The carbon monoxide (CO) sensitivity of a mixed-potential-type yttria-stabilized zirconia (YSZ)-based tubular-type sensor utilizing a ZnCr(2)O(4) sensing electrode (SE) was tuned by the addition of different precious metal nanoparticles (Ag, Au, Ir, Pd, Pt, Ru and Rh; 1 wt % each) into the sensing layer. After measuring the electromotive force (emf) response of the fabricated SEs to 100 ppm of CO against a Pt/air-reference electrode (RE), the ZnCr(2)O(4)-Au nanoparticle composite electrode (ZnCr(2)O(4)(+Au)-SE) was found to give the highest response to CO. A linear dependence on the logarithm of CO concentration in the range of 20-800 ppm at an operational temperature of 550 °C under humid conditions (5 vol % water vapor) was observed. From the characterization of the ZnCr(2)O(4)(+Au)-SE, we can conclude that the engineered high response toward CO originated from the specific properties of submicrometer sized Au particles, formed via the coalescence of nanosized Au particles located on ZnCr(2)O(4) grains, during the calcining process at 1100 °C for 2 h. These particles augmented the catalytic activities of the gas-phase CO oxidation reaction in the SE layer, as well as to the anodic reaction of CO at the interface; while suppressing the cathodic reaction of O(2) at the interface. In addition, the response of the ZnCr(2)O(4)(+Au)-SE sensor toward 100 ppm of CO gradually increased throughout the 10 days of operation, and plateaued for the remainder of the month that the sensor was examined. Correlations between SEM observations and the CO sensing characteristics of the present sensor were suggestive that the sensitivity was mostly affected by the morphology of the Au particles and their catalytic activities, which were in close proximity to the ZnCr(2)O(4) grains. Furthermore, by measuring the potential difference (emf) between the ZnCr(2)O(4)(+Au) and a ZnCr(2)O(4) electrode, sensitivities to typical exhaust component gases other than CO were found to be negligible at 550 °C.
© 2011 American Chemical Society