Nickel-Based Single-Atom Alloys for Methane Dehydrogenation and the Effect of Subsurface Carbon: First-Principles Investigations
Using ab initio calculations, the reaction path for methane dehydrogenation over a series of Ni-based single-atom alloys (Cu, Fe, Pt, Pd, Zn, Al) and the effect that subsurface carbon at the Ni(111) surface has on the reaction barriers are investigated. Due to the well-known problem of coking for Ni...
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MDPI AG
2024-02-01
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| Online Access: | https://www.mdpi.com/2073-4344/14/2/145 |
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| author | Naiyuan Dong Tanglaw Roman Catherine Stampfl |
| author_facet | Naiyuan Dong Tanglaw Roman Catherine Stampfl |
| author_sort | Naiyuan Dong |
| collection | DOAJ |
| description | Using ab initio calculations, the reaction path for methane dehydrogenation over a series of Ni-based single-atom alloys (Cu, Fe, Pt, Pd, Zn, Al) and the effect that subsurface carbon at the Ni(111) surface has on the reaction barriers are investigated. Due to the well-known problem of coking for Ni-based catalysts, the adsorption and associated physical properties of 0.25 ML, 1.0 ML, and 2 ML of carbon on the Ni(111) surface of various sites are first studied. It is found that the presence of subsurface carbon reduces the stability of the intermediates and increases the reaction barriers, thus reducing the performance of the Ni(111) catalyst. The presence of Al, Zn, and Pt is found to reduce the barriers for the CH<sub>4</sub> → CH<sub>3</sub> + H and CH<sub>3</sub> → CH<sub>2</sub> + H (Pt); and CH → C + H (Al, Zn) reactions, while Ni(111) yields the lowest barriers for the CH<sub>2</sub> → CH + H reaction. These results thus suggest that doping the Ni surface with both Al or Zn atoms and Pt atoms, functioning as distinct active sites, may bring about an improved reactivity and/or selectivity for methane decomposition. Furthermore, the results show that there can be significant adparticle–adparticle interactions in the simulation cell, which affect the reaction energy diagram and thus highlight the importance of ensuring a common reference energy for all steps. |
| first_indexed | 2024-03-07T22:39:16Z |
| format | Article |
| id | doaj.art-fbbd7662a90549d9b931af50566aae95 |
| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-07T22:39:16Z |
| publishDate | 2024-02-01 |
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| spelling | doaj.art-fbbd7662a90549d9b931af50566aae952024-02-23T15:11:34ZengMDPI AGCatalysts2073-43442024-02-0114214510.3390/catal14020145Nickel-Based Single-Atom Alloys for Methane Dehydrogenation and the Effect of Subsurface Carbon: First-Principles InvestigationsNaiyuan Dong0Tanglaw Roman1Catherine Stampfl2School of Physics, The University of Sydney, Sydney, NSW 2006, AustraliaFlinders Institute for Nanoscale Science and Technology, College of Science Engineering, Flinders University, Bedford Park, SA 5042, AustraliaSchool of Physics, The University of Sydney, Sydney, NSW 2006, AustraliaUsing ab initio calculations, the reaction path for methane dehydrogenation over a series of Ni-based single-atom alloys (Cu, Fe, Pt, Pd, Zn, Al) and the effect that subsurface carbon at the Ni(111) surface has on the reaction barriers are investigated. Due to the well-known problem of coking for Ni-based catalysts, the adsorption and associated physical properties of 0.25 ML, 1.0 ML, and 2 ML of carbon on the Ni(111) surface of various sites are first studied. It is found that the presence of subsurface carbon reduces the stability of the intermediates and increases the reaction barriers, thus reducing the performance of the Ni(111) catalyst. The presence of Al, Zn, and Pt is found to reduce the barriers for the CH<sub>4</sub> → CH<sub>3</sub> + H and CH<sub>3</sub> → CH<sub>2</sub> + H (Pt); and CH → C + H (Al, Zn) reactions, while Ni(111) yields the lowest barriers for the CH<sub>2</sub> → CH + H reaction. These results thus suggest that doping the Ni surface with both Al or Zn atoms and Pt atoms, functioning as distinct active sites, may bring about an improved reactivity and/or selectivity for methane decomposition. Furthermore, the results show that there can be significant adparticle–adparticle interactions in the simulation cell, which affect the reaction energy diagram and thus highlight the importance of ensuring a common reference energy for all steps.https://www.mdpi.com/2073-4344/14/2/145density functional theorysingle-atom alloysmethane reduction |
| spellingShingle | Naiyuan Dong Tanglaw Roman Catherine Stampfl Nickel-Based Single-Atom Alloys for Methane Dehydrogenation and the Effect of Subsurface Carbon: First-Principles Investigations Catalysts density functional theory single-atom alloys methane reduction |
| title | Nickel-Based Single-Atom Alloys for Methane Dehydrogenation and the Effect of Subsurface Carbon: First-Principles Investigations |
| title_full | Nickel-Based Single-Atom Alloys for Methane Dehydrogenation and the Effect of Subsurface Carbon: First-Principles Investigations |
| title_fullStr | Nickel-Based Single-Atom Alloys for Methane Dehydrogenation and the Effect of Subsurface Carbon: First-Principles Investigations |
| title_full_unstemmed | Nickel-Based Single-Atom Alloys for Methane Dehydrogenation and the Effect of Subsurface Carbon: First-Principles Investigations |
| title_short | Nickel-Based Single-Atom Alloys for Methane Dehydrogenation and the Effect of Subsurface Carbon: First-Principles Investigations |
| title_sort | nickel based single atom alloys for methane dehydrogenation and the effect of subsurface carbon first principles investigations |
| topic | density functional theory single-atom alloys methane reduction |
| url | https://www.mdpi.com/2073-4344/14/2/145 |
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