The performance of anion-exchange membranes (AEMs) in Reverse Electrodialysis is hampered by both presence of multivalent ions and fouling phenomena, thus leading to reduced net power density. Therefore, we propose a monolayer surface modification procedure to functionalize Ralex-AEMs with poly(acrylic) acid (PAA) in order to (i) render a monovalent permselectivity, and (ii) minimize organic fouling. Membrane surface modification was carried out by putting heterogeneous AEMs in contact with a PAA-based aqueous solution for 24 h. The resulting modified membranes were firstly characterized by contact angle, water uptake, ion exchange capacity, fixed charge density, and swelling degree measurements, whereas their electrochemical responses were evaluated through cyclic voltammetry. Besides, their membrane electro-resistance was also studied via electrochemical impedance spectroscopy analyses. Finally, membrane permselectivity and fouling behavior in the presence of humic acid were evaluated through mass transport experiments using model NaCl containing solutions. The use of modified PAA-AEMs resulted in a significantly enhanced monovalent permselectivity (sulfate rejection improved by >35%) and membrane hydrophilicity (contact angle decreased by >15%) in comparison with the behavior of unmodified Ralex-AEMs, without compromising the membrane electro-resistance after modification, thus demonstrating the technical feasibility of the proposed membrane modification procedure. This study may therefore provide a feasible way for achieving an improved Reverse Electrodialysis process efficiency.
Reverse electrodialysis (RED) technology represents a promising electro-membrane process for renewable energy harvesting from aqueous streams with different salinity. However, the performance of the key components of the system, that is, the ion exchange membranes, is limited by both the presence of multivalent ions and fouling phenomena, thus leading to a reduced generated net power density. In this context, the behavior of anion exchange membranes (AEMs) in RED systems is more severely affected, due to the undesirable interactions between their positively charged fixed groups and, mostly negatively charged, foulant materials present in natural streams. Therefore, controlling both the monovalent anion permselectivity and the membrane surface hydrophilicity is crucial. In this respect, different surface modification procedures were considered in the literature, to enhance the above-mentioned properties. This review reports and discusses the currently available approaches for surface modifications of AEMs, such as graft polymerization, dip coating, and layer-by-layer, among others, mainly focusing on preparing monovalent permselective AEMs with antifouling characteristics, but also considering hydrophilicity aspects and identifying the most promising modifying agents to be utilized. Thus, the present study aimed at providing new insights for the further design and development of selective, durable, and cost-effective modified AEMs for an enhanced RED process performance, which is indispensable for a practical implementation of this electro-membrane technology at an industrial scale.
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