Journal of Membrane Science Letters最新文献

Water channel-based biomimetic membranes (WBMs) are gaining increasing attention due to the effectiveness of water channels in enhancing water permeability and breaking the permselectivity trade-off. However, the ultra-permeable WBMs may suffer from severe membrane fouling issue because a high-water flux tends to result in an accelerated fouling and thus compromises the benefits gained from the usage of water channels. Herein, a novel in-situ modification protocol was proposed to enhance the antifouling performance of ultra-permeable WBMs. The nanovesicles incorporated with aquaporin (AQP) water channels were functionalized with polyethylene glycol brushes (i.e., PEGylation) via a facile self-assembly approach and subsequently encapsulated in the selective layer of thin-film composite membranes through interfacial polymerization. The modification had minimal impact on the function of AQPs, resulting in WBMs with a high water permeance (∼8.2 LMH/bar) and good NaCl rejection (96.4%) comparable to the unmodified WBMs. Moreover, the in-situ modification drastically enhanced the surface hydrophilicity, which endowed the membrane with a superior fouling resistance to organic foulants. The improved fouling resistance ensured a more sustainable operation of ultra-permeable WBMs, particularly in scenarios that favor high water fluxes. This facile modification strategy provides an efficient way to fabricate ultra-permeable and antifouling WBMs for sustainable water purification.

The surface of polyamide reverse osmosis (RO) membranes which regulates interface-dominated phenomena, such as partitioning and fouling, is the one facing the feed during operation. However, the opposite surface of the polyamide selective layer, the one facing the permeate and in contact with the polysulfone porous support, is commonly analyzed in quartz crystal microbalance (QCM) measurements due to limitations of state-of-the-art transfer methodologies. Such measurements on the back surface cannot be generalized because the polyamide layer is chemically and morphologically asymmetric. Herein, we introduce a simple method to coat QCM sensors with polyamide active layers in the correct orientation (i.e., exposing their front surface) and show that interface-dominated phenomena differ significantly between orientations. We start by describing a transfer protocol to coat any surface with a polyamide layer on its front surface orientation. We then systematically analyze the chemical and morphological differences between the two surfaces of the polyamide layer of a commercial RO membrane. Finally, we demonstrate that interface-dominated phenomena depend on the orientation by showing that NaCl partitioning at pH 6 was 1.3 to 2.3-fold higher on the front surface and that organic fouling with humic acid occurred at a lower rate on this surface. The new method presented herein enables measurements on the front surface of polyamide RO membranes, which should be the standard in any future QCM studies.

Although helium is a valuable inert gas available in abundance in the earth's atmosphere, the major source of helium is from natural gas reservoirs. Membrane based separation processes pose many advantages like being cost effective and non-energy intensive. In this current study, we have successfully demonstrated the synthesis of continuous Porous Organic Cage: CC3 membranes to separate equimolar helium methane mixture with permeance of 4.45 × 10⁻⁷ mol/ (m²s Pa) and separation selectivity ($\alpha )$ as high as 8. We also compared the diffusion coefficients of the gases through the membrane to evaluate the dominant mechanism for separation. Lastly, we compared the performance of our membranes to the state-of-the-art membranes with the help of a Robeson plot and found that our membranes outperformed the upper bound.

Sulfur poisoning could result in fast deterioration of Pd-based membranes by the formation of metal sulfides and reduction of hydrogen purity. The introduction of an MoO₂/TS-1 layer could provide an effective protection of the Pd layer. Therefore, in this paper a synthetic method is presented for preparation of sulfur-resistant MoO₂/TS-1 zeolite modified PdCu alloy composite membranes and their application in hydrogen separation under H₂S containing steam. According to the stability test results, the MoO₂/TS-1 zeolite armored layer obviously prolonged the stability of Pd based membrane. After 50 h stability test with 100 ppm H₂S, there were no obvious structural changes and metal sulfide formation detected in the PdCu bulk from SEM images and XRD patterns, indicating that MoO₂/TS-1 armor structure was good enough for protecting the PdCu alloy bulk.

Directly recovering ammonia from waste streams is a sustainable approach for ammonia management since it saves energy from both the Haber-Bosch process, the major industrial method for ammonia synthesis, and wastewater treatment. Membrane distillation (MD), an evaporation-based membrane separation process, has been employed to recover ammonia from ammonia-rich wastewater due to the high volatility of ammonia. In this study, the photothermal effect is incorporated into MD to enhance the ammonia recovery from ammonia-rich wastewater. Carbon black particles are coated on the membrane surface to increase its absorption of solar irradiation at the solution-membrane interface and facilitate the ammonia transport across the membrane. We demonstrate that the system can recover ammonia at a maximum ammonia flux of 4.52 g-N·m⁻²·h⁻¹ with a solar intensity of 1.7 kW·m⁻². The estimated mass transfer coefficient of carbon black coated membrane is 2.67 × 10⁻² m·h⁻¹ with solar irradiation, enhanced by 30.8% when compared to that in a pristine membrane. We also confirm that the improvement of ammonia flux by photothermal effect is equivalent to heating the feed solution by 20–30 °C. Our study demonstrates a promising pathway for utilizing solar energy by photothermal effects to enhance MD for ammonia recovery from ammonia-rich wastewater.

All-silica DD3R zeolite has been recognized as a promising CO₂-selective membrane material owing to its appropriate pore size (0.36 nm × 0.44 nm), strong hydrophobicity, excellent thermal and chemical stabilities. In order to reduce membrane cost, it is meaningful to synthesize thin DD3R zeolite membranes that possess high gas permeance. In this work, high-performance DD3R zeolite membranes were synthesized on TiO₂/α-Al₂O₃ composite hollow fibers by secondary growth method. Sigma-1 zeolite seeds were ball-milled and then fractionated into different-sized seeds by gradient centrifugation. Smaller seed particles were collected after centrifuged at higher rotation speed rate. A very thin and dense DD3R zeolite membrane (thickness: 1.2 µm) was synthesized by using the smallest seeds (ZS4) with average particle size of 163 nm, which were obtained from the supernatant of the third centrifugation at 11,000 rpm. The as-synthesized membranes were employed in separation of equimolar CO₂/CH₄ mixture. Compared with the original ball-milled seeds (ZS1)-induced membrane, the seed ZS4-induced membrane exhibited an improved CO₂ permeance of 1.2 × 10⁻⁷ mol m⁻² Pa⁻¹ s⁻¹ by 62%. All the resultant membranes performed good CO₂/CH₄ separation selectivities between 262 and 364.

Metal-organic frameworks (MOFs) host intrinsically porous structure and rich structural and chemical features. Several MOFs with pore aperture comparable to the size of gas molecules have attracted interest to form the selective layer of membranes. Synthesis of MOFs in nanosheet morphology is highly attractive for this because one can use highly-scalable filter coating to make MOF membranes. However, conventional nanosheet based processing route require several processing steps including centrifugation to prepare a coating dispersion. Herein, we report facile preparation of zeolitic imidazolate frameworks (ZIF) membranes by a straightforward assembly of nanosheets. ZIF-8 nanosheets were obtained by a direct bottom-up synthesis route where crystallization was optimized to obtain large, well-faceted 40-nm-thick nanosheets. Membranes, preferentially oriented along the c-out-of-plane direction, were fabricated by directly filtering the growth solution over a porous polymeric support without any further purification of nanosheets. This also ensures that only a small amount of precursor solution is used minimizing waste. The obtained membranes were compact and free of pinhole defects and yielded H₂/C₃H₈ ideal selectivity over 3000 at 25 °C. We anticipate that this approach can be applied to several MOFs which can be synthesized in nanosheet morphology, advancing the scalability prospects of MOF membranes.

The modification of membranes with polyelectrolytes via the Layer-by-Layer (LBL) method has become state of the art in recent years. It is used to fabricate nanofiltration hollow fiber membranes or to immobilize biomolecules on a membrane surface. However, it still remains a time consuming process. In contrast, this work explores a single-step membrane modification with coating solutions containing both polyanions and polycations. High salt concentration in the coating solution suppresses the complexation of the polyelectrolytes prior to the coating. Then, the controlled reduction of the salt concentration during the coating triggers the formation of a polyelectrolyte complex layer on the membrane. Three coating methods are proposed: (1) In interfacial complexation (IC), the polyelectrolyte solution coats the membrane and is subsequently precipitated by flushing with water. (2) Diffusive desalination (DDS) uses the concentration difference between the coating solution in the lumen and a water stream in the shell side to remove salt ions continuously. (3) In polyelectrolyte concentration (PC), the polyelectrolyte solution is coated at a constant flux. Here, the membrane retains the polyelectrolyte while ions permeate through. First, we evaluate the coating methods regarding their ability to produce nanofiltration membranes, which varies depending on the coating method used. With PC, membranes with up to 79% MgCl₂ rejection and a permeability of 30 LMH/bar are obtained. Moreover, in-situ functionalization of the membranes is investigated by the addition of enzymes. Here, with DDS enzymes are immobilized, mostly achieved through adsorption via electrostatic interactions.

Thin-film nanocomposite (TFN) membranes are promising in improving water treatment due to their high permeability and selectivity. However, little is known about the mechanism by which nanoparticles enhance their performance. In this study, we prepared two series of TFN membranes containing ∼40 nm-sized zeolitic imidazolate framework (ZIF-8) nanoparticles, one with a hydrophobic porous form and the other with a nonporous amorphous form (aZIF-8). The TFN membranes containing 0.15 w/v% ZIF-8 exhibited a 100% increase in water permeance while maintaining a similar NaCl rejection (98.38%) compared to thin-film composite (TFC) membranes used in brackish water reverse osmosis (BWRO). In contrast, adding the same amount of aZIF-8 resulted in almost no water permeance enhancement. By comparing the physicochemical properties of the two materials and the two series of membranes, we found that the only difference was the presence or absence of internal hydrophobic pore structures. We proposed that the hydrophobic internal pores of nanoparticles served as extra water channels while preventing the passage of NaCl during BWRO.

Compared with traditional membrane separation methods such as distillation and chromatography, nanofiltration (NF) affords decreased waste generation and energy consumption. Despite the multiple advantages of NF and materials available for NF membranes, the industrial applicability of this process requires improvement. To address these challenges, we propose four important pillars for the future of membrane materials and process development. These four pillars are digitalization, structure–property analysis, miniaturization, and automation. We fill gaps in the development of NF membranes and processes by fostering the most promising contemporary technologies, e.g., the integration of process analytical technologies and the development of a parallel artificial nanofiltration permeability assay (PANPA) or large online databases. Moreover, we propose the extensive use of density functional theory-aided structure–property relationship methods to understand solute transport process at a molecular level. Realizing an inverse design would allow researchers and industrial scientists to develop custom membranes for specific applications using optimized properties.