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Facile Size-Selective Defect Sealing in Large-Area Atomically Thin Graphene Membranes for Sub-Nanometer Scale Separations

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    Facile Size-Selective Defect Sealing in Large-Area Atomically Thin Graphene Membranes for Sub-Nanometer Scale Separations
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    • Peifu Cheng
      Peifu Cheng
      Department of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville, Tennessee 37212, United States
      More by Peifu Cheng
    • Mattigan M. Kelly
      Mattigan M. Kelly
      Department of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville, Tennessee 37212, United States
      More by Mattigan M. Kelly
    • Nicole K. Moehring
      Nicole K. Moehring
      Department of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville, Tennessee 37212, United States
      Interdisciplinary Materials Science Program, Vanderbilt University, Nashville, Tennessee 37212, United States
      More by Nicole K. Moehring
    • Wonhee Ko
      Wonhee Ko
      Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      More by Wonhee Ko
    • An-Ping Li
      An-Ping Li
      Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      More by An-Ping Li
      Orcidhttp://orcid.org/0000-0003-4400-7493
    • Juan Carlos Idrobo
      Juan Carlos Idrobo
      Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
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    • Michael S. H. Boutilier
      Michael S. H. Boutilier
      Department of Chemical and Biochemical Engineering, Western University, London, Ontario N6A 5B9, Canada
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    • Piran R. Kidambi*
      Piran R. Kidambi
      Department of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville, Tennessee 37212, United States
      Interdisciplinary Materials Science Program, Vanderbilt University, Nashville, Tennessee 37212, United States
      *E-mail: [email protected]
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      Orcidhttp://orcid.org/0000-0003-1546-5014
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    Nano Letters

    Cite this: Nano Lett. 2020, 20, 8, 5951–5959
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    https://doi.org/10.1021/acs.nanolett.0c01934
    Published July 6, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Atomically thin graphene with a high-density of precise subnanometer pores represents the ideal membrane for ionic and molecular separations. However, a single large-nanopore can severely compromise membrane performance and differential etching between pre-existing defects/grain boundaries in graphene and pristine regions presents fundamental limitations. Here, we show for the first time that size-selective interfacial polymerization after high-density nanopore formation in graphene not only seals larger defects (>0.5 nm) and macroscopic tears but also successfully preserves the smaller subnanometer pores. Low-temperature growth followed by mild UV/ozone oxidation allows for facile and scalable formation of high-density (4–5.5 × 1012 cm–2) useful subnanometer pores in the graphene lattice. We demonstrate scalable synthesis of fully functional centimeter-scale nanoporous atomically thin membranes (NATMs) with water (∼0.28 nm) permeance ∼23× higher than commercially available membranes and excellent rejection to salt ions (∼0.66 nm, >97% rejection) as well as small organic molecules (∼0.7–1.5 nm, ∼100% rejection) under forward osmosis.

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.nanolett.0c01934.

    • Experimental section; Figure S1, experimental setup; Figures S2 and S7, calculated pore size distributions adjusted to the carbon electron radius and carbon van der Waals radius; Figure S3, solute diffusion comparison between membranes; Figure S4, water flux through graphene membrane when draw solution is placed on the graphene side versus the PCTE membrane side; Figure S5, water level change on the feed side for PCTE+IP membrane during water flux measurement; Figure S6, performance of NATMs; Table S1, model fit pore density values; Table S2 and Table S3, comparison of performance among different FO membranes reported in the literature and this work; Table S4, solutions in the feed and permeate side for solute diffusion, water transport, and solute rejection experiments; Note 1, assessment of Raman spectra of graphene lattice after UV/ozone etch; Note 2, Table S5 and Figures S8–S10, transport model (PDF)

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    Cited By

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    This article is cited by 47 publications.

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    Nano Letters

    Cite this: Nano Lett. 2020, 20, 8, 5951–5959
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.nanolett.0c01934
    Published July 6, 2020
    Copyright © 2020 American Chemical Society
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