Effect of reaction atmosphere on catalytic CO oxidation over Cu-based bimetallic nanoclusters on a CeO2 support

Long Zhang; Jing Pan; Min Li; Ivo A.W. Filot; Emiel J.M. Hensen; Hui Wang

doi:10.1103/PhysRevApplied.20.034051

Effect of reaction atmosphere on catalytic CO oxidation over Cu-based bimetallic nanoclusters on a CeO2 support

Long Zhang (Corresponding author), Jing Pan, Min Li, Ivo A.W. Filot, Emiel J.M. Hensen (Corresponding author), Hui Wang (Corresponding author)

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Abstract

Understanding the nature of active sites and the catalytic properties of oxide-supported bimetallic clusters under reaction conditions remains challenging. In this study, we combine first-principles calculations with genetic algorithm and grand canonical Monte Carlo methods to reveal the structures and compositions of CeO2-supported Cu-based bimetallic clusters in an oxygen-rich environment. Oxidized Cu4X4 (X = Pd, Pt, and Rh) bimetallic clusters on CeO2(111) are stable and exhibit different catalytic properties during CO oxidation compared with the pristine bimetallic clusters. Microkinetic simulations predict that CeO2(111)-supported Cu4Pd4O10, Cu4Pt4O11, and Cu4Rh4O14 clusters have much higher CO oxidation activity than the supported Cu4Pd4, Cu4Pt4, and Cu4Rh4 clusters; this is ascribed to the moderate CO adsorption strength and active oxygen on oxidized alloy clusters. A mechanistic study suggests that CO oxidation occurs via the O2 associative reaction mechanism on the Cu4Pd4O10 and Cu4Pt4O11 clusters, while it proceeds through the O2 dissociative reaction mechanism on the Cu4Rh4O14 cluster. Our calculations further predict that CO oxidation on the Cu4Rh4O14 cluster exhibits a low apparent activation energy, indicating that the oxidized cluster possesses excellent CO oxidation activity. This work demonstrates that the catalytic activity and reaction mechanism vary with the composition and oxidation state of the alloy nanocluster under the reaction conditions and emphasizes the influence of the reaction atmosphere on the reaction mechanisms and catalytic activity of oxide-supported alloy catalysts.

Original language	English
Article number	034051
Number of pages	14
Journal	Physical Review Applied
Volume	20
Issue number	3
DOIs	https://doi.org/10.1103/PhysRevApplied.20.034051
Publication status	Published - Sept 2023

Funding

This work was supported by the National Natural Science Foundation of China (Grants No. 22203105, No. 11874429, and No. 12174450); the Hunan Provincial Natural Science Foundation of China (Grant No. 2023JJ40713); the National Talents Program of China, Distinguished Youth Foundation of Hunan Province (Grant No. 2020JJ2039); Hunan Provincial Key Research and Development Program (Grant No. 2022WK2002); the Project of High-Level Talents Accumulation of Hunan Province (Grant No. 2018RS3021); and the Program of Hundreds of Talents of Hunan Province, State Key Laboratory of Powder Metallurgy, Start-up Funding and Innovation-Driven Plan (Grant No. 2019CX023) of Central South University. Fundamental Research Funds for the Central Universities of Central South University (2023ZZTS0386). E.J.M.H. acknowledges financial support from a NWO Vici personal grant. The supercomputing facilities used in the calculations were supported by the NWO. Calculations and simulations were also performed at the High-Performance Computing facilities of Central South University. We thank Dr. Ming-Wen Chang for useful discussions.

Funders	Funder number
National Natural Science Foundation of China	22203105, 12174450, 11874429
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Central South University	2023ZZTS0386

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title = "Effect of reaction atmosphere on catalytic CO oxidation over Cu-based bimetallic nanoclusters on a CeO2 support",

abstract = "Understanding the nature of active sites and the catalytic properties of oxide-supported bimetallic clusters under reaction conditions remains challenging. In this study, we combine first-principles calculations with genetic algorithm and grand canonical Monte Carlo methods to reveal the structures and compositions of CeO2-supported Cu-based bimetallic clusters in an oxygen-rich environment. Oxidized Cu4X4 (X = Pd, Pt, and Rh) bimetallic clusters on CeO2(111) are stable and exhibit different catalytic properties during CO oxidation compared with the pristine bimetallic clusters. Microkinetic simulations predict that CeO2(111)-supported Cu4Pd4O10, Cu4Pt4O11, and Cu4Rh4O14 clusters have much higher CO oxidation activity than the supported Cu4Pd4, Cu4Pt4, and Cu4Rh4 clusters; this is ascribed to the moderate CO adsorption strength and active oxygen on oxidized alloy clusters. A mechanistic study suggests that CO oxidation occurs via the O2 associative reaction mechanism on the Cu4Pd4O10 and Cu4Pt4O11 clusters, while it proceeds through the O2 dissociative reaction mechanism on the Cu4Rh4O14 cluster. Our calculations further predict that CO oxidation on the Cu4Rh4O14 cluster exhibits a low apparent activation energy, indicating that the oxidized cluster possesses excellent CO oxidation activity. This work demonstrates that the catalytic activity and reaction mechanism vary with the composition and oxidation state of the alloy nanocluster under the reaction conditions and emphasizes the influence of the reaction atmosphere on the reaction mechanisms and catalytic activity of oxide-supported alloy catalysts.",

author = "Long Zhang and Jing Pan and Min Li and Filot, {Ivo A.W.} and Hensen, {Emiel J.M.} and Hui Wang",

year = "2023",

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AU - Pan, Jing

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AU - Hensen, Emiel J.M.

AU - Wang, Hui

PY - 2023/9

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N2 - Understanding the nature of active sites and the catalytic properties of oxide-supported bimetallic clusters under reaction conditions remains challenging. In this study, we combine first-principles calculations with genetic algorithm and grand canonical Monte Carlo methods to reveal the structures and compositions of CeO2-supported Cu-based bimetallic clusters in an oxygen-rich environment. Oxidized Cu4X4 (X = Pd, Pt, and Rh) bimetallic clusters on CeO2(111) are stable and exhibit different catalytic properties during CO oxidation compared with the pristine bimetallic clusters. Microkinetic simulations predict that CeO2(111)-supported Cu4Pd4O10, Cu4Pt4O11, and Cu4Rh4O14 clusters have much higher CO oxidation activity than the supported Cu4Pd4, Cu4Pt4, and Cu4Rh4 clusters; this is ascribed to the moderate CO adsorption strength and active oxygen on oxidized alloy clusters. A mechanistic study suggests that CO oxidation occurs via the O2 associative reaction mechanism on the Cu4Pd4O10 and Cu4Pt4O11 clusters, while it proceeds through the O2 dissociative reaction mechanism on the Cu4Rh4O14 cluster. Our calculations further predict that CO oxidation on the Cu4Rh4O14 cluster exhibits a low apparent activation energy, indicating that the oxidized cluster possesses excellent CO oxidation activity. This work demonstrates that the catalytic activity and reaction mechanism vary with the composition and oxidation state of the alloy nanocluster under the reaction conditions and emphasizes the influence of the reaction atmosphere on the reaction mechanisms and catalytic activity of oxide-supported alloy catalysts.

AB - Understanding the nature of active sites and the catalytic properties of oxide-supported bimetallic clusters under reaction conditions remains challenging. In this study, we combine first-principles calculations with genetic algorithm and grand canonical Monte Carlo methods to reveal the structures and compositions of CeO2-supported Cu-based bimetallic clusters in an oxygen-rich environment. Oxidized Cu4X4 (X = Pd, Pt, and Rh) bimetallic clusters on CeO2(111) are stable and exhibit different catalytic properties during CO oxidation compared with the pristine bimetallic clusters. Microkinetic simulations predict that CeO2(111)-supported Cu4Pd4O10, Cu4Pt4O11, and Cu4Rh4O14 clusters have much higher CO oxidation activity than the supported Cu4Pd4, Cu4Pt4, and Cu4Rh4 clusters; this is ascribed to the moderate CO adsorption strength and active oxygen on oxidized alloy clusters. A mechanistic study suggests that CO oxidation occurs via the O2 associative reaction mechanism on the Cu4Pd4O10 and Cu4Pt4O11 clusters, while it proceeds through the O2 dissociative reaction mechanism on the Cu4Rh4O14 cluster. Our calculations further predict that CO oxidation on the Cu4Rh4O14 cluster exhibits a low apparent activation energy, indicating that the oxidized cluster possesses excellent CO oxidation activity. This work demonstrates that the catalytic activity and reaction mechanism vary with the composition and oxidation state of the alloy nanocluster under the reaction conditions and emphasizes the influence of the reaction atmosphere on the reaction mechanisms and catalytic activity of oxide-supported alloy catalysts.

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Effect of reaction atmosphere on catalytic CO oxidation over Cu-based bimetallic nanoclusters on a CeO2 support

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