Advances in Materials Science and Engineering

Advances in Materials Science and Engineering / 2009 / Article

Research Article | Open Access

Volume 2009 |Article ID 612130 | 4 pages | https://doi.org/10.1155/2009/612130

Temperature Dependent Electrical Properties and Catalytic Activities of Phase System

Academic Editor: Steven Suib
Received10 Jul 2009
Accepted20 Sep 2009
Published28 Dec 2009

Abstract

We present a study of electrical properties and catalytic activities of materials belonging to the hydrated carbonated system . The polycrystalline hydroxycarbonate, dioxycarbonate, and oxide are prepared via a coprecipitation route followed by heat treatment. The electrical conduction of the phases obtained by thermal decomposition from , is analyzed by electrical impedance spectroscopy, from to , under air. The catalytic properties of , and polycrystalline phases are studied by FTIR spectroscopy, in presence of gas mixtures CO-air and -air, at temperatures ranging between to . The three materials behave differently in presence of CO or gases.

1. Introduction

The general aim of this study is to test the reactivity of materials sensitive to environmental water and , and interacting with toxic gases (CO, ). Presently we deal with the system that presents hydrated and carbonated phases, stable at various temperatures [16]; the hydroxycarbonate phase LaOHC stable up to 380°C [7]; the dioxycarbonate phase stable up to 700°C, and finally the La2O3 phase stable above this temperature, under air atmosphere. Each phase can be sensitive to partial pressure of or . Consequently, these phases can be used as sensing materials reacting with wet air and . In a first step, we try to determine the evolution of electrical conduction of these phases with increasing temperature; in a second step, we compare the temperature and time dependent catalytic efficiencies of LaOHC, , and , to convert and CO present in air- and air-CO flows.

2. Experimental

The samples were prepared by a coprecipitation route described in a recent work [8]. A first step consisted in mixing three aqueous solutions: (1) , (2) urea CO, and (3) polyvinyl-pyrrolydine (PVP) polymer. The initial pH was 3.2. A similar approach was proposed by Li et al. [9]. A second step consisted in heating the solution in a reactor equipped with a vapor condenser, at 80°C. In all experiments, solutions were permanently agitated through a magnet rotating with a fixed rate of 300 rpm. During heating, temperature was fixed, and vapors were condensed through a water-cooled circuit to avoid vanishing of the aqueous solution. A white solid was obtained by precipitation.

The thermal decomposition of this solid (the polycrystalline initial hydroxycarbonate phase ) was initially studied by thermogravimetry, from room temperature to 1100°C. Then, the same LaOHCO3, H2O phase was compacted in form of cylindrical pellet, and placed in a heating cell, in a Solartron electrical impedance equipment. Platinum circular electrodes were fixed on the two faces of pellet. The electrical analyses that were performed in the temperature range of 25 to 950°C and in the frequency range of 1 to  Hz, with a maximal tension of 1 V. The conductivities were determined from extrapolation of the Nyquist representations delivered by the software of the equipment, and taking into account the dimensions of samples.

The catalytic activities were determined using an infrared (FTIR) spectrometer, adapted for analyses of emitted gases. This homemade equipment was described in previous works [10]. Samples are placed in a catalytic cell and a gas flow cross through the powder at various temperatures and various flow rates. The polycrystalline phases , , and were subjected successively to air- and air-CO flows, at various temperatures and as a function of time. In all experiments, we used flow rates of 10 sccm and gas concentrations in air of 2500 ppm. The catalytic efficiency is defined as being the intensity of the vibrational band at 2340–2360  resulting from the following transformations:

or

Additional studies by transmission electron microscopy allowed to determine the distributions of sizes and shapes of crystal grains in each sample (not presented here). From these microstructural analyses, we could define calculated grain surfaces and grain volumes for each phase noted i (the index i represents , or LaOH). This allowed calculation of specific surfaces . Then, from the mass of each sample used for catalytic analyses, it has been possible to determine an approximate total surface for each powdered sample. This surface has been used to normalize our FTIR data and allow comparison of catalytic efficiencies. The normalized intensities (I/) are calculated by dividing the intensities of bands by the surfaces of samples. The values are successively in : S() = 0.61, , .

3. Results and Discussion

3.1. Thermal Analyses and Electrical Responses

Using first classical TG-TDA analysis of the hydrated hydroxycarbonate sample, we have determined the various temperature ranges of phase stabilities. These preliminary results were useful to better interpret our electrical measurements. Figure 1(a) gives the conventional thermal analysis using thermogravimetry data coupled with differential thermal analysis (TG-DTA). The various mass losses versus temperature in °C are clearly visible with a first lattice water departure, then the change of hydroxycarbonate into and, finally, the final formation of .

Figure 1(b) gives the corresponding thermal evolution of the logarithm of conductivityln as a function of 1000/T (T being in K) of the initial hydrated hydroxycarbonate phase; as temperature increases, the electrical modifications due to thermal decomposition are observed through undulations on the curve lnσ versus 1000/T. In Figure 1(b), as 1000/T decreases, several domains are observed as follows

(a)At low temperature (25–300°C), an increasing low conductivity is observed, with weak activation energy; this is typically relative to extrinsic conduction linked to surface water and proton (O) mobility;(b)Between 350 and 700°C, if we extrapolate the previous lower temperature results, we can observe an abnormal variation of conductivity; it is due to the O and species departure, involving defect formation in hydroxycarbonate and formation of dioxycarbonate ;(c)Between 700°C and 800°C, a very weak abnormal evolution is observed (undulation), probably due to the last departure from the oxycarbonate, with transformation into oxide (phase with higher activation energy).

Taking into account the logarithmic scale of the graph, we observe a relatively strong variation of the electrical signal between 300 and 600°C; this domain, in which the O and one of the species are unstable in the lattice, should be highly sensitive to water and exchanges. This might be used to detect water and molecules in a gas sensor.

3.2. Catalytic Studies

Figures 2(a), 2(b) give the normalized catalytic efficiencies (intensities of vibrational frequency band) of and subjected to -air flow (2500 ppm ) at different temperatures. Because of thermal decomposition occurring at a temperature greater than 350°C, no experiment was possible for LaOHCO3. Figure 3(a) reports the results for the LaOHCO3 phase at various temperatures. The maximum catalytic efficiency of each material interacting with CO is obtained at a relatively low temperature (275°C).The catalysis of CH4 is obtained at higher temperatures (above 450°C). Figure 3(b) gives the normalized catalytic efficiencies of the three phases in presence of air-CO flows at a given temperature of 275°C. It is clearly evidenced that the catalytic efficiency of (per surface unit) is greater than that of the two other compounds.

4. Conclusion

In this study, we have developed an electrical approach allowing determining the electrical responses of a phase change involving and molecules elimination, from electrical impedance analyses. The departure of the couple can be linked to an increase of conductivity (the slope of the ln() curve increases in the range of 400–600°C) followed by a stabilization of the conductivity (in the range of 600 to 700°C) associated with last carbonate phase formation. The increase of conductivity might be ascribed to the high mobility of unstable chemical specie, mainly protons that can jump easily from oxygen to oxygen or species that can migrate from vacancies to vacancies as soon as they are formed. In this temperature range, the variation of conductivity should be sufficiently significant to be used to detect presence of . Specific experiments involving action of on are in progress and will be published elsewhere. In the range of 700 to 800°C, the observed smooth undulation might be due to a last departure and formation of final stable oxide. From the analyses of catalytic interactions, it should be noted that LaOH and can be good catalysts for CO in air-CO mixtures. These phases might have some interest in selectivity of gas sensors interacting with environmental gas mixtures (); they might be stable in presence of and could interact with CO. At low temperature, they might only interact with environmental or . At higher temperature, they might only interact with CO, not with these environmental gases.

Acknowledgments

The authors acknowledge Council of Region PACA for financial support. This study has been developed in the framework of ARCUS CERES project (2009).

References

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Copyright © 2009 Bahcine Bakiz et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


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