Reduction and Agglomeration of Supported Metal Clusters Induced by High-Flux X-ray Absorption Spectroscopy Measurements

Malik Albrahim; Coogan Thompson; Denis Leshchev; Abhijit Shrotri; Raymond R. Unocic; Jiyun Hong; Adam S. Hoffman; Michael J. Meloni; Ron C. Runnebaum; Simon R. Bare; Eli Stavitski; Ayman M. Karim

doi:10.1021/acs.jpcc.1c01823

Reduction and Agglomeration of Supported Metal Clusters Induced by High-Flux X-ray Absorption Spectroscopy Measurements

Malik Albrahim, Coogan Thompson, Denis Leshchev, Abhijit Shrotri, Raymond R. Unocic, Jiyun Hong, Adam S. Hoffman, Michael J. Meloni, Ron C. Runnebaum, Simon R. Bare, Eli Stavitski, Ayman M. Karim

Materials MicroAnalysis

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Abstract

Supported metal clusters are widely used in catalysis for many important reactions. To understand the catalytic properties, in situ/operando characterization techniques, such as X-ray absorption spectroscopy (XAS), provide essential details of the size, shape, and chemical composition of the cluster and the nature of the active sites. New-generation synchrotrons combined with focusing beamlines provide high-flux-density X-rays for improved detection sensitivity as well as higher time and spatial resolution. Understanding the effects of a high-flux-density X-ray beam on the catalyst during the actual measurement, whether XAS or another synchrotron-based technique, is crucial. This is especially important for in situ and operando studies where both the high flux density and reaction conditions can affect the catalyst structure. In this work, we investigated the effect of the flux density on rhodium clusters supported on Al2O3 at two different beamlines: National Synchrotron Light Source II beamline 08-ID and Stanford Synchrotron Radiation Light Source (SSRL) beamline 4-1. We show that the higher flux density at beamline 08-ID causes the reduction of the highly dispersed RhOx/Al2O3 catalyst, even at room temperature. Additionally, exposure to the higher flux density X-rays at beamline 08-ID during in situ reduction results in significant agglomeration of the Rh clusters. The final size of the Rh nanoparticles reduced at 310 °C is equivalent to that of particles formed after the reduction at 600-650 °C in the absence of the beam. Significant beam-induced reduction and agglomeration is also shown for Ni supported on beta zeolite during in situ reduction at an intermediate-flux-density beamline 9-3 at SSRL, indicating that beam-induced changes in heterogeneous catalysts could be common at intermediate- and high-flux-density beamlines. We provide precautions and recommendations for detecting and minimizing beam damage during in situ/operando XAS measurements.

Original language	English
Pages (from-to)	11048-11057
Number of pages	10
Journal	Journal of Physical Chemistry C
Volume	125
Issue number	20
DOIs	https://doi.org/10.1021/acs.jpcc.1c01823
State	Published - May 27 2021

Funding

This research was primarily sponsored by the Army Research Office and was accomplished under grant number W911NF-19-1-0308. A part of this work was supported by the Cooperative Research Program of Institute for Catalysis, Hokkaido University (20A1004). Support from the Nanotechnology Platform Program of the Ministry of Education, Culture, Sports, Science and Technology (MEXT) is also acknowledged. STEM imaging was conducted at the Center for Nanophase Materials Sciences, which is a Department of Energy Office of Science User Facility (R.R.U.) 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 4-1, 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. This research used beamline 08-ID (ISS) 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.

Funders	Funder number
Institute for Catalysis, Hokkaido University	20A1004
U.S. Department of Energy
Army Research Office	W911NF-19-1-0308
Office of Science
Basic Energy Sciences	DE-AC02-76SF00515
Brookhaven National Laboratory	DE-SC0012704
Chemical Sciences, Geosciences, and Biosciences Division
Ministry of Education, Culture, Sports, Science and Technology
University of Hail
Saudi Arabian Cultural Mission

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10.1021/acs.jpcc.1c01823

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Albrahim, M., Thompson, C., Leshchev, D., Shrotri, A., Unocic, R. R., Hong, J., Hoffman, A. S., Meloni, M. J., Runnebaum, R. C., Bare, S. R., Stavitski, E., & Karim, A. M. (2021). Reduction and Agglomeration of Supported Metal Clusters Induced by High-Flux X-ray Absorption Spectroscopy Measurements. Journal of Physical Chemistry C, 125(20), 11048-11057. https://doi.org/10.1021/acs.jpcc.1c01823

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title = "Reduction and Agglomeration of Supported Metal Clusters Induced by High-Flux X-ray Absorption Spectroscopy Measurements",

abstract = "Supported metal clusters are widely used in catalysis for many important reactions. To understand the catalytic properties, in situ/operando characterization techniques, such as X-ray absorption spectroscopy (XAS), provide essential details of the size, shape, and chemical composition of the cluster and the nature of the active sites. New-generation synchrotrons combined with focusing beamlines provide high-flux-density X-rays for improved detection sensitivity as well as higher time and spatial resolution. Understanding the effects of a high-flux-density X-ray beam on the catalyst during the actual measurement, whether XAS or another synchrotron-based technique, is crucial. This is especially important for in situ and operando studies where both the high flux density and reaction conditions can affect the catalyst structure. In this work, we investigated the effect of the flux density on rhodium clusters supported on Al2O3 at two different beamlines: National Synchrotron Light Source II beamline 08-ID and Stanford Synchrotron Radiation Light Source (SSRL) beamline 4-1. We show that the higher flux density at beamline 08-ID causes the reduction of the highly dispersed RhOx/Al2O3 catalyst, even at room temperature. Additionally, exposure to the higher flux density X-rays at beamline 08-ID during in situ reduction results in significant agglomeration of the Rh clusters. The final size of the Rh nanoparticles reduced at 310 °C is equivalent to that of particles formed after the reduction at 600-650 °C in the absence of the beam. Significant beam-induced reduction and agglomeration is also shown for Ni supported on beta zeolite during in situ reduction at an intermediate-flux-density beamline 9-3 at SSRL, indicating that beam-induced changes in heterogeneous catalysts could be common at intermediate- and high-flux-density beamlines. We provide precautions and recommendations for detecting and minimizing beam damage during in situ/operando XAS measurements.",

author = "Malik Albrahim and Coogan Thompson and Denis Leshchev and Abhijit Shrotri and Unocic, {Raymond R.} and Jiyun Hong and Hoffman, {Adam S.} and Meloni, {Michael J.} and Runnebaum, {Ron C.} and Bare, {Simon R.} and Eli Stavitski and Karim, {Ayman M.}",

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Albrahim, M, Thompson, C, Leshchev, D, Shrotri, A, Unocic, RR, Hong, J, Hoffman, AS, Meloni, MJ, Runnebaum, RC, Bare, SR, Stavitski, E & Karim, AM 2021, 'Reduction and Agglomeration of Supported Metal Clusters Induced by High-Flux X-ray Absorption Spectroscopy Measurements', Journal of Physical Chemistry C, vol. 125, no. 20, pp. 11048-11057. https://doi.org/10.1021/acs.jpcc.1c01823

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T1 - Reduction and Agglomeration of Supported Metal Clusters Induced by High-Flux X-ray Absorption Spectroscopy Measurements

AU - Albrahim, Malik

AU - Thompson, Coogan

AU - Leshchev, Denis

AU - Shrotri, Abhijit

AU - Unocic, Raymond R.

AU - Hong, Jiyun

AU - Hoffman, Adam S.

AU - Meloni, Michael J.

AU - Runnebaum, Ron C.

AU - Bare, Simon R.

AU - Stavitski, Eli

AU - Karim, Ayman M.

PY - 2021/5/27

Y1 - 2021/5/27

N2 - Supported metal clusters are widely used in catalysis for many important reactions. To understand the catalytic properties, in situ/operando characterization techniques, such as X-ray absorption spectroscopy (XAS), provide essential details of the size, shape, and chemical composition of the cluster and the nature of the active sites. New-generation synchrotrons combined with focusing beamlines provide high-flux-density X-rays for improved detection sensitivity as well as higher time and spatial resolution. Understanding the effects of a high-flux-density X-ray beam on the catalyst during the actual measurement, whether XAS or another synchrotron-based technique, is crucial. This is especially important for in situ and operando studies where both the high flux density and reaction conditions can affect the catalyst structure. In this work, we investigated the effect of the flux density on rhodium clusters supported on Al2O3 at two different beamlines: National Synchrotron Light Source II beamline 08-ID and Stanford Synchrotron Radiation Light Source (SSRL) beamline 4-1. We show that the higher flux density at beamline 08-ID causes the reduction of the highly dispersed RhOx/Al2O3 catalyst, even at room temperature. Additionally, exposure to the higher flux density X-rays at beamline 08-ID during in situ reduction results in significant agglomeration of the Rh clusters. The final size of the Rh nanoparticles reduced at 310 °C is equivalent to that of particles formed after the reduction at 600-650 °C in the absence of the beam. Significant beam-induced reduction and agglomeration is also shown for Ni supported on beta zeolite during in situ reduction at an intermediate-flux-density beamline 9-3 at SSRL, indicating that beam-induced changes in heterogeneous catalysts could be common at intermediate- and high-flux-density beamlines. We provide precautions and recommendations for detecting and minimizing beam damage during in situ/operando XAS measurements.

AB - Supported metal clusters are widely used in catalysis for many important reactions. To understand the catalytic properties, in situ/operando characterization techniques, such as X-ray absorption spectroscopy (XAS), provide essential details of the size, shape, and chemical composition of the cluster and the nature of the active sites. New-generation synchrotrons combined with focusing beamlines provide high-flux-density X-rays for improved detection sensitivity as well as higher time and spatial resolution. Understanding the effects of a high-flux-density X-ray beam on the catalyst during the actual measurement, whether XAS or another synchrotron-based technique, is crucial. This is especially important for in situ and operando studies where both the high flux density and reaction conditions can affect the catalyst structure. In this work, we investigated the effect of the flux density on rhodium clusters supported on Al2O3 at two different beamlines: National Synchrotron Light Source II beamline 08-ID and Stanford Synchrotron Radiation Light Source (SSRL) beamline 4-1. We show that the higher flux density at beamline 08-ID causes the reduction of the highly dispersed RhOx/Al2O3 catalyst, even at room temperature. Additionally, exposure to the higher flux density X-rays at beamline 08-ID during in situ reduction results in significant agglomeration of the Rh clusters. The final size of the Rh nanoparticles reduced at 310 °C is equivalent to that of particles formed after the reduction at 600-650 °C in the absence of the beam. Significant beam-induced reduction and agglomeration is also shown for Ni supported on beta zeolite during in situ reduction at an intermediate-flux-density beamline 9-3 at SSRL, indicating that beam-induced changes in heterogeneous catalysts could be common at intermediate- and high-flux-density beamlines. We provide precautions and recommendations for detecting and minimizing beam damage during in situ/operando XAS measurements.

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Reduction and Agglomeration of Supported Metal Clusters Induced by High-Flux X-ray Absorption Spectroscopy Measurements

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