RESUMO
Polyamide reverse osmosis (PA-RO) membranes achieve remarkably high water permeability and salt rejection, making them a key technology for addressing water shortages through processes including seawater desalination and wastewater reuse. However, current state-of-the-art membranes suffer from challenges related to inadequate selectivity, fouling, and a poor ability of existing models to predict performance. In this Perspective, we assert that a molecular understanding of the mechanisms that govern selectivity and transport of PA-RO and other polymer membranes is crucial to both guide future membrane development efforts and improve the predictive capability of transport models. We summarize the current understanding of ion, water, and polymer interactions in PA-RO membranes, drawing insights from nanofiltration and ion exchange membranes. Building on this knowledge, we explore how these interactions impact the transport properties of membranes, highlighting assumptions of transport models that warrant further investigation to improve predictive capabilities and elucidate underlying transport mechanisms. We then underscore recent advances in in situ characterization techniques that allow for direct measurements of previously difficult-to-obtain information on hydrated polymer membrane properties, hydrated ion properties, and ion-water-membrane interactions as well as powerful computational and electrochemical methods that facilitate systematic studies of transport phenomena.
RESUMO
The role of steric hindrance and charge interactions in governing ionic transport through reduced graphene oxide (rGO) and commercial (DOW-Filmtec NF270) membranes was elucidated by a comprehensive study of experimental and established mathematical analysis based on Nernst-Planck equation. A charge-dominated salt exclusion mechanism was observed for the rGO membranes, which exhibited retention from low (7%) to moderate (70%) extent depending on the nature of ions (5 mM). Swelling of GO (1.2 nm interlayer distance) in water beyond the hydrated diameter of ions was attributed as a primary cause for lowering steric hindrance effects. The influence of parameters affecting charge interactions, such as pH and ionic strength, on the extent of salt rejection was modelled. The potential impact of the membrane's charge density, GO loading and interlayer spacing on salt retention was quantified by performing sensitivity analyses. For a high TDS produced water sample, the rGO membranes partially retained divalent cations (Ca:13%) and exhibited high dissolved oil rejection. The membranes were found to be suitable for the treatment of high TDS water with the goal of selectively removing organic impurities, and thus minimizing the impact of osmotic pressure effect. Performance of the membranes was also investigated for retention of water remediation related organic anions, using perfluoro octanoic (PFOA) acid as a model compound. rGO membranes exhibited a charge-dominated exclusion mechanism for retention (90%) of PFOA (1 ppm).
RESUMO
This study explores the integration of separation performance of rGO membrane with heterogeneous oxidation reactions for remediation of organic contaminants from water. Herein, an approach was introduced based on layer-by-layer assembly for functionalizing rGO membranes with polyacrylic acid and then by in situ synthesis of Fe based reactive nanoparticles. TEM characterization of the cross-section lamella of the membranes showed a high density of nanoparticles (12% Fe) in the functionalized domain, signifying the importance of polyacrylic acid for in situ synthesis of nanoparticles. The membranes exhibited a pure water permeability of 1.9 LMH bar-1. The membranes had low to moderate salt retention, and more than 90% neutral red retention (organic probe molecule, size: 1.2 nm). The membranes also exhibited high retention of humic acids (80%), preventing these organics from entering the reactive domain, and thus potentially reducing the formation of undesired by-products. A persulfate mediated oxidative pathway was employed to demonstrate the reactive removal of organic contaminants. The membranes achieved >95% conversion by convectively passing 2 mM persulfate feed at a transmembrane pressure of 0.4 bar. Successful degradation of TCE (up to 61%) was achieved in a single pass by convective flowing of the feed solution through the membrane, generating up to 80% of the theoretical maximum chloride as one of the byproducts. Elevated temperatures significantly enhanced persulfate mediated TCE oxidation extent from 24% at 23 oC to 54% at 40 o C under batch operating conditions.