DFT-based microkinetic model analysis of dry reforming of methane over Ru7/CeO2(111) and Ru7/CeO2(110): key role of surface lattice oxygen vacancy

Qu, Pengfei; Wang, Gui‐Chang

doi:10.1039/d1cy01934a

Cited by 14 publications

(1 citation statement)

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“…The dissociation of HCOO* leads to HCO* and O*. , Another CO 2 dissociation pathway via a Mars-van Krevelen mechanism involves an oxygen vacancy in the support. The formation of oxygen vacancies in the CeO 2 surface can be facilitated by spillover H from metal particles …”

Section: Resultsmentioning

confidence: 99%

Computational Study of CO₂ Methanation on Ru/CeO₂ Model Surfaces: On the Impact of Ru Doping in CeO₂

Chen,

Filot,

Hensen

2023

ACS Catal.

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The Sabatier reaction (CO 2 + H 2 → CH 4 + H 2 O) can contribute to renewable energy storage by converting green H 2 with waste CO 2 into CH 4 . Highly dispersed Ru on CeO 2 represents an active catalyst for the CO 2 methanation. Here, we investigated the support effect by considering a single atom of Ru and a small Ru cluster on CeO 2 (Ru 6 /CeO 2 ). The influence of doping CeO 2 with Ru was investigated as well (Ru 6 /RuCe x−1 O 2x−1 ). Density functional theory was used to compute the reaction energy diagrams. A single Ru atom on CeO 2 can only break one of the C−O bonds in adsorbed CO 2 , making it only active in the reverse water−gas shift reaction. In contrast, Ru 6 clusters on stoichiometric and Ru-doped CeO 2 are active methanation catalysts. CO is the main reaction intermediate formed via a COOH surface intermediate. Compared to an extended Ru(11−21) surface containing step-edge sites where direct C−O bond dissociation is facile, C−O dissociation proceeds via H-assisted pathways (CO → HCO → CH) on Ru 6 /CeO 2 and Ru 6 /RuCe x−1 O 2x−1 . A higher CO 2 methanation rate is predicted for Ru 6 /RuCe x−1 O 2x−1 . Electronic structure analysis clarifies that the lower activation energy for HCO dissociation on Ru 6 /RuCe x−1 O 2x−1 is caused by stronger electron−electron repulsion due to its closer proximity to Ru. Strong H 2 adsorption on small Ru clusters explains the higher CO 2 methanation activity of Ru clusters on CeO 2 compared to a Ru step-edge surface, representative of Ru nanoparticles, where the H coverage is low due to stronger competition with adsorbed CO.

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Section: Resultsmentioning

confidence: 99%

Computational Study of CO₂ Methanation on Ru/CeO₂ Model Surfaces: On the Impact of Ru Doping in CeO₂

Chen,

Filot,

Hensen

2023

ACS Catal.

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Screening the optimal Cox/CeO2(110) (x = 1–6) catalyst for methane activation in coalbed gas

Huang,

Li,

Jiang

et al. 2024

Int J Coal Sci Technol

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The challenges posed by energy and environmental issues have forced mankind to explore and utilize unconventional energy sources. It is imperative to convert the abundant coalbed gas (CBG) into high value-added products, i.e., selective and efficient conversion of methane from CBG. Methane activation, known as the “holy grail”, poses a challenge to the design and development of catalysts. The structural complexity of the active metal on the carrier is of particular concern. In this work, we have studied the nucleation growth of small Co clusters (up to Co6) on the surface of CeO2(110) using density functional theory, from which a stable loaded Co/CeO2(110) structure was selected to investigate the methane activation mechanism. Despite the relatively small size of the selected Co clusters, the obtained Cox/CeO2(110) exhibits interesting properties. The optimized Co5/CeO2(110) structure was selected as the optimal structure to study the activation mechanism of methane due to its competitive electronic structure, adsorption energy and binding energy. The energy barriers for the stepwise dissociation of methane to form CH3*, CH2*, CH*, and C* radical fragments are 0.44, 0.55, 0.31, and 1.20 eV, respectively, indicating that CH* dissociative dehydrogenation is the rate-determining step for the system under investigation here. This fundamental study of metal-support interactions based on Co growth on the CeO2(110) surface contributes to the understanding of the essence of Co/CeO2 catalysts with promising catalytic behavior. It provides theoretical guidance for better designing the optimal Co/CeO2 catalyst for tailored catalytic reactions.

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Theoretical study of the mechanism of dry reforming of methane over Pd-doped CeO2 supported-Ru catalyst: The importance of oxygen self-spillover behavior

Qu,

Wang

2023

Applied Surface Science

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DFT-based microkinetic model analysis of dry reforming of methane over Ru₇/CeO₂(111) and Ru₇/CeO₂(110): key role of surface lattice oxygen vacancy

Abstract: CeO2 supported metal cluster catalysts play the vital roles on dry reforming (DRM) reaction which convert greenhouse gases (CH4 and CO2) to syngas, but the mechanism of surface lattice oxygen...

Cited by 14 publications

References 59 publications

Computational Study of CO₂ Methanation on Ru/CeO₂ Model Surfaces: On the Impact of Ru Doping in CeO₂

Computational Study of CO₂ Methanation on Ru/CeO₂ Model Surfaces: On the Impact of Ru Doping in CeO₂

Screening the optimal Cox/CeO2(110) (x = 1–6) catalyst for methane activation in coalbed gas

Theoretical study of the mechanism of dry reforming of methane over Pd-doped CeO2 supported-Ru catalyst: The importance of oxygen self-spillover behavior

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DFT-based microkinetic model analysis of dry reforming of methane over Ru7/CeO2(111) and Ru7/CeO2(110): key role of surface lattice oxygen vacancy

Abstract: CeO2 supported metal cluster catalysts play the vital roles on dry reforming (DRM) reaction which convert greenhouse gases (CH4 and CO2) to syngas, but the mechanism of surface lattice oxygen...

Cited by 14 publications

References 59 publications

Computational Study of CO2 Methanation on Ru/CeO2 Model Surfaces: On the Impact of Ru Doping in CeO2

Computational Study of CO2 Methanation on Ru/CeO2 Model Surfaces: On the Impact of Ru Doping in CeO2

Screening the optimal Cox/CeO2(110) (x = 1–6) catalyst for methane activation in coalbed gas

Theoretical study of the mechanism of dry reforming of methane over Pd-doped CeO2 supported-Ru catalyst: The importance of oxygen self-spillover behavior

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DFT-based microkinetic model analysis of dry reforming of methane over Ru₇/CeO₂(111) and Ru₇/CeO₂(110): key role of surface lattice oxygen vacancy

Computational Study of CO₂ Methanation on Ru/CeO₂ Model Surfaces: On the Impact of Ru Doping in CeO₂

Computational Study of CO₂ Methanation on Ru/CeO₂ Model Surfaces: On the Impact of Ru Doping in CeO₂