Mingrui He

Antifouling membranes for sustainable water purification: strategies and mechanisms

One of the greatest challenges to the sustainability of modern society is an inadequate supply of clean water. Due to its energy-saving and cost-effective features, membrane technology has become an indispensable platform technology for water purification, including seawater and brackish water desalination as well as municipal or industrial wastewater treatment. However, membrane fouling, which arises from the nonspecific interaction between membrane surface and foulants, significantly impedes the efficient application of membrane technology. Preparing antifouling membranes is a fundamental strategy to deal with pervasive fouling problems from a variety of foulants. In recent years, major advancements have been made in membrane preparation techniques and in elucidating the antifouling mechanisms of membrane processes, including ultrafiltration, nanofiltration, reverse osmosis and forward osmosis. This review will first introduce the major foulants and the principal mechanisms of membrane fouling, and then highlight the development, current status and future prospects of antifouling membranes, including antifouling strategies, preparation techniques and practical applications. In particular, the strategies and mechanisms for antifouling membranes, including passive fouling resistance and fouling release, active off-surface and on-surface strategies, will be proposed and discussed extensively.

Zwitterionic materials for antifouling membrane surface construction.

UNLABELLED Membrane separation processes are often perplexed by severe and ubiquitous membrane fouling. Zwitterionic materials, keeping electric neutrality with equivalent positive and negative charged groups, are well known for their superior antifouling properties and have been broadly utilized to construct antifouling surfaces for medical devices, biosensors and marine coatings applications. In recent years, zwitterionic materials have been more and more frequently utilized for constructing antifouling membrane surfaces. In this review, the antifouling mechanisms of zwitterionic materials as well as their biomimetic prototypes in cell membranes will be discussed, followed by the survey of common approaches to incorporate zwitterionic materials onto membrane surfaces including surface grafting, surface segregation, biomimetic adhesion, surface coating and so on. The potential applications of these antifouling membranes are also embedded. Finally, we will present a brief perspective on the future development of zwitterionic materials modified antifouling membranes. STATEMENT OF SIGNIFICANCE Membrane fouling is a severe problem hampering the application of membrane separation technology. The properties of membrane surfaces play a critical role in membrane fouling and antifouling behavior/performance. Antifouling membrane surface construction has evolved as a hot research issue for the development of membrane processes. Zwitterionic modification of membrane surfaces has been recognized as an effective strategy to resist membrane fouling. This review summarizes the antifouling mechanisms of zwitterionic materials inspired by cell membranes as well as the popular approaches to incorporate them onto membrane surfaces. It can help form a comprehensive knowledge about the principles and methods of modifying membrane surfaces with zwitterionic materials. Finally, we propose the possible future research directions of zwitterionic materials modified antifouling membranes.

Improving Permeation and Antifouling Performance of Polyamide Nanofiltration Membranes through the Incorporation of Arginine

Inspired by the hydrophilicity effect of arginine (Arg) in water channel aquaporins (AQPs), Arg was incorporated into the polyamide layer during interfacial polymerization to enhance the permeation and antifouling performance of the nanofiltration (NF) membranes. Due to the presence of active amine groups, Arg became another aqueous phase monomer along with piperazine (PIP) to react with trimesoyl chloride (TMC) during interfacial polymerization, which was incorporated into the polyamide network. The resulting polyamide NF membranes were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM), static water contact angle, zeta potential, and positron annihilation spectroscopy (PAS) measurement. The effects of incorporating Arg in aqueous phase on water permeability and the rejection of dyes and inorganic salts of the NF membranes were studied, respectively. Similar to its function in AQPs, Arg apparently increased the hydrophilicity and the negative charges of the membrane surface and, consequently, the permeation performance. When the addition of Arg reached 40% to PIP, the water flux was doubled and the rejection ratios of Congo red and Orange GII were still >90%. Meanwhile, the antifouling experiments verified that the modified polyamide NF membranes possessed excellent fouling-resistant performance for negatively charged foulants of BSA, emulsified oil droplet, and humic acid. The flux was decreased below 15%, and recovery even rose to 89%.

Asymmetric Aerogel Membranes with Ultrafast Water Permeation for the Separation of Oil-in-Water Emulsion

Owing to highly porous and low density attributes, aerogels have been actively utilized in catalysis and adsorption processes, but their great potential in filtration requires exploitation. In this study, an asymmetric aerogel membrane is fabricated via one-pot hydrothermal reaction-induced self-cross-linking of poly(vinyl alcohol) (PVA), which exhibits ultrafast permeation for the separation of oil-in-water emulsion. Meanwhile, carbon nanotubes are added to improve the mechanical strength of the aerogel membranes. The self-cross-linking of PVA forms the supporting layer, and the exchange of water and vapor at the interface of PVA solution and air generates the separating layer as well as abundant hydroxyl groups on the membrane surface. The density, porosity, pore size, and wettability of the aerogel membrane can be tuned by the PVA concentration. Owing to high porosity (>95%) and suitable pore size (<85 nm), the aerogel membrane exhibits high rejection (99.0%) for surfactant-stabilized oil-in-water emulsion with an ultrahigh permeation flux of 135.5 × 103 L m-2 h-1 bar-1 under gravity-driven flow, which is 2 orders of magnitude higher than commercial filtration membranes with similar rejection. Meanwhile, the aerogel membrane exhibits superhydrophilicity, superoleophobicity underwater, and excellent antifouling properties for various surfactant-stabilized oil-in-water emulsions, as indicated by the fact that the flux recovery ratio maintains more than 93% after five cycles of the filtration experiment. The findings in this study may offer a novel idea to fabricate high-throughput filtration membranes.

Graphene Oxide Membranes with Conical Nanochannels for Ultrafast Water Transport

Membrane-based separations have been increasingly utilized to address global energy crisis and water scarcity. However, the separation efficiency often suffers from the trade-off between membrane permeability and selectivity. Although great efforts have been devoted, a membrane with both high permeability and high selectivity remains a distant prospect. Inspired by the hourglass structure and ultrafast water transport in aquaporins, we propose a novel approach to fabricating membranes with conical nanochannels to reduce the mass transfer resistance and to introduce Laplace pressure as the internal driving force, which successfully breaks the permeability/selectivity trade-off. First, sulfonated polyaniline (SPANI) nanorods were in situ-synthesized and vertically aligned on sulfonated graphene oxide (SGO) nanosheets, forming SGO-SPANI X composites. Then, the graphene oxide (GO) membranes were fabricated by assembling SGO-SPANI X composites through pressure-assisted filtration, in which the SPANI nanorods would bend and flatten on the SGO nanosheets under low shear force, forming stripe arrays on SGO nanosheets. The tilted stripe arrays between the adjacent SGO nanosheets form the conical nanochannels inside GO membranes. The conical nanochannels significantly decreased the steric hindrance and enabled the generation of Laplace pressure as the internal driving force within membranes. Consequently, the resulting membranes exhibit an ultrahigh water permeability of 1222.77 L·m-2·h-1·bar-1 and high efficiency in dye removal from water with a rejection of 90.44% and permeability of 528 L·m-2·h-1·bar-1.