Free-Energy Landscapes and Surface Dynamics in Methane Activation on Ni(511) via Machine Learning and Enhanced Sampling.
| Title: | Free-Energy Landscapes and Surface Dynamics in Methane Activation on Ni(511) via Machine Learning and Enhanced Sampling. |
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| Authors: | Jin Y; Pritzker School of Molecular Engineering, The University of Chicago, 640 S Ellis Avenue, Chicago, Illinois 60637, United States.; Xu Y; Pritzker School of Molecular Engineering, The University of Chicago, 640 S Ellis Avenue, Chicago, Illinois 60637, United States.; García Sánchez JS; Pritzker School of Molecular Engineering, The University of Chicago, 640 S Ellis Avenue, Chicago, Illinois 60637, United States.; Pérez-Lemus GR; Pritzker School of Molecular Engineering, The University of Chicago, 640 S Ellis Avenue, Chicago, Illinois 60637, United States.; Zubieta Rico PF; Pritzker School of Molecular Engineering, The University of Chicago, 640 S Ellis Avenue, Chicago, Illinois 60637, United States.; Delferro M; Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States.; de Pablo JJ; Department of Chemical and Biomolecular Engineering, Tandon School of Engineering, New York University, 6 MetroTech Center, Brooklyn, New York 11201, United States.; Courant Institute of Mathematical Sciences, New York University, 251 Mercer Street, New York, New York 10012, United States.; Department of Physics, New York University, 726 Broadway, New York, New York 10003, United States. |
| Source: | ACS catalysis [ACS Catal] 2025 May 12; Vol. 15 (11), pp. 8931-8942. Date of Electronic Publication: 2025 May 12 (Print Publication: 2025). |
| Publication Type: | Journal Article |
| Language: | English |
| Journal Info: | Publisher: American Chemical Society Country of Publication: United States NLM ID: 101562209 Publication Model: eCollection Cited Medium: Print ISSN: 2155-5435 (Print) NLM ISO Abbreviation: ACS Catal Subsets: PubMed not MEDLINE |
| Imprint Name(s): | Original Publication: Washington, DC : American Chemical Society, c2011- |
| Abstract: | Methane activation on stepped Ni(511) surfaces involves the rearrangement of surface atoms as the chemical reaction proceeds. This process is particularly sensitive to temperature. Using machine-learned interatomic potentials (MLIPs) coupled with enhanced sampling techniques, we investigate the activation of methane under realistic operando conditions. Our analysis reveals that methane dissociation occurs predominantly at step-edge nickel atoms. As CH x (where x = 3 or 4) species bind to additional surface nickel atoms, their reduced mobility leads to entropic penalties that suppress certain configurations and transition states. This is reflected in the underlying free energy surfaces, where configurations such as methyl binding to hollow sites and activation routes involving two nickel atoms become unfavorable as temperature increases. At elevated temperatures, methane activation extends from step-edge sites to terrace regions because of reduced free-energy barriers and enhanced surface dynamics. By decomposing the free-energy into enthalpic and entropic contributions, we uncover temperature-dependent shifts in the preferences of methane for the relevant active sites and arrive at a detailed molecular picture of methane activation.; (© 2025 The Authors. Published by American Chemical Society.) |
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| Contributed Indexing: | Keywords: dynamic sampling; entropy effects in catalysis; machine-learned interatomic potentials; methane activation; surface defects; transition metal catalysts |
| Entry Date(s): | Date Created: 20250612 Latest Revision: 20250613 |
| Update Code: | 20260130 |
| PubMed Central ID: | PMC12150266 |
| DOI: | 10.1021/acscatal.5c00724 |
| PMID: | 40502979 |
| Database: | MEDLINE |
Journal Article