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Polymer nanofilms with enhanced microporosity by interfacial polymerization


Highly permeable and selective membranes are desirable for energy-efficient gas and liquid separations. Microporous organic polymers have attracted significant attention in this respect owing to their high porosity, permeability and molecular selectivity. However, it remains challenging to fabricate selective polymer membranes with controlled microporosity that are stable in solvents. Here we report a new approach to designing crosslinked, rigid polymer nanofilms with enhanced microporosity by manipulating the molecular structure. Ultrathin polyarylate nanofilms with thickness down to 20 nm are formed in situ by interfacial polymerization. Enhanced microporosity and higher interconnectivity of intermolecular network voids, as rationalized by molecular simulations, are achieved by using contorted monomers for the interfacial polymerization. Composite membranes comprising polyarylate nanofilms with enhanced microporosity fabricated in situ on crosslinked polyimide ultrafiltration membranes show outstanding separation performance in organic solvents, with up to two orders of magnitude higher solvent permeance than membranes fabricated with nanofilms made from non-contorted planar monomers.

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Figure 1: Interfacial synthesis of polyarylate nanofilms.
Figure 2: Polyarylate nanofilms.
Figure 3: Organic solvent nanofiltration.
Figure 4: Gas sorption and transport properties.
Figure 5: Structural analysis of amorphous polymer models.


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This work was financially supported by the Engineering and Physical Sciences Research Council (EPSRC, UK), 7th Framework Programme of the European Commission’s Marie Curie Initiative, NEMOPUR Project (M.F.J.-S.), Imperial College Junior Research Fellowship (Q.S.), and Royal Society University Research Fellowship (K.E.J.). The authors are grateful to P. R. J. Gaffney for assisting with monophasic reactions.

Author information




M.F.J.-S. and A.G.L. conceived the idea. M.F.J.-S., Q.S. and A.G.L. designed the research. M.F.J.-S. and Q.S. performed experiments, including synthesis of materials and membranes, and characterization analyses. M.F.J.-S. carried out organic solvent nanofiltration. Q.S. performed gas permeation measurements. K.E.J. performed molecular simulations. M.M.-I. assisted with synthesis of PAR/PI nanofilm composite membranes. M.F.J.-S., Q.S. and A.G.L. wrote the manuscript. A.G.L. guided the project. All of the authors participated in the discussion and read the manuscript.

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Correspondence to Andrew G. Livingston.

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The authors declare no competing financial interests.

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Jimenez-Solomon, M., Song, Q., Jelfs, K. et al. Polymer nanofilms with enhanced microporosity by interfacial polymerization. Nature Mater 15, 760–767 (2016).

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