NO sensitivity of perovskite-type electrode materials La0.6Ca0.4B′1−xB″xO3±δ (B′ = Mn, Cr; B″ = Ni, Fe, Co; x = 0, 0.1, …, 0.6) in mixed potential sensors

doi:10.1016/j.snb.2015.09.134

Sensors and Actuators B: Chemical

Volume 223, February 2016, Pages 723-729

https://doi.org/10.1016/j.snb.2015.09.134 Get rights and content

Abstract

Perovskite-type electrode materials of the compositions La_0.6Ca_0.4B′_1−xB″_xO_3±δ (B = Mn, Cr; B″ = Ni, Co, Fe; x = 0, …, 0.6) were investigated with regard to their NO sensitivity and the cross-sensitivity to NO₂ and propylene in a potentiometric solid electrolyte measuring setup. The highest NO sensitivity was found for nickel and iron manganites with x = 0.2 and 0.3. Dependencies on the NO gas concentration were found using impedance spectroscopy. For some materials, the catalytic conversion of NO, NO₂, methane and propene was determined by thermal investigation in the temperature range of 25–800 °C.

Introduction

During the last decades, a growing demand for in situ NO_x gas sensors based on solid electrolytes has been developed in the field of monitoring and control of automotive and industrial exhausts. In addition to the ability of being highly sensitive to NO at temperatures above 500 °C, the sensors should be resistant in harsh atmosphere, compact, inexpensive in production and of minor complexity. The development of these sensors is tied to the production of non-polluting automotive engines and industrial combustion processes in line with tightening emission standards.

Many metal oxides have been tested, regarding their sensing qualities in NO sensing devices. Miura et al. screened binary metal oxides such as Me_xO_y with Me = W, Cd, Ti, Cr, Mn, Ni, Co, La and Ln. Mn₂O₃ and CeO₂ were found to be the most sensitive electrode materials [1]. Miura also described experiments with spinel-type AB₂O₄ (A = Zn, Ni, Cd and B = Mn, Fe, Cr) [1], [2], [3], [4], [5] and perovskite-type ABO₃ (A = Ln, Ni, Y; B = Cr, Mn, Fe, Co, Ni) [2]. The potentiometric measurements showed that most of the spinel-type electrode materials are sensitive to NO whereas the perovskites are not. Dutta as well showed that the partial substitution of the A and B ions in a perovskite does not increase the NO sensitivity of the electrode [6]. Nevertheless, the substitution of A and B ions with earth alkali and transition metal ions does vary the electronic structure, and thus, the electronic and catalytic character of the perovskite type oxide is changed as described elsewhere [7], [8], [9], [10], [11], [12], [13] and may also have an influence on the NO sensitivity of the electrode material. The oxidic materials mentioned above mostly show NO sensitivity up to 500 °C or 600 °C as well as poor selectivity.

In this work, the dependency of the NO sensitivity on the composition of the perovskites La_0.6Ca_0.4B′_1−xB″_xO_3±δ (B′ = Mn, Cr; B″ = Ni, Fe, Co; x = 0, 0.1, …, 0.6) was investigated by means of potentiometric measurements and impedance spectroscopy at temperatures 500 °C, 550 °C and 650 °C. The cross-sensitivity to other possible gas components of exhaust gases (NO₂, C₃H₆) was ascertained at the same conditions.

Section snippets

Materials and methods

The electrode materials La_0.6Ca_0.4B′_1−xB″_xO_3±δ (with B′ = Mn, Cr; B″ = Ni, Fe, Co) were prepared via solid-state reaction. La₂O₃, CaCO₃ and Me_yO_z (Me = Mn, Cr, Ni, Fe, Co) powders were mixed and ground in a planetary ball mill for 24 h and tempered in alumina crucibles for 17 h. After the reaction, the products were milled again for 8 h and used without further treatment.

The product powders were mixed with an organic binding agent and screen printed on YSZ disks (∅ 12 mm, height 1 mm) followed by

Crystal structure and specific surface area

XRD studies of the manganite and chromite powders given in Fig. 1 for selected materials show the typical reflections of the orthorhombic GdFeO₃ crystal structure. Materials with low B″ content (x ≤ 0.2) are pure while a higher B″ content induces impurities of reactants and related perovskites up to 7 mass%. Detailed evaluation of the XRD data of the manganites is described elsewhere [14], [15], [16]. The XRD analysis of the chromites can be understood similarly.

Sorption measurements using the

Conclusions

XRD studies show that the main product of the solid-state reaction is a perovskite-type oxide with GdFeO₃ structure. The materials with low B″ content emerge as pure phases. With increasing B″ metal content the perovskites contain impurities of reactants B″_yO_z in the range of 1–7%.

The electrode materials La_0.6Ca_0.4Mn_0.8Ni_0.2O_3±δ, La_0.6Ca_0.4Mn_0.7Ni_0.3O_3±δ, La_0.6Ca_0.4Mn_0.9Fe_0.1O_3±δ, La_0.6Ca_0.4Mn_0.8Fe_0.2O_3±δ and La_0.75Ca_0.25Mn_0.5Fe_0.5O_3±δ turned out to be most suitable for the use in

Acknowledgements

The authors would like to thank K. Ahlborn and F. Gerlach (both Kurt Schwabe Institute for Measurement and Sensor Technology) for preparing the screen printed YSZ disks and K. Ahlborn for performing the sorption measurements.

Financial support by the German Federal Ministry of Economics and Technology in the program PRO INNO II (No. KF0137601DA5) is gratefully acknowledged.

Daniela Franke received her diploma in chemistry in 2006 and her Ph.D. in 2012 at Technische Universität Dresden (Germany). Until 2014, her scientific work included the development and synthesis of new electrode materials and their behavior in electrochemical solid state sensors for different gases as well as the electrochemical behavior of oxygen-deficient perovskite-type oxides. She is currently involved in the synthesis and characterization of responsive polymers for microelectronics at

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NO sensitivity of perovskite-type electrode materials La0.6Ca0.4B′1−xB″xO3±δ (B′ = Mn, Cr; B″ = Ni, Fe, Co; x = 0, 0.1, …, 0.6) in mixed potential sensors

Abstract

Introduction

Section snippets

Materials and methods

Crystal structure and specific surface area

Conclusions

Acknowledgements

Solid State Ionics

Sens. Actuators B: Chem.

Solid State Ionics

Sens. Actuators B: Chem.

Electrochem. Commun.

Solid State Ionics

Physica

J. Catal.

Solid State Ionics

Electrochim. Acta

J. Magn. Magn. Mater.

J. Alloys Compd.

J. Alloys Compd.

Solid State Ionics

Solid State Ionics

NO sensitivity of perovskite-type electrode materials La_0.6Ca_0.4B′_1−xB″_xO_3±δ (B′ = Mn, Cr; B″ = Ni, Fe, Co; x = 0, 0.1, …, 0.6) in mixed potential sensors