Operando Spectroscopy Unveils the Catalytic Role of Different Palladium Oxidation States in CO Oxidation on Pd/CeO2 Catalysts

Valery Muravev; Jérôme F.M. Simons; Alexander Parastaev; Marcel A. Verheijen; Job J.C. Struijs; Nikolay Kosinov; Emiel J.M. Hensen

doi:10.1002/anie.202200434

Operando Spectroscopy Unveils the Catalytic Role of Different Palladium Oxidation States in CO Oxidation on Pd/CeO₂ Catalysts

Valery Muravev, Jérôme F.M. Simons, Alexander Parastaev, Marcel A. Verheijen, Job J.C. Struijs, Nikolay Kosinov, Emiel J.M. Hensen (Corresponding author)

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Abstract

Aiming at knowledge-driven design of novel metal–ceria catalysts for automotive exhaust abatement, current efforts mostly pertain to the synthesis and understanding of well-defined systems. In contrast, technical catalysts are often heterogeneous in their metal speciation. Here, we unveiled rich structural dynamics of a conventional impregnated Pd/CeO₂ catalyst during CO oxidation. In situ X-ray photoelectron spectroscopy and operando X-ray absorption spectroscopy revealed the presence of metallic and oxidic Pd states during the reaction. Using transient operando infrared spectroscopy, we probed the nature and reactivity of the surface intermediates involved in CO oxidation. We found that while low-temperature activity is associated with sub-oxidized and interfacial Pd sites, the reaction at elevated temperatures involves metallic Pd. These results highlight the utility of the multi-technique operando approach for establishing structure–activity relationships of technical catalysts.

Original language	English
Article number	e202200434
Number of pages	10
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	23
DOIs	https://doi.org/10.1002/anie.202200434
Publication status	Published - 7 Jun 2022

Bibliographical note

Funding Information:
V.M. and E.J.M.H. acknowledge support by the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), a NWO Gravitation program funded by the Ministry of Education, Culture and Science of the government of the Netherlands. We acknowledge access to synchrotron radiation facilities under proposal I‐20200722 EC at beamline P65 of PETRAIII, DESY and under proposal SP22225 at B18 beamline of Diamond Light Source. We thank E. Uslamin for help with operando XAS experiments. Solliance and the Dutch province of Noord‐Brabant are acknowledged for funding the TEM facility.

Funding Information:
V.M. and E.J.M.H. acknowledge support by the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), a NWO Gravitation program funded by the Ministry of Education, Culture and Science of the government of the Netherlands. We acknowledge access to synchrotron radiation facilities under proposal I-20200722 EC at beamline P65 of PETRAIII, DESY and under proposal SP22225 at B18 beamline of Diamond Light Source. We thank E. Uslamin for help with operando XAS experiments. Solliance and the Dutch province of Noord-Brabant are acknowledged for funding the TEM facility.

Publisher Copyright:
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Keywords

Ceria
CO Oxidation
NAP-XPS
Operando DRIFTS
Structure–Activity Relationships

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title = "Operando Spectroscopy Unveils the Catalytic Role of Different Palladium Oxidation States in CO Oxidation on Pd/CeO2 Catalysts",

abstract = "Aiming at knowledge-driven design of novel metal–ceria catalysts for automotive exhaust abatement, current efforts mostly pertain to the synthesis and understanding of well-defined systems. In contrast, technical catalysts are often heterogeneous in their metal speciation. Here, we unveiled rich structural dynamics of a conventional impregnated Pd/CeO2 catalyst during CO oxidation. In situ X-ray photoelectron spectroscopy and operando X-ray absorption spectroscopy revealed the presence of metallic and oxidic Pd states during the reaction. Using transient operando infrared spectroscopy, we probed the nature and reactivity of the surface intermediates involved in CO oxidation. We found that while low-temperature activity is associated with sub-oxidized and interfacial Pd sites, the reaction at elevated temperatures involves metallic Pd. These results highlight the utility of the multi-technique operando approach for establishing structure–activity relationships of technical catalysts.",

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author = "Valery Muravev and Simons, {J{\'e}r{\^o}me F.M.} and Alexander Parastaev and Verheijen, {Marcel A.} and Struijs, {Job J.C.} and Nikolay Kosinov and Hensen, {Emiel J.M.}",

note = "Funding Information: V.M. and E.J.M.H. acknowledge support by the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), a NWO Gravitation program funded by the Ministry of Education, Culture and Science of the government of the Netherlands. We acknowledge access to synchrotron radiation facilities under proposal I‐20200722 EC at beamline P65 of PETRAIII, DESY and under proposal SP22225 at B18 beamline of Diamond Light Source. We thank E. Uslamin for help with operando XAS experiments. Solliance and the Dutch province of Noord‐Brabant are acknowledged for funding the TEM facility. Funding Information: V.M. and E.J.M.H. acknowledge support by the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), a NWO Gravitation program funded by the Ministry of Education, Culture and Science of the government of the Netherlands. We acknowledge access to synchrotron radiation facilities under proposal I-20200722 EC at beamline P65 of PETRAIII, DESY and under proposal SP22225 at B18 beamline of Diamond Light Source. We thank E. Uslamin for help with operando XAS experiments. Solliance and the Dutch province of Noord-Brabant are acknowledged for funding the TEM facility. Publisher Copyright: {\textcopyright} 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

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AU - Muravev, Valery

AU - Simons, Jérôme F.M.

AU - Parastaev, Alexander

AU - Verheijen, Marcel A.

AU - Struijs, Job J.C.

AU - Kosinov, Nikolay

AU - Hensen, Emiel J.M.

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M1 - e202200434

ER -

Operando Spectroscopy Unveils the Catalytic Role of Different Palladium Oxidation States in CO Oxidation on Pd/CeO₂ Catalysts

Abstract

Bibliographical note

Keywords

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Center for Multiscale Electron Microscopy (CMEM)

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Operando Spectroscopy Unveils the Catalytic Role of Different Palladium Oxidation States in CO Oxidation on Pd/CeO2 Catalysts

Abstract

Bibliographical note

Keywords

Access to Document

Other files and links

Fingerprint

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Center for Multiscale Electron Microscopy (CMEM)

Cite this

Operando Spectroscopy Unveils the Catalytic Role of Different Palladium Oxidation States in CO Oxidation on Pd/CeO₂ Catalysts