Vapor/Vapor-Solid Interfacial Growth of Covalent Organic Framework Membranes on Alumina Hollow Fiber for Advanced Molecular Separation.

Covalent organic frameworks (COFs), known for their chemical stability and porous crystalline structure, hold promises as advanced separation membranes. However, fabricating high-quality COF membranes, particularly on industrial-preferred hollow fiber substrates, remains challenging. This study introduces a novel vapor/vapor-solid (V/V-S) method for growing ultrathin crystalline TpPa-1 COF membranes on the inner lumen surface of alumina hollow fibers (TpPa-1/Alumina). Through vapor-phase monomer introduction onto polydopamine-modified alumina at 170 °C and 1 atm, efficient polymerization and crystallization occur at the confined V-S interface. This enables one-step growth within 8 h, producing 100 nm thick COF membranes with strong substrate adhesion. TpPa-1/Alumina exhibits exceptional stability and performance over 80 h in continuous cross-flow organic solvent nanofiltration (OSN), with methanol permeance of about 200 L m-2 h-1 bar-1 and dye rejection with molecular weight cutoff (MWCO) of approximately 700 Da. Moreover, the versatile V/V-S method synthesizes two additional COF membranes (TpPa2Cl/Alumina and TpHz/Alumina) with different pore sizes and chemical environments. Adjusting the COF membrane thickness between 100-500 nm is achievable easily by varying the growth cycle numbers. Notably, TpPa2Cl/Alumina demonstrates excellent OSN performance in separating the model active pharmaceutical ingredient glycyrrhizic acid (GA) from dimethyl sulfoxide (DMSO), highlighting the method's potential for large-scale industrial applications.

Forward Osmosis Membranes: The Significant Roles of Selective Layer.

Forward osmosis (FO) is a promising separation technology to overcome the challenges of pressure-driven membrane processes. The FO process has demonstrated profound advantages in treating feeds with high salinity and viscosity in applications such as brine treatment and food processing. This review discusses the advancement of FO membranes and the key membrane properties that are important in real applications. The membrane substrates have been the focus of the majority of FO membrane studies to reduce internal concentration polarization. However, the separation layer is critical in selecting the suitable FO membranes as the feed solute rejection and draw solute back diffusion are important considerations in designing large-scale FO processes. In this review, emphasis is placed on developing FO membrane selective layers with a high selectivity. The effects of porous FO substrates in synthesizing high-performance polyamide selective layer and strategies to overcome the substrate constraints are discussed. The role of interlayer in selective layer synthesis and the benefits of nanomaterial incorporation will also be reviewed.

Thermo-responsive nonionic amphiphilic copolymers as draw solutes in forward osmosis process for high-salinity water reclamation.

Recently, thermo-responsive nonionic amphiphilic copolymers have shown a great potential as forward osmosis (FO) draw solutes for high-salinity water desalination and zero-liquid discharge (ZLD). However, the relationship between the copolymer structural properties and key characteristics as draw solutes, as well as copolymer's chemical stability after regeneration have not been much studied. In this work, we systematically investigated poly (ethylene oxide)-block-poly (propylene oxide)-block-poly (ethylene oxide) (PEO-PPO-PEO) copolymers as draw solute. The results showed that the PEO segments significantly influenced the viscosity, osmotic pressure and lowest phase separation temperature of the copolymer aqueous solutions. Among four commercial copolymers studied, Pluronic® L35 with moderate molecular weight (Mn 1,900 Da), 50% PEO, and relatively high hydrophilic-lipophilic balance (HLB) showed the best draw solution (DS) performance. It also showed great stability in physiochemical properties and draw capacity after more than ten cycles of regeneration. On the other hand, despite the fact that membrane fouling was observed due to the use of copolymer DS, the FO flux (∼1.2 L m‒2 h‒1, as similar with the virgin membrane) was not affected when high-salinity feedwater such as seawater RO brine was applied. Overall, our study has provided a more comprehensive understanding on the characteristics of nonionic amphiphilic copolymer DS and showcased the promise of copolymer-driven FO process in high-salinity water desalination and ZLD.

Effective separation of water-DMSO through solvent resistant membrane distillation (SR-MD).

The treatment of organic waste or wastewater with high organic solvent content has been challenging in industries as it cannot be done effectively using conventional wastewater treatment technologies such as biodegradation and advanced oxidation process. Solvent resistant membrane distillation (SR-MD) was proposed as an energy-efficient alternative to treat these waste streams but its application is hampered by the lack of solvent-resistant membranes, and there is a research gap in studying the feeds with water-solvent mixtures. In this work, ceramic tubular membranes with different pore sizes and structures were molecularly grafted with 1H,1H,2H,2H-perfluorodecyltriethoxysilane to obtain hydrophobic ceramic membranes for SR-MD. The modified membranes exhibited excellent hydrophobicity and solvent resistant properties, and they were tested for SR-MD performance with a wide range of dimethyl sulfoxide (DMSO) feed concentrations, from 3.5 to 85 wt%. The membranes exhibited a high DMSO rejection of >98% and the separation factor of >170, with permeation flux >4.4 kg m-2 h-1 when the DMSO concentration in feed was below 65 wt%. The separation performance was found strongly dependent on the evaporation step and the vapour-liquid equilibrium near the interface. The DMSO rejection was also comparable to pervaporation while the permeation flux was much higher at the feed concentration of 50 wt%. This study establishes the strategy of using SR-MD as a promising membrane process in treating complex industrial wastes with high organic solvent content.