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CO detection with a dynamically operated solid-electrolyte sensor (SES) was investigated at 700 °C–750 °C in the concentration range between 0 and 150 vol.-ppm CO. Dynamic voltage variations by electrochemical impedance spectroscopy, cyclic voltammetry, and square-wave voltammetry showed a pronounced sensitivity to the presence of carbon monoxide in gas mixtures in the investigated concentration range at optimized experimental conditions. Specific differences of CO detection in reducing and oxidizing conditions are described in detail. Selectivity to oxygen, nitrogen monoxide, and hydrogen are discussed. Since the methods can also be used to selectively determine oxygen, nitrogen oxide and hydrogen, they open up new possibilities for complex multiple gas analysis.

Abstract. Solid electrolyte gas sensors (SESs) based on yttria-stabilized zirconia (YSZ) are suitable to detect traces of redox components in inert gases. Usually, their signals are generated as a voltage between two electrodes at open circuit potential or as a current flowing between constantly polarized electrodes. In these rather stationary modes of operation, SESs often lack the desired selectivity. This drawback can be circumvented if SESs are operated in dynamic electrochemical modes that utilize the differences of electrode kinetics for single components to distinguish between them. Accordingly, this contribution is directed to the investigation of cyclic voltammetry and square-wave voltammetry as methods to improve the selectivity of SESs. For this, a commercial SES of the type “sample gas, Pt|YSZ|Pt, air” was exposed to mixtures containing NO and O2 in N2 in the temperature range between 550 and 750 ∘C. On cyclic voltammograms (CVs), NO-related peaks occur in the cathodic direction at polarization voltages between −0.3 and −0.6 V at scan rates between 100 and 2000 mV s−1 and temperatures between 550 and 750 ∘C. Their heights depend on the NO concentration, on the temperature and on the scan rate, providing a lower limit of detection below 10 ppmv, with the highest sensitivity at 700 ∘C. The O2-related peaks, appearing also in the cathodic direction between −0.1 and −0.3 V at scan rates between 100 and 5000 mV s−1, are well separated from the NO-related peaks if the scan rate does not exceed 2000 mV s−1. Square-wave voltammograms (SWVs) obtained at a pulse frequency of 5 Hz, pulses of 0.1 mV and steps of 5 mV in the polarization range from 0 to −0.6 V also exhibit NO-related peaks at polarization voltages between −0.3 and −0.45 V compared to the Pt–air (platinum–air) electrode. In the temperature range between 650 and 750 ∘C the highest NO sensitivity was found at 700 ∘C. O2-related peaks arise in the cathodic direction between −0.12 and −0.16 V, increase with temperature and do not depend on the concentration of NO. Since capacitive currents are suppressed with square-wave voltammetry, this method provides improved selectivity. In contrast to cyclic voltammetry, a third peak was found with square-wave voltammetry at −0.48 V and a temperature of 750 ∘C. This peak does not depend on the NO concentration. It is assumed that this peak is due to the depletion of an oxide layer on the electrode surface. The results prove the selective detection of NO and O2 with SESs operated with both cyclic voltammetry and square-wave voltammetry.

Introduction Solid electrolyte sensors (SES) based on yttria stabilized zirconia (YSZ) can be used to detect traces of other components in inert gases such as Ar or N2. The O2--conducting solid electrolyte YSZ is thermodynamically highly stable and can be operated at high temperatures with stationary (potentiometry, amperometry) or dynamic methods (pulse polarization [1], cyclovoltammetry (CV) [2]). In the stationary mode, the selectivity of such sensors is limited to an extend that it is usually not possible to distinguish between individual gas components. In contrast to that, dynamic methods allow a significantly increased selectivity by using different rates of electrode reactions of the individual components in order to detect them independently in a gas mixture [2]. Dynamic electrochemical methods have been successfully used in liquids for many decades, and preliminary investigations on solid electrolyte gas sensors also show that such methods can be used to measure the concentrations of several redox-active gases, for example, oxygen and carbon monoxide [3]. The commercial solid electrolyte sensor used in this work was previously successfully tested to measure selectively different gases such as hydrogen, oxygen and water vapor [4] in nitrogen by using CV. In this work, these studies will be continued to investigate the ability of CV for selective detection of nitrogen oxides (NOx) and to elucidate the mechanisms of signal formation. Experimental setup The experimental setup shown in Fig. 1 and described in detail in [2] was used to adjust the O2 concentration (SES 1) and the measurement of the concentrations of O2 and NO in nitrogen (SES 2). Both SES of the type "Test gas, Pt|YSZ|Pt, air" contain a YSZ-tube equipped with two cylindrical platinum mesh electrodes at the inner and outer surface. The area of the inner measuring electrode was estimated by SEM to be about 3.5 cm2. A porous YSZ sintered layer was applied to join electrolyte and electrodes. Covering large parts of the reference and measuring electrode this porous layer offers an extended three-phase boundary for the oxygen transfer. SES 1 was continuously polarized during each experiment providing a constant O2 concentration in the purified carrier gas N2. At SES 2, the CVs were obtained at polarization voltages between -0.1 and -0.9 V against the Pt air reference electrode and scan rates in the range 100 ... 5000 mV/s. In each experiment, the second cycle was evaluated to obtain reproducible results. Between two consecutive cyclovoltammograms (CVM), the open circuit potential (OCP) was measured to monitor depolarization of the measuring electrode. Results and discussion The CVMs shown in Fig. 2 exhibit NO-related peaks developing in the cathodic scan direction between -0.2 and -0.7 V at scan rates between 100 and 2000 mV/s. The peak maximum shifts in the cathodic direction with increasing scan rate. The highest sensitivity was achieved at 2000 mV/s for 650 °C. At higher scan rates it decreases again. This is apparently caused by the shift of the oxygen reduction peaks from range -0.1 ... -0.3 V at lower scan rates to the cathodic direction at higher scan rates and leads to their superposition with the NO peaks. The curve shifts to higher electrolysis currents with increasing NO-concentration in the cathodic region, visible for every scan rate at U < -0.7 V correspond to the Faraday currents calculable for the NO reduction. The different peak potentials for O2 and NO enable a highly selective determination NO in O2 containing gases at scan rates between 200 – 2000 mV/s at concentrations c(NO) ≥ 10 vol.-ppm. The height of the NO peak as a suitable NO-related signal was calculated and plotted in Fig. 3 for different scan rates. This peak height rises almost linearly with the NO concentration and the curve slopes increase with the scan rate up to 2000 mV/s. Further investigations revealed that this scan rate-induced slope increase depends also on flow rate. OCP measurements at different NO concentrations and sensor temperatures (Fig. 4) indicate the known tendency of NO to decompose at hot and catalytically active platinum electrodes into N2 and O2. Therefore, in the investigated temperature range, the absolute value of the OCP decreases with increasing NO concentration, coming with rising oxygen partial pressure according to NO decomposition. Another process guiding the OCP in the NO-free carrier gas is the electronic conductivity of the solid electrolyte that increases exponentially with temperature [5]. References [1] S. Fischer, R. Pohle, E. Magori, M. Fleischer, R. Moos, Detection of NO by pulsed polarization of Pt I YSZ, Solid State Ionics 262, 288–291 (2014) [2] M. Schelter J. Zosel, W. Oelßner, U. Guth, M. Mertig, Electrolyte sensor for the analysis of gaseous mixtures, J. Sens. Sens. Syst. 5, 319–324 (2016) [3] X. Zhang, Electrochemical and structural investigations of a layered Au, Pt-YSZ mixed potential gas sensing electrode, Technische Universität Dresden, Dissertation, 2018 [4] A. Ruchets, N. Donker, D.Schönauer-Kamin, R. Moos, J. Zosel, U. Guth, M. Mertig, Selectivity improvement towards hydrogen and oxygen of solid electrolyte sensors by dynamic electrochemical methods, Sensors and Actuators B: Chemical 290, 53–58 (2019) [5] J.-H. Park, R. N. Blumenthal, Electronic Transport in 8 Mole Percent Y2O3-ZrO2, J. Electrochem. Soc., Vol. 136, 10, 2867-2876 (1989) Figure 1