Author, as appears in the article.: Salom-Català A; Strugovshchikov E; Kaźmierczak K; Curulla-Ferré D; Ricart JM; Carbó JJ
Department: Química Física i Inorgànica
URV's Author/s: Ricart Pla, Jose Manuel
Abstract: Propane dehydrogenation (PDH) is an on-purpose catalytic technology to produce propylene from propane that operates at high temperatures, 773-973 K. Several key industry players have been active in developing new catalysts and processes with improved carbon footprint and economics, where Pt-based catalysts have played a central role. The optimization of these catalytic systems through computational and atomistic simulations requires large-scale models that account for their reactivity and dynamic properties. To address this challenge, we developed a new reactive ReaxFF force field (2023-Pt/C/H) that enables large-scale simulations of PDH reactions catalyzed on Pt surfaces. The optimization of force-field parameters relies on a large training set of density functional theory (DFT) calculations of Pt-catalyzed PDH mechanism, including geometries, adsorption and relative energies of reaction intermediates, and key C-H and C-C bond-breaking/forming reaction steps on the Pt(111) surface. The internal validation supports the accuracy of the developed 2023-Pt/C/H force-field parameters, resulting in mean absolute errors (MAE) against DFT data of 14 and 12 kJ mol-1 for relative energies of intermediates and energy barriers, respectively. We demonstrated the applicability of the 2023-Pt/C/H force field with reactive molecular dynamics simulations of propane on different Pt surface topologies and temperatures. The simulations successfully model the formation of propene in the gas phase as well as competitive, unproductive reactions such as deep dehydrogenation and C-C bond cleavage that produce H, C1 and C2 adsorbed species responsible of catalytic deactivation of Pt surface. Results show the following reactivity order: Pt(111) < Pt(100) < Pt(211), and that for the stepped Pt(211) surface, propane activation occurs on low-coordinated Pt atoms at the steps. The measured selectivity as a function of surface topology follows the same trend as activity, the Pt(211) facet being the most selective. The 2023-Pt/C/H reactive force field can also describe the increase of reactivity with the temperature. From these simulations, we were able to estimate the Arrhenius activation energy, 73 kJ mol-1, whose value is close to those reported experimentally for PDH catalyzed by large, supported Pt nanoparticles . The newly developed 2023-Pt/C/H reactive force field can be used in subsequent investigations of different Pt topologies and of collective effects such as temperature, propane pressure, or H surface coverage.
Thematic Areas: Surfaces, coatings and films Química Physical and theoretical chemistry Nanoscience and nanotechnology Nanoscience & nanotechnology Medicina ii Medicina i Materials science, multidisciplinary Materiais Interdisciplinar General energy Farmacia Ensino Engenharias iv Engenharias iii Engenharias ii Engenharias i Energy (miscellaneous) Energy (all) Electronic, optical and magnetic materials Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências ambientais Ciências agrárias i Chemistry, physical Biotecnología Biodiversidade Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: josep.ricart@urv.cat
Author identifier: 0000-0002-2610-5535
Record's date: 2024-03-23
Papper version: info:eu-repo/semantics/publishedVersion
Link to the original source: https://pubs.acs.org/doi/10.1021/acs.jpcc.3c07126
Papper original source: Journal Of Physical Chemistry c. 128 (7): 2844-2855
APA: Salom-Català A; Strugovshchikov E; Kaźmierczak K; Curulla-Ferré D; Ricart JM; Carbó JJ (2024). Reactive Force Field Development for Propane Dehydrogenation on Platinum Surfaces. Journal Of Physical Chemistry c, 128(7), 2844-2855. DOI: 10.1021/acs.jpcc.3c07126
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Article's DOI: 10.1021/acs.jpcc.3c07126
Entity: Universitat Rovira i Virgili
Journal publication year: 2024
Publication Type: Journal Publications
Repositori URV