In polymer electrolyte fuel cell (PEFC) systems, small amounts of ammonia (NH3 ) present in the reformate gas deactivate the supported ruthenium catalysts used for preferential oxidation (PROX) of carbon monoxide (CO). In this study, we investigated how the addition of a small amount of platinum to a Ru/α-Al2 O3 catalyst (Pt/Ru=1:9 w/w) affected the catalyst's PROX activity in both the absence and the presence of NH3 (130 ppm) under conditions mimicking the reformate conditions during steam reforming of natural gas. The activity of undoped Ru/α-Al2 O3 decreased sharply upon addition of NH3 , whereas Pt/Ru/α-Al2 O3 exhibited excellent PROX activity even in the presence of NH3 . Ruthenium K-edge X-ray absorption near-edge structure (XANES) spectra indicated that in the presence of NH3 , some of the ruthenium in the undoped catalyst was oxidized in the presence of NH3 , whereas ruthenium oxidation was not observed with Pt/Ru/α-Al2 O3 . These results suggest that ruthenium oxidation is retarded by the platinum, so that the catalyst shows high activity even in the presence of NH3 .

Hydrogen is a promising clean energy source. In domestic polymer electrolyte fuel cell systems, hydrogen is produced by reforming of natural gas; however, the reformate contains carbon monoxide (CO) as a major impurity. This CO is removed from the reformate by a combination of the water–gas shift reaction and preferential oxidation of CO (PROX). Currently, Ru-based catalysts are the most common type of PROX catalyst; however, their durability against ammonia (NH 3 ) as an impurity produced in situ from trace amounts of nitrogen also contained in the reformate is an important issue. Previously, we found that addition of Pt to an Ru catalyst inhibited deactivation by NH 3 . Here, we conducted operando XAFS and FT-IR spectroscopic analyses with simultaneous gas analysis to investigate the cause of the deactivation of an Ru-based PROX catalyst (Ru/α-Al 2 O 3 ) by NH 3 and the mechanism of suppression of the deactivation by adding Pt (Pt/Ru/α-Al 2 O 3 ). We found that nitric oxide (NO) produced by oxidation of NH 3 induces oxidation of the Ru nanoparticle surface, which deactivates the catalyst via a three-step process: First, NO directly adsorbs on Ru 0 to form NO-Ru δ+ , which then induces the formation of O-Ru n + by oxidation of the surrounding Ru 0 . Then, O-Ru m + is formed by oxidation of Ru 0 starting from the O-Ru n + nuclei and spreading across the surface of the nanoparticle. Pt inhibits this process by alloying with Ru and inducing the decomposition of adsorbed NO, which keeps the Ru in a metallic state.

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