Supramolecular-coordinated nanofiltration membranes with quaternary-ammonium Cyclen for efficient lithium extraction from high magnesium/lithium ratio brine.

Ion-selective membranes (ISM) with sub-nanosized pore channels hold significant potential for applications in saline wastewater treatment and resource recovery. Herein, novel synergistic ion channels featuring bi-periodic structures were constructed through the coordination of functional Cyclen (quaternary_1,4,7,10-tetraazacyclododecane, Q_Cyclen) and Cu-m-Phenylenediamine (Cu-MPD) to develop supramolecular membranes for lithium extraction. The exterior quaternary ammonium-rich sites exhibit a significant Donnan exclusion effect, resulting in tremendous mono/divalent (Li/Mg) ion selectivity; while the interior regular-confined channels of Cyclen yield a fast vehicular pathway, facilitating water molecules and Li ion-selective transport. The optimized membrane exhibited an increased water permeance of 19.2 L·m·h·bar and simultaneously promoted Li/Mg selectivity (achieving a selectivity of 18.5 under a Mg/Li mass ratio of 30), surpassing the trade-off limit of conventional nanofiltration membranes. Due to the acquired excellent Li/Mg selectivity, lithium extraction from simulated salt-lake brines was successfully achieved through a two-stage nanofiltration process, reducing the Mg/Li mass ratio from 40 to 1.1. This work validates the applicability of macrocyclic with intrinsic sub-nanosized channels and desired multifunctionality for developing high-performance ISM for efficient lithium separation and beyond.