ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

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
Copyright © 2021 American Chemical Society

    Article Views





    Other access options
    Supporting Info (1)»


    Abstract Image

    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.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.


    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    Jump To

    The Supporting Information is available free of charge at

    • 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)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 13 publications.

    1. Shuang Luo, Rahul Prasanna Misra, Daniel Blankschtein. Water Electric Field Induced Modulation of the Wetting of Hexagonal Boron Nitride: Insights from Multiscale Modeling of Many-Body Polarization. ACS Nano 2024, 18 (2) , 1629-1646.
    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.
    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.
    4. Phillip Helms, Anthony R. Poggioli, David T. Limmer. Intrinsic Interface Adsorption Drives Selectivity in Atomically Smooth Nanofluidic Channels. Nano Letters 2023, 23 (10) , 4226-4233.
    5. Mathieu Salanne, (Associate Editor, ACS Nano)Jillian M. Buriak, (Executive Editor, ACS Nano)Xiaodong Chen, (Editor-in-Chief, ACS Nano)William Chueh, (Associate Editor, ACS Nano)Mark C. Hersam, (Executive Editor, ACS Nano)Raymond E. Schaak (Associate Editor, ACS Nano, Deputy Editor, ACS Nanoscience Au). Best Practices for Simulations and Calculations of Nanomaterials for Energy Applications: Avoiding “Garbage In, Garbage Out”. ACS Nano 2023, 17 (7) , 6147-6149.
    6. Md Masuduzzaman, BoHung Kim. Unraveling the Molecular Interface and Boundary Problems in an Electrical Double Layer and Electroosmotic Flow. Langmuir 2022, 38 (23) , 7244-7255.
    7. Chenxia Xie, Hui Li. Multiscale simulations of nanofluidics: Recent progress and perspective. WIREs Computational Molecular Science 2023, 30
    8. Anton Robert, Hélène Berthoumieux, Marie-Laure Bocquet. Coupled Interactions at the Ionic Graphene-Water Interface. Physical Review Letters 2023, 130 (7)
    9. Weijie Wang, Jinlin Hao, Qian Sun, Minqi Zhao, Huiyi Liu, Chao Li, Xin Sui. Carbon nanofibers membrane bridged with graphene nanosheet and hyperbranched polymer for high-performance osmotic energy harvesting. Nano Research 2023, 16 (1) , 1205-1211.
    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.
    11. Philip Loche, Laura Scalfi, Mustakim Ali Amu, Otto Schullian, Douwe J. Bonthuis, Benjamin Rotenberg, Roland R. Netz. Effects of surface rigidity and metallicity on dielectric properties and ion interactions at aqueous hydrophobic interfaces. The Journal of Chemical Physics 2022, 157 (9) , 094707.
    12. Kuo-Yang Chiang, Takakazu Seki, Chun-Chieh Yu, Tatsuhiko Ohto, Johannes Hunger, Mischa Bonn, Yuki Nagata. The dielectric function profile across the water interface through surface-specific vibrational spectroscopy and simulations. Proceedings of the National Academy of Sciences 2022, 119 (36)
    13. Jing-tao Huang, Yong Liu, Zhong-hong Lai, Jin Hu, Fei Zhou, Jing-chuan Zhu. Electronic structure and optical properties of non-metallic modified graphene: a first-principles study. Communications in Theoretical Physics 2022, 74 (3) , 035501.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect