Inherent strain and kinetic coupling determine the kinetics of ammonia synthesis over Ru nanoparticles

Abstract The large-scale ammonia synthesis using the Haber-Bosch process is crucial in modern society and the reaction is known to be facile over Ru-based catalysts. Herein, first-principles kinetic Monte Carlo (kMC) simulations are utilized to explore the reaction kinetics on Ru nanoparticles (NPs)...

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Main Authors: Yuqi Yang, Anders Hellman, Henrik Grönbeck
Format: Article
Language:English
Published: Nature Portfolio 2025-02-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-56765-2
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author Yuqi Yang
Anders Hellman
Henrik Grönbeck
author_facet Yuqi Yang
Anders Hellman
Henrik Grönbeck
author_sort Yuqi Yang
collection DOAJ
description Abstract The large-scale ammonia synthesis using the Haber-Bosch process is crucial in modern society and the reaction is known to be facile over Ru-based catalysts. Herein, first-principles kinetic Monte Carlo (kMC) simulations are utilized to explore the reaction kinetics on Ru nanoparticles (NPs), extending the current knowledge that is mainly based on calculations of single crystal surfaces. It is only by accounting for the effects of kinetic couplings between different sites and inherent strain in the NPs that experimental turnover frequencies (TOFs) can be reproduced. The enhanced activity of inherently strained NPs is attributed to the co-existence of sites with both tensile and compressive strain, which simultaneously promotes N2 dissociation and NHx (x = 0, 1 and 2) hydrogenation. We propose that kinetic couplings on Ru NPs with tailored strain-patterns offer a strategy to break the limitations of linear scaling relations in the design of ammonia synthesis catalysts.
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spelling doaj-art-b007a4a1ad1142f99c5c596c66529ccd2025-08-20T02:48:12ZengNature PortfolioNature Communications2041-17232025-02-011611810.1038/s41467-025-56765-2Inherent strain and kinetic coupling determine the kinetics of ammonia synthesis over Ru nanoparticlesYuqi Yang0Anders Hellman1Henrik Grönbeck2Department of Physics and Competence Centre for Catalysis, Chalmers University of TechnologyDepartment of Physics and Competence Centre for Catalysis, Chalmers University of TechnologyDepartment of Physics and Competence Centre for Catalysis, Chalmers University of TechnologyAbstract The large-scale ammonia synthesis using the Haber-Bosch process is crucial in modern society and the reaction is known to be facile over Ru-based catalysts. Herein, first-principles kinetic Monte Carlo (kMC) simulations are utilized to explore the reaction kinetics on Ru nanoparticles (NPs), extending the current knowledge that is mainly based on calculations of single crystal surfaces. It is only by accounting for the effects of kinetic couplings between different sites and inherent strain in the NPs that experimental turnover frequencies (TOFs) can be reproduced. The enhanced activity of inherently strained NPs is attributed to the co-existence of sites with both tensile and compressive strain, which simultaneously promotes N2 dissociation and NHx (x = 0, 1 and 2) hydrogenation. We propose that kinetic couplings on Ru NPs with tailored strain-patterns offer a strategy to break the limitations of linear scaling relations in the design of ammonia synthesis catalysts.https://doi.org/10.1038/s41467-025-56765-2
spellingShingle Yuqi Yang
Anders Hellman
Henrik Grönbeck
Inherent strain and kinetic coupling determine the kinetics of ammonia synthesis over Ru nanoparticles
Nature Communications
title Inherent strain and kinetic coupling determine the kinetics of ammonia synthesis over Ru nanoparticles
title_full Inherent strain and kinetic coupling determine the kinetics of ammonia synthesis over Ru nanoparticles
title_fullStr Inherent strain and kinetic coupling determine the kinetics of ammonia synthesis over Ru nanoparticles
title_full_unstemmed Inherent strain and kinetic coupling determine the kinetics of ammonia synthesis over Ru nanoparticles
title_short Inherent strain and kinetic coupling determine the kinetics of ammonia synthesis over Ru nanoparticles
title_sort inherent strain and kinetic coupling determine the kinetics of ammonia synthesis over ru nanoparticles
url https://doi.org/10.1038/s41467-025-56765-2
work_keys_str_mv AT yuqiyang inherentstrainandkineticcouplingdeterminethekineticsofammoniasynthesisoverrunanoparticles
AT andershellman inherentstrainandkineticcouplingdeterminethekineticsofammoniasynthesisoverrunanoparticles
AT henrikgronbeck inherentstrainandkineticcouplingdeterminethekineticsofammoniasynthesisoverrunanoparticles