Improved Pd/CeO2 Catalysts for Low-Temperature NO Reduction: Activation of CeO2 Lattice Oxygen by Fe Doping: Activation of CeO2Lattice Oxygen by Fe Doping

Long Zhang; Giulia Spezzati; Valery Muravev; Marcel A. Verheijen; Bart Zijlstra; Ivo A.W. Filot; Ya Qiong Su; Ming Wen Chang; Emiel J.M. Hensen

doi:10.1021/acscatal.1c00564

Improved Pd/CeO2 Catalysts for Low-Temperature NO Reduction: Activation of CeO2 Lattice Oxygen by Fe Doping: Activation of CeO₂Lattice Oxygen by Fe Doping

Long Zhang, Giulia Spezzati, Valery Muravev, Marcel A. Verheijen, Bart Zijlstra, Ivo A.W. Filot, Ya Qiong Su, Ming Wen Chang, Emiel J.M. Hensen (Corresponding author)

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Abstract

Developing better three-way catalysts with improved low-temperature performance is essential for cold start emission control. Density functional theory in combination with microkinetics simulations is used to predict reactivity of CO/NO/H2 mixtures on a small Pd cluster on CeO2(111). At low temperatures, N2O formation occurs via a N2O2 dimer over metallic Pd3. Part of the N2O intermediate product re-oxidizes Pd, limiting NO conversion and requiring rich conditions to obtain high N2 selectivity. High N2 selectivity at elevated temperatures is due to N2O decomposition on oxygen vacancies. Doping CeO2 by Fe is predicted to lead to more oxygen vacancies and a higher N2 selectivity, which is validated by the lower onset of N2 formation for a Pd catalyst supported on Fe-doped CeO2 prepared by flame spray pyrolysis. Activating ceria surface oxygen by transition metal doping is a promising strategy to improve the performance of three-way catalysts.

Original language	English
Pages (from-to)	5614-5627
Number of pages	14
Journal	ACS Catalysis
Volume	11
Issue number	9
DOIs	https://doi.org/10.1021/acscatal.1c00564
Publication status	Published - 7 May 2021

Funding

This study has received funding from the European Union’s Horizon 2020 research and innovation programme under grant no. 686086 (Partial-PGMs). The supercomputing facilities used in the calculations were supported by the Netherlands Organization for Scientific Research. Solliance and the Dutch province of Noord-Brabant are acknowledged for funding the STEM facility.

Keywords

density functional theory
Fe doping
mechanism
NO reduction
Pd/CeO

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10.1021/acscatal.1c00564

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Cite this

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title = "Improved Pd/CeO2 Catalysts for Low-Temperature NO Reduction: Activation of CeO2 Lattice Oxygen by Fe Doping: Activation of CeO2Lattice Oxygen by Fe Doping",

abstract = "Developing better three-way catalysts with improved low-temperature performance is essential for cold start emission control. Density functional theory in combination with microkinetics simulations is used to predict reactivity of CO/NO/H2 mixtures on a small Pd cluster on CeO2(111). At low temperatures, N2O formation occurs via a N2O2 dimer over metallic Pd3. Part of the N2O intermediate product re-oxidizes Pd, limiting NO conversion and requiring rich conditions to obtain high N2 selectivity. High N2 selectivity at elevated temperatures is due to N2O decomposition on oxygen vacancies. Doping CeO2 by Fe is predicted to lead to more oxygen vacancies and a higher N2 selectivity, which is validated by the lower onset of N2 formation for a Pd catalyst supported on Fe-doped CeO2 prepared by flame spray pyrolysis. Activating ceria surface oxygen by transition metal doping is a promising strategy to improve the performance of three-way catalysts.",

keywords = "density functional theory, Fe doping, mechanism, NO reduction, Pd/CeO",

author = "Long Zhang and Giulia Spezzati and Valery Muravev and Verheijen, {Marcel A.} and Bart Zijlstra and Filot, {Ivo A.W.} and Su, {Ya Qiong} and Chang, {Ming Wen} and Hensen, {Emiel J.M.}",

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doi = "10.1021/acscatal.1c00564",

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T1 - Improved Pd/CeO2 Catalysts for Low-Temperature NO Reduction: Activation of CeO2 Lattice Oxygen by Fe Doping

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AU - Zhang, Long

AU - Spezzati, Giulia

AU - Muravev, Valery

AU - Verheijen, Marcel A.

AU - Zijlstra, Bart

AU - Filot, Ivo A.W.

AU - Su, Ya Qiong

AU - Chang, Ming Wen

AU - Hensen, Emiel J.M.

PY - 2021/5/7

Y1 - 2021/5/7

N2 - Developing better three-way catalysts with improved low-temperature performance is essential for cold start emission control. Density functional theory in combination with microkinetics simulations is used to predict reactivity of CO/NO/H2 mixtures on a small Pd cluster on CeO2(111). At low temperatures, N2O formation occurs via a N2O2 dimer over metallic Pd3. Part of the N2O intermediate product re-oxidizes Pd, limiting NO conversion and requiring rich conditions to obtain high N2 selectivity. High N2 selectivity at elevated temperatures is due to N2O decomposition on oxygen vacancies. Doping CeO2 by Fe is predicted to lead to more oxygen vacancies and a higher N2 selectivity, which is validated by the lower onset of N2 formation for a Pd catalyst supported on Fe-doped CeO2 prepared by flame spray pyrolysis. Activating ceria surface oxygen by transition metal doping is a promising strategy to improve the performance of three-way catalysts.

AB - Developing better three-way catalysts with improved low-temperature performance is essential for cold start emission control. Density functional theory in combination with microkinetics simulations is used to predict reactivity of CO/NO/H2 mixtures on a small Pd cluster on CeO2(111). At low temperatures, N2O formation occurs via a N2O2 dimer over metallic Pd3. Part of the N2O intermediate product re-oxidizes Pd, limiting NO conversion and requiring rich conditions to obtain high N2 selectivity. High N2 selectivity at elevated temperatures is due to N2O decomposition on oxygen vacancies. Doping CeO2 by Fe is predicted to lead to more oxygen vacancies and a higher N2 selectivity, which is validated by the lower onset of N2 formation for a Pd catalyst supported on Fe-doped CeO2 prepared by flame spray pyrolysis. Activating ceria surface oxygen by transition metal doping is a promising strategy to improve the performance of three-way catalysts.

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