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. 
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                            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. 
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                            - Award ID(s):
- 1739884
- PAR ID:
- 10224538
- 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
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