Hydrogen-bonded organic frameworks for membrane separation.

Hydrogen-bonded organic frameworks (HOFs) are a new class of crystalline porous materials that are formed through the interconnection of organic or metal-organic building units via intermolecular hydrogen bonds. The remarkable flexibility and reversibility of hydrogen bonds, coupled with the customizable nature of organic units, endow HOFs with mild synthesis conditions, high crystallinity, solvent processability, and facile self-healing and regeneration properties. Consequently, these features have garnered significant attention across various fields, particularly in the realm of membrane separation. Herein, we present an overview of the recent advances in HOF-based membranes, including their advanced fabrication strategies and fascinating applications in membrane separation. To attain the desired HOF-based membranes, careful consideration is dedicated to crucial factors such as pore size, stability, hydrophilicity/hydrophobicity, and surface charge of the HOFs. Additionally, diverse preparation methods for HOF-based membranes, including blending, in situ growth, solution-processing, and electrophoretic deposition, have been analyzed. Furthermore, applications of HOF-based membranes in gas separation, water treatment, fuel cells, and other emerging application areas are presented. Finally, the challenges and prospects of HOF-based membranes are critically pointed out.

Effects of polysaccharides' molecular structure on membrane fouling and the related mechanisms.

Fouling behaviors of polysaccharides vary with their structure, while the mechanisms underlying this phenomenon remain unexplored. This work was carried out to explore the thermodynamic fouling mechanisms of polysaccharides with different structure. Carrageenan and xanthan gum were selected as the model polysaccharides with structure of straight and branch chains, respectively. Batch filtration experiments showed that xanthan gum solution corresponded to a more rapid flux decline trend, and specific filtration resistance (SFR) of xanthan gum (2.32 × 1015 m-1 kg-1) was over 10 times than that of carrageenan (2.21 × 1014 m-1 kg-1). It was found that, xanthan gum possessed a more disordered structure and a rather higher viscosity (15.03 mPa·s V.S. 1.98 mPa·s for carrageenan). Calculation of extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory showed higher adhesion energy of xanthan gum (-42.82 my m-2 V.S. -23.26 mJ m-2 for carrageenan). Scanning electron microscopy (SEM) analyses showed that xanthan gum gel layer had a more homogenous structure and rigid polymer backbone, indicating better mixing with water to form a gel. As verified by heating experiments, such a structure tended to contain more bound water. According to this information, Flory-Huggins lattice theory was introduced to build a bridge between polymeric structure and SFR. It was revealed that branch structure corresponded to higher chemical potential change during gel layer formation, and higher ability to carry bound water, resulting in higher filtration resistance during filtration process. This work revealed the fundamental thermodynamic mechanism of membrane fouling caused by polysaccharides with different structure, deepening understanding of membrane fouling.

Self-standing and flexible covalent organic framework (COF) membranes for molecular separation.

Almost all covalent organic framework (COF) materials conventionally fabricated by solvothermal method at high temperatures and pressures are insoluble and unprocessable powders, which severely hinder their widespread applications. This work develops an effective and facile strategy to construct flexible and free-standing pure COF membranes via the liquid-liquid interface-confined reaction at room temperature and atmospheric pressure. The aperture size and channel chemistry of COF membranes can be rationally designed by bridging various molecular building blocks via strong covalent bonds. Benefiting from the highly-ordered honeycomb lattice, high solvent permeances are successfully obtained and follow the trend of acetonitrile > acetone > methanol > ethanol > isopropanol. Interestingly, the imine-linked COF membrane shows higher nonpolar solvent permeances than b-ketoenamine-linked COF due to their difference in pore polarity. Both kinds of COF membranes exhibit high solvent permeances, precise molecular sieving, excellent shape selectivity, and sufficient flexibility for membrane-based separation science and technology.

Zwitterions coated hollow fiber membranes with enhanced antifouling properties for osmotic power generation from municipal wastewater.

Fouling on pressure-retarded osmosis (PRO) membranes leads to severe declines in water flux and power density because their porous substrates are facing the wastewater feed. Thus, inorganics, organics and microorganisms in the wastewater are prone to depositing on the substrate surface and even in its pores. In order to reduce the fouling propensity, coating the substrate surface of PRO membranes with zwitterionic materials proves to be an effective way. In this work, 2-methacryloyloxyethylphosphorylcholine (MPC), is modified and grafted onto the polydopamine (PDA) coated poly (ether sulfone) (PES) hollow fiber substrate. Both the synthesis and surface coating of MPC are easy and facile to be scaled up. Compared with the pristine PES and PES-PDA substrates, the MPC modified substrate (PES-PDA-MPC) exhibits high resistance to protein adsorption as well as bacteria adhesion. By using a state-of-the-art thin-film composite poly (ether sulfone) (TFC-PES) hollow fiber membrane as the control for power generation, the power density of the TFC-PES-PDA-MPC membrane can achieve as high as 7.7 W/m2 while the unmodified one has only 6.0 W/m2 after 3 h's PRO tests. In conclusion, the osmotic power generation of PRO membranes can be significantly sustained by modifying the membrane surface with zwitterions.

Na⁺-functionalized carbon quantum dots: a new draw solute in forward osmosis for seawater desalination.

A new type of biocompatible draw solute, Na(+)-functionalized carbon quantum dots (Na_CQDs) with ultra-small size and rich ionic species, in forward osmosis (FO) is developed for seawater desalination. The aqueous dispersion of Na_CQDs demonstrates a high osmotic pressure, which allows high FO water flux and negligible reverse solute permeation.

Thermoresponsive magnetic nanoparticles for seawater desalination.

Thermoresponsive magnetic nanoparticles (MNPs) as a class of smart materials that respond to a change in temperature may by used as a draw solute to extract water from brackish or seawater by forward osmosis (FO). A distinct advantage is the efficient regeneration of the draw solute and the recovery of water via heat-facilitated magnetic separation. However, the osmotic pressure attained by this type of draw solution is too low to counteract that of seawater. In this work, we have designed a FO draw solution based on multifunctional Fe3O4 nanoparticles grafted with copolymer poly(sodium styrene-4-sulfonate)-co-poly(N-isopropylacrylamide) (PSSS-PNIPAM). The resulting regenerable draw solution shows high osmotic pressure for seawater desalination. This is enabled by three essential functional components integrated within the nanostructure: (i) a Fe3O4 core that allows magnetic separation of the nanoparticles from the solvent, (ii) a thermoresponsive polymer, PNIPAM, that enables reversible clustering of the particles for further improved magnetic capturing at a temperature above its low critical solution temperature (LCST), and (iii) a polyelectrolyte, PSSS, that provides an osmotic pressure that is well above that of seawater.