Tethered electrolyte active-layer membranes

Abstract

Polyelectrolyte multilayer membranes (PEMs) produced by the sequential, layer-by-layer deposition of polyelectrolytes on porous supports have been shown to significantly reject ions in dilute saline solutions. However, polyelectrolyte thin films are susceptible to swelling or detachment from the substrate in higher salinities and extreme pH conditions, such that their performance is highly dependent on feed water composition. In this study, we introduce tethered electrolyte active-layer membranes (TEAMs), whereby charged block copolymers are covalently grafted-from a porous support, in aim of reducing the stimuli response of layered polyelectrolyte membranes under variable solution conditions. Cellulose support layers were modified using surface-initiated atom transfer radical polymerization of neutral precursor polymers, which were then converted into charged blocks after polymerization. An ultrathin layer of a single negative or positive block with a degree of polymerization (DP) ≥ 770 exhibited ∼15–20 L m-2 h-1 bar-1 pure water permeability, 45–60% rejection of monovalent co-ions, and ∼75% rejection of divalent co-ions. In mixed feed solutions, selectivity of monovalent over divalent co-ions with single-block TEAMs fell within the range of 2–4. Single-block TEAMs slightly shrank under high salt concentration, contrary to the typical substantial swelling of PEMs. As such, this new form of polyelectrolyte membrane may provide greater stability than conventional PEMs and may have potential applications in water softening and salinity reduction of surface waters.