Solid State Ionics 107 (1998) 213216

NOx detection using the electrolysis of water vapour in a YSZ cell

Part I. NOx detection
a, a b b b T. Hibino *, Y. Kuwahara , T. Otsuka , N. Ishida , T. Oshima
a

National Industrial Research Institute of Nagoya, 1 -1, Hirate-cho, Kita-ku, Nagoya 462, Japan b NGK Spark Plug Co., Ltd., 2808 Iwasaki, Komaki-shi, Aichi 485, Japan Received 3 October 1997; accepted 4 November 1997

Abstract The reaction of NO with the hydrogen formed by electrolyzing water vapour in a YSZ cell has been applied to detect NO with output signal of magnitude in millivolt or milliampere. The experimental apparatus consisted of two YSZ cells, PtuYSZuPt, which served as an electrolysis cell and an oxygen sensor, respectively. A mixture of 03000 ppm NO and 3% H 2 O in argon was successively fed to the two cells at 8008C. In the upstream cell, the hydrogen formed by electrolyzing water vapour in the sample gas reacted with NO in the sample gas. In the downstream cell, the electromotive force (EMF) value was measured using air as a reference gas. The EMF value of the oxygen sensor was used as a sensor signal, when a current of 6.7 mA was applied to the electrolysis cell. The EMF signal decreased with increasing NO concentration in the sample gas. Furthermore, the current applied to the electrolysis cell was used as another sensor signal, when the EMF value of the oxygen sensor was held at 700 mV. The current signal increased with increasing NO concentration in the sample gas. 1998 Elsevier Science B.V. All rights reserved.
Keywords: YSZ cell; Water vapour electrolysis; NOx detection

1. Introduction NOx sensors are becoming increasingly important for the improvement of the environmental pollution such as acid rain and photochemical smog and for the further introduction of lean-burn and diesel vehicles into the market. So far many kinds of NOx sensors have been investigated using oxide semiconductors [14], metal phytalocyamine [5,6], solid electrolytes [714] and so on. Among these sensors, those using YSZ can be expected to exhibit the best durability. As for such NOx sensors, there has been
*Corresponding author. Fax: 81 52 911 2422

potentiometric [12] and amperometric ones [13,14]. In the former, the YSZ cells using metal nitrates as sensing electrodes show the EMF value following Nernsts equation. However, the operation temperature of the sensor is limited up to the melting point of the nitrate electrodes, many of which are lower than the highest temperature of the exhaust gases from lean-burn or diesel engines. In the latter, when a constant voltage is applied to the YSZ cells, the current based on the electrolysis of NOx is proportional to its concentration. However, the current signal observed is only several mA per 1000 ppm NOx. We have proposed a new NOx sensor in order to

0167-2738 / 98 / $19.00 1998 Elsevier Science B.V. All rights reserved. PII S0167-2738( 97 )00538-9

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solve the above problems. When water vapour is present in the sample gas, it can be easily electrolyzed to hydrogen in the YSZ cell. Since hydrogen is generally reactive to oxidizing gases, it will react with NOx in the sample gas. This paper deals with the application of the electrolysis of water vapour to the detection of NOx. It is shown that this method makes it possible to detect NOx with output signals in a practical use. Furthermore, it is demonstrated that this method can be applied to both potentiometric and amperometric sensors.

the oxygen sensor, where the operation temperature was 8008C and air was used as a reference gas. The EMF value of the oxygen sensor was measured by an electrometer (Hokuto Denko HE-104). As an additional experiment, the concentrations of NO and hydrogen in the outlet gas from the electrolysis cell were analyzed by an NOx analyzer (Shimazu NOA7000) and GC (Shimazu GC 8A), respectively.

3. Results and discussion Fig. 2 shows the changes in EMF of the oxygen sensor with the current applied to the electrolysis cell. The EMF value drastically increased at more than 6 mA, indicating that water vapour is electrolyzed to hydrogen. The EMF value, however, was strongly dependent on the concentration of NO in the sample gas. At the same current, the EMF value became smaller as the concentration of NO increased. In order to elucidate this reason, we measured the gas composition in the outlet gas from the electrolysis cell. The results are summarized in Fig. 3. The formation of hydrogen was depressed in the presence of NO. Also, the concentration of NO decreased at more than 6 mA. These suggest that the formed hydrogen reacts with NO in the sample gas as follows: H 2 O 1 2e 2 H 2 1 O 2 2 , (1)

2. Experimental The experimental apparatus consisted of an electrolysis cell and an oxygen sensor, as shown in Fig. 1. YSZ disks were used as solid electrolytes of the two elements. The YSZ powders were purchased from Tosoh. These powders were pressed at 250 kg cm 2 2 and then sintered at 14508C for 10 h in air. The sintered compact was sliced into the form of a disk (12 mm diameter and 1.0 mm thickness). Two platinum electrodes, in the form of a porous lm, were attached to the surfaces of the disk by heating the assembly to 9008C for 1 h. The electrolysis cell was heated to 8008C. A mixture of 03000 ppm NO and 3% H 2 O in argon was introduced into the upper gas compartment at a ow-rate of 10 ml min 2 1 . Direct currents were applied from a galvanostat (Hokuto Denko HA-501) to the cell via two platinum wires. The outlet gas from the electrolysis cell was then introduced into

Fig. 1. Experimental apparatus consisting of two YSZ cells.

Fig. 2. Plots of EMF of oxygen sensor against current applied to electrolysis cell: solid electrolyte YSZ; operation temperature 8008C; 03000 ppm NO and 3% H 2 O in argon at a ow-rate of 10 ml min 2 1 .

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Fig. 4. Change in EMF of oxygen sensor with NO concentration in sample gas: operation temperature 8008C; 0500 ppm NO and 3% H 2 O in argon at a ow-rate of 10 ml min 2 1 ; current applied to electrolysis cell was kept at 6.7 mA.

Fig. 3. Concetrations of NO (a) and H 2 (b) in outlet gas from electrolysis cell: experimental conditions are as in Fig. 2.

H 2 1 NO H 2 O 1 1 / 2N 2 .

(2)

Probably, this reaction will occur on the platinum electrode of the electrolysis cell. The consumption of hydrogen for Eq. (2) will decrease the EMF value of the oxygen sensor in the presence of NO. As another reason, it can be considered that the electrolysis of NO directly occurs at the platinum electrode of the electrolysis cell. The electrolysis of water vapour is inhibited during this process, so that the formation of hydrogen is suppressed in the presence of NO. As shown in Fig. 3, however, the decrease in NO concentration began at 6 mA, where the voltage between the two electrodes of the electrolysis cell was 1.2 V. The electrolysis of NO is thermodynamically possible from 0 V. Thus, this consideration seems to be not suitable for the above reason. We applied the reaction represented by Eq. (2) to detect NO. Two potentiometric and amperometric manners were adopted to observe the sensor signal for the NO concentration. In the rst manner, the EMF value of the oxygen sensor was used as a

sensor signal, when a constant current was applied to the electrolysis cell. Fig. 4 shows a typical change in EMF of the oxygen sensor with the concentration of NO in the sample gas. In this case, the current applied to the electrolysis cell was kept at 6.7 mA. The EMF values observed at less than 200 ppm NO drastically decreased from 700 to 200 mV, while those observed at more than 200 ppm NO were held constant at 200 mV. This is due to the fact that the hydrogen formed by electrolyzing water vapour at 6.7 mA is entirely consumed by the reaction with 200 ppm NO in the sample gas. As described in the following part of this paper, when currents of more than 6.7 mA are applied to the electrolysis cell, the drastic decreases in EMF are observed at more than 200 ppm NO. In the secondary manner, the current applied to the electrolysis cell was used as another sensor signal, when the EMF value of the oxygen sensor was kept at a constant value. Fig. 5 shows the result keeping the EMF at 700 mV. The applied current almost linearly increased with NO concentration. This is due to additional application of current to the electrolysis cell so as to compensate for the amount of hydrogen consumed by reacting with NO. The present manner can be characterized by the fact that the relationship

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present method disappear when excess oxygen is present in the sample gas. In the following part of this paper, we will propose an approach for such a disadvantage.

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Fig. 5. Change in current applied to electrolysis cell with NO concentration in sample gas: EMF of oxygen sensor was kept at 700 mV; other conditions are as shown in Fig. 5.

between the sensor signal and the NO concentration is linear, although the sensitivity to NO is somewhat small at low concentrations. As described above, the use of electrolysis of water vapour enables one to detect NO with sensor signals of magnitude in millivolt or milliampere. However, there is a large need for the NOx sensors capable of monitoring NOx in the exhaust gases from lean-burn or diesel engines. Such gases generally contain more than several % oxygen. It is apparent that both the EMF and current signals in the