NASICON (Na
3Zr
2Si
2PO
12)-based solid electrolyte-type sensors equipped with various metal oxides (MO)-added Pt sensing electrode (SE, Pt(
nMO) (
n: MO additive amount in wt%) and Pt counter electrode (CE, Pt) on the same side of the NASICON disc were fabricated and their (Pt(
nMO)/Pt sensors) CO-sensing properties were examined at 25–300°C. The Pt(
15Bi
2O
3)/Pt sensor showed the largest CO response with a change in electromotive force to a positive direction (positive response) at 25°C, while the Pt(
15CeO
2)/Pt sensor showed the largest negative CO response at 25°C. The CO response of the Pt(
15CeO
2)/Pt sensor seems to be determined by mixed potential at the triple phase boundaries (TPBs) containing the electrochemical reactions of CO oxidation and oxygen reduction. X-ray photoelectron spectroscopy of the Pt(
15Bi
2O
3) SE before and after exposure to CO indicated a slight reduction of Bi
3+ after the exposure to CO. Therefore, the additional electrochemical reactions containing the reduction of Bi
2O
3 were anticipated to occur at the TPBs of the Pt(
15Bi
2O
3) SE, which resulted in the large positive CO response of the Pt(
15Bi
2O
3)/Pt sensor. Furthermore, the addition of
15 wt% CeO
2 to Pt CE of the Pt(
15Bi
2O
3)/Pt sensor largely enhanced the magnitude of CO response and attained relatively excellent CO selectivity against H
2.
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