Sensors and Actuators B 134 (2008) 133139

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Sensors and Actuators B: Chemical

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

Au-doped WO3 -based sensor for NO2 detection at low operating temperature
Huijuan Xia, Yan Wang, Fanhong Kong, Shurong Wang, Baolin Zhu, Xianzhi Guo, Jun Zhang, Yanmei Wang, Shihua Wu
Department of Chemistry, Nankai University, Tanjin 300071, China

a r t i c l e

i n f o

a b s t r a c t
Pure and Au-doped WO3 powders for NO2 gas detection were prepared by a colloidal chemical method, and characterized via X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The NO2 sensing properties of the sensors based on pure and Au-doped WO3 powders were investigated by HW-30A gas sensing measurement. The results showed that the gas sensing properties of the doped WO3 sensors were superior to those of the undoped one. Especially, the 1.0 wt% Au-doped WO3 sensor possessed larger response, better selectivity, faster response/recovery and better longer term stability to NO2 than the others at relatively low operating temperature (150 C). 2008 Elsevier B.V. All rights reserved.

Article history: Received 8 January 2008 Received in revised form 16 April 2008 Accepted 17 April 2008 Available online 22 April 2008 Keywords: Au-doped WO3 Gas sensor NO2 Structural characterization Low temperature

1. Introduction In recent years, air pollution has been becoming more and more serious with the development of industry and the increase of people life. Especially, nitrogen oxide NOx (NO2 or NO) is toxic itself and, furthermore, is a main source of acid rain and photochemical smog [1]. In order to detect such hazardous NOx gas, there have been lots of efforts in developing a variety of NOx gas sensors such as electrochemical sensors [2], SAW sensors [3], and polymer sensors [4]. As we all know, NO gas is very easily oxidized into NO2 gas in air. As a result, it is an urgent assignment to develop a small NO2 gas sensor with high sensitivity and excellent selectivity to NO2 gas of low concentrations. Recently, many semiconductive oxides have been widely investigated as sensing materials for NO2 detection by either thin or thick lm fabrication technique [57]. Among the metallic oxides, tungsten trioxide (WO3 ), which is a wide band-gap n-type semiconductor, has been considered as a promising sensing material of solid-state semiconductor gas sensors for NO2 monitoring because of its excellent sensitivity and selectivity. Many attempts have been made to enhance the gas sensitivity of semiconductor gas sensors, one of which involved the doping of impurities in the lms. Penza

et al. [7,8] have shown that a high sensitivity was achieved when noble metals such as Pt, Au and Pd were deposited as activator layers on WO3 lms. However, there are few reports on the study of NO2 gas sensing properties of Au-doped WO3 sensors, especially at relatively low operating temperature. In this paper, thick lm sensors based on pure and Au-doped WO3 powders were prepared by a simple method. The structural properties of the prepared Au-doped WO3 were analyzed by XRD, TEM and XPS. The gas sensing properties of pure and Au-doped WO3 sensors were investigated in detail by an HW-30A gas sensing measurement system. The sensing mechanism of the Au-doped WO3 sensors to NO2 was also discussed.

2. Experimental 2.1. Preparation of sensor materials Au-doped WO3 nanocrystalline powders were synthesized by a colloidal chemical method based on sodium tungstate dihydrate (Na2 WO4 2H2 O, analytical grade). Na2 WO4 2H2 O was dissolved into a certain amount of deionized water. Then a certain concentration of aqueous solution of HCl was dropwise added to the sodium tungstate solution under stirring at room temperature till no white precipitate was further formed. Then an aqueous solution of HAuCl4 4H2 O (0.25, 0.5, 1.0 and 1.5 wt%) was immediately added to the above solution. The pH of the solution was adjusted with an

Corresponding author. Tel.: +86 22 2350 5896; fax: +86 22 2350 2458. E-mail address: wushh@nankai.edu.cn (S. Wu). 0925-4005/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.snb.2008.04.018

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aqueous solution of HCl in the reaction process. Then the solution was aged for 24 h, after which a quantity of cetyltrimethyl ammonium bromide (CTAB) solution (15 ml, 0.15 mol/l) was immediately added to the solution and abundant white occulent precipitate was formed. The white occulent precipitate was treated by ultrasonication for 40 min. Then the precipitate was ltrated and centrifuged with deionized water to remove Cl , Br and any other possible remnants, dried at 80 C and calcined at 600 C for 2 h. A series of 0.25, 0.5, 1.0 and 1.5 wt% Au-doped WO3 powders were obtained. 2.2. Characterization of materials The X-ray diffraction (XRD) analyses of the as-prepared powders were carried out on a D/MAX-RAX diffractometer operating scanning at 40 kV and 100 mA, using Cu K radiation ( = 1.5418 A, range 2 : 1080 ). Diffraction peaks of the crystalline phase were compared with those of the standard compounds reported in the JCPDS Data Files. The mean particle sizes were estimated by using DebyScherrer equation. TEM experiments were carried out using a Phillips-T20ST electron microscope, operating at 200 kV. The electronic structure of the surface of WO3 was performed by a method of X-ray photoelectron spectroscopy (XPS) with a Kratos Sxis Ultra DLD spectrometer employing a monochromated Al K Xray source (h = 1.486.6 eV), hybrid (magnetic/electrostatic) optics and a multi-channel plate and delay line detector (DLD). All XPS spectra were recorded using an aperture slot of 300 m 700 m; survey spectra were recorded with a pass energy of 150 eV, and high-resolution spectra with a pass energy of 40 eV. All binding energies were referred to the adventitious C 1s line at 284.6 eV. 2.3. Gas sensing properties test The gas sensing properties were detected by the gas sensing measurement system of HW-30A (a computer-controlled static gas sensing characterization system) from Henan Hanwei Electronical Technology Co. Ltd. Gas sensors were screen printed on an alumina substrate (4 mm in length). Electrical contacts were made with two platinum wires attached to the electrodes. A small NiCr alloy coil was placed through the tube to control the operating temperature from 100 to 500 C. The schematic diagram of a typical gas sensor is shown in Fig. 1(a). The Au-doped WO3 powders were mixed with deionized water to form pastes. Then the pastes were coated onto the alumina tubes. Then the gas sensors were sintered at 300 C for 10 days in air in order to improve their stability and repeatability. These gas sensor devices were placed in a glass chamber (15 l). Gas response of the side-heated gas sensors was measured under a steady-state condition. The measuring electric circuit is shown in Fig. 1(b). The operating voltage (Vh ) was supplied to either of the coils for heating the sensors and the circuit voltage (Vc ) was supplied across. A load resistor RL was connected in series with the sensor element. By monitoring Vout , the resistance of the sensor in air or a test gas can be measured. In the gas response measurement, a given amount of sample gases were injected into a closed chamber by a microinjector and mixed by a fan for several seconds (liquids were rstly evaporated and then mixed by a fan). After each measurement, the sensor was exposed to the atmospheric air by opening the chamber. The gas response was dened as the ratio (S = Rg /Ra ) of the electrical resistance in a target gas (Rg ) to that in air (Ra ). The target gas was produced by chemical reaction (3NaNO2 (s) + 3HCl(aq) = 2NO(g) + H2 O(l) + 3NaCl(l) + HNO3 (l); 2NO(g) + O2 (g) = 2NO2 (g)). Operating temperature of the sensor devices was varied between 100 and 300 C. The operating temperature was controlled through adjusting the heating power.

Fig. 1. (a) Schematic diagram of the Au-doped WO3 thick lm sensor: (1) Pt wire; (2) NiCr-heated wire; (3) Al2 O3 tube; (4) Au/WO3 thick lm; (5) Au electrode and (b) graphic of testing principle.

3. Results and discussion 3.1. X-ray diffraction (XRD) The diffraction spectra of pure WO3 and Au-doped WO3 with different Au contents are presented in Fig. 2. These diffraction peaks and their relative intensities match very well with those given by the JCPDS le no. 20-1324 for orthorhombic WO3 . The sharp peaks suggest that the crystal of WO3 is perfect. When the dopant content is 0.25 wt%, there are no Au peaks in the pattern, which may be due to the low content of Au. But

Fig. 2. XRD patterns of pure and Au-doped WO3 samples.

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with an increase of Au concent, the Au peaks can be observed obviously at the angle of around 38.1 and 64.5 of 2 . The mean size of Au-doped WO3 particles was close to that of pure WO3 , around 28 nm, calculated by the DebyScherrer equation, which indicated that the size of WO3 particle was not affected by Au doping.

3.3. X-ray photoelectron spectroscopy (XPS) The XPS were performed in order to illuminate the surface composition and the chemical state of the elements existed in the Au-doped WO3 sensor calcined in air at 600 C for 2 h. Fig. 4 shows W 4f, O 1s and Au 4f of 1.0 wt% Au-doped WO3 thick lm. In Fig. 4a, the binding energy of W 4f7/2 and W 4f5/2 were determined to be 35.7 and 37.9 eV, respectively, which well agree with literature values for W6+ [9].

3.2. Transmission electron microscopy (TEM) The TEM micrograph pattern of 1.0 wt% Au-doped WO3 is shown in Fig. 3. It can be seen that the particles are anomalistic and the mean size of Au-doped WO3 nanoparticles is larger than that calculated from XRD data, which can be attributed to the particles conglomeration because of the high-temperature treatment. Its corresponding selected-area electron diffraction (SAED) pattern (Fig. 3b) shows that the Au-doped WO3 powder was single crystalline in structure.

Fig. 3. (a) A TEM micrograph and (b) the corresponding SAED pattern of 1.0 wt% Au-doped WO3 .

Fig. 4. XPS of 1.0 wt% Au-doped WO3 : (a) W 4f; (b) O 1s; (c) Au 4f.

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O 1s XPS peaks are shown in Fig. 4b. An intense peak is observed at 530.5 eV, and a second component is at 531.5 eV. The intense peak can be assigned to the presence of O2 ions. And the second peak can be described as the existence of O ions. The two opinions can be supported by the previous paper [9]. The analyses on transition metal oxides have shown the following peaks: (i) in the 529.5530.5 eV range, O 1s peaks characteristic of the O2 ions of the crystalline network; and (ii) in the 531532 eV range, O 1s lateral structures of variable intensity. Although a precise assignment is not possible it seems reasonable to consider ionizations of weakly adsorbed species and also of oxygen ions with particular coordination more specically integrated in the subsurface (bulk structure near the surface). This suggests the existence in the subsurface of oxygen ions which bear lower electron density than the O2 ions; formally these oxide ions could be described as O species. They can be associated with sites where the coordination number of oxygen ions is smaller than in a regular site, with a higher covalence of the M O bonds. A reasonable hypothesis is to consider the existence, in variable proportions for the different transition metal oxides of defects in the subsurface. As shown in Fig. 4c, the gold chemical state has two separate peaks located at 84.0 and 87.7 eV which are due to Au 4f7/2 and Au 4f5/2 transitions, respectively. These values are in good agreement with the previous report for Au [10]. The peaks located at 84.0 and 87.7 eV were assigned to the spinorbit splitting component of Au (4 f7/2 ) level in metallic Au [10,11]. 3.4. NO2 sensing properties The gas sensing properties of pure and Au-doped WO3 were tested. It is well known that the gas sensitivity as well as the rate of gas response to NO2 is much dependent on the operating temperatures and the amounts of additives. Such tendencies are illustrated in Fig. 5. It can be seen that the response of these sensors to 10 ppm NO2 varies with not only the operating temperature but also the concentration of Au. In the range of the operating temperatures studied, from 100 to 300 C, the response values increased sharply at rst and decreased rapidly for all the sensors except the 1.5 wt% Au-doped WO3 sensor with an increase in operating temperature, which is similar to the behavior of WO3 nanowire sensors to NO2 [12]. Each curve presents a maximum at an optimal operating temperature. The pure and 1.5 wt% Au-doped WO3 sensors have the maximum gas response at 200 C, while the 0.25, 0.5 and 1.0 wt% Au-doped WO3 sensors have the maximum gas

response at 150 C. The operating temperature of Au-doped WO3 sensors is lower, compared with previous reports about NO2 sensors [1315]. Furthermore, the doped sensors exhibit much higher response than the undoped one. Especially, the 1.0 wt% Au-doped WO3 sensor presents the largest response to NO2 at 150 C, which leads us to believe that the Au-doped WO3 sensor is superior to others in monitoring NO2 gas. As has been reported, WO3 is a typical n-type semiconductor, and its gas-sensing mechanism belongs to the surface-controlled type, and the change of resistance is dependent on the species and the amount of chemisorbed oxygen on the surface. In the case of n-type semiconductor oxides [16,17], the intrinsic conductance increases with increasing the temperature, whereas the adsorbed oxygen molecules transform into oxygen ions (O , O2 and O2 ) by capturing free electrons from the oxide, which causes a decrease in conductance of the oxide with increasing the temperature. The process can be expressed in the following reactions [18]: O2 (gas) O2 (ads) O2 (ads) + e O2 (ads) O2 (ads) + e 2O (ads) O (ads) + e O
2

(1) (2) (3) (4)

(ads)

Adsorption of NO2 on WO3 nanoparticles results in a decrease in conductivity, which may be explained by the following reactions [19]: NO2 (g) + e NO2 (ads) NO2 (g) + e NO (g) + O (ads)

(5) (6)

Both of these reactions require electrons from the conduction band of WO3 , which then leads to a decrease in conductivity. When NO2 gas was introduced into the reaction chamber, it would be subjected to two stages: the chemisorption and the removal of chemisorbed oxygen. They can be described as in the literature [20] ((Z)s and (ZO)s present the chemisorption sites and the surface species, respectively). NO2 (g) + (Z)s (ZO)s + NO (g) 2(ZO)s 2 (Z)s + O2 (g) (7) (8)

Fig. 5. Responses of pure and Au-doped WO3 sensors to 10 ppm NO2 .

Reaction (8) is limited in the decomposition of NO2 on the oxides, which is testied by the long recovery time after treatment with NO2 and it is dependent on the operating temperature. Noble metals (Pt, Pd, Au and Ag) are the most common metal catalysts that are used to improve the gas sensing properties of semiconductor gas sensors. Catalytic reactions on the semiconductor surfaces form the receptor function of the semiconductor gas sensors and catalytically active metal surfaces are used as additives to strengthen these reactions in order to increase the selectivity and sensitivity of the sensors, and also to reduce the response and recovery times. Correlative works have been widely studied [7,2123]. At present, as for the effects of the noble metals on the improvement of sensor response, two types of mechanisms are discussed commonly to explain the role of metallic dopants. The two mechanisms are the chemical and electronic sensitization. The observed increase in sensor response with Au is predominantly due to the change which is termed as the electronic sensitization [24]. In the electronic mechanism, the reaction with target gas molecules takes place on the surface of the additives and not in the substrates. These additives change their charge state, which results in a variation of the surface barrier height and as a result leads to a conductance change on the metallic oxide. Besides, the Au additive as an active catalyst creates more active sites that are believed to be crucial for the enhanced sensitivity obtained over this material.

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Fig. 6. Responses of pure and Au-doped WO3 sensors to different concentration NO2 at 150 C.

Fig. 8. Comparison of responses of pure and 1.0 wt% Au-doped WO3 sensors to various gases at their optimal operating temperatures (150 C for NO2 , 100 C for H2 S, 200 C for C2 H5 OH, 250 C for NH3 and acetone, respectively).

An interesting phenomenon is noticed in Fig. 5; the response of 1.5 wt% Au-doped WO3 sensor is the lowest compared with that of the others. From the XRD patterns, it can be seen that the size of Au particles of the 1.5 wt% Au-doped WO3 is larger than those of the other samples. The result indicates that the large Au particle is adverse to the gas sensitivity of sensor. The fact that Au particles with diameters of about 5 nm or less have unique catalytic properties, which has been widely reported in previous papers [2528], in which these small Au particles were calcined below 400 C or sputtered on the base semiconductors. However, in our study, the samples were calcined at 600 C, the size of Au particles calculated by the DebyScherrer equation from the data of XRD patterns are around 20 nm, and it can be observed from the TEM micrograph that the particles are agglomerated because of the high-temperature calcination. The particle size of gold cannot be gotten from the TEM because of the poor contrast between gold and WO3 . Though the Au particles are relatively large, the gas response of Au-doped WO3 sensors is higher than that of the undoped one. The gas response may be further improved if the Au particles are smaller; the further studies about it are being carried out. The responses of pure and Au-doped WO3 sensors to different concentrations of NO2 (520 ppm) were measured at the same operating temperature (150 C). The results are shown in Fig. 6. It can be seen that the gas response of the doped sensors is higher

than that of the undoped one. And the response values of the sensors increased with an increase of the NO2 gas concentration in the range of 520 ppm except the 1.5 wt% Au-doped WO3 sensor. Furthermore, the increasing rate of the response of the sensor to above 10 ppm is smaller than that in the range of 510 ppm, which suggests that the sensors could meet the application demand to monitor NO2 gas, especially of low concentrations. Selectivity is an important factor in gas sensing, and the sensor has to present rather high selectivity for its application. As we all know, a WO3 sensor also responds to other gases such as H2 S, NH3 and C2 H5 OH. Therefore, we investigated the responses of the 1.0 wt% Au-doped WO3 sensor to other ve gases at different operating temperatures from 100 to 300 C. From Fig. 7 it can be observed that the sensor exhibits the largest response to NO2 , among all the tested gases. Furthermore, the optimal operating temperature is 250 C to NH3 and acetone and 200 C to C2 H5 OH, both being higher than that to NO2 . The selectivity to NO2 is higher when the operating temperature is 150 C. As a result, it is possible for Au-doped WO3 to monitor NO2 at lower operating temperatures. The gas responses of pure and 1.0 wt% Au-doped WO3 sensors to various gases at their optimal operating temperature are compared and the results are shown in Fig. 8. It can be seen that the responses

Fig. 7. Responses of 1.0 wt% Au-doped WO3 to various gases at different operating temperatures.

Fig. 9. Responserecovery characteristics of a 1.0 wt% Au-doped WO3 sensor to NO2 of different concentrations at 150 C.

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The long-term stability is another important factor for gas sensors. The stability of the 1.0 wt% Au-doped WO3 sensor was measured at a level of 10 ppm NO2 for 3 months. The results are shown in Fig. 11. It can be observed that the sensor still showed excellent response performance to NO2 gas even after 3 months, which indicated that the sensors based on Au-doped WO3 have the enough stability to detect NO2 gas for a relatively long period. 4. Conclusions Pure and Au-doped WO3 nanoparticles were prepared by a colloidal chemical method. The crystalline phase of WO3 nanoparticles calcined in air at 600 C for 2 h was orthorhombic. XPS analyses showed that W6+ and Au0 existed on the surface of the as-prepared materials. The sensors based on these materials showed high gas response, excellent selectivity and long-term stability to NO2 gas. The response of the sensors were strongly dependent on the operating temperature and the amounts of additives. The optimum performance was obtained at 150 C for the WO3 sensor doped with 1.0 wt% Au. The doped sensors also presented rapid response characteristics. However, the gas sensors need to be further investigated to shorten the recovery times. In summary, the sensor based on WO3 with a proper Au loading is suitable for detecting NO2 at relatively low operating temperature. Acknowledgements This work was supported by the National Nature Science Foundation of China (No. 20771061) and 973 program (2005CB623607). References
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Fig. 10. Responserecovery characteristics of a 1.0 wt% Au-doped WO3 sensor to 10 ppm NO2 at different operating temperatures.

of the two sensors to NO2 are much higher than those to other ve gases. Furthermore, the responses of 1.0 wt% Au-doped WO3 sensor to all of these gases are higher than those of the undoped one, especially to NO2 . As a result, the Au-doped WO3 sensor is a very promising semiconductor to monitor NO2 at relatively low temperature; both sensitivity and selectivity are taken into consideration. According to the measurement methods introduced by the sensor measurement section, the responserecovery characteristics of the sensors are shown in Figs. 9 and 10. From the two gures, the voltage of sensor decreased rapidly, when NO2 was introduced into the measurement chamber. Upon exposing the sensor to air by opening the chamber, the voltage of the sensor increased to the initial value gradually. From Fig. 9, we can see that the fast response characteristics were almost unchanged at all the concentrations of NO2 , but the recovery times were longer and longer with an increase of NO2 concentration. From Fig. 10, it is clear that the initial voltage values were higher and higher with an increase of operating temperature. The response time decreased with an increase of operating temperature. On the other hand, the recovery times were long but became shorter when the operating temperature was increased.

Fig. 11. The long-term response values of a 1.0-wt% Au-doped WO3 sensor to 10 ppm NO2 at 150 C.

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Yan Wang received her MS degree in chemistry from Nankai University in 2006. She is now studying in Shihua Wus group for her PhD degree in Department of Chemistry, Nankai University in China. Her research focuses on the synthesis, characterization and gas-sensing properties of metal oxide nanomaterials. Fanhong Kong is student in Department of Chemistry, Nankai University now. Her interest is devoted to the preparation and application of gas-sensitive materials. Shurong Wang is working at Nankai University. She received her PhD degree in chemistry from Nankai University in 2007. Her research covers nanomaterials, catalysis and gas sensors. Baolin Zhu received her PhD degree in chemistry from Nankai University in 2006. Now, she is working at Nankai University. Her research is focused on the preparation of nanomaterials. Xianzhi Guo associate professor. Her research is focused on the eld of macromolecule chemistry and physics. Jun Zhang received his bachelor degree in chemistry from Qufu normal University in 2006. He is currently a postgraduate in the Department of Chemistry in Nankai University. His research is focused on the development and application of gas-sensitive materials. Yanmei Wang is currently a postgraduate in the College of Chemistry in Nankai University. Her research is focused on the development and application of gas-sensitive materials. Shihua Wu received his degree in chemistry from Nankai University in 1970. At present he is professor of chemistry at the Department of Nankai University, where he has been working for many years in the eld of preparation, characterization and catalytic and gas-sensing properties of metal oxides nanomaterials.

Biographies
Huijuan Xia is studying in Shihua Wus group for her MS degree in Department of Chemistry, Nankai University in China. Her research focuses on the synthesis and gas-sensing properties of metal oxide nanomaterials.