TY - JOUR
T1 - Structure Matters
T2 - Asymmetric CO Oxidation at Rh Steps with Different Atomic Packing
AU - García-Martínez, Fernando
AU - Rämisch, Lisa
AU - Ali, Khadiza
AU - Waluyo, Iradwikanari
AU - Bodero, Rodrigo Castrillo
AU - Pfaff, Sebastian
AU - Villar-García, Ignacio J.
AU - Walter, Andrew Leigh
AU - Hunt, Adrian
AU - Pérez-Dieste, Virginia
AU - Zetterberg, Johan
AU - Lundgren, Edvin
AU - Schiller, Frederik
AU - Ortega, J. Enrique
N1 - Funding Information:
We acknowledge financial support from Grant Nos. PID2020-116093RB-C44 and PID2019-107338RB-C6-3, funded by the Spanish MCIN/AEI/10.13039/501100011033 and by ERDF A way of making Europe, the Basque Government (Grant No. IT-1591-22), Knut and Alice Wallenberg (KAW) project Atomistic design of new catalysts (Project No. KAW2015.0058), the Swedish Research Council (Project No. 2018-03434), the Swedish Foundation for Strategic Research (Project No. ITM17-0045), the Å Forsk Foundation, and the Crafoord Foundation. This research used resources of the 23-ID-2 (IOS) beamline of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory, under Contract No. DE-SC0012704. Part of these experiments were performed at Circe beamline at ALBA Synchrotron with the collaboration of ALBA staff. Open Access funding is provided by the University of the Basque Country
Funding Information:
We acknowledge financial support from Grant Nos. PID2020-116093RB-C44 and PID2019-107338RB-C6-3, funded by the Spanish MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe”, the Basque Government (Grant No. IT-1591-22), Knut and Alice Wallenberg (KAW) project “Atomistic design of new catalysts” (Project No. KAW2015.0058), the Swedish Research Council (Project No. 2018-03434), the Swedish Foundation for Strategic Research (Project No. ITM17-0045), the Å Forsk Foundation, and the Crafoord Foundation. This research used resources of the 23-ID-2 (IOS) beamline of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory, under Contract No. DE-SC0012704. Part of these experiments were performed at Circe beamline at ALBA Synchrotron with the collaboration of ALBA staff. Open Access funding is provided by the University of the Basque Country.
Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/8/24
Y1 - 2022/8/24
N2 - 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 CO2fluorescence 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.
AB - 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 CO2fluorescence 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.
U2 - 10.1021/jacs.2c06733
DO - 10.1021/jacs.2c06733
M3 - Article
C2 - 35960901
AN - SCOPUS:85136602390
VL - 144
SP - 15363
EP - 15371
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 1520-5126
IS - 33
ER -