Size-Dependent Dispersion of Rhodium Clusters into Isolated Single Atoms at Low Temperature and the Consequences for CO Oxidation Activity

Malik A. Albrahim; Abhijit Shrotri; Raymond R. Unocic; Adam S. Hoffman; Simon R. Bare; Ayman M. Karim

doi:10.1002/anie.202308002

Size-Dependent Dispersion of Rhodium Clusters into Isolated Single Atoms at Low Temperature and the Consequences for CO Oxidation Activity

Malik A. Albrahim, Abhijit Shrotri, Raymond R. Unocic, Adam S. Hoffman, Simon R. Bare, Ayman M. Karim

Materials MicroAnalysis

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

Understanding the dynamic structural evolution of supported metal clusters under reaction conditions is crucial to develop structure reactivity relations. Here, we followed the structure of different size Rh clusters supported on Al₂O₃ using in situ/operando spectroscopy and ex situ aberration-corrected electron microscopy. We report a dynamic evolution of rhodium clusters into thermally stable isolated single atoms upon exposure to oxygen and during CO oxidation. Rh clusters partially disperse into single atoms at room temperature and the extent of dispersion increases as the Rh size decreases and as the reaction temperature increases. A strong correlation is found between the extent of dispersion and the CO oxidation kinetics. More importantly, dispersing Rh clusters into single atoms increases the activity at room temperature by more than two orders of magnitude due to the much lower activation energy on single atoms (40 vs. 130 kJ/mol). This work demonstrates that the structure and reactivity of small Rh clusters are very sensitive to the reaction environment.

Original language	English
Article number	e202308002
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	44
DOIs	https://doi.org/10.1002/anie.202308002
State	Published - Oct 26 2023

Funding

This research was primarily sponsored by the Army Research Office and was accomplished under grant number W911NF-19-1-0308. A. M. K. also acknowledges support from the Army Research Office under Grant number W911NF-20-2-0058. A part of this work was supported by the Cooperative Research Program of Institute for Catalysis, Hokkaido University (20A1004 and 22DS0123). Support from the Nanotechnology Platform Program of the Ministry of Education, Culture, Sports, Science and Technology (MEXT) is also acknowledged. M. A. acknowledges support by the graduate fellowship sponsored by the Saudi Arabian Cultural Mission (SACM) and University of Hail (UOH). Use of the Stanford Synchrotron Radiation Light Source (SSRL, beamline 9–3, user proposal 4645), SLAC National Accelerator Laboratory is supported by the U.S. Department of Energy, office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. Additional support by the Consortium for Operando and Advanced Catalyst Characterization via Electronic Spectroscopy and Structure (Co-ACCESS) at SLAC is acknowledged. Co-ACCESS, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences under Contract DE-AC02-76SF00515. STEM imaging was conducted as part of a user project at the Center for Nanophase Materials Sciences (CNMS), which is a U.S. Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. This research was primarily sponsored by the Army Research Office and was accomplished under grant number W911NF‐19‐1‐0308. A. M. K. also acknowledges support from the Army Research Office under Grant number W911NF‐20‐2‐0058. A part of this work was supported by the Cooperative Research Program of Institute for Catalysis, Hokkaido University (20A1004 and 22DS0123). Support from the Nanotechnology Platform Program of the Ministry of Education, Culture, Sports, Science and Technology (MEXT) is also acknowledged. M. A. acknowledges support by the graduate fellowship sponsored by the Saudi Arabian Cultural Mission (SACM) and University of Hail (UOH). Use of the Stanford Synchrotron Radiation Light Source (SSRL, beamline 9–3, user proposal 4645), SLAC National Accelerator Laboratory is supported by the U.S. Department of Energy, office of Basic Energy Sciences under Contract No. DE‐AC02‐76SF00515. Additional support by the Consortium for Operando and Advanced Catalyst Characterization via Electronic Spectroscopy and Structure (Co‐ACCESS) at SLAC is acknowledged. Co‐ACCESS, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences under Contract DE‐AC02‐76SF00515. STEM imaging was conducted as part of a user project at the Center for Nanophase Materials Sciences (CNMS), which is a U.S. Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory.

Keywords

CO oxidation
in situ spectroscopy
reconstruction
single atom catalysts
structure sensitivity

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10.1002/anie.202308002

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title = "Size-Dependent Dispersion of Rhodium Clusters into Isolated Single Atoms at Low Temperature and the Consequences for CO Oxidation Activity",

abstract = "Understanding the dynamic structural evolution of supported metal clusters under reaction conditions is crucial to develop structure reactivity relations. Here, we followed the structure of different size Rh clusters supported on Al2O3 using in situ/operando spectroscopy and ex situ aberration-corrected electron microscopy. We report a dynamic evolution of rhodium clusters into thermally stable isolated single atoms upon exposure to oxygen and during CO oxidation. Rh clusters partially disperse into single atoms at room temperature and the extent of dispersion increases as the Rh size decreases and as the reaction temperature increases. A strong correlation is found between the extent of dispersion and the CO oxidation kinetics. More importantly, dispersing Rh clusters into single atoms increases the activity at room temperature by more than two orders of magnitude due to the much lower activation energy on single atoms (40 vs. 130 kJ/mol). This work demonstrates that the structure and reactivity of small Rh clusters are very sensitive to the reaction environment.",

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AU - Albrahim, Malik A.

AU - Shrotri, Abhijit

AU - Unocic, Raymond R.

AU - Hoffman, Adam S.

AU - Bare, Simon R.

AU - Karim, Ayman M.

PY - 2023/10/26

Y1 - 2023/10/26

N2 - Understanding the dynamic structural evolution of supported metal clusters under reaction conditions is crucial to develop structure reactivity relations. Here, we followed the structure of different size Rh clusters supported on Al2O3 using in situ/operando spectroscopy and ex situ aberration-corrected electron microscopy. We report a dynamic evolution of rhodium clusters into thermally stable isolated single atoms upon exposure to oxygen and during CO oxidation. Rh clusters partially disperse into single atoms at room temperature and the extent of dispersion increases as the Rh size decreases and as the reaction temperature increases. A strong correlation is found between the extent of dispersion and the CO oxidation kinetics. More importantly, dispersing Rh clusters into single atoms increases the activity at room temperature by more than two orders of magnitude due to the much lower activation energy on single atoms (40 vs. 130 kJ/mol). This work demonstrates that the structure and reactivity of small Rh clusters are very sensitive to the reaction environment.

AB - Understanding the dynamic structural evolution of supported metal clusters under reaction conditions is crucial to develop structure reactivity relations. Here, we followed the structure of different size Rh clusters supported on Al2O3 using in situ/operando spectroscopy and ex situ aberration-corrected electron microscopy. We report a dynamic evolution of rhodium clusters into thermally stable isolated single atoms upon exposure to oxygen and during CO oxidation. Rh clusters partially disperse into single atoms at room temperature and the extent of dispersion increases as the Rh size decreases and as the reaction temperature increases. A strong correlation is found between the extent of dispersion and the CO oxidation kinetics. More importantly, dispersing Rh clusters into single atoms increases the activity at room temperature by more than two orders of magnitude due to the much lower activation energy on single atoms (40 vs. 130 kJ/mol). This work demonstrates that the structure and reactivity of small Rh clusters are very sensitive to the reaction environment.

KW - CO oxidation

KW - in situ spectroscopy

KW - reconstruction

KW - single atom catalysts

KW - structure sensitivity

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ER -

Size-Dependent Dispersion of Rhodium Clusters into Isolated Single Atoms at Low Temperature and the Consequences for CO Oxidation Activity

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Keywords

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