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Sensors and Actuators B 132 (2008) 334339

Studies on alcohol sensing mechanism of ZnO based gas sensors

Jiaqiang Xu a,c, , Jianjun Han b , Yuan Zhang a , Yuan Sun c , Bing Xie c
Department of Chemistry, College of Science, Shanghai University, Shanghai 200444, PR China b Department of Pharmacy, Tongren Technology College, Tongren, Guizhou 554300, PR China c College of Materials and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, PR China Received 16 July 2007; received in revised form 22 January 2008; accepted 23 January 2008 Available online 14 February 2008
a

Abstract Nanosized ZnO powder was synthesized by using a chemical precipitation method, and loaded with different dopants through impregnation. The as-prepared ZnO powder was characterized by XRD and TEM. The characterization results show that the as-prepared sample is wurtzite polycrystalline ZnO, the mean grain size is 3040 nm, and there are three types of adsorbed oxygen (O2 , O2 2 , and O2 ) on the surface of the sample. The as-prepared ZnO powder shows excellent gas responses to alcohol and acetaldehyde, but no response to ethene. The sensing mechanism of ZnO was further studied with the help of gas chromatography (GC) associated with a xed-bed reactor. The studies show that acetaldehyde, carbon dioxide and water are the only oxidation products of C2 H5 OH over ZnO. The gas response to C2 H5 OH is strongly dependent on the conversion ratio of C2 H5 OH to acetaldehyde. In addition, among all the dopants tested, Ru is the optimal dopant which can increase the response to C2 H5 OH, but cannot increase the conversion ratio of C2 H5 OH to acetaldehyde. Thus we suggest that the gas sensing mechanism of ZnO to C2 H5 OH is the mode controlled by chemisorption of negatively charged oxygen, and the sensitizing role of Ru in the ZnO sensor belongs to the electronic sensitization mechanism. 2008 Elsevier B.V. All rights reserved.
Keywords: Zinc oxide; Gas sensing mechanism; Gas sensor; Alcohol; Catalytic oxidation

1. Introduction Zinc oxide (ZnO) is a wide band gap (3.37 eV) semiconductor with a large exciton binding energy (60 eV) [1], and an exceptionally important material for applications in solar cells, solid-state optoelectronic devices, and so on [2,3]. As one of the earliest discovered and most widely applied gas sensing materials, the research of ZnO gas sensing properties has now become highlighted because of its high mobility of conduction electrons, good chemical and thermal stability, low-cost, etc. [4,5]. Semiconductor gas sensors are widely used for the detection of inammable gases (CH4 , C3 H8 , H2 , etc.) and toxic gases (CO, H2 S, etc.) in indoor as well as outdoor spaces [6], because they have many advantages, such as high response, low-cost, convenient for schlepping [79] and so on. However, up to now,

Corresponding author at: Department of Chemistry, College of Science, Shanghai University, Shanghai 200444, PR China. Tel.: +86 21 66132406; fax: +86 21 66134725. E-mail address: xujiaqiang@shu.edu.cn (J. Xu).

it is very difcult to explain the gas sensing mechanism of the material itself and the role of dopants used in sensors. The gas sensing properties of metal oxides depend naturally on their catalytic or surface chemical properties as well as their physical or morphological properties [10], such as grain size [11], porosity and thickness [12]. In this way, catalytic properties and semi-conducting properties of sensing materials are combined together to build up the gas sensing function [13]. For example, it is reported that ethanol gas over the surface of tin oxide (SnO2 ) can undergo two forms of decomposition [14], i.e., dehydration and dehydrogenation. The product in the former decomposition process is ethene, while acetaldehyde will be obtained in the latter decomposition process. Tamaki and coworkers [15] conrmed that acetaldehyde is the matter of lifting alcohol sensitivity of tin oxide, but Tsang et al. [16] got the opposite conclusion. However, there is still no detailed report on alcohol sensing mechanism of ZnO-based gas sensors. In this paper, we try to explain alcohol-sensing mechanism of ZnO and Ru-doped ZnO, on the basis of analyzing catalytic oxidation products of C2 H5 OH and the relation between conversion ratio and gas response of C2 H5 OH.

0925-4005/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.snb.2008.01.062

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2. Experimental 2.1. Synthesis 2.1.1. Chemical precipitation method for ZnO nanoparticles Before the precipitation reaction, zinc acetate [Zn(CH3 COO)2 ] (AR grade, Beijing chemical reagent Co.) was dissolved into deionized water, and ammonia (Kaihua corporation, Kaifeng) was diluted with deionized water to a concentration 1.5 mol/L. Then the ammonia diluted was dropped into the Zn(CH3 COO)2 solution under continuous stirring, and the pH value of the nal solution was controlled as 8. The precipitate was aged for 1 h, and then ltered, washed with deionized water, followed by drying at 378 K and sintering at 873 K for 1 h, and nally cooled down naturally. 2.1.2. Procedure for doped ZnO with different dopants Dopants (Ru, Mg, Pd, Y, La, V, and Na)-doped ZnO were obtained through an impregnation method. The compound sources of dopants were magnesium oxalate, ruthenium trichloride, iridium trichloride, palladium chloride, lanthanum chloride, ammonium metavanadate and sodium carbonate, respectively. The amount of dopants was about 0.5 wt.% based on ZnO for gas sensing materials or catalyst coatings. The detailed procedure was referred to the way described in the literature [17]. 2.2. Characterization of the samples The powder samples were characterized by X-ray powder diffraction (XRD) on a D8 Advance Bruker X-ray diffractometer with monochromatized Cu K ( = 1.5418 A) incident radiation. XRD patterns were recorded from 20 to 70 (2) with a scanning step of 0.03 s1 . The morphology (particle size) of the sample was observed on a transmission electron microscope (TEM) (JEM-100CX, Japan). 2.3. Fabrication of gas sensor For the fabrication of gas sensors, the nal powders were ground in an agate mortar with a sort of adhesive (the terpinol saturation solution of methyl cellulose) to form a paste. The paste was coated onto an alumina ceramic tube attached with a pair of Pt electrodes for resistance measurement, followed by drying under IR light, sintering at 873 K for 1 h in a vertical furnace to provide good mechanical strength. A small NiCr alloy coil was placed through the tube as a heater, which provided the working temperature of the gas sensor. Fig. 1 shows a schematic drawing of an as-fabricated sensor. These sensors can be used to measure immediately without any further annealing and aging. 2.4. Gas response test of the samples A stationary state gas distribution method was used for the test of gas sensing properties (air humidity: 47%). In the measuring electric circuit for gas sensors (shown in Fig. 2), a load

Fig. 1. Sketch of the gas sensor structure.

resistor (load resistor value: 470 K ) was connected in series with a gas sensor. The circuit voltage was 10 V, and output voltage (Vout ) was the terminal voltage of the load resistor. The working temperature of a sensor was adjusted through varying the heating voltage (Vh ). The resistance of a sensor in air or a test gas was measured by monitoring by Vout . The test was operated in a measuring system of HW-30A (Hanwei Electronics Co. Ltd., PR China). Detecting gases, such as C2 H5 OH, were injected into a test chamber and mixed with air. Applying this measuring system, the steady-state value of resistance can be reached and the sensor response is repeatable over time. The gas response of the sensor in this paper was dened as S = Ra /Rg , where Ra and Rg were the resistance in air and in a test gas, respectively. The response or recovery time was expected as the time taken for the sensor output to reach 90% of its saturation after applying or switching off the gas in a step function [18]. 2.5. Catalytic oxidation property testing Catalytic oxidation experiments assisted with GC product analysis were conducted in a continuous-ow micro-reactor at precisely controlled temperatures. The same powder sample as the sensor elements were pressed, ground and sieved in 4060 mesh before being packed as a catalyst bed (1.0 g) in the reactor. A gaseous mixture of alcohol (or acetaldehyde) vapor and air was fed to the reactor. The efuent gases out from the reactor were analyzed by gas chromatography in a temperature range of 473623 K. The conversion ratio of alcohol gas was derived from the decrease of alcohol concentration after the reaction.

Fig. 2. The measuring electric circuit of gas sensor.

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3. Results and discussion 3.1. Crystal structure of the powder Crystal structure of the powder was characterized by X-ray diffraction. Fig. 3A shows a representative XRD pattern of the powder. All the diffraction peaks could be indexed to wurtzite ZnO (JCPDS card No.36-1451, a = 0.3249 nm, c = 0.5206 nm) with high crystallinity. The XRD pattern of 0.5 wt.% Rudoped ZnO is also shown in Fig. 3B. It shows that the powder consisted of wurtzite ZnO and RuO2 (JCPDS card No.43-1027). The mean grain size of the powder was about 3040 nm as calculated by the Scherrer formula. This result agrees with the observation of TEM (Fig. 4). 3.2. Gas sensing properties of ZnO-based sensor In order to research the gas sensing properties of ZnO-based sensor, we tested the responses to different gases in a temperature range of 463656 K. There were six gases selected for detecting: C2 H5 OH (100 ppm), CH3 CHO (100 ppm), H2 (500 ppm), CO (500 ppm), i-C4 H10 (500 ppm) and C2 H4 (500 ppm). The relations between working temperature and response toward different gases are shown in Fig. 5. As shown in this gure, obviously, the response of the ZnO sensor is greater toward

Fig. 4. A TEM image of the as-obtained ZnO by a precipitation method.

alcohol and acetaldehyde than to the other gases. What is more, the response increased with an increase in working temperature. That is to say, the greater the response to acetaldehyde is, the higher the response toward alcohol is, whereas when the response to acetaldehyde decreases, the response to alcohol also falls. It drops a hint that there is a potential relationship between the response to alcohol and acetaldehyde. In addition, the response is higher toward acetaldehyde than toward alcohol at every temperature tested, indicating that the existence of acetaldehyde will favor the increase of response to alcohol. In addition, the response to other gases tested, such as C2 H4 , H2 , CO, i-C4 H10 , etc., are poor under the same testing condition. Fig. 6 shows the responses of doped ZnO samples to 50 ppm C2 H5 OH at a xed temperature (623 K) as a function of dopants. Compared with the un-doped ZnO sensor, the alcohol response of Ru-doped ZnO sensor increased remarkably, while those of

Fig. 3. XRD patterns of ZnO samples: (A) pure and (B) Ru-doped ZnO nanoparticles.

Fig. 5. Relation between working temperature and responses to different gases.

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Fig. 6. Responses of doped ZnO samples to 50 ppm C2 H5 OH at a xed temperature (623 K).

Mg, Y, Pd, V or La-doped ZnO changed indistinctively. Thus, we selected Ru as the typical catalyst to improve the gas response of the ZnO sensor. Applying Ru to enhance the response of ZnO powder has been reported in our previous work [19]; however, the role of Ru in enhancing the response has not been discussed. 3.3. Catalytic oxidation of alcohol over ZnO powder To better understand the sensing mechanism of the ZnO sensor and the promoting effect of Ru, the catalytic oxidation of alcohol over ZnO powder was studied in a xed-bed reactor, and the reaction products were analyzed by gas chromatography. Based on the equipment, response gases (C2 H5 OH, CH3 CHO), the intermediate products (CH3 CHO, C2 H4 or H2 ), and the reaction products (CO2 and H2 O) were identied by a thermal conductivity detector. Fig. 7 shows a typical gas chromatography pattern of the C2 H5 OH oxidation over ZnO at 573 K. It can be seen that there are four products detected by GC, which are intermediate oxidized products (CH3 CHO and H2 ) and thorough oxidized products (CO2 and H2 O), respectively. The similar results were also obtained over Ru-doped ZnO (the pattern is not shown here). As shown in Fig. 8, the conversion

Fig. 8. Relationship between the alcohol response and the conversion ratio of ZnO at different temperatures.

ratio of C2 H5 OH increased with an increase in operating temperature; the changing trends were the same as those in gas response as a function of operating temperature. That is to say, the response of the ZnO sensor toward C2 H5 OH is dependent on the conversion of C2 H5 OH. In accordance with this result, the response to CH3 CHO is greater than that to C2 H5 OH in Fig. 3. Based on the experimental results mentioned above, we could suggest that the formation of acetaldehyde, which is one of the intermediate products, increases the response to alcohol. Fig. 9 shows the relationship between the alcohol response and the conversion ratio of C2 H5 OH when we replaced un-doped ZnO by Ru-doped ZnO as a catalyst. Compared with un-doped ZnO, the conversion ratio of alcohol on Ru-doped ZnO has nearly no variety, which shows that the increase in C2 H5 OH response is not attributed to the increase in C2 H5 OH conversion. However, the difference in response of Ru-doped and un-doped ZnO appears evident only at high temperature. Since the operating temperature of gas sensor is high (above 573 K), this phenomenon will not affect the discussion of gas sensing mechanism.

Fig. 7. The typical gas chromatography pattern of C2 H5 OH oxidation over ZnO at 573 K.

Fig. 9. Relationship between the alcohol response and the conversion ratio of Ru-doped ZnO at different temperatures.

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3.4. Gas sensing mechanism of ZnO sensor It is well known that when an n-type semiconductor particle is exposed to air, oxygen molecules can adsorb on the surface of the particle and form O2 , O2 2 , O2 ions by capturing electrons from the conductance band, which in turn produces an electron-depleted space-charge layer in the surface region of the particle [20]. The fewer electrons present in the conduction band lead to a higher surface potential barrier, and therefore, result in a higher resistance [21]. Molecular-type adsorbates (O2 , O2 ), dissociative type one (O2 2 ) and surface (lattice) oxygen (O2 ) are conrmed to exist on the surface of an n-type semiconductor particle [22]. In addition, all of these adsorbed oxygen species are discerned to desorb depending on the adsorption conditions. Since gas sensors are usually operated at 573 K and above, the O2 2 species is more important than other oxygen adsorbates [23]. The target gas (ethanol) may undergo different reactions, and then can take two routes of decomposition reaction, i.e., dehydration and dehydrogenation: C2 H5 OH C2 H4 + H2 O (acidicoxide) 2C2 H5 OH 2CH3 CHO + H2 (basicoxide) (1) (2)

Fig. 10. Resistancetemperature curves of ZnO and Ru-doped ZnO (in air).

These primary products thus formed are consecutively oxidized to CO, CO2 and H2 O. C2 H4 + 3O2 2 (ad) 2CO2 + 2H2 O + 6e 2CH3 CHO (ad) + 5O2 2 (ad) 4CO2 + 4H2 O + 10e (4) (3)

The resistancetemperature curves of ZnO and Ru-doped ZnO sensors (in air) are shown in Fig. 10. From this gure, it can be seen that the addition of Ru into the as-prepared ZnO powder increases the resistance of the ZnO sample in the temperature range of 453663 K. This result also conrms the hypothesis of the sensitizing role of Ru in the ZnO sensor. On the basis of these ideas, we can propose the electronic sensitization mechanism of the Ru-doped ZnO sensor. 4. Conclusions Nanosized ZnO powder was synthesized by using a chemical precipitation method, and loaded with different dopants (Ru, Mg, Pd, Y, La, V and Na) through impregnation. The as-prepared ZnO powder shows an excellent gas response to alcohol and acetaldehyde, but no response to ethene. In addition, among all the dopants, Ru is the optimal dopant which can increase the response to C2 H5 OH. The sensing mechanism of pure ZnO and Ru-doped ZnO was further studied with the help of gas chromatography (GC) associated with a xed-bed reactor. The results show that the gas sensing mechanism of ZnO to C2 H5 OH is the mode controlled by chemisorption of negatively charged oxygen, and the sensitizing role of Ru in the ZnO sensor belongs to the electronic sensitization mechanism. Acknowledgements We appreciate the nancial supports of NSFC (No. 20471055) and the Science & Research Fund of Education Commission of Shanghai (No. 07ZZ12). References
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Since ZnO is a basic oxide, dehydrogenation is favored. The catalytic oxidation of alcohol over ZnO agrees with the above results because only one intermediate product (CH3 CHO) can be detected. As shown in Fig. 8, both the alcohol response and the conversion ratio of C2 H5 OH increased with an increase in working temperature, and their changing trends are similar to each other. That is to say, the response of the ZnO sensor toward C2 H5 OH is dependent on the conversion ratio of C2 H5 OH or formation of CH3 CHO. Combined with Fig. 3, the response to CH3 CHO is greater than that to C2 H5 OH. We suggest that the formation of intermediate product (CH3 CHO) increases the response to alcohol. Namely, formation of acetaldehyde plays a key role in the gas sensing process of alcohol. 2C2 H5 OH (ad) + O2 2 (ad) 2C2 H4 O (ad) + 2H2 O (5) C2 H4 O (ad) CH3 CHO (ad) + e (6)

Fig. 9 shows the relationship between the alcohol response and the conversion ratio of the Ru-doped ZnO gas sensing material at different temperatures. Compared with the un-doped ZnO, the conversion ratio of alcohol over Ru-doped ZnO has nearly no variety. Thus we suggest that the gas sensing mechanism of ZnO toward C2 H5 OH is the mode controlled by chemisorption of negatively charged oxygen, and the sensitizing role of Ru in the ZnO sensor belongs to the electronic sensitization mechanism.

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Biographies
Jiaqiang Xu obtained his masters degree in inorganic chemistry from University of Science and Technology of China in 1988. He got his doctors degree in materials science from Shanghai University in 2005. He had been a professor in applied chemistry at Zhengzhou University of Light Industry since 2001. He has been a vice-director of China special committee of gas and humidity sensor technology. His research interests include the synthesis of nanomaterial and their application in gas sensor and other elds, as well as improving gas properties of metal oxide semiconductor gas sensor. Now, he is a professor in Department of Chemistry at Shanghai University. Jianjun Han obtained his bachelor degree in applied chemistry from Zhengzhou University of Light Industry in 2004. He started to pursue his masters degree in material science under the direction of Professor Xu Jiaqiang. His study work is focused on the synthesis of nanometer materials and their application in gas sensor. Now, he is a lecturer in Department of Pharmacy at Tongren Technology College. Yuan Zhang received her bachelor degree in applied chemistry from Zhengzhou University of Light Industry in 2005. She has been pursuing her masters degree in inorganic chemistry in Shanghai University since 2006. Now, her main efforts are taken to the synthesis and assembly of one-dimensional ZnO nanomaterials, as well as to exploit their potential application in gas sensors and electronic, optoelectronic devices. Yuan Sun obtained his bachelor degree in chemistry from Henan Normal University in 1985. His research interests include modern analysis and testing technology, separation technology, as well as the synthesis of organic chemistry. Now, he is the director of applied chemistry department in Zhengzhou University of Light Industry. Bing Xie obtained his bachelor degree in analytical chemistry from China University of Geosciences in 1992. His research interests include modern analysis and testing technology and separation technology.