The CO oxidation reaction on the Pd(111) model catalyst at various temperatures (200–400 °C) under hundreds mTorr pressure conditions has been monitored by in situ ambient pressure X-ray photoelectron spectroscopy and mass spectroscopy. In situ observation of the reaction revealed that the Pd(111) surface is covered by CO molecules at a lower temperature (200 °C), while at higher temperatures (300–400 °C) several oxide phases are formed on the surface. We found that the reactivity is enhanced in the presence of a surface oxide and significantly suppressed by formation of a cluster oxide and the PdO bulk oxide. CO titration experiments suggest that less coordinated oxygen atoms are more reactive for CO oxidation.

Catalytic CO oxidation reaction on a Pd(100) single-crystal surface under several hundred mTorr pressure conditions has been studied by ambient pressure X-ray photoelectron spectroscopy and mass spectroscopy. In-situ observation of the reaction reveals that two reaction pathways switch over alternatively depending on the surface temperature. At lower temperatures, the Pd(100) surface is covered by CO molecules and the CO2 formation rate is low, indicating CO poisoning. At higher temperatures above 190 °C, an O-Pd-O trilayer surface oxide phase is formed on the surface and the CO2 formation rate drastically increases. It is likely that the enhanced rate of CO2 formation is associated with an active oxygen species that is located at the surface of the trilayer oxide.

We investigated the high-density CO adsorption phase formed on a Pt(111) surface when exposed to CO gas of pressure ranging from UHV to 100 mTorr using near-ambient-pressure (NAP)-XPS. Combined results from the NAP-XPS measurements and DFT calculations reveal the adsorption structure of CO molecules in the dense CO overlayer, which is stable under realistic conditions.

CO oxidation reaction on a Pd(110) single crystal surface at various temperatures under near-ambient-pressure conditions has been investigated using in situ X-ray photoemission spectroscopy and mass spectroscopy. At lower temperature conditions, the CO2 formation rate is low, where the surface is covered by CO molecules (i.e., CO poisoning). Above a critical temperature 165 °C the Pd(110) surface converts to a catalytically active surface and is dominated by chemisorbed oxygen species. Further at the higher temperatures up to 320 °C, the CO2 formation rate is gradually decreased to about 80% of the maximum rate. At this moment, the amount of chemisorbed O was also decreased, which suggests that the CO oxidation reaction proceeds via the conventional Langmuir–Hinshelwood mechanism even under near-ambient pressure conditions.

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