Structure Matters: Asymmetric CO Oxidation at Rh Steps with Different Atomic Packing

García-Martínez, Fernando; Rämisch, Lisa; Ali, Khadiza; Waluyo, Iradwikanari; Bodero, Rodrigo Castrillo; Pfaff, Sebastian; Villar-García, Ignacio J.; Walter, Andrew Leigh; Hunt, Adrian; Pérez-Dieste, Virginia; Zetterberg, Johan; Lundgren, Edvin; Schiller, Frederik; Ortega, J. Enrique

doi:10.1021/jacs.2c06733

Title: Structure Matters: Asymmetric CO Oxidation at Rh Steps with Different Atomic Packing

Journal Article · 11 August 2022 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.2c06733 · OSTI ID:2319175

^[1]; Rämisch, Lisa ^[2]; Ali, Khadiza ^[3];

^[4];

^[3];

^[2]; Villar-García, Ignacio J. ^[5]; Walter, Andrew Leigh ^[4];

^[4]; Pérez-Dieste, Virginia ^[5];

^[2];

^[3];

^[6]

Universidad del País Vasco, San Sebastián (Spain)
Lund Univ. (Sweden)
Centro de Física de Materiales CSIC/UPV-EHU-Materials Physics Center, San Sebastián (Spain)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
NAPP Station, CIRCE Beamline, ALBA synchrotron, Cerdanyola del Vallès (Spain)
Universidad del País Vasco, San Sebastián (Spain); Centro de Física de Materiales CSIC/UPV-EHU-Materials Physics Center, San Sebastián (Spain); Donostia International Physics Centre, San Sebastián (Spain)

Curved crystals are a simple but powerful approach to bridge the gap between single crystal surfaces and nanoparticle catalysts, by allowing a rational assessment of the role of active step sites in gas-surface reactions. Using a curved Rh(111) crystal, here, we investigate the effect of A-type (square geometry) and B-type (triangular geometry) atomic packing of steps on the catalytic CO oxidation on Rh at millibar pressures. Imaging the crystal during reaction ignition with laser-induced CO₂ fluorescence demonstrates a two-step process, where B-steps ignite at lower temperature than A-steps. Such fundamental dissimilarity is explained in ambient pressure X-ray photoemission (AP-XPS) experiments, which reveal partial CO desorption and oxygen buildup only at B-steps. AP-XPS also proves that A-B step asymmetries extend to the active stage: at A-steps, low-active O–Rh–O trilayers buildup immediately after ignition, while highly active chemisorbed O is the dominant species on B-type steps. We conclude that B-steps are more efficient than A-steps for the CO oxidation.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: Basque Government; Ministry of Science, Innovation and Universities (MICINN); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2319175

Report Number(s):: BNL--225367-2024-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 33 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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