Hydrogen-Bond Heterogeneity Boosts Hydrophobicity of Solid Interfaces

Experimental and theoretical studies suggest that the hydrophobicity of chemically heterogeneous surfaces may present important nonlinearities as a function of composition. In this article, this issue is systematically explored using molecular simulations. The hydrophobicity is characterized by comp...

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Autores principales:	Factorovich, M.H., Molinero, V., Scherlis, D.A.
Formato:	JOUR
Materias:	Atoms Binary mixtures Contact angle Hydrophilicity Hydrophobicity Coarse-grained potential Cylindrical nanopores Heterogeneous surface Hydrophilic and hydrophobic Hydrophilic components Hydrophobic interface Molecular simulations Tetrahedral coordination Hydrogen bonds hydrogen water Article contact angle desorption hydrogen bond hydrophobicity molecular dynamics nanopore vapor pressure
Acceso en línea:	http://hdl.handle.net/20.500.12110/paper_00027863_v137_n33_p10618_Factorovich
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	todo:paper_00027863_v137_n33_p10618_Factorovich
record_format	dspace
spelling	todo:paper_00027863_v137_n33_p10618_Factorovich2023-10-03T13:54:26Z Hydrogen-Bond Heterogeneity Boosts Hydrophobicity of Solid Interfaces Factorovich, M.H. Molinero, V. Scherlis, D.A. Atoms Binary mixtures Contact angle Hydrophilicity Hydrophobicity Coarse-grained potential Cylindrical nanopores Heterogeneous surface Hydrophilic and hydrophobic Hydrophilic components Hydrophobic interface Molecular simulations Tetrahedral coordination Hydrogen bonds hydrogen water Article contact angle desorption hydrogen bond hydrophobicity molecular dynamics nanopore vapor pressure Experimental and theoretical studies suggest that the hydrophobicity of chemically heterogeneous surfaces may present important nonlinearities as a function of composition. In this article, this issue is systematically explored using molecular simulations. The hydrophobicity is characterized by computing the contact angle of water on flat interfaces and the desorption pressure of water from cylindrical nanopores. The studied interfaces are binary mixtures of hydrophilic and hydrophobic sites, with and without the ability to form hydrogen bonds with water, intercalated at different scales. Water is described with the mW coarse-grained potential, where hydrogen-bonds are modeled in the absence of explicit hydrogen atoms, via a three-body term that favors tetrahedral coordination. We found that the combination of particles exhibiting the same kind of coordination with water gives rise to a linear dependence of contact angle with respect to composition, in agreement with the Cassie model. However, when only the hydrophilic component can form hydrogen bonds, unprecedented deviations from linearity are observed, increasing the contact angle and the vapor pressure above their values in the purely hydrophobic interface. In particular, the maximum enhancement is seen when a 35% of hydrogen bonding molecules is randomly scattered on a hydrophobic background. This effect is very sensitive to the heterogeneity length-scale, being significantly attenuated when the hydrophilic domains reach a size of 2 nm. The observed behavior may be qualitatively rationalized via a simple modification of the Cassie model, by assuming a different microrugosity for hydrogen bonding and non-hydrogen bonding interfaces. © 2015 American Chemical Society. Fil:Molinero, V. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00027863_v137_n33_p10618_Factorovich
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	Atoms Binary mixtures Contact angle Hydrophilicity Hydrophobicity Coarse-grained potential Cylindrical nanopores Heterogeneous surface Hydrophilic and hydrophobic Hydrophilic components Hydrophobic interface Molecular simulations Tetrahedral coordination Hydrogen bonds hydrogen water Article contact angle desorption hydrogen bond hydrophobicity molecular dynamics nanopore vapor pressure
spellingShingle	Atoms Binary mixtures Contact angle Hydrophilicity Hydrophobicity Coarse-grained potential Cylindrical nanopores Heterogeneous surface Hydrophilic and hydrophobic Hydrophilic components Hydrophobic interface Molecular simulations Tetrahedral coordination Hydrogen bonds hydrogen water Article contact angle desorption hydrogen bond hydrophobicity molecular dynamics nanopore vapor pressure Factorovich, M.H. Molinero, V. Scherlis, D.A. Hydrogen-Bond Heterogeneity Boosts Hydrophobicity of Solid Interfaces
topic_facet	Atoms Binary mixtures Contact angle Hydrophilicity Hydrophobicity Coarse-grained potential Cylindrical nanopores Heterogeneous surface Hydrophilic and hydrophobic Hydrophilic components Hydrophobic interface Molecular simulations Tetrahedral coordination Hydrogen bonds hydrogen water Article contact angle desorption hydrogen bond hydrophobicity molecular dynamics nanopore vapor pressure
description	Experimental and theoretical studies suggest that the hydrophobicity of chemically heterogeneous surfaces may present important nonlinearities as a function of composition. In this article, this issue is systematically explored using molecular simulations. The hydrophobicity is characterized by computing the contact angle of water on flat interfaces and the desorption pressure of water from cylindrical nanopores. The studied interfaces are binary mixtures of hydrophilic and hydrophobic sites, with and without the ability to form hydrogen bonds with water, intercalated at different scales. Water is described with the mW coarse-grained potential, where hydrogen-bonds are modeled in the absence of explicit hydrogen atoms, via a three-body term that favors tetrahedral coordination. We found that the combination of particles exhibiting the same kind of coordination with water gives rise to a linear dependence of contact angle with respect to composition, in agreement with the Cassie model. However, when only the hydrophilic component can form hydrogen bonds, unprecedented deviations from linearity are observed, increasing the contact angle and the vapor pressure above their values in the purely hydrophobic interface. In particular, the maximum enhancement is seen when a 35% of hydrogen bonding molecules is randomly scattered on a hydrophobic background. This effect is very sensitive to the heterogeneity length-scale, being significantly attenuated when the hydrophilic domains reach a size of 2 nm. The observed behavior may be qualitatively rationalized via a simple modification of the Cassie model, by assuming a different microrugosity for hydrogen bonding and non-hydrogen bonding interfaces. © 2015 American Chemical Society.
format	JOUR
author	Factorovich, M.H. Molinero, V. Scherlis, D.A.
author_facet	Factorovich, M.H. Molinero, V. Scherlis, D.A.
author_sort	Factorovich, M.H.
title	Hydrogen-Bond Heterogeneity Boosts Hydrophobicity of Solid Interfaces
title_short	Hydrogen-Bond Heterogeneity Boosts Hydrophobicity of Solid Interfaces
title_full	Hydrogen-Bond Heterogeneity Boosts Hydrophobicity of Solid Interfaces
title_fullStr	Hydrogen-Bond Heterogeneity Boosts Hydrophobicity of Solid Interfaces
title_full_unstemmed	Hydrogen-Bond Heterogeneity Boosts Hydrophobicity of Solid Interfaces
title_sort	hydrogen-bond heterogeneity boosts hydrophobicity of solid interfaces
url	http://hdl.handle.net/20.500.12110/paper_00027863_v137_n33_p10618_Factorovich
work_keys_str_mv	AT factorovichmh hydrogenbondheterogeneityboostshydrophobicityofsolidinterfaces AT molinerov hydrogenbondheterogeneityboostshydrophobicityofsolidinterfaces AT scherlisda hydrogenbondheterogeneityboostshydrophobicityofsolidinterfaces
_version_	1782029268440580096

Hydrogen-Bond Heterogeneity Boosts Hydrophobicity of Solid Interfaces

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