Highly Active and Stable CH4 Oxidation by Substitution of Ce4+ by Two Pd2+ Ions in CeO2 (111)

ACS Catalysis
Yaqiong SuEmiel J M Hensen

Abstract

Methane (CH4) combustion is an increasingly important reaction for environmental protection, for which Pd/CeO2 has emerged as the preferred catalyst. There is a lack of understanding of the nature of the active site in these catalysts. Here, we use density functional theory to understand the role of doping of Pd in the ceria surface for generating sites highly active toward the C-H bonds in CH4. Specifically, we demonstrate that two Pd2+ ions can substitute one Ce4+ ion, resulting in a very stable structure containing a highly coordinated unsaturated Pd cation that can strongly adsorb CH4 and dissociate the first C-H bond with a low energy barrier. An important aspect of the high activity of the stabilized isolated Pd cation is its ability to form a strong σ-complex with CH4, which leads to effective activation of CH4. We show that also other transition metals like Pt, Rh, and Ni can give rise to similar structures with high activity toward C-H bond dissociation. These insights provide us with a novel structural view of solid solutions of transition metals such as Pt, Pd, Ni, and Rh in CeO2, known to exhibit high activity in CH4 combustion.

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Citations

Oct 26, 2018·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Lan QinXiang-Fei Zhang
Jul 18, 2019·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Victor FungDe-En Jiang
Aug 6, 2019·Journal of Computational Chemistry·Ping LiuBaojun Wang
Jan 29, 2020·Inorganic Chemistry·Yuming WangJames A Dorman

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Software Mentioned

Vienna Ab initio Simulation Package ( VASP )

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