Sensors and Actuators B 111112 (2005) 7883

A study of the catalytic activity and sensitivity to different alcohols of CeO2Fe2O3 thin lms
G. Neri a, , A. Bonavita a , G. Rizzo a , S. Galvagno a , S. Capone b , P. Siciliano b
a

Department of Industrial Chemistry and Materials Engineering, University of Messina, Salita Sperone 31, 98166 Messina, Italy b CNR, IMM Lecce, Italy Available online 10 August 2005

Abstract CeO2 Fe2 O3 thin lms with different Ce/Fe ratios have been tested as alcohol gas sensors. The microstructure, acidbase properties and reactivity of CeO2 Fe2 O3 powders were investigated by X-ray diffraction (XRD), temperature programmed desorption of adsorbed CO2 (TPD-CO2 ) and gas-phase oxidation of alcohols, respectively. The addition of Ce to Fe2 O3 modify the particles size distribution, surface basicity, electrical conductivity and the catalytic activity in the oxidation of methanol and ethanol. These factors have been discussed and correlated with the electrical response of CeO2 Fe2 O3 mixed oxides to both alcohols. 2005 Elsevier B.V. All rights reserved.
Keywords: Alcohol sensors; Thin lms; CeO2 Fe2 O3 mixed oxides

1. Introduction Alcohol gas sensors nd many practical applications such as in the control of fermentation and other chemical processes, food analyses, wine identication, breath analyzer and other medical devices. Many metal oxides (pure, mixed or doped) have been proposed as alcohol sensing materials [16]. In previous studies we have extensively investigated the sensing characteristics of Fe2 O3 thin lms prepared by LPD (liquid-phase deposition) [7,8]. Fe2 O3 is a basic oxide showing good properties for alcohols detection when properly doped [911]. Here, we focused our attention on Ce-doped iron oxide thin lms. CeO2 is more basic than Fe2 O3 and could act as a promoter improving the sensing characteristic of the pure iron oxide towards alcohols. Besides the very large data available, the sensing mechanism for alcohols detection is still not fully claried [2]. It was proposed that the preferential formation on the sur

Corresponding author. Tel.: +39 090 393134; fax: +39 090 391518. E-mail address: neri@ingegneria.unime.it (G. Neri).

face of the sensor of intermediate products of oxidative dehydrogenation is a key factor to obtain high sensitivity to alcohols [12]. In according, the increase of sensitivity was found to be favoured by the addition of basic promoters, which address the reaction towards the dehydrogenation route. These studies are however devoted to the study of the response to a single alcohol, whereas little it is reported on the investigation of different alcohols. Comparing the sensitivity to alcohols of different structure on a tin oxide gas sensor, Gong et al. suggested that the sensitivity order observed reects the order of the rate of consumption of adsorbed oxygen species [4]. They found in fact that the sensitivity to ethanol is higher than observed for methanol, in according with data reported by other authors [4,6]. However, many points remain obscure and deserve further study. Therefore, we started to investigate the sensing properties of CeFe mixed oxides towards alcohols of different structure with aim to nd correlation between the catalytic and electrical properties. In a study of this series we have investigated the microstructural, acidbase and catalytic properties

0925-4005/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.snb.2005.06.045

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of CeO2 Fe2 O3 metal oxides of different composition and their inuence in the methanol gas sensing [3]. In this work we present data obtained in the gas sensing of methanol and ethanol on these sensors, making a comparison between these alcohols.

helium. Catalytic runs were carried by using a total ow of 50 cm3 /min and using 200 mg of sample. A mass spectrometer (FISONS Instruments) was used for on-line analysis of both the feed and the product streams. 2.2. Sensor fabrication and gas-sensing tests

2. Experimental 2.1. Preparation and characterization of CeO2 Fe2 O3 powders CeO2 Fe2 O3 powders for characterization studies were prepared by coprecipitation by adding a solution containing the suitable ratio of the metal oxide precursors, CeCl3 7H2 O and Fe(NO3 )3 9H2 O (Fluka), to an aqueous solution of NH4 OH 1 M under vigorous stirring (500 rpm) at 7.5 ml/min rate and at a temperature of 80 C. The precipitate was digested overnight at room temperature, washed several times with water, dried under vacuum (P = 102 mbar) at 80 C and then calcined at the temperature of 400 C for 2 h. Table 1 shows the main characteristics of the CeO2 Fe2 O3 powders investigated. XRD analysis was carried out on a Ital-Structures diffractometer. The mean particles diameter was calculated from line broadening analysis of the diffraction peaks by using the Scherrer equation. TPD experiments of adsorbed CO2 were performed in a ow apparatus. The sample (200 mg) was rst placed in the reactor and treated at 400 C for 2 h in air. After cooling to room temperature the sample was exposed to a CO2 owing until saturation. TPD spectra were collected raising the temperature of the reactor up to 400 C at a heating rate of 10 C min1 and by using a quadrupole mass spectrometer (FISONS Instruments) as detector. The reactivity in the alcohol oxidation was tested in the gas-phase in a temperature programmed reaction apparatus operated at atmospheric pressure equipped with a quartz Utube and an internal coaxial thermocouple connected with a PID temperature controller. Alcohol gas were generated in a saturator kept at a xed temperature (25 0.5 C) uxed with a oxygen/helium mixture (O2 /He ratio 1:4) diluted in
Table 1 Main characteristics of the mixed oxide investigated Sample FC00 FC20 FC50 FC80 FC100
a b

Sensors were fabricated by depositing CeO2 Fe2 O3 thin lms on alumina substrates (3 mm 3 mm) with gold interdigitated electrodes and a Pt heater located on the backside. CeO2 Fe2 O3 thin lms have been deposited by a liquid phase method as follows: an aqueous mixture containing the metal oxide precursors in the suitable ratio, in order to obtain the desired composition, was prepared. Ten microliter of the solution was then dropped on the alumina substrate by micropipetting. The sample was placed in a deposition chamber under a NH3 /He mixture ushing. After completion of the deposition, the chamber was evacuated and the lm was dried at 80 C and calcined in the same apparatus at 400 C in air for 2 h. The sensors were then bounded as suspended devices onto TO-8 supports and introduced in a Teon test chamber for the sensing tests to methanol. The experimental bench for the electrical characterization of the sensors allows to carry out measurements in controlled atmosphere. Different gases coming from certied bottles can be further diluted in air at a given concentration variable by different mass ow controllers (MFCs of MKS) connected to a gas mixing system (MKS mod. 647B). The experiments were carried out by measuring the electrical current of the sensor devices taken under a voltage of 10 V by an electrometer (Keithley mod. 6517A) equipped with a multiplexer (Keithley mod. 6521). A personal computer by a LABview software via a GPIB interface controls, all the operations related to the gas protocol and to data acquisition, storage and plotting in real time. The gas response is dened as the ratio Ig /Ib , where Ig is the electrical current at different alcohols concentrations and Ib is the electrical current of the baseline in dry air.

3. Results and discussion 3.1. CeFe mixed oxides preparation and characterization

[Ce/(Fe + Ce)] 100 20 50 80 100

Basic sitesa (mmol/g) 0.92 0.55 1.70 1.36 0.97

Currentb (A) 7.6 109 9.3 108 5.1 108 9.6 1011 3.1 1011

Particle sizec (nm) 27 5 6.1 4.5 7.3

Number of basic sites measured by TPD of adsorbed CO2 . Current on the sensor measured in air at 300 C under working conditions. c As determined by peak broadening in the XRD measurements.

Much emphasis is being placed in recent years on developing chemical solution-based lm deposition technologies as an economical alternative to the more expensive chemical vapor deposition and reactive sputtering processes [14]. Recognizing the usefulness of a porous lm for gas sensing, a modied chemical solution-based technique such as the liquid-phase deposition (LPD) techniques, able to directly deposit in one-step lms of metal oxides, has been recently developed by us [8]. Film preparation by the LPD process

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provides the direct nanoparticles deposition on the substrate and the optimization of the lm microstructure is made easier, simply by controlling the deposition parameters precisely. Thus, LPD is an one-step process suitable for the formation of thin lms, eliminating the need for powder processing. Recent works on CeFe mixed oxides have shown that their synthesis via a wet route carried out under mild conditions can favour the formation of a Fex Ce1x O2 solid solution, with Fe2 O3 entering in the uorite structure of ceria [15]. Our observations support this, as shown by a detailed XRD analysis of CeFe mixed oxides prepared by LPD and reported elsewhere [13]. Data reported of the Ce-doped samples calcined at 400 C indicate moreover that Ce inhibits the crystallization of iron oxide through the formation of the above solid solution. Line broadening analysis indicate a smaller grain size of the mixed oxides (see Table 1) respect to the pure Fe2 O3 sample. XRD shows also that the above solid solution is not stable to thermal treatments, the annealing of samples at temperature above 600 C leading to the formation of separate phases of ceria and hematite (Fig. 1). The basicity of the mixed oxides was investigated by temperature programmed desorption of adsorbed CO2 . Complex desorption patterns with a main desorption peak around 70 C and additional weak peaks at higher temperature (in the range 250700 C) were registered. Increasing the Ce loading, the low temperature desorption peak increases of intensity, whereas the high temperature desorption peaks change in the position and intensity. The overall amount of CO2 desorbed, expressed for gram of sample, evaluated from the area under the desorption peaks, it has been taken as a measure of the number of basic sites and is reported in Table 1. The amount of basic sites increases with Ce loading up to 50% in moles, then decreases, thus suggesting that the formation of mixed oxides leads to the development of new basic sites. An electrical characterization was also carried out in order to evaluate the potential use of these mixed oxides as sensing materials. Data reported in Table 1 indicate as the electrical current measured on these materials is strongly dependent

Fig. 2. Ethanol conversion with reaction temperature on: (a) the FC20 mixed oxide calcined at different temperature; (b) different samples calcined at 600 C.

on the Ce loading. A detailed explanation of this is given elsewhere [13]. It can be observed further that at loading up to 50% in moles, Ce increase the conductivity of pure iron oxide material, but at higher content it strongly suppress the conductivity, making the high-loaded Ce-mixed oxides not suitable for a practical use. 3.2. Reactivity tests Reactivity tests of methanol and ethanol on CeO2 Fe2 O3 samples have shown that the oxidation activity depends on the alcohol nature and the composition and annealing temperature of the mixed oxides. Fig. 2a and b shows proles of alcohol conversion with reaction temperature on CeFe mixed oxides of different composition and annealed at different temperature. Under the experimental conditions used, the FC50 sample calcined at 400 C was found the most active, the conversion of methanol and ethanol reaching 100% at 210 and 190 C, respectively. Increasing the annealing temperature the oxidation activity decrease strongly, as a consequence of the lower surface area of sample due to grains growth. To compare the reactivity of both alcohols towards oxygen over the mixed oxides investigated, the oxidation activity was normalised as follow: AN(i) = 1/[T50(i)/T50(FC00)], where AN(i) is the normalised activity of the sample (i), T50(i) the temperature at which the conversion of alcohol reaches 50% on the sample (i), and T50(FC00) the temperature at which the conversion of methanol reaches 50% on the reference catalyst FC00. Normalised activity values calculated in this way have been correlated with the microstructural, acidbase and sensing properties of the mixed oxides investigated. Fig. 3 reports the normalised activity in the oxidation of alcohols versus the amount of basic sites as determined by TPD of adsorbed CO2 . The trend observed indicate that: (i) the activity is strictly correlated to the amount of basic sites on the mixed oxides; (ii) the variations in the acidbase properties of the mixed oxides inuence in a similar way

Fig. 1. XRD analysis of the FC20 mixed oxide at different annealing temperatures.

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Fig. 3. Normalised activity of the mixed oxides vs. the amount of basic sites: ( ) methanol; ( ) ethanol.

the reactivity to both alcohols. These data further remark the higher reactivity of ethanol on the surface of the investigated oxides, in comparison to methanol. As reported in the general scheme (Scheme 1), different pathways are possible during the catalytic oxidation of alcohols on the CeFe mixed oxides. The described intermediate species play a key role in the sensing of alcohols on semiconducting oxides. In particular, it is believed that the preferential formation on the surface of the sensor of intermediate products of oxidative dehydrogenation is a key factor to obtain high sensitivity [2]. This explains the increase of sensitivity at the addition of basic promoters, which address the reaction towards the dehydrogenation route [12]. During the oxidation of alcohols on the CeFe mixed oxides the main product observed was CO2 . Formaldehyde (CH2 O) as reaction product of the oxidative dehydrogenation pathway and dimethylether (CH3 OCH3 ) as reaction product of the dehydration pathway, were the relevant reaction intermediates detected in the oxidation of methanol [13,16]. A detailed discussion about the correlation between the reaction intermediates in the oxidation of methanol and the acidbase properties of the metal oxides has been reported elsewhere [13]. Containing more carbon atoms than methanol, ethanol reveals much more complicated oxidation scheme with a great number of possible intermediates, and much less is

known about the course of the oxidation process [17]. In spite of dissimilarities reecting differences in composition and structure, there are several marked common features of methanol and ethanol in adsorption and oxidation. Similarly to methanol, the rst step of the oxidation of ethanol involves the cleavage of O H bond and formation of ethoxy species CH3 CH2 O. Further transformation of ethoxy species can gives acetaldehyde CH3 CHO, and H2 through the dehydrogenation route, whereas acetone (CH3 COCH3 ), ethylacetate (CH3 COOC2 H5 ) and ethylene derive from the dehydration path [17]. In conclusion, the transformation of the adsorbed alkoxy groups to the oxidative dehydrogenation products depends on the dual acidbase site formed by a metal cation and surface oxygen ions, being favoured by a strong acid site surrounded by basic active sites. On the other hand, the desorption of this product is favoured by a weak rather than a strong acid site. These latter, infact, could favour the dehydration step. More detailed data reported elsewhere in the study carried out in the oxidation of methanol, indicate that the dehydrogenation route is favoured with the increase of Ce loading, while it decreases further the dehydration pathway [13]. 3.3. Sensing tests Sensing tests to both alcohols carried out on the mixed oxides thin lms are shown in Figs. 47. The response to methanol and ethanol as a function of the operating temperature (in the range between 200 and 400 C) on the Ce-promoted FC50 sensor annealed at 600 C is reported in Fig. 4. The FC50 sensor shows the higher sensitivity to methanol and ethanol compared to undoped sensor. This was conrmed further by data reported in Fig. 5 for all sensor investigated, acquired at the operating temperature of 400 C. The response to methanol and ethanol was found to increase with increasing Ce loading up to 50% in moles. At higher Ce loading the response is instead negligible. It should be consider that the conductance on these latter sensors is very high

Scheme 1. Main pathways and related intermediates in the oxidation of simple alcohols on metal oxides.

Fig. 4. Response of the FC50 sensor to 220 ppm of methanol and ethanol at different temperatures. The lm has been calcined at 600 C.

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Fig. 5. Comparison of the sensors response to methanol and ethanol as a function of the Ce content. Films have been calcined at 600 C.

and the measure suffer of a noticeable degree of uncertainty due to a high noise level. The sensors were then calibrated by exposing them to different concentrations of alcohols in dry air. Fig. 6 shows a typical example of the dynamic response of these sensors. In Fig. 7 the responses at the operating temperature of 400 C in function of alcohol concentration are plotted in a loglog scale. The response is linear in the range of concentration investigated (25200 ppm) on all samples investigated irrespective of the annealing temperature. A comparison of the activity tests with results of sensing measurements indicate that more active the mixed oxide, more sensitive is. Fig. 8 summarise data for some sensors, correlating the normalised activity with the sensors response for both alcohols. The correlation is quite good and, recalling a similar correlation between the normalised activity and the amount of basic sites (Fig. 3), it follows that the acidbase characteristics of samples are of primary importance. By taking into account the reactivity studies here reported and literature data, we can suppose that alcohols oxidation occurs through a rst step where adsorbed molecules on the oxide surface decompose in alkoxy groups (ROads ) after hydrogen extraction [2,12,13,18]. These surface species react with adsorbed oxygen (for example Oads ) to give CO2 as

Fig. 7. Calibration curves for methanol and ethanol at the temperature of 400 C. Films have been calcined at 600 C: (a) methanol; (b) ethanol.

follows: 2CH3 O + 5Oads 2CO2 + 3H2 O + 5e 2CH3 CH2 O + 11Oads 4CO2 + 5H2 O + 11e (1) (2)

It is evident that more electrons are involved (per molecule oxidised) in the surface reaction, larger results the variation of resistance. Electrons are then returned back to metal oxide, resulting in an increase of conductance that represents the response of the sensor. The ratio between electrons released in the processes (1) and (2) is 0.45. This value agree very well with experimental data showing an average response to methanol which is about half of that registered for ethanol.

Fig. 6. Dynamic response to different ethanol concentrations at the temperature of 400 C. Films have been calcined at 600 C.

Fig. 8. Correlation between the sensor response and normalised activity for methanol and ethanol.

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In order to discriminate if the alcohol structure can have an inuence on the sensor response, investigations of alcohols with different structure (such as n-propanol and isopropanol) are under way. We hope these studies will contribute to better understand the alcohol sensing mechanism on these metal oxides.

Biographies
G. Neri was born in 1956 and received his degree in chemistry from the University of Messina in 1980. Since 2001 he is Full Professor of Chemistry and actually Director of the Department of Industrial Chemistry and Materials Engineering of the University of Messina. His research activity, documented by more than 100 papers on international journals and books, cover many aspects of the synthesis, characterization and chemical-physics of solids with particular emphasis to catalytic and sensing properties. In the latter research area his work has been focused on the preparation of metal oxide thick and thin lms and their application in gas sensors. A. Bonavita was born in 1972. She received her degree in materials engineering from the University of Messina in 1997 and PhD degree in materials engineering and chemistry in 2000. At present time she is at the Department of Industrial Chemistry and Materials Engineering of the University of Messina. Her research activity concerns with the preparation, characterization and development of semiconductor lms for gas sensing applications. G. Rizzo was born in 1975 and received his degree in chemistry from the University of Messina in 1999 and PhD degree in materials engineering and chemistry in 2002. Actually he works at the Department of Industrial Chemistry and Materials Engineering of the University of Messina. His research activity is focused on the synthesis and characterization of materials by solgel method for catalytic, optical and sensing applications. S. Galvagno was born in 1950. He received his degree in industrial chemistry from the University of Catania. Since 1994 he is Full Professor of Chemistry at the Department of Industrial Chemistry and Materials Engineering of the University of Messina where he is involved in research projects on the catalytic and electrical properties of highly porous materials. S. Capone was born in 1970 and graduated cum laude in physics at the University of Lecce in 1996 with a thesis on semiconductor gas sensors. In January 2001 she received the PhD degree in physics by discussing a thesis on metal oxide gas sensors for applications in electronic nose. At present she works as a researcher at the Institute for Microelectronic and Microsystems of the Council National of Research (IMM-CNR) in Lecce (Italy). Research topics are the characterization of metal oxide-based gas sensors to be used in electronic nose and gas sensors based on metal oxide hetero-junctions. P. Siciliano, physicist, senior researcher, received his degree in physics in 1985 from the University of Lecce. He received his PhD in physics in 1989 at the University of Bari. During the rst years of activities he was involved in research in the eld of electrical characterization of semiconductors devices. He is currently a senior member of the National Council of Research in Lecce, where he has been working from many years in the eld of preparation and characterization of thin lm for gas sensor, being in charge of the Sensors Group. He is author of about 180 scientic papers, on national and international journals, and a lot of communication, some invited, to International Conferences. He is responsible for several national and international projects at IMMCNR in eld of sensors and microsystems, mainly for environmental, automotive and agro-food applications. He has been organiser and Chairman of International Conferences and Director of International Schools on Sensors and Microsystems. He is member of the Steering Committee of AISEM, the Italian Association on Sensors and Microsystems. At the moment he is Director of IMM-CNR in the Department of Lecce.

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