Nanoporous membranes based on self‐assembled block polymer precursors are an emerging class of promising separation, purification, and sensing devices due to the ability of researchers to control the nanostructure and chemistry of these multifunctional materials and devices. In fact, modern polymer chemistry provides techniques for the facile, controlled synthesis of the block polymers that constitute these devices. These designer macromolecules, in turn, can then self‐assemble into functional nanostructures depending upon the chemical identity of the synthesized block polymers and the thin film fabrication methods employed. After fabrication, these nanoporous membranes offer a highly tunable platform for applications that require high throughput, high surface area, homogeneous pore size, and varying material properties. And, with these readily tunable chemical and structural properties, block polymer membranes will allow for significant improvements in myriad applications. In this Review, we summarize the key advances, with a specific emphasis on the previous 5 years of work, that have allowed block polymer‐based membranes to reach their current level of technology. Furthermore, we project how these state‐of‐art, self‐assembled block polymer membrane technologies can be utilized in present‐day and future application arenas. In this way, we aim to demonstrate that the rigorous work performed on block polymer‐based membranes has laid a strong foundation that will allow these macromolecular systems to: (1) be major avenues of fundamental scientific research and (2) be parlayed into transferable technologies for the betterment of society in the imminent future. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41683.
Self-assembled materials are attractive for next-generation membranes. However, the need to align self-assembled nanostructures (e.g. cylinders, lamellae) and the narrow stability windows for ordered bicontinuous systems present serious challenges. We propose and demonstrate a novel approach that circumvents these challenges by exploiting size-selective transport in the water-continuous medium of a nanostructured polymer templated from a self-assembled lyotropic H1 mesophase. Optimization of the mesophase composition enables high-fidelity retention of the H1 structure on photoinduced cross-linking. The resulting material is a mechanically robust nanostructured polymer possessing internally and externally cross-linked nanofibrils surrounded by a continuous aqueous medium. Fabricated membranes show size selectivity at the 1- to 2-nm length scale and water permeabilities of ~10 liters m−2 hour−1 bar−1 μm. Moreover, the membranes display excellent antimicrobial properties due to the quaternary ammonium groups on the nanofibril surfaces. These results represent a breakthrough for the potential use of polymerized lyotropic mesophase membranes in practical water purification applications.
The well-defined nanostructure of membranes manufactured from self-assembled block polymers enables highly selective separations; however, recent efforts to push the pore size of block polymer-based membranes to the lower end of the size spectrum have only been moderately successful for a variety of reasons. For instance, the conformational changes of the stimuli-responsive functional groups lining the pore walls of some block polymer membranes result in varied pore sizes that limit their operational range. Here, we overcome this challenge through the directed design of the third moiety of an A-B-C triblock polymer. The use of this macromolecular design paradigm allows for the preparation of a 500 nm thick polyisoprene-b-polystyrene-b-poly(2-acrylamido-ethane-1,1-disfulonic acid) (PI-PS-PADSA) coating atop a hollow fiber membrane support. This nanoporous test bed, which exhibits an average pore radius of 1 nm, demonstrates an extremely high solute selectivity by fully gating solutes that have only an 8 Å size difference, a separation that is based solely on a sieving mechanism. Furthermore, the nanoscale structural characteristics of the solvated PADSA pore walls are elucidated by quantifying the rejection of neutral solutes and calculating the hydraulic permeability values in solutions of high ionic strength (1 mM ≤ I ≤ 3 M) and over a broad range of solution pH (1 ≤ pH ≤ 13). These key results provide a solid foundation for defining structure–property–performance relationships in the emerging area of nanoporous triblock polymer thin films. Moreover, the successful demonstration of the test bed separation device offers a tangible means by which to manufacture next-generation nanofiltration membranes that require a robust performance profile over a dynamic range of conditions.
Continued stresses on fresh water supplies necessitate the utilization of non-traditional resources to meet the growing global water demand. Desalination and hybrid membrane processes are capable of treating non-traditional water sources to the levels demanded by users. Specifically, desalination can produce potable water from seawater, and hybrid processes have the potential to recover valuable resources from wastewater while producing water of a sufficient quality for target applications. Despite the demonstrated successes of these processes, state-of-the-art membranes suffer from limitations that hinder the widespread adoption of these water treatment technologies. In this review, we discuss nanoporous membranes derived from self-assembled block polymer precursors for the purposes of water treatment. Due to their well-defined nanostructures, myriad chemical functionalities, and the ability to molecularly-engineer these properties rationally, block polymer membranes have the potential to advance water treatment technologies. We focus on block polymer-based efforts to: (1) nanomanufacture large areas of highperformance membranes; (2) reduce the characteristic pore size and push membranes into the reverse osmosis regime; and (3) design and implement multifunctional pore wall chemistries that enable solute-specific separations based on steric, electrostatic, and chemical affinity interactions. The use of molecular dynamics simulations to guide block polymer membrane design is also discussed because its ability to systematically examine the available design space is critical for rapidly translating fundamental understanding to water treatment applications. Thus, we offer a full review regarding the computational and experimental approaches taken in this arena to date while also providing insights into the future outlook of this emerging technology.
Adsorptive membranes offer one possible solution to the challenge of removing and recovering heavy metal ion contaminants and resources from water supplies. However, current membrane-based sorbents suffer from low binding affinities, leading to issues when contaminants are present at trace concentrations or when the source waters have a high concentration of background electrolytes that compete for open binding sites. Here, these challenges are addressed in the design of a highly permeable (i.e., permeability of ∼2.8 × 104 L m–2 h–1 bar–1) sorbent platform based on polysulfone and polystyrene-b-poly(acrylic acid) composite membranes. The membranes possess a fully interconnected network of poly(acrylic acid)-lined pores, which enables the surface chemistry to be tailored through sequential attachment of polyethylenimine brushes and metal-binding terpyridine ligands. The polyethylenimine brushes increase the saturation capacity, while the addition of terpyridine enables high-affinity binding to a diversity of transition metal ions (i.e., Pd2+, Cd2+, Hg2+, Pb2+, Zn2+, Co2+, Ni2+, Fe2+, Nd3+, and Sm3+). This platform removes these metal contaminants from solution with a sorbent capacity of 1.2 mmol g–1 [based on Cu2+ uptake]. The metal capture performance of the functionalized membranes persists in spite of high concentrations of competitive ions, with >99% removal of Pb2+ and Cd2+ ions from artificial groundwater and seawater solutions. Breakthrough experiments demonstrate the efficient purification of feed solutions containing multiple heavy metal ions under dynamic flow conditions. Finally, fluorescence quenching of the terpyridine moiety upon metal ion complexation offers an in situ probe to monitor the extent of sorbent saturation with a Stern–Volmer association constant of 2.9 × 104 L mol–1. The permeability, capacity, and affinity of these membranes, with high-density display of a metal-binding ligand, offer a chemically tailored platform to address the challenges that arise in ensuring clean water.
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