Membranes with ultrahigh ion selectivity and high liquid permeance are needed to produce high-quality product water with increased recovery and process efficiency in water desalination. The narrow pore size distribution and controlled surface charge in the separation layer of nanofiltration membranes significantly improve the ion selectivity through molecular sieving and Donnan exclusion of co-ions. Here, the ultraselective and yet highly water permeable polyamide nanofilm composite nanofiltration membranes developed by precisely controlling the kinetics of the interfacial polymerization reaction by maintaining the stoichiometric equilibrium at the interface is reported. The kinetically favorable stoichiometric equilibrium condition prohibits the formation of aggregate pores in the nanofilm and leads to the formation of narrow network pores with a high surface negative charge. Nanofilms are designed with a controlled degree of crosslinking and made as thin as ≈7 nm to achieve increased water permeance. The ultraselective membranes exhibit up to 99.99% rejection of divalent salt (Na 2 SO 4) and demonstrate monovalent to divalent ion selectivity of >4000. The selectivity of these nanofilm composite membranes is beyond the permeance-selectivity upper-bound line of the state-of-the-art nanofiltration membranes and one to two orders of magnitude higher than the commercially available membranes with pure water permeances of up to 23 L m −2 h −1 bar −1. The fabrication process is scalable for membrane manufacturing.
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.
Liquid transport through the composite membrane is inversely proportional to the thickness of its separation layer. While the scalable fabrication of ultrathin polymer membranes is sought for their commercial exploitation,...
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