Conformationally tunable calix[4]pyrrole-based nanofilms for efficient molecular separation.

Preparation of nanofilms which are able to reject water-soluble low molecular weight organic compounds in nanofiltration remains to be a challenge. Herein, we report a new kind of self-standing, defect-free, robust, centimeter-sized and thickness controllable calix[4]pyrrole (C[4]P)-based nanofilms with excellent molecular sieving performance in nanofiltration. The nanofilms were prepared via confined dynamic condensation of the tetra-benzoyl-hydrazine derivative of calix[4]pyrrole (CPTBH) with 1,3,5-benzenetricarboxaldehyde (BTC) at the air/dimethyl sulfoxide (DMSO) interface. Nanofiltration tests under 2 bar pressure with porous polyethylene terephthalate (PET) as the support and a CsF treated CPTBH-BTC nanofilm (∼100 nm) as the selective layer depicted a water permeance of 15 L mh bar and a methanol permeance of 45 L mh bar. High rejection rates (>95%) were found in aqueous solution for most of the tested dyes and pharmaceuticals. Remarkably, the composite membrane also demonstrated good separation performance in aqueous phase to some amino acids and organic dyes with molecular weights around 200 g/mol. High-performance nanofiltration in methanol was also realized. In this case, the molecular weight cutoff value is ∼ 800 g/mol. These findings showed that introduction of macrocyclic hosts is an effective way to develop nanofilms with high solvent permeance but low molecular weight cutoff value.