispersion of Pd on the surface of the WO3 grains (Fig. 8) increases the global electrical resistance of the sensor compared to pure WO3 [11]. This is due to the changes in the number of carriers (electrons) in the conducting band because the catalyst,

Fig. 5. Response of PdWO3 sensor to 50200 ppm H2 at 200 and 280 C (RH = 50% measured at 22 C).

Fig. 7. Response of PdWO3 sensor versus (a) operating temperature and (b) hydrogen concentration (CH2 = 50200 ppm, 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 WO3 and consequently, 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 WO3 and hydrogen, the sensor was exposed to 200 ppm H2 (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 mechanisms related to the reaction Steps (a)(d) can be described by the following reactions: Step (a): The resistance of the sensor in contact with hydrogen (in moist/or dried) decreases following the upper reactions (1)(3). Step (b): The resistance (in moist/or dried air) increases to reach the equilibrium following the reactions: Hx WO3 + O2 (air) WO3 + H2 O O2 (air) + 2e 2O (ads) (4) (5)

Step (c): When the hydrogen is replaced by air, the resistance increases following the reactions: Hx WO3 + 1/2O2 (air) WO3 + H2 O O2 (air) + 2e 2O (ads)

(6) (7)

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 can appear and react 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 resistance 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 temperature (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 WO3 [29], the formation of the hydrogen tungsten bronze described by the reactions (1) and (3) respectively [30,31] can happen on the surface or in the bulk. These reactions on the surface and in the bulk are put in evidence using in situ characterization by (a) UVvisNIR spectrometry and (b) X-ray diffraction respectively.

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: H2 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]: H2 O (gas) 2OH + VO +2e` VO V + 2e

(9) (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

3.5.1. In situ characterization (PdWO3 in contact with 0.4% H2 ) by UVvisNIR spectrometry The reectance measurements were carried out on PdWO3 sensor in contact with 0.4% H2 diluted in synthetic air at 200 C. The colour change of PdWO3 from yellow to dark blue when the sensor is exposed to hydrogen (change of WO3 to Hx WO3 , 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 W6+ to W5+ or W4+ . The reectance decreased in contact with hydrogen (30 min) from 45% to 30% around 2000 nm. After 60 min of contact with hydrogen, the sensor was exposed to synthetic air for 60 min; the reectance comes back to the base line showing that the reaction Eq. (3) is reversible (oxidation of Hx WO3 to form WO3 ).

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Fig. 9. (a) Response of PdWO3 sensor to 200 ppm H2 at 200 C: (i) 200 ppm H2 diluted in dried air (RH = 0%, 1% oxygen), (ii) 200 ppm H2 diluted in dried air (RH = 0%, 21% oxygen) and (iii) 200 ppm hydrogen diluted in moist air (RH = 50%, 21% oxygen); (b and c) response of the sensor to 200 ppm H2 in dried and moist air respectively showing the different steps of the evolution of the resistance.

3.5.2. In situ characterization (PdWO3 in contact with 3% H2 ) by XRD analysis In situ characterization using XRD analysis were carried out on PdWO3 and pure WO3 nanopowders depending on the

Fig. 10. Evolution of the reectance of PdWO3 sensor in air and contact with 0.4% H2 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 PdWO3 are shown in Fig. 11(a) and (b); the data showed that the diffusion of hydrogen and its insertion into WO3 lattice is governed essentially by the presence of oxygen. The XRD data presented in Fig. 11(a) showed that WO3 is transformed to Hx WO3 y after 60 min of contact with 3% hydrogen (diluted in in nitrogen), while in the presence of oxygen (3% H2 diluted in air), no change in the crystal phase is observed. The monoclinic WO3 phase remains unchanged even after 16 h at 200 C (Fig. 11(b)). To understand the effect of Pd on the kinetic reactions of WO3 with hydrogen (reactions (1)(3)), XRD analyses were carried out on pure WO3 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 WO3 was not changed to tetragonal hydrogen tungsten bronze even after 16 h of contact with hydrogen diluted in nitrogen (Fig. 12(b)). This means that the reactions are essentially governed by the catalyst which is necessary to dissociate hydrogen before its insertion in the lattice of WO3 to form hydrogen tungsten bronze. Table 3 summarizes the change in the crystal phase of WO3 for different operating conditions. The tetragonal hydrogen tungsten bronze phase was observed only for PdWO3 in condition (I): temperature range from

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Fig. 11. XRD patterns of PdWO3 versus working temperature showing the (a) formation of tetragonal hydrogen tungsten bronze (t 60 min) in contact with 3% diluted hydrogen in N2 ; (b) the crystal phase remains monoclinic in contact with 3% hydrogen diluted in air (t 16 hours).

Fig. 12. XRD patterns of pure WO3 versus working temperature of (a) in contact with 3% hydrogen diluted in air and (b) in contact with 3% hydrogen diluted in N2 .

Table 3 Summary of the change in the crystal phases obtained by XRD analysis of pure WO3 and Pd-loaded WO3 in contact with hydrogen (3% diluted hydrogen in synthetic air/or diluted in nitrogen). Temperature 200 C 200 C 27200 C 27200 C Sample Pure WO3 Pure WO3 PdWO3 PdWO3 Atmospheres 3% of H2 3% of H2 3% of H2 3% of H2 in air in N2 in air in N2 Crystal phase Monoclinic WO3 Monoclinic WO3 Monoclinic WO3 Tetragonal hydrogen tungsten bronze

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 WO3 nanocomposites were prepared and characterized. 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

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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 oxidation. 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 Opti2 mat Programme Excellence supported by the Walloon Region of Belgium. Rony Snyders acknowledges the Belgian Government through the Ple dAttraction Interuniversitaire (PAI, P6/08, PlasmaSurface Interaction, ). References
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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 18 months between Nanocyl SA (Belgium) and Technical University of Eindhoven (Nederland) as a Research-Engineer on Carbon Nanotube-Polymer Composites. Since October 2008, he entered in Material Science 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 transition metal oxides compounds and new approaches of the structural studies. He is responsible of the X-ray diffraction facilities of Lille 1 University (10 diffractometers), 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 Technology University of Belfort-Montbliard. Since February 2009, he is a postdoctoral researcher in Material Science Department of Faculty of Engineering of University 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 industrial 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 from the 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 position 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 in press as: A. Boudiba, et al., Sensing mechanism of hydrogen sensors based on palladium-loaded tungsten oxide (PdWO3 ), Sens. Actuators B: Chem. (2012), http://dx.doi.org/10.1016/j.snb.2012.09.063

G Model SNB-14585; No. of Pages 10 10

ARTICLE IN PRESS
A. Boudiba et al. / Sensors and Actuators B xxx (2012) xxxxxx 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.

Marc Debliquy received his Ph.D. at Faculty of Engineering in Mons (Belgium) in 1999 in the 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

Please cite this article in press as: A. Boudiba, et al., Sensing mechanism of hydrogen sensors based on palladium-loaded tungsten oxide (PdWO3 ), Sens. Actuators B: Chem. (2012), http://dx.doi.org/10.1016/j.snb.2012.09.063