Selective acetylene hydrogenation over single metal atoms supported on Fe3O4(001): A first-principle study

Simuck F. Yuk; Greg Collinge; Manh Thuong Nguyen; Mal Soon Lee; Vassiliki Alexandra Glezakou; Roger Rousseau

doi:10.1063/1.5142748

Selective acetylene hydrogenation over single metal atoms supported on Fe₃O₄(001): A first-principle study

Simuck F. Yuk, Greg Collinge, Manh Thuong Nguyen, Mal Soon Lee, Vassiliki Alexandra Glezakou, Roger Rousseau

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

Abstract

Supported single-atom catalysts (SACs) have gained increasing attention for improved catalytic activity and selectivity for industrially relevant reactions. In this study, we explore the hydrogenation of acetylene over single Pt, Ru, Rh, Pd, and Ir atoms supported on the Fe₃O₄(001) surface using density functional theory calculations. The thermodynamic profile of H diffusion is significantly modified by the type of single metal atoms used, suggesting that H spillover from the single atom dopant to the Fe₃O₄(001) surface is favored and will likely lead to high H coverages of the functioning catalyst. Correspondingly, as the surface H coverage increases, the important desorption step of ethylene becomes energetically competitive against the detrimental hydrogenation steps of ethylene to ethane. A kinetic model is employed to explore how the activity and selectivity of SACs toward ethylene production change as a function of mass of the catalyst loaded into a flow reactor. Overall, we show that the selectivity of SACs toward ethylene production can be tuned by considering the proper type of metal and controlling the redox state of the support.

Original language	English
Article number	154703
Journal	Journal of Chemical Physics
Volume	152
Issue number	15
DOIs	https://doi.org/10.1063/1.5142748
State	Published - Apr 21 2020
Externally published	Yes

Funding

This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, and was performed using the Molecular Sciences Computing Facility (MSCF) in the William R. Wiley Environmental Molecular Sciences Laboratory, a DOE national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory (PNNL) and the National Energy Research Scientific Computing Center (NERSC) located at Lawrence Berkley National Laboratory provided by a user proposal. PNNL is operated by Battelle for DOE.

Funders	Funder number
National Energy Research Scientific Computing Center
Office of Basic Energy Sciences
Office of Biological and Environmental Research
William R. Wiley Environmental Molecular Sciences Laboratory
U.S. Department of Energy
Office of Science
Pacific Northwest National Laboratory
Chemical Sciences, Geosciences, and Biosciences Division

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title = "Selective acetylene hydrogenation over single metal atoms supported on Fe3O4(001): A first-principle study",

abstract = "Supported single-atom catalysts (SACs) have gained increasing attention for improved catalytic activity and selectivity for industrially relevant reactions. In this study, we explore the hydrogenation of acetylene over single Pt, Ru, Rh, Pd, and Ir atoms supported on the Fe3O4(001) surface using density functional theory calculations. The thermodynamic profile of H diffusion is significantly modified by the type of single metal atoms used, suggesting that H spillover from the single atom dopant to the Fe3O4(001) surface is favored and will likely lead to high H coverages of the functioning catalyst. Correspondingly, as the surface H coverage increases, the important desorption step of ethylene becomes energetically competitive against the detrimental hydrogenation steps of ethylene to ethane. A kinetic model is employed to explore how the activity and selectivity of SACs toward ethylene production change as a function of mass of the catalyst loaded into a flow reactor. Overall, we show that the selectivity of SACs toward ethylene production can be tuned by considering the proper type of metal and controlling the redox state of the support.",

author = "Yuk, {Simuck F.} and Greg Collinge and Nguyen, {Manh Thuong} and Lee, {Mal Soon} and Glezakou, {Vassiliki Alexandra} and Roger Rousseau",

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AU - Yuk, Simuck F.

AU - Collinge, Greg

AU - Nguyen, Manh Thuong

AU - Lee, Mal Soon

AU - Glezakou, Vassiliki Alexandra

AU - Rousseau, Roger

PY - 2020/4/21

Y1 - 2020/4/21

N2 - Supported single-atom catalysts (SACs) have gained increasing attention for improved catalytic activity and selectivity for industrially relevant reactions. In this study, we explore the hydrogenation of acetylene over single Pt, Ru, Rh, Pd, and Ir atoms supported on the Fe3O4(001) surface using density functional theory calculations. The thermodynamic profile of H diffusion is significantly modified by the type of single metal atoms used, suggesting that H spillover from the single atom dopant to the Fe3O4(001) surface is favored and will likely lead to high H coverages of the functioning catalyst. Correspondingly, as the surface H coverage increases, the important desorption step of ethylene becomes energetically competitive against the detrimental hydrogenation steps of ethylene to ethane. A kinetic model is employed to explore how the activity and selectivity of SACs toward ethylene production change as a function of mass of the catalyst loaded into a flow reactor. Overall, we show that the selectivity of SACs toward ethylene production can be tuned by considering the proper type of metal and controlling the redox state of the support.

AB - Supported single-atom catalysts (SACs) have gained increasing attention for improved catalytic activity and selectivity for industrially relevant reactions. In this study, we explore the hydrogenation of acetylene over single Pt, Ru, Rh, Pd, and Ir atoms supported on the Fe3O4(001) surface using density functional theory calculations. The thermodynamic profile of H diffusion is significantly modified by the type of single metal atoms used, suggesting that H spillover from the single atom dopant to the Fe3O4(001) surface is favored and will likely lead to high H coverages of the functioning catalyst. Correspondingly, as the surface H coverage increases, the important desorption step of ethylene becomes energetically competitive against the detrimental hydrogenation steps of ethylene to ethane. A kinetic model is employed to explore how the activity and selectivity of SACs toward ethylene production change as a function of mass of the catalyst loaded into a flow reactor. Overall, we show that the selectivity of SACs toward ethylene production can be tuned by considering the proper type of metal and controlling the redox state of the support.

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Selective acetylene hydrogenation over single metal atoms supported on Fe₃O₄(001): A first-principle study

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