skip to main content


Title: Polyamide nanofiltration membrane with highly uniform sub-nanometre pores for sub-1 Å precision separation
Abstract

Separating molecules or ions with sub-Angstrom scale precision is important but technically challenging. Achieving such a precise separation using membranes requires Angstrom scale pores with a high level of pore size uniformity. Herein, we demonstrate that precise solute-solute separation can be achieved using polyamide membranes formed via surfactant-assembly regulated interfacial polymerization (SARIP). The dynamic, self-assembled network of surfactants facilitates faster and more homogeneous diffusion of amine monomers across the water/hexane interface during interfacial polymerization, thereby forming a polyamide active layer with more uniform sub-nanometre pores compared to those formed via conventional interfacial polymerization. The polyamide membrane formed by SARIP exhibits highly size-dependent sieving of solutes, yielding a step-wise transition from low rejection to near-perfect rejection over a solute size range smaller than half Angstrom. SARIP represents an approach for the scalable fabrication of ultra-selective membranes with uniform nanopores for precise separation of ions and small solutes.

 
more » « less
Award ID(s):
1739884
NSF-PAR ID:
10224538
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ;
Publisher / Repository:
Nature Publishing Group
Date Published:
Journal Name:
Nature Communications
Volume:
11
Issue:
1
ISSN:
2041-1723
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract Polymer membranes have been used extensively for Angstrom-scale separation of solutes and molecules. However, the pore size of most polymer membranes has been considered an intrinsic membrane property that cannot be adjusted in operation by applied stimuli. In this work, we show that the pore size of an electrically conductive polyamide membrane can be modulated by an applied voltage in the presence of electrolyte via a mechanism called electrically induced osmotic swelling. Under applied voltage, the highly charged polyamide layer concentrates counter ions in the polymer network via Donnan equilibrium and creates a sizeable osmotic pressure to enlarge the free volume and the effective pore size. The relation between membrane potential and pore size can be quantitatively described using the extended Flory-Rehner theory with Donnan equilibrium. The ability to regulate pore size via applied voltage enables operando modulation of precise molecular separation in-situ. This study demonstrates the amazing capability of electro-regulation of membrane pore size at the Angstrom scale and unveils an important but previously overlooked mechanism of membrane-water-solute interactions. 
    more » « less
  2. Abstract

    Atomically thin membranes comprising nanopores in a 2D material promise to surpass the performance of polymeric membranes in several critical applications, including water purification, chemical and gas separations, and energy harvesting. However, fabrication of membranes with precise pore size distributions that provide exceptionally high selectivity and permeance in a scalable framework remains an outstanding challenge. Circumventing these constraints, here, a platform technology is developed that harnesses the ability of oppositely charged polyelectrolytes to self‐assemble preferentially across larger, relatively leaky atomically thin nanopores by exploiting the lower steric hindrance of such larger pores to molecular interactions across the pores. By selectively tightening the pore size distribution in this manner, self‐assembly of oppositely charged polyelectrolytes simultaneously introduced on opposite sides of nanoporous graphene membranes is demonstrated to discriminate between nanopores to seal non‐selective transport channels, while minimally compromising smaller, water‐selective pores, thereby remarkably attenuating solute leakage. This improved membrane selectivity enables desalination across centimeter‐scale nanoporous graphene with 99.7% and >90% rejection of MgSO4and NaCl, respectively, under forward osmosis. These findings provide a versatile strategy to augment the performance of nanoporous atomically thin membranes and present intriguing possibilities of controlling reactions across 2D materials via exclusive exploitation of pore size‐dependent intermolecular interactions.

     
    more » « less
  3. Abstract

    Polyamide thin‐film composite (PA‐TFC) membranes make large‐scale desalination effective. Interfacial polymerization (IP) is used to make PA‐TFC membranes, but it may limit the range of monomers that can be used, which hinders progress toward advanced membranes. Layer‐by‐layer (LbL) sequential deposition could circumvent kinetic and thermodynamic limitations of the conventional IP process to facilitate incorporation of different co‐monomers into the membrane. The selective layer needs to be deposited onto a microporous support, but depositing LbL coatings on microporous supports often results in defective membranes. Using a poly(vinyl alcohol) (PVA) primer between the support and the LbL polyamide layer may prevent defect formation. The water permeance and salt rejection of a three layer, PVA‐primed, LbL‐based PA‐TFC membrane are discussed and compared to a membrane made without the PVA primer and a commercially available membrane. Mass transfer resistances are analyzed using a series resistance model and appear to be small or even negligible compared to that of the polyamide layer. Incorporation of a sulfonated co‐monomer into the polyamide via LbL is reported. The combination of a PVA primer layer and LbL sequential deposition may expand the range of co‐monomers that could be used relative to polyamide membranes prepared by the conventional IP process.

     
    more » « less
  4. Abstract

    2D covalent organic frameworks (2D COFs) are attractive candidates for next‐generation membranes due to their robust linkages and uniform, tunable pores. Many publications have claimed to achieve selective molecular transport through COF pores, but reported performance metrics for similar networks vary dramatically, and in several cases the reported experiments are inadequate to support such conclusions. These issues require a reevaluation of the literature. Published examples of 2D COF membranes for liquid‐phase separations can be broadly divided into two categories, each with common performance characteristics: polycrystalline COF films (most >1 µm thick) and weakly crystalline or amorphous films (most <500 nm thick). Neither category has demonstrated consistent relationships between the designed COF pore structure and separation performance, suggesting that these imperfect materials do not sieve molecules through uniform pores. In this perspective, rigorous practices for evaluating COF membrane structures and separation performance are described, which will facilitate their development toward molecularly precise membranes capable of performing previously unrealized chemical separations. In the absence of this more rigorous standard of proof, reports of COF‐based membranes should be treated with skepticism. As methods to control 2D polymerization improve, precise 2D polymer membranes may exhibit exquisite and energy efficient performance relevant for contemporary separation challenges.

     
    more » « less
  5. Abstract

    Monodispersed angstrom-size pores embedded in a suitable matrix are promising for highly selective membrane-based separations. They can provide substantial energy savings in water treatment and small molecule bioseparations. Such pores present as membrane proteins (chiefly aquaporin-based) are commonplace in biological membranes but difficult to implement in synthetic industrial membranes and have modest selectivity without tunable selectivity. Here we present PoreDesigner, a design workflow to redesign the robust beta-barrel Outer Membrane Protein F as a scaffold to access three specific pore designs that exclude solutes larger than sucrose (>360 Da), glucose (>180 Da), and salt (>58 Da) respectively. PoreDesigner also enables us to design any specified pore size (spanning 3–10 Å), engineer its pore profile, and chemistry. These redesigned pores may be ideal for conducting sub-nm aqueous separations with permeabilities exceeding those of classical biological water channels, aquaporins, by more than an order of magnitude at over 10 billion water molecules per channel per second.

     
    more » « less