Polyelectrolyte Complex Hollow Fiber Membranes Prepared via Aqueous Phase Separation.

Hollow fiber (HF) membrane geometry is the preferred choice for most commercial membrane operations. Such fibers are conventionally prepared via the non-solvent-induced phase separation technique, which heavily relies on hazardous and reprotoxic organic solvents such as N-methyl pyrrolidone. A more sustainable alternative, i.e., aqueous phase separation (APS), was introduced recently that utilizes water as a solvent and non-solvent for the production of polymeric membranes. Herein, for the first time, we demonstrate the preparation of sustainable and functional HF membranes via the APS technique in a dry-jet wet spinning process. The dope solution comprising poly(sodium 4-styrenesulfonate) (PSS) and polyethyleneimine (PEI) at high pH along with an aqueous bore liquid is pushed through a single orifice spinneret into a low pH acetate buffer coagulation bath. Here, PEI becomes charged resulting in the formation of a polyelectrolyte complex with PSS. The compositions of the bore liquid and coagulation bath were systematically varied to study their effect on the structure and performance of the HF membranes. The microfiltration-type membranes (permeability ∼500 to 800 L·m-2·h-1·bar-1) with complete retention of emulsion droplets were obtained when the precipitation rate was slow. Increasing the concentration of the acetate buffer in the bath led to the increase in precipitation rate resulting in ultrafiltration-type membranes (permeability ∼12 to 15 L·m-2·h-1·bar-1) having molecular weight cut-offs in the range of ∼7.8-11.6 kDa. The research presented in this work confirms the versatility of APS and moves it another step closer to large-scale use.

In Situ Ag-MOF Growth on Pre-Grafted Zwitterions Imparts Outstanding Antifouling Properties to Forward Osmosis Membranes.

In this study, a polyamide forward osmosis membrane was functionalized with zwitterions followed by the in situ growth of metal-organic frameworks with silver as a metal core (Ag-MOFs) to improve its antibacterial and antifouling activity. First, 3-bromopropionic acid was grafted onto the membrane surface after its activation with N,N-diethylethylenediamine. Then, the in situ growth of Ag-MOFs was achieved by a simple membrane immersion sequentially in a silver nitrate solution and in a ligand solution (2-methylimidazole), exploiting the underlying zwitterions as binding sites for the metal. The successful membrane functionalization and the enhanced surface wettability were verified through an array of characterization techniques. When evaluated in forward osmosis tests, the modified membranes exhibited high performance and improved permeability compared to pristine membranes. Static antibacterial experiments, evaluated by confocal microscopy and colony-forming unit plate count, resulted in a 77% increase in the bacterial inhibition rate due to the activity of the Ag-MOFs. Microscopy micrographs of the Escherichia coli bacteria suggested the deterioration of the biological cells. The antifouling properties of the functionalized membranes translated into a significantly lower flux decline in forward osmosis filtrations. These modified surfaces displayed negligible depletion of silver ions over 30 days, confirming the stable immobilization of Ag-MOFs on their surface.