Steps on Pt stereodynamically filter sticking of O2

TitleSteps on Pt stereodynamically filter sticking of O2
Publication TypeJournal Article
Year of Publication2019
AuthorsK. Cao, R. van Lent, A.W Kleyn, M. Kurahashi, L.BF Juurlink
JournalProceedings of the National Academy of Sciences
Volume116
Issue28
Pagination13862-13866
Date Published07/2019
Abstract

Platinum is widely applied as an oxidation catalyst. The surfaces of metallic catalyst particles are generally composed of atomically flat planes connected by edges. In this paper, we unveil how Pt edges affect O2 sticking. Opposing types of behaviors are observed for high and low incident energies. The dependencies identify the mechanisms by which O2 molecules stick, which is the first step in the oxidation reactions.Low coordinated sites on catalytic surfaces often enhance reactivity, but the underlying dynamical processes are poorly understood. Using two independent approaches, we investigate the reactivity of O2 impinging onto platinum and resolve how step edges on (111) terraces enhance sticking. At low incident energy, the linear dependence on step density, independence of step type, and insensitivity to O2's molecular alignment show that trapping into a physisorbed state precedes molecular chemisorption and dissociation. At higher impact energies, direct molecular chemisorption occurs in parallel on steps and terraces. While terraces are insensitive to alignment of the molecule within the (111) plane, steps favor molecules impacting with their internuclear axis parallel to the edge. Stereodynamical filtering thus controls sticking and dissociation of O2 on Pt with a twofold role of steps.

DOI10.1073/pnas.1902846116
Division

MaSF

Department

MSS

PID1c4482d6ac0305887910cb515820f621
Alternate TitleProc. Nat. Acad. Sci. USA
LabelOA

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