Unraveling the H(2) Promotional Effect on Palladium-Catalyzed CO Oxidation Using a Combination of Temporally and Spatially Resolved Investigations

[Image: see text] The promotional effect of H(2) on the oxidation of CO is of topical interest, and there is debate over whether this promotion is due to either thermal or chemical effects. As yet there is no definitive consensus in the literature. Combining spatially resolved mass spectrometry and X-ray absorption spectroscopy (XAS), we observe a specific environment of the active catalyst during CO oxidation, having the same specific local coordination of the Pd in both the absence and presence of H(2). In combination with Temporal Analysis of Products (TAP), performed under isothermal conditions, a mechanistic insight into the promotional effect of H(2) was found, providing clear evidence of nonthermal effects in the hydrogen-promoted oxidation of carbon monoxide. We have identified that H(2) promotes the Langmuir–Hinshelwood mechanism, and we propose this is linked to the increased interaction of O with the Pd surface in the presence of H(2). This combination of spatially resolved MS and XAS and TAP studies has provided previously unobserved insights into the nature of this promotional effect.