Escalating global water scarcity necessitates high-performance desalination membranes, for which fundamental understanding of structure–property–performance relationships is required. In this study, we comprehensively assess the ionization behavior of nanoporous polyamide selective layers in state-of-the-art nanofiltration (NF) membranes. In these films, residual carboxylic acids and amines influence permeability and selectivity by imparting hydrophilicity and ionizable moieties that can exclude coions. We utilize layered interfacial polymerization to prepare physically and chemically similar selective layers of controlled thickness. We then demonstrate location-dependent ionization of carboxyl groups in NF polyamide films. Specifically, only surface carboxyl groups ionize under neutral pH, whereas interior carboxyl ionization requires pH >9. Conversely, amine ionization behaves invariably across the film. First-principles simulations reveal that the low permittivity of nanoconfined water drives the anomalous carboxyl ionization behavior. Furthermore, we report that interior carboxyl ionization could improve the water–salt permselectivity of NF membranes over fourfold, suggesting that interior charge density could be an important tool to enhance the selectivity of polyamide membranes. Our findings highlight the influence of nanoconfinement on membrane transport properties and provide enhanced fundamental understanding of ionization that could enable novel membrane design.
Biological membranes can achieve remarkably high permeabilities, while maintaining ideal selectivities, by relying on well-defined internal nanoscale structures in the form of membrane proteins. Here, we apply such design strategies to desalination membranes. A series of polyamide desalination membranes—which were synthesized in an industrial-scale manufacturing line and varied in processing conditions but retained similar chemical compositions—show increasing water permeability and active layer thickness with constant sodium chloride selectivity. Transmission electron microscopy measurements enabled us to determine nanoscale three-dimensional polyamide density maps and predict water permeability with zero adjustable parameters. Density fluctuations are detrimental to water transport, which makes systematic control over nanoscale polyamide inhomogeneity a key route to maximizing water permeability without sacrificing salt selectivity in desalination membranes.more » « less
- NSF-PAR ID:
- Publisher / Repository:
- American Association for the Advancement of Science (AAAS)
- Date Published:
- Journal Name:
- Page Range / eLocation ID:
- p. 72-75
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
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.more » « less
Polyamide thin‐film composite (PA‐TFC) membranes make large‐scale desalination effective. Interfacial polymerization (IP) is used to make PA‐TFC membranes, but it may limit the range of monomers that can be used, which hinders progress toward advanced membranes. Layer‐by‐layer (LbL) sequential deposition could circumvent kinetic and thermodynamic limitations of the conventional IP process to facilitate incorporation of different co‐monomers into the membrane. The selective layer needs to be deposited onto a microporous support, but depositing LbL coatings on microporous supports often results in defective membranes. Using a poly(vinyl alcohol) (PVA) primer between the support and the LbL polyamide layer may prevent defect formation. The water permeance and salt rejection of a three layer, PVA‐primed, LbL‐based PA‐TFC membrane are discussed and compared to a membrane made without the PVA primer and a commercially available membrane. Mass transfer resistances are analyzed using a series resistance model and appear to be small or even negligible compared to that of the polyamide layer. Incorporation of a sulfonated co‐monomer into the polyamide via LbL is reported. The combination of a PVA primer layer and LbL sequential deposition may expand the range of co‐monomers that could be used relative to polyamide membranes prepared by the conventional IP process.
Nanofiltration membranes have evolved as a promising solution to tackle the clean water scarcity and wastewater treatment processes with their low energy requirement and environment friendly operating conditions. Thin film composite nanofiltration membranes with high permeability, and excellent antifouling and antibacterial properties are important component for wastewater treatment and clean drinking water production units. In the scope of this study, thin film composite nanofiltration membranes were fabricated using polyacrylonitrile (PAN) support and fast second interfacial polymerization modification methods by grafting polyethylene amine and zwitterionic sulfobutane methacrylate moieties. Chemical and physical alteration in structure of the membranes were characterized using methods like ATR-FTIR spectroscopy, XPS analysis, FESEM and AFM imaging. The effects of second interfacial polymerization to incorporate polyamide layer and ‘ion pair’ characteristics, in terms of water contact angle and surface charge analysis was investigated in correlation with nanofiltration performance. Furthermore, the membrane characteristics in terms of antifouling properties were evaluated using model protein foulants like bovine serum albumin and lysozyme. Antibacterial properties of the modified membranes were investigated using E. coli as model biofoulant. Overall, the effect of second interfacial polymerization without affecting the selectivity layer of nanofiltration membrane for their potential large-scale application was investigated in detail.more » « less
Membrane desalination is a leading technology for treating saline waters to augment fresh water supply. The need for high-performance desalination membranes, particularly with high water/salt selectivity, has stimulated research into the fundamental structure-property-performance relationship of state-of-the-art membranes. In this study, we utilize a facile method for tuning properties of a polymeric desalination membrane to shed light on water and salt transport mechanisms of such membranes. A desalination membrane made of cellulose triacetate is treated in a plasticizer solution, followed by water rinsing. The modified membranes exhibit reduced salt flux without compromising water flux, indicating enhanced water/salt selectivity. An inspection of material characteristics using a model film system reveals a plasticizing-extracting process in changing the polymeric structure, which leads to the reduction of crystallite size in the polymer matrix, consequently affecting the transport properties of the membranes. Our findings highlight the potential of the plasticizing-extracting process in fabricating membranes with desired desalination performance.