Sensors and Actuators B 89 (2003) 6875

Ag doped WO3-based powder sensor for the detection of NO gas in air

Ling Chen, Shik Chi Tsang*
Surface and Catalysis Research Centre, University of Reading, Whiteknights, Reading RG6 6AD, UK Received 21 August 2002; received in revised form 3 November 2002; accepted 11 November 2002

Abstract WO3-based materials as sensors for the monitor of environmental gases such as NOx (NO NO2 ) have been rapidly developed for various potential applications (stationary and mobile uses). It has been reported that these materials are highly sensitive to NOx with the sensitivity further enhanced by adding precious group metals (PGM such as Pt, Pd, Au, etc.). However, there has been limited work in revealing the sensing mechanism for these gases over the WO3-based sensors. In particular, the role of promoter is not yet clear though speculations on their catalytic, electronic and structural effects have been made in the past. In parallel to these PGM promoters here we report, for the rst time, that Ag promotion can also enhance WO3 sensitivity signicantly. In addition, this promotion decreases the optimum sensor temperature of 300 8C for most WO3-based sensors, to below 200 8C. Characterizations (XRD, TEM, and impedance measurement) reveal that there is no signicant bulk structure change nor particle size alteration in the WO3 phases during the NO exposure. However, it is found that the Ag doping creates a high concentration of oxygen vacancies in form of coordinated crystallographic shear (CS) planes onto the underneath WO3. It is thus proposed that the Ag particle facilitates the oxidative conversion of NO to NO2 followed by a subsequent NO2 adsorption on the defective WOx sites created at the AgWO3 interface; hence, accounting for the high molecular sensitivity. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: NO; Gas sensor; Sliver; WO3-based powder

1. Introduction In recent years, the demand for gas sensors based on safety and process control requirements has been expanding [1]. Much interest is centered on studies of tin oxide as gas sensitive resistors since it is inexpensive, robust, highly sensitive to ammable hydrocarbon gases [2] and can be tuned to differentiate gases with good selectivity [3]. However, this sensor material is not suitable for detecting some of the most dangerous of air pollutants, namely nitric oxide (NO) and nitrogen dioxide (NO2) (collectively referred to as NOx), because of its poor sensitivity. Currently, approximately one-half of all NOx emissions into the environment are due to power plants and industrial boilers [4]. NOx gas, which is the precursor to nitric and nitrous acid, causes acid rain and photochemical smog; and hence, constitutes the critical factor for the destruction of ozone in the troposphere. In fossil fuel combustion, NOx is formed by high temperature chemical processes from both nitrogen present in the fuel and oxidation of nitrogen in the air.
Corresponding author. Tel.: 44-1189-316346; fax: 44-1189-316632. E-mail address: s.c.e.tsang@reading.ac.uk (S.C. Tsang).
*

Typically, the NOx emissions consist of 9095% NO with the remainder being N2O and NO2 ranging 04000 ppm [4,5]. In case of environmental monitoring, according to the American Conference of Governmental Industrial Hygienist (ACGIH), the threshold limit values (TLV) for NO2 and NO are 3 and 25 ppm, respectively [5]. Therefore, a NOx sensor requires high sensitivity for detecting low concentration of gases. Another enormous driving force for developing high sensitivity NOx sensor comes from automotive industry. In order to decrease both fuel consumption and carbon dioxide production, new engines with excess of air versus stoichiometry have been developed. Unfortunately, the conventional catalytic converter of exhaust gas does not work without careful control of NOx [6]. Tungsten trioxide (WO3) is a wide band-gap n-type semiconductor that has attracted much recent interest as a promising sensor because of its excellent sensitivity and selectivity [7]. WO3 thin lms were used initially for detecting H2S and H2. Yamazoe and Miura [8] were amongst the rst to report that tungsten trioxide sintered lms are selective sensors for low concentrations of nitrogen oxides. WO3 thin lms activated by noble metals (Pd, Pt, Au) layers have later been found to be more sensitive, selective and shown to give a quicker response to NOx [5]. The sensing

0925-4005/02/$ see front matter # 2002 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 5 - 4 0 0 5 ( 0 2 ) 0 0 4 3 0 - 6

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materials of WO3 promoted with 1 wt.% metal or metal oxides for NO detection were then systematically screened. It was found that some of these promoters were critical for improving the sensitivity [9]. The sensing mechanism of semiconductor oxides lie, in general, on the changes in the resistance resulting from physisorption, chemisorption, catalytic reactions and species migration (spillover) on the promotersensor particles upon analytical gas exposure [10]. It has been acknowledged that the thin lm microstructure plays a major role in this behavior [11,12]. This is mainly because grains and grain boundary regions are expected to have signicantly different electronic properties and, accordingly, to show a different electronic response after the interaction with gases [11]. However, there is limited work reported in the literature on addressing the precise sensing mechanism for the NOx gases detection over WO3-based sensors and there is no work to reveal the roles of the promoter. It is known that sensitivity of NO2 is many times higher than NO over the WO3-based sensors and most of the best-reported promoters are also known to be good oxidation catalysts. As a result, one of the roles of promoter may be to provide a surface for the catalytic conversion of NO to NO2 that are responsible for the high sensitivity associated with the promotion. However, whether a specic interaction(s) between the promoter and the WO3 exists is not yet clear. In addition, WO3 phases generally regarded as distortions of the cubic ReO3 structure [13] are known to easily form non-stoichiometric oxides in which the oxidation state of the W is less than 6 [14]. Their stability, relationship with promoter and to the overall NOx sensing are still unclear. In this paper, we report the screening of WO3 powder doped with different promoters as sensor candidates. Amongst all the promoters tested, Ag/WO3 shows the best response to 50 ppm NO in air at the temperature range of 150350 8C. It is found that the intrinsic high sensitivity of Ag/WO3 could not be mimicked via passing the same gas mixture over a separate Ag/Al2O3 bed (a good catalyst for NO to NO2) prior to a pure WO3 sensor arranged in series under identical conditions. This suggests that Ag particles supported on WO3 not only provide NO2 but also give some kinds of benecial interfacial effects with the underneath WO3. It is evident from the XRD and the TEM that the Ag doping creates oxygen-decient sites that are believed to be crucial for the enhanced sensitivity obtained over this material. 2. Experimental 2.1. Sensor material preparation Analytical grade WO3 powder (Aldrich, 99.9%) was purchased and used without further purication. Doping of WO3 was achieved by mixing 1 wt.% precursors (soluble salts) dissolved in a minimum amount of deionized water

Fig. 1. The apparatus for the sensing measurements.

(DI) with a dried WO3 powder. The resulting mixture was kept stirring at 80 8C until it was completely dried. All solids were calcined at 600 8C for 2 h in air. The calcined powder, 0.6 g, was cold pressed at 10 tonnes into a pellet (area 1 cm2) using an infra-red press. 2.2. Testing conditions The sensor pellet was then sandwiched between two platinum electrodes (Fig. 1), which were in turn connected to an impedance analyzer (Solartron SI 1260) via two jacketed co-axial cables. The electrical responses of the sensor materials were measured in a owing stream of pure air or in 40 ppm NO in air (60:40 mixture from an air cylinder with another cylinder (BOC special gases) containing ca. 100 ppm NO balanced with air) by the ac impedance analyzer (Fig. 1). The ow rate of the gases was kept at 100 ml/min throughout the measurement using mass ow controllers. The schematic diagram is presented below. 3. Results and discussion 3.1. Pure WO3 Before conducting the screening 1% doped WO3 sensors, pure tungsten trioxide sensor pellet was initially tested for the detection of NO in air in order to optimize acquisition parameters. It was found that the resistance (collected from the impedance at 0.5 Hz) of the material decreased at increasing temperature, thus the observation is consistent with the semiconducting behavior of the material. The resistance of our WO3 increased when the sensor was exposed to NO gas in a similar way to WO3 sensors reported in [5,9,15]. WO3 is an n-type semiconductor, which means that NO forms an anionic adsorbate on the surface of WO3 particles under the present conditions. Although the material responded almost instantaneously to the change of air to NO gas, it required 2030 min for the resistance to settle (response time to reach steady state). This presumably is the minimum time for the gas molecules to diffuse through the compressed WO3 powder with reference to this particular sensor conguration (the gaseous molecules likely

70 Table 1 Temperature effect for NO sensitivity Temperature (8C) 250 300 350

L. Chen, S.C. Tsang / Sensors and Actuators B 89 (2003) 6875 Table 3 The sensitivity of doped materials Sensitivity (30 min) 2.8 10.0 5.0 Entry 1 2 3 4 5 6 Material WO3a WO3b Sensitivity 7.1 10.6 8.0 21.5 12.8 3.9

Sensitivity (5 min) 1.8 7.1 3.0

Typical conditions: 0.6 g WO3 compressed pellet in a flowing stream of 40 ppm NO in air at 100 ml/min.

Pb/WO3 Ag/WO3 Sr/WO3 La/WO3

diffuse into the compressed powder through the edges of the pellets). As a result, all data presented in this paper were then collected at least 30 min after the gas exposure. It is interesting to note from Table 1 that the sensitivity, S (S resistance in NO/resistance in air) peaked at around 300 8C. This is in a good agreement with the optimum temperature of around 300 8C reported in the literature using WO3-based sensors [5,15]. It is accepted that lower sensitivity is obtained at higher temperatures since the thermal energy of the carrier (electrons) can overcome the charge depletion layer in WO3. On the other hand, the poor sensitivity at low temperature is related to the high activation barrier for NO to form adsorbate on the oxide surface. As typical of compressed powder, there are some variations in the absolute response to the same gas mixture over different sensors, but comparisons with different temperature, gas composition, ow, etc. can be reliably made by using the same sensor [16]. As seen from Table 2, the optimum sensitivity for 40 ppm NO in air using our pure WO3 is about S 9 2 collected at 300 8C. This value is slightly higher than but comparable with the results presented by Yamazoe and co-workers [15], who obtained S 4:6 using a milled WO3 powder sensor. It is noted that Penza et al. [5] achieved S 4 using a WO3 thin lm sensor and Tomchenko et al. [17] achieved S 1:5 using a WO3 (Bi2O3) thick lm sensor at 300 8C at atmosphere of 40 ppm NO in air. 3.2. Screening 1% doped WO3 sensors After the rst report of using WO3-based sensor for NO analysis, Yamazoe and co-workers [9] carried out extensive screening of the WO3 sensors doped with each of the 48 elements at 1% level. Elements such as Pb and Re were
Table 2 Variations over different WO3 sensors using same experimental conditions Temperature (8C) 300 300 300 300 300 Sensitivity 11.1 10.0 9.6 9.1 6.8

Typical conditions: 0.6 g WO3-based compressed pellet in a flowing stream of 40 ppm NO in air at 100 ml/min 8C at 300 8C. The powder mixture was filtered, washed, dried and calcined at 600 8C for 2 h. Characteristic FTIR bands confirmed the nature of theWO3. a Commercial WO3. b WO3 prepared by a spray method using 4 g Na2WO4 (Aldrich, 99.8%) pre-dissolved in 100 ml DM water, followed by spraying into a 6 M HCl solution with stirring at 80 8C.

shown to be exceptionally effective in enhancing the sensitivity for NO gas. Penza et al. [5] reported the benecial effect of doping (Pd, Pt, Au). It is noted that these dopants are also known to be effective as NO oxidation catalysts. In light of these works, here we investigated only doping with a few elements to see the promotion effect (Pb, Ag, Sr, La). Particular emphasis was on the effect of Ag since Ag/Al2O3 is a well-accepted catalyst in the catalysis community for NO conversion to NO2 in air. As seen from Table 3, the sensitivity is indeed enormously improved by doping the WO3 with silver giving S 21:5. The order of effectiveness of dopants is Ag @ Sr > Pb > La. 3.3. Ag doped WO3 With regards to the signicant improvement in sensitivity at 300 8C as the WO3 is promoted with silver, it is interesting to investigate whether this doped sensor gives the same temperature response as the pure WO3 (Table 1). Table 4 shows that the sensitivity of this sensor increases with decreasing temperature (250 8C versus 300 and 350 8C). This is interesting and may be important since this new sensor offers lower operation temperature than most of the reported WO3-based sensors. A sensitivity as high as 38.3 can be obtained at 250 8C over this Ag/WO3 sensor as compared to 2.8 without the Ag promotion (13.7 times higher in sensitivity). There was no apparent change in the time ($2030 min) required to reach steady conditions
Table 4 Sensitivity change of Ag doped WO3 at different temperature Temperature (8C) 250 300 350 Sensitivity 38.3 21.5 8.8

Typical conditions: 0.6 g WO3 compressed pellet in a flowing stream of 40 ppm NO in air at 100 ml/min.

Typical conditions: 0.6 g WO3 compressed pellet in a flowing stream of 40 ppm NO in air at 100 ml/min.

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(rate of response) at different temperatures, which suggests that the gas diffusion into the porous powder is not critically dependent on the operation temperature but perhaps on the ow characteristics/porosity within the powder. The sensitivity enhancement with the decrease of optimum temperature for NO detection in air associated with the Ag doping on WO3 has not been reported before this present study. However, Penza et al. [5] reported that noble metals (Pd, Pt, Au) promotions to WO3 give similar observations. Typically, WO3 promoted with Pd shifts the optimum temperature from 300 to 200 8C with a four-fold sensitivity increase (from S 4 to 16 for 40 ppm NO). It is noted that these metal promoters including Ag are also well known to be capable of catalyzing NO to NO2 and NO2 is known to display a much higher molecular sensitivity than NO at the same concentration. Experiments were designed to investigate the role of Ag particles on WO3. A catalyst of 2% Ag/Al2O3 was synthesized according to [18], which is efcient for the conversion of NO to NO2 in air. The material was sandwiched between two silica wool plugs in a 5 cm in length, 4 mm i.d. vertical Pyrex tube housed in a temperature controlled furnace. Thus, this bed of 5 g of 2% Ag/Al2O3 catalyst was inserted between the gas supply and the pure WO3 sensor. This setup allowed the physical separation of the Ag from WO3 with different temperature controls. Fig. 2A shows clearly that when the temperature of the Ag catalyst is increased to 250 8C, the sensitivity of the WO3 sensor kept at 150 8C

increased by three times. Without heating the Ag catalyst or bypassing the gas stream from the Ag catalyst bed no sensitivity enhancement was encountered. Similar observation was obtained when the sensor was kept at 250 8C (Fig. 2B). Although no attempt was carried out to monitor the concentration of NO and NO2 gases because of the low concentration, one of the roles of the Ag is apparent to provide surface for the conversion of NO to NO2 according to the literature [18]. It is worth noting that the sensitivity enhancement (three to four times) for separate beds (Ag/ Al2 O3 WO3 ) is still far less than those observed using the Ag doped WO3 sensor (13.7 times) despite using a long catalyst bed and/or a higher silver content. This indicates that Ag doping onto the WO3 may also provide a unique interface for the interactions with NOx molecules. 3.4. Characterization of the sensor materials Impedance analysis has been increasingly used to characterize the inter-granular particles and interface phenomena. It has been found that the simultaneous measurement of resistance and capacitance of a specimen over a wide range of frequency gives much more information than dc or a single-frequency ac measurement [19,20]. Fig. 3 shows the complex impedance spectra of 1% Ag/WO3 at 350 8C in air and in 40 ppm NO in air mixture, respectively. Both of the impedance values (resistance at variable frequencies) are found to depend on the input frequency, giving typical

Fig. 2. Histogram of NO sensitivity vs. Ag/Al2O3 bed temperature. An increase in temperature of the Ag/Al2O3 bed (production of NO2) results in the increase in NO sensitivity over the WO3 sensor.

Fig. 3. Complex impedance plots of Ag/WO3 (with simulated RC elements) in air and in 40 ppm NO.

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Fig. 4. XRD spectra of WO3 before and after the NO exposure.

semi-circle impedance spectra. Their simulated values using equivalent circuitry with RC elements (C to mimic the surface charge depletion layers on particle and between particles, R granular and inter-granular resistance of the sensor material in the parallel mode) are also presented in Fig. 3. It is interesting to note that when 40 ppm NO in air mixture was passed over the sensor, the impedance of the material was dramatically increased. In general, resistance of WO3-based sensors reported in the literature increases upon exposure to NO in air using dc measurement. It is ascribed to the NO or NO2 (product of NO oxidation over metal doper) adsorption on WO3 surface generating strongly anionic adsorbates which create a large charge depletion layer (increase in capacitance) to restrict the dc current ow [15]. It is noted however, our simulation results indicate that the capacitance and the contact resistance (Ra) of the Ag/ WO3 were only marginally altered to a small extent but the main change was in its granular/inter-granular resistance.

Thus, it is likely that adsorption of these gases may somehow interfere with the main pathway for a current ow through the sensor particles in this particular sensor. Studies of electrical conductivity of WO3 have been extensively carried out in the past. It is generally accepted that the electrical conductivity of WO3 depends critically on its stoichiometry and particularly the presence of oxygen vacancies in WO3. Electrical conductivity increases at higher defect concentration [21,22]. Thus, NOx adsorption on these oxygen-decient W sites blocking the current passage through the material is therefore envisaged. 3.4.1. X-ray diffraction (XRD) XRD analyses of this sensor material were carried out using a Spectrolab Series 1300 CPS 120 X-ray powder diffractometer equipped with a capillary sample holder. The data were collected in DebyeScherrer geometry using a monochromated X-ray beam of nickel ltered Cu Ka radiation (l 0:154 nm). This was obtained from a curved

Fig. 5. XRD spectra of 1% Ag/WO3 before and after the NO exposure.

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quartz monochromatic crystal. The X-ray beam was passed through the capillary, which contained the sample and was then diffracted onto the detector. The detector collected data for all angles in the range 4648, 2y, simultaneously. Fig. 4 gives the diffraction spectra of the WO3 before and after the NO exposure, which shows a triclinic polycrystalline structure matching most of the major peaks collected. From Fig. 4, we can see that the (0 0 1) peak has the highest intensity. The lattice constants of the WO3 were computed to , b 7:512(3) A , c 3:846(2) A . These be a 7:311(2) A values and their relative intensities match very well with , those given by the JCPDS le no. 201323 (a 7:300 A b 7:520 A, c 3:845 A) for triclinic WO3. It was observed that there is no new peak or any peak shift before or after the NO treatment. This suggests that the crystal structures were identical throughout the sensing. It is noted that this observation is in an agreement with the previous report [19] that revealed no bulk structural change in the WO3 after its exposure to NO gas in air. In contrast, it is interesting to nd that there is a very low but clearly observable diffraction hump at the 2y angle between 10 and 188 in the 1% Ag/WO3 sample (Fig. 5). Such low angles do not match with any possible diffraction peaks from silver or possible compounds (in fact, no peaks can be assigned to Ag at this doping level) but merely reect some local orders with relatively large lattice parameters. WO3 is easy to form local non-stochiometric regions, especially oxygen deciency in WO3 can generate crystallographic shear (CS) structures giving a wide range of

Fig. 6. A low-resolution TEM micrograph showing the 1 wt.% doped WO3 material after the NO exposure (magnification 152,000 showing average particle size of 300 nm).

local non-stoichiometry of WO3x [23]. Detailed XRD characterizations of intermediate phases of W5O14, W18O49 and W20O58 derived from the parent WO3 with long-range order structures have been reported [24]. It is therefore speculated that silver doping might have introduced some degree of local order non-stoichiometry structure in the sensor material. However, identication of this phase(s) by XRD in the background of WO3 was proved to be very difcult because of the low concentration and the poor diffraction region. It is noted however, that the well-characterized W5O14 phases

Fig. 7. A high-resolution TEM micrograph and a model showing that the 1 wt.% doped WO3 material after the NO exposure generates a high concentration of local ordered CS structures.

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show a maximum peak value at 2y of 148 [24] which ts coincidentally into the hump region of our XRD. 3.4.2. Transmission electron microscopy (TEM) TEM experiments were carried out using a Phillips CM 20, 200 kV (0.26 nm point resolution) under bright eld conditions. It was shown from Fig. 6 that the average particle size of the 1% Ag/WO3-based material before or after test is about 300 nm in diameter. There was no obvious change in particle size and morphology after this material was quenched from 40 ppm NO in air during the sensing. Fig. 7 shows the high-resolution TEM images of 1% Ag/ WO3 which revealed high concentration of the defective regions (enriched with CS structure at [0 1 0] with respect to [0 0 1] WO3). It is found that the separation of these defective lines is not always identical reecting their lack of a long-range order (non-stoichiometry region of disorder nature). However, some local regions show ordered patterns (the lack of their long-range order and their heterogeneity may explain the poor reection hump obtained in XRD). Typically, as seen in the gure, a region containing ca. inter-planar separation can be visualized. It is inter6.93 A esting to note that these defective lines in WO3 are much easily found in the regions at a close proximity to the Ag particles (at or near to surface). The reason for the creation of CS defects associated with Ag doping is not yet known. So far, there is no evidence that Ag atoms are incorporated into these local ordered defective structures (from XRD, HRTEM). It is however, interesting to point out that silver nanoparticle, upon melting, can absorb a large amount of oxygen from environment (reaching about 10 times its volume, or 0.3% of its weight in oxygen). On cooling to a few degrees above solidication, it abruptly releases much of its oxygen adsorbed in a dramatic phenomenon known as `spit' [25]. There are many recent studies on catalytic oxidation using supported silver nanoparticles based upon these interesting properties. Thus, when the Ag particles are in a close contact with WO3, it is likely that oxygen migration between the silver nanoparticles and the WO3 support is involved. The phenomenon of metaloxide support interaction and the implications on catalysis are currently being explored in copper, silver or gold on oxide supports [26]. 4. Conclusion Initial development of NO sensor to monitor NO gas in air based on WO3 is presented here. As far as we are aware, 1% Ag promotion to WO3 is for the rst time disclosed in the open literature. Thus, the Ag promotion can dramatically enhance sensitivity and decrease the optimum sensor temperature of the compressed WO3 powder sensor. Attempts to understand the benecial effects of Ag have been carried out. It is evident that Ag surface can oxidize NO to NO2 that shows a high molecular response (sensitivity) to WO3-based

materials. Thus, one of the roles of Ag promotion is to provide metal surface for the NO conversion to NO2. It is however, also found that small silver particles residented on WO3 produce a much higher sensitivity than those using two separate beds (Ag/Al2O3 and WO3). This result indicates a structural synergy between silver and WO3 (metalsupport interaction) for optimum sensitivity. Impedance measurement suggests that adsorption of NOx, possibly takes place on the oxygen defective WO3x sites; hence, interrupting this main electrical conductive pathway of the material. Thus, other roles of Ag promotion may include creation of these defective sites on the WO3 at and near the interface between the small Ag particles and the bulk WO3 particles as indicated by the present XRD and the TEM results. A detailed study on the WO3 promoted at different Ag loadings will be very useful in correlating the active sites (created at the AgWO3 interface) with the sensing sensitivity, which is being carried out at the present laboratory. References
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L. Chen, S.C. Tsang / Sensors and Actuators B 89 (2003) 6875 [16] S. Morrison, M. Madou, Chemical Sensing with Solid State Devices, Academic Press, Boston, 1989. [17] A.A. Tomchenko, V.V. Khatko, I.L. Emelianov, WO3 thick-film gas sensors, Sens. Actuators, B, Chem. 46 (1998) 814. [18] N. Bogdanchilova, FC. Meunier, M. Avalos-Borja, J.P. Breen, A. Pestryakov, On the nature of the silver phases of Ag/Al2O3 catalysts for reactions involving nitric oxide, Appl. Catal., B, Environ. 36 (4) (2002) 287297. [19] T. Ishihara, H. Fujita, Y. Takita, Effects of Pt addition for SrSnO3WO3 capacitive type sensor on NO detection at high temperature, Sens. Actuators, B, Chem. 52 (1998) 100106. [20] W.B. Johnson, W.L. Worrell, in: J.R. Macdonald (Ed.), Impedance Spectroscopy, Wiley, New York, 1987, 238 pp. [21] S.C. Moulzolf, L.J. Legore, R.J. Lad, Heteroepitaxial growth of tungsten oxide films on sapphire for chemical gas sensors, Thin Solid Films 400 (1/2) (2001) 5663. [22] H. Hosono, M. Miyakawa, H. Kawazoe, K. Shimizu, Formation of electronic conducting amorphous WO3 thin films by ion implantation, J. Non-Cryst. Solids 241 (2/3) (1998) 190. [23] J.S. Anderson, R.J.D. Tilley, in: M.W. Roberts, J.M. Thomas (Eds.), Surface and Defect Properties of Solid, vol. 3, The Chemical Society, London, 1974. [24] G.L.F. Rey, A. Rothschild, J. Sloan, R. Rosentsveig, R. PopovitzBiro, R. Tenne, Investigations of nonstoichiometric tungsten oxide nanoparticles, J. Solid State Chem. 162 (2001) 300314.

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Biographies
Ling Chen received a BSc degree in chemistry at Guangxi Teachers College, China in 1995. She is currently completing her postgraduate course under the supervision of Dr. Tsang in the Catalysis Research Centre at Reading. Her research was concerned with solid state sensors and catalysis. Shik Chi Tsang obtained a first class degree in chemistry from Birbeck College, London University in 1987. He received his PhD from Reading University in 1991. After spending 4 years as a departmental research fellow in the Inorganic Chemistry Laboratory at Oxford University, he returned to Reading in 1995. Dr. Tsang currently holds a readership at Reading University and a Royal Society University Fellowship for catalysis research. His main research interests are catalysis, mesoporous materials, supercritical CO2 and sensors.