Entropy-driven difference in interfacial water reactivity between slab and nanodroplet

Abstract Interfacial water activity plays a critical role in governing chemical reactivity and catalytic efficiency, yet a quantitative understanding of how hydrogen-bond (H-bond) network structure influences this reactivity remains limited. Herein, we employ ab initio molecular metadynamics simulat...

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Main Authors: Shiwei Chen, Jiabao Zhu, Jifan Li, Pan Guo, Jinrong Yang, Xiao He
Format: Article
Language:English
Published: Nature Portfolio 2025-06-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-60298-z
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author Shiwei Chen
Jiabao Zhu
Jifan Li
Pan Guo
Jinrong Yang
Xiao He
author_facet Shiwei Chen
Jiabao Zhu
Jifan Li
Pan Guo
Jinrong Yang
Xiao He
author_sort Shiwei Chen
collection DOAJ
description Abstract Interfacial water activity plays a critical role in governing chemical reactivity and catalytic efficiency, yet a quantitative understanding of how hydrogen-bond (H-bond) network structure influences this reactivity remains limited. Herein, we employ ab initio molecular metadynamics simulations to delineate the relationship between the H-bond network and the reactivity of interfacial water molecules at the slab and nanodroplet systems. Interfacial water at nanodroplets, characterized by microscopic inhomogeneity, tends to adopt a donor–acceptor dimer configuration, in contrast to the more homogeneous H-bond network at the slab. This disparity in local structure, corroborated by the quantified differences in solvation configurational entropy, results in a reduction of the reaction free energy barrier by 1–2 kcal·mol⁻1 at the slab interface, corresponding to an order-of-magnitude enhancement in reaction rate. These results provide a fresh perspective to understand the interfacial water reactivity and highlight the critical role of H-bond network in optimizing catalytic performance.
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spelling doaj-art-3eaa67051cf645d7bdfcf0d0676257e82025-08-20T03:26:43ZengNature PortfolioNature Communications2041-17232025-06-0116111210.1038/s41467-025-60298-zEntropy-driven difference in interfacial water reactivity between slab and nanodropletShiwei Chen0Jiabao Zhu1Jifan Li2Pan Guo3Jinrong Yang4Xiao He5Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal University, 3663 North Zhongshan RdShanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal University, 3663 North Zhongshan RdShanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal University, 3663 North Zhongshan RdDepartment of Physics, Shanghai Key Laboratory of High Temperature Superconductors, International Centre of Quantum and Molecular Structures, Shanghai UniversityShanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal University, 3663 North Zhongshan RdShanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal University, 3663 North Zhongshan RdAbstract Interfacial water activity plays a critical role in governing chemical reactivity and catalytic efficiency, yet a quantitative understanding of how hydrogen-bond (H-bond) network structure influences this reactivity remains limited. Herein, we employ ab initio molecular metadynamics simulations to delineate the relationship between the H-bond network and the reactivity of interfacial water molecules at the slab and nanodroplet systems. Interfacial water at nanodroplets, characterized by microscopic inhomogeneity, tends to adopt a donor–acceptor dimer configuration, in contrast to the more homogeneous H-bond network at the slab. This disparity in local structure, corroborated by the quantified differences in solvation configurational entropy, results in a reduction of the reaction free energy barrier by 1–2 kcal·mol⁻1 at the slab interface, corresponding to an order-of-magnitude enhancement in reaction rate. These results provide a fresh perspective to understand the interfacial water reactivity and highlight the critical role of H-bond network in optimizing catalytic performance.https://doi.org/10.1038/s41467-025-60298-z
spellingShingle Shiwei Chen
Jiabao Zhu
Jifan Li
Pan Guo
Jinrong Yang
Xiao He
Entropy-driven difference in interfacial water reactivity between slab and nanodroplet
Nature Communications
title Entropy-driven difference in interfacial water reactivity between slab and nanodroplet
title_full Entropy-driven difference in interfacial water reactivity between slab and nanodroplet
title_fullStr Entropy-driven difference in interfacial water reactivity between slab and nanodroplet
title_full_unstemmed Entropy-driven difference in interfacial water reactivity between slab and nanodroplet
title_short Entropy-driven difference in interfacial water reactivity between slab and nanodroplet
title_sort entropy driven difference in interfacial water reactivity between slab and nanodroplet
url https://doi.org/10.1038/s41467-025-60298-z
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AT jifanli entropydrivendifferenceininterfacialwaterreactivitybetweenslabandnanodroplet
AT panguo entropydrivendifferenceininterfacialwaterreactivitybetweenslabandnanodroplet
AT jinrongyang entropydrivendifferenceininterfacialwaterreactivitybetweenslabandnanodroplet
AT xiaohe entropydrivendifferenceininterfacialwaterreactivitybetweenslabandnanodroplet