Catalytic Oxidation of CO on a Curved Pt(111) Surface: Simultaneous Ignition at All Facets through a Transient CO‐O Complex**
Fernando García‐Martínez, Carlos Iglesias Fernández, Juan Pablo Simonovis, Adrian Hunt, Andrew L. Walter, Iradwikanari Waluyo, Florian Bertram, Lindsay R. Merte, Mikhail Shipilin, Sebastian Pfaff, Sara Blomberg, Johan Zetterberg, Johan Gustafson, Edvin Lundgren, Daniel Sánchez‐Portal, Frederik Schiller, J. Enrique Ortega
Abstract
The catalytic oxidation of CO on transition metals, such as Pt, is commonly viewed as a sharp transition from the CO-inhibited surface to the active metal, covered with O. However, we find that minor amounts of O are present in the CO-poisoned layer that explain why, surprisingly, CO desorbs at stepped and flat Pt crystal planes at once, regardless of the reaction conditions. Using near-ambient pressure X-ray photoemission and a curved Pt(111) crystal we probe the chemical composition at surfaces with variable step density during the CO oxidation reaction. Analysis of C and O core levels across the curved crystal reveals that, right before light-off, subsurface O builds up within (111) terraces. This is key to trigger the simultaneous ignition of the catalytic reaction at different Pt surfaces: a CO-Pt-O complex is formed that equals the CO chemisorption energy at terraces and steps, leading to the abrupt desorption of poisoning CO from all crystal facets at the same temperature.