Crystalline Porous Organic Cage Membranes Constructed Using Fortified Intermolecular Interactions for Molecular Sieving.

Among the various types of materials with intrinsic porosity, porous organic cages (POCs) are distinctive as discrete molecules that possess intrinsic cavities and extrinsic channels capable of facilitating molecular sieving. However, the fabrication of POC membranes remains highly challenging due to the weak noncovalent intermolecular interactions and most reported POCs are powders. In this study, we constructed crystalline free-standing porous organic cage membranes by fortifying intermolecular interactions through the induction of intramolecular hydrogen bonds, which was confirmed by single-crystal X-ray analysis. To elucidate the driving forces behind, a series of terephthaldehyde building blocks containing different substitutions were reacted with flexible triamine under different conditions via interfacial polymerization (IP). Furthermore, density functional theory (DFT) calculations suggest that intramolecular hydrogen bonding can significantly boost the intermolecular interactions. The resulting membranes exhibited fast solvent permeance and high rejection of dyes not only in water, but also in organic solvents. In addition, the membrane demonstrated excellent performance in precise molecular sieving in organic solvents. This work opens an avenue to designing and fabricating free-standing membranes composed of porous organic materials for efficient molecular sieving.

Ultrafast Interfacial Self-Assembly toward Bioderived Polyester COF Membranes with Microstructure Optimization.

The precise manipulation of the microstructure (pore size, free volume distribution, and connectivity of the free-volume elements), thickness, and mechanical characteristics of membranes holds paramount significance in facilitating the effective utilization of self-standing membranes. In this contribution, the synthesis of two innovative ester-linked covalent-organic framework (COF) membranes is first reported, which are generated through the selection of plant-derived ellagic acid and quercetin phenolic monomers in conjunction with terephthaloyl chloride as a building block. The optimization of the microstructure of these two COF membranes is systematically achieved through the application of three different interfacial electric field systems: electric neutrality, positive electricity, and negative electricity. It is observed that the positively charged system facilitates a record increase in the rate of membrane formation, resulting in a denser membrane with a uniform pore size and enhanced flexibility. In addition, a correlation is identified wherein an increase in the alkyl chain length of the surfactants leads to a more uniform pore size and a decrease in the molecular weight cutoff of the COF membrane. The resulting COF membrane exhibits an unprecedented combination of high water permeance, superior sieving capability, robust mechanical strength, chemical robustness for promising membrane-based separation science and technology.

Polyethylene separator supported thin-film composite forward osmosis membranes for concentrating lithium enriched brine.

To extract lithium from salt lake brine involves a process of separation and concentration. After separating lithium from brine, the lithium ion concentration is generally a few hundred mg/L which is far below the required 20-30 g/L (as Li+) before precipitation as lithium carbonate. The concentration step of a lithium enriched brine is crucial but highly energy-intensive. Spontaneous forward osmosis (FO) technology offers the possibility for concentrating lithium ions with low energy. Because the concentrating process involves both feed and draw solution with very high salinity, it is highly desirable to have a high performance FO membrane with a low structural parameter as well as a high rejection to ions. In this work, thin polyethylene separator supported FO (PE-FO) membranes were prepared and post-treated stepwise with benzyl alcohol (BA) and hydraulic compaction. The effect of the post-treatment on the FO performance was systematically analyzed. Excellent FO performance was achieved: the water flux and reverse salt flux selectivity were 66.3 LMH and 5.25 L/g, respectively, when the active layer is oriented towards the 0.5 M NaCl draw solution with deionized water as the feed. To the best of our knowledge, this FO flux is the highest ever reported in the open literature under similar test conditions. Applied in concentrating lithium enriched brine, the membrane showed superior water flux using saturated MgCl2 as draw solution. A new FO model was established to simulate the water flux during the concentration process with good agreement with the experimental results. The promising results using PE-FO membrane for lithium enrichment opens a new frontier for the potential application of FO membranes.

Sustainable fertilizer-drawn forward osmosis for the vegetable industry in reducing liquor from vegetable waste.

Forward osmosis has been widely used due to its advantages such as low energy consumption and low membrane fouling. Conventional treatment of vegetable industry wastes leaving the liquor an additional puzzle. The objective of this study is to evaluate the feasibility of reducing energy consumption by using forward osmotic membrane technology to concentrate vegetable liquor. In this research, the suitable draw solutes' condition was investigated, results showed 1 M ammonium sulphate could reach 7.21 LMH water flux and it was chosen as the draw solution for concentrating vegetable liquor, then the long-term FO performance was compared with theoretical water flux showing that the difference of water flux decrease is caused by the organic matter. Further identification of the major foulant via a control variable method using simulated vegetable liquor leads to anthocyanins as the major foulant. This novel application of the fertilizer drawn FO process provided an environmentally friendly solution to the vegetable industry, which would potentially transform an industry into a sustainable cyclic economy.

Feasibility of osmotic dilution for recycling spent dialysate: Process performance, scaling, and economic evaluation.

Hemodialysis is one of the therapies for patients with kidney failure. Hemodialysis requires large amounts of pure water, and is one of the most water-hungry medical procedures, and thus represents a clear opportunity where improvements should be made concerning the consumption and wastage of water. In this paper, we explored the potential of forward osmosis (FO) membrane for recycling the spent dialysate using the dialysis concentrate as the draw solution. Partially diluted dialysis concentrate could be further diluted with pure water to form dialysate for further dialysis process. Using commercial cellulose triacetate (CTA) FO membranes, the water recovery of approximately 64% was achieved and the final volume of the partially diluted dialysis concentrate was about four times the initial volume. Flux decline of the FO process was observed, mainly due to concentration of synthetic spent dialysate and dilution of dialysis concentrate, while membrane scaling had little impact on the flux decline. The urea rejection was found to be relatively low owing to the small size and electroneutral nature of the urea molecule. Obvious membrane scaling was observed after three FO cycles. The energy dispersive spectroscopy analysis of the scaling layer indicated that the scalants were phosphates and carbonates. The scaling was removed via osmotic backwash and almost completely recovery of FO flux was obtained. Economic analysis showed that the centralized treatment of spent dialysate in a dialysis center using the proposed osmotic dilution process could greatly save water resources and cost. Improving the urea rejection of FO membrane was identified as an important research focus for future research on the potential application of FO technology for recycling the spent dialysate in hemodialysis.