Empowering ultrathin polyamide membranes at the water-energy nexus: strategies, limitations, and future perspectives.

Membrane-based separation is one of the most energy-efficient methods to meet the growing need for a significant amount of fresh water. It is also well-known for its applications in water treatment, desalination, solvent recycling, and environmental remediation. Most typical membranes used for separation-based applications are thin-film composite membranes created using polymers, featuring a top selective layer generated by employing the interfacial polymerization technique at an aqueous-organic interface. In the last decade, various manufacturing techniques have been developed in order to create high-specification membranes. Among them, the creation of ultrathin polyamide membranes has shown enormous potential for achieving a significant increase in the water permeation rate, translating into major energy savings in various applications. However, this great potential of ultrathin membranes is greatly hindered by undesired transport phenomena such as the geometry-induced "funnel effect" arising from the substrate membrane, severely limiting the actual permeation rate. As a result, the separation capability of ultrathin membranes is still not fully unleashed or understood, and a critical assessment of their limitations and potential solutions for future studies is still lacking. Here, we provide a summary of the latest developments in the design of ultrathin polyamide membranes, which have been achieved by controlling the interfacial polymerization process and utilizing a number of novel manufacturing processes for ionic and molecular separations. Next, an overview of the in-depth assessment of their limitations resulting from the substrate membrane, along with potential solutions and future perspectives will be covered in this review.

Unraveling Anomalies in Preferential Liquid Transport through the Intrinsic Pores of Cyclodextrin in Polyester Nanofilms.

The precise manipulation of the porous structure of the nanofiltration membrane is critical for unlocking enhanced separation efficiencies across various liquids and solutes. Ultrathin films of crosslinked macrocycles, specifically cyclodextrins (CDs), have drawn considerable attention in this area owing to their ability to facilitate precise molecular separation with high liquid permeance for both polar and non-polar liquids, resembling Janus membranes. However, the functional role of the intrinsic cavity of CD in liquid transport remains inadequately understood, demanding immediate attention in designing nanofiltration membranes. Here, the synthesis of polyester nanofilms derived from crosslinked ß-CD, demonstrating remarkable Na2SO4 rejection (≈92 - 99.5%), high water permeance (≈4.4 - 37.4 Lm-2h-1bar-1), extremely low hexane permeance (<1 Lm-2h-1bar-1), and extremely high ratio (α > 500) of permeances for polar and non-polar liquids, is reported. Molecular simulations support the findings, indicating that neither the polar nor the non-polar liquids flow through the ß-CD cavity in the nanofilm. Instead, liquid transport predominantly occurs through the 2.2 nm hydrophilic aggregate pores. This challenges the presumed functional role of macrocyclic cavities in liquid transport and raises questions about the existence of the Janus structure in nanofiltration membranes produced from the macrocyclic monomers.

Enhancing the removal of organic micropollutants by nanofiltration membrane with Fe (III)-tannic acid interlayer: Mechanisms and environmental implications.

Nanofiltration technology has been applied in a variety of water treatment scenarios. However, conventional thin-film composite (TFC) membranes fail to remove emerging organic micropollutants (OMPs) efficiently. Here we applied thin-film nanocomposite membrane with an interlayer (TFNi) of Fe (III)-tannic acid to remove various types of OMPs, such as endocrine disrupting chemicals (EDCs), pharmaceutically active compounds (PhACs), and perfluoroalkyl substances (PFASs). Compared to the pristine TFC membrane, TFNi membrane exhibited crumpled morphology and its rejection layer was denser, better cross-linked and possessed smaller average pore size with narrower distribution. Significant enhancement in water-OMPs selectivity of PhACs and PFASs was observed. The mechanism lies in the effects of interlayer in improving the membrane permeance to water and meanwhile reducing the permeance to some OMPs by enhancing size exclusion effects. This work confirms the effectiveness of using TFNi membrane to simultaneously enhance the OMPs rejection and water permeance. The unraveled mechanism might inspire the future development of high-performance nanofiltration membranes targeting OMPs removal.

Interfacial synthesis of large-area ultrathin polyimine nanofilms as molecular separation membrane.

Thin film membranes of covalent organic frameworks are promising for high-permeance molecular separation. However, their synthesis needs a high temperature or longer reaction time, unsuitable for large-scale fabrication of thin film composite membranes. The ultrathin film of porous organic polymers as a separation layer of the composite membrane could be a close alternative to COF membranes. Here we report transition metal ion-catalyzed room temperature fabrication of the ultrathin (≈12 nm) polyimine nanofilms via interfacial polymerization of melamine and triformylphloroglucinol onto hydrolyzed polyacrylonitrile support within a short reaction time. Composite membranes exhibit high water permeance (≈78 L m-2 h-1 bar-1), high rejection (99.6%) of brilliant blue R (825.9 g mol-1), low rejection of NaCl (≈1.8%) and Na2SO4 (≈17%), and enable efficient molecular separation. The role of metal ion catalysts for large-area fabrication of the ultrathin polyimine nanofilm membranes used for molecular separation is demonstrated.

Large Area Self-Assembled Ultrathin Polyimine Nanofilms Formed at the Liquid-Liquid Interface Used for Molecular Separation.

Separation membranes with higher molecular weight cut-offs are needed to separate ions and small molecules from a mixed feed. The molecular sieving phenomenon can be utilized to separate smaller species with well-defined dimensions from a mixture. Here, the formation of freestanding polyimine nanofilms with thicknesses down to ≈14 nm synthesized via self-assembly of pre-synthesized imine oligomers is reported. Nanofilms are fabricated at the water-xylene interface followed by reversible condensation of polymerization according to the Pieranski theory. Polyimine nanofilm composite membranes are made via transferring the freestanding nanofilm onto ultrafiltration supports. High water permeance of 49.5 L m-2 h-1 bar-1 is achieved with a complete rejection of brilliant blue-R (BBR; molecular weight = 825 g mol-1 ) and no more than 10% rejection of monovalent and divalent salts. However, for a mixed feed of BBR dye and monovalent salt, the salt rejection is increased to ≈18%. Membranes are also capable of separating small dyes (e.g., methyl orange; MO; molecular weight = 327 g mol-1 ) from a mixed feed of BBR and MO. Considering a thickness of ≈14 nm and its separation efficiency, the present membrane has significance in separation processes.