Electrochemical solid electrolyte gas sensors — hydrocarbon and NO_x analysis in exhaust gases

Abstract

For the in situ measurement of the free oxygen concentration and the equilibrium oxygen partial pressure oxygen sensors based on zirconia solid electrolytes are widely used in order to monitor and control technical high temperature processes. Similarly combustibles (HC, CO) and NO_x can be determined in non equilibrated oxygen containing gas mixtures of exhausts by mixed potential sensors and amperometric solid electrolyte sensors. It is expected that their long-term stability is similar to that of oxygen sensors. In both cases the electrode material with the desired electrochemical and catalytic properties is the key component. Different electrode materials made of perovskites (La_1-xSr_xCr_1-yGa_yO_3-δ) and composites (Au/Metal oxide) were investigated in different combustibles including CO, C₃H_6/8, C₇H₈ and CH₄. The response behaviour of mixed potential sensors is determined by the catalytic activity of the measuring electrode, which is closely connected with the defect structure and depends on the measuring conditions. Furthermore the electrode response can be understood by electrokinetic data. Gas symmetrical mixed potential sensors with electrodes made of Au/Nb₂O₅ composites show maximum sensitivity. By using Ptreference electrodes without equilibrium behaviour the sensors are applicable in lean and rich mixtures as well. In the amperometric sensor mode the consecutive determination of oxygen and NO_x or combustibles at two working electrodes is possible. The catalytic activity of the oxygen pumping electrode should be low in order to avoid the decomposition of NO and HC respectively. Alternatively, the electrochemical reduction of NO can be performed at a single working electrode, made of materials with improved NO selectivity, without the previous reduction of oxygen.