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Osmotic Transport at the Aqueous Graphene and hBN Interfaces: Scaling Laws from a Unified, First-Principles Description

Cite this: ACS Nano 2021, 15, 9, 15249–15258
Publication Date (Web):September 7, 2021
https://doi.org/10.1021/acsnano.1c05931
Copyright © 2021 American Chemical Society

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    Abstract

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    Osmotic transport in nanoconfined aqueous electrolytes provides alternative venues for water desalination and “blue energy” harvesting. The osmotic response of nanofluidic systems is controlled by the interfacial structure of water and electrolyte solutions in the so-called electrical double layer (EDL), but a molecular-level picture of the EDL is to a large extent still lacking. Particularly, the role of the electronic structure has not been considered in the description of electrolyte/surface interactions. Here, we report enhanced sampling simulations based on ab initio molecular dynamics, aiming at unravelling the free energy of prototypical ions adsorbed at the aqueous graphene and hBN interfaces, and its consequences on nanofluidic osmotic transport. Specifically, we predicted the zeta potential, the diffusio-osmotic mobility, and the diffusio-osmotic conductivity for a wide range of salt concentrations from the ab initio water and ion spatial distributions through an analytical framework based on Stokes equation and a modified Poisson–Boltzmann equation. We observed concentration-dependent scaling laws, together with dramatic differences in osmotic transport between the two interfaces, including diffusio-osmotic flow and current reversal on hBN but not on graphene. We could rationalize the results for the three osmotic responses with a simple model based on characteristic length scales for ion and water adsorption at the surface, which are quite different on graphene and on hBN. Our work provides fundamental insights into the structure and osmotic transport of aqueous electrolytes on 2D materials and explores alternative pathways for efficient water desalination and osmotic energy conversion.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsnano.1c05931.

    • Further computational details and tests on the structure and dynamics of water at the interface with graphene and hBN from force field and ab initio simulations; derivation of integral expressions for the transport coefficients; details of the modified Poisson–Boltzmann description; details of the effective surface charge model (PDF)

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    Cited By

    This article is cited by 13 publications.

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    2. Nima Nazemzadeh, Caetano R. Miranda, Yunfeng Liang, Martin P. Andersson. First-Principles Prediction of Amorphous Silica Nanoparticle Surface Charge: Effect of Size, pH, and Ionic Strength. The Journal of Physical Chemistry B 2023, 127 (44) , 9608-9619. https://doi.org/10.1021/acs.jpcb.3c04405
    3. Chen Qian, Ke Zhou. Ab Initio Molecular Dynamics Investigation of the Solvation States of Hydrated Ions in Confined Water. Inorganic Chemistry 2023, 62 (43) , 17756-17765. https://doi.org/10.1021/acs.inorgchem.3c02443
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    10. Youngoh Kim, Joonmyung Choi. Chemo-mechano-structural interplay in fully hydrated ion clusters on hexagonal boron nitride nanosheet surfaces. Materials Today Chemistry 2022, 26 , 101161. https://doi.org/10.1016/j.mtchem.2022.101161
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