In situ acid production by organic matter induced with trace homogeneous Fenton reagent for membrane fouling control.

The homogeneous Fenton process involves both coagulation and oxidation, but it requires added acidity, so it is rarely used to control membrane fouling. This work found that the pH of neutral simulated wastewater sharply declined to 4.1 after pre-treatment with 0.1 mM Fenton reagent (Fe2+:H2O2=1:1) without added acidity. This occurred mainly because the trace homogeneous Fenton reagent induced in situ acid production by organic matter in the wastewater, which supplied the acidic conditions required for the Fenton reaction and ensured that the reaction could proceed continuously. Then, oxidation during the pre-Fenton process enhanced the electrostatic repulsion forces and effectively weakened the hydrogen bonds of organic matter at the membrane surface by altering the net charge and hydroxyl content of organic matter, while coagulation caused the foulants to gather and form large aggregates. These changes diminished the deposition of foulants onto the membrane surface and resulted in a looser fouling layer, which eventually caused the membrane fouling rate to decline from 83 % to 24 % and the flux recovery rate to increase from 44 % to 98 % during 2 h of filtration. This membrane fouling mitigation ability is much superior to that of pre-H2O2, pre-Fe2+ or pre-Fe3+ processes with equivalent doses.

Light-responsive and ultrapermeable two-dimensional metal-organic framework membrane for efficient ionic energy harvesting.

Nanofluidic membranes offer exceptional promise for osmotic energy conversion, but the challenge of balancing ionic selectivity and permeability persists. Here, we present a bionic nanofluidic system based on two-dimensional (2D) copper tetra-(4-carboxyphenyl) porphyrin framework (Cu-TCPP). The inherent nanoporous structure and horizontal interlayer channels endow the Cu-TCPP membrane with ultrahigh ion permeability and allow for a power density of 16.64 W m-2, surpassing state of-the-art nanochannel membranes. Moreover, leveraging the photo-thermal property of Cu-TCPP, light-controlled ion active transport is realized even under natural sunlight. By combining solar energy with salinity gradient, the driving force for ion transport is reinforced, leading to further improvements in energy conversion performance. Notably, light could even eliminate the need for salinity gradient, achieving a power density of 0.82 W m-2 in a symmetric solution system. Our work introduces a new perspective on developing advanced membranes for solar/ionic energy conversion and extends the concept of salinity energy to a notion of ionic energy.

Unlocking osmotic energy harvesting potential in challenging real-world hypersaline environments through vermiculite-based hetero-nanochannels.

Nanochannel membranes have demonstrated remarkable potential for osmotic energy harvesting; however, their efficiency in practical high-salinity systems is hindered by reduced ion selectivity. Here, we propose a dual-separation transport strategy by constructing a two-dimensional (2D) vermiculite (VMT)-based heterogeneous nanofluidic system via an eco-friendly and scalable method. The cations are initially separated and enriched in micropores of substrates during the transmembrane diffusion, followed by secondary precise sieving in ultra-thin VMT laminates with high ion flux. Resultantly, our nanofluidic system demonstrates efficient osmotic energy harvesting performance, especially in hypersaline environment. Notably, we achieve a maximum power density of 33.76 W m-2, a 6.2-fold improvement with a ten-fold increase in salinity gradient, surpassing state-of-the-art nanochannel membranes under challenging conditions. Additionally, we confirm practical hypersaline osmotic power generation using various natural salt-lake brines, achieving a power density of 25.9 W m-2. This work triggers the hopes for practical blue energy conversion using advanced nanoarchitecture.

Forward osmosis membrane doped with water-based zirconium fumarate MOFs to enhance dye pollutant removal and membrane antifouling performance.

Metal-organic frameworks (MOFs) can be applied to enhance the property of forward osmosis membranes. However, organic solvents can easily remain in organic synthetic metal-organic frame materials and cause membrane fouling and a decrease in membrane permeability. In this study, water-based Zr-fumarate MOFs were synthesized and doped into the membrane active layer by interfacial polymerization to provide a water-based MOF-doped thin-film composite membrane (TFC membrane). It was found that doping the water-based MOFs effectively improved membrane hydrophilicity, and nanowater passages were introduced in the active layer to improve permeability. The water flux of the water-based MOF-doped TFC membranes was increased by 21% over that of the original membrane, and the selectivity performance of the membrane was improved while keeping the salt rejection basically unchanged. Additionally, the water-based MOF-doped TFC membrane showed good removal efficiency (Rd > 94%) and strong antipollution performance in the treatment of dye pollutants.

Recent advances in thin film nanocomposite membranes containing an interlayer (TFNi): fabrication, applications, characterization and perspectives.

Polyamide (PA) reverse osmosis and nanofiltration membranes have been applied widely for desalination and wastewater reuse in the last 5-10 years. A novel thin-film nanocomposite (TFN) membrane featuring a nanomaterial interlayer (TFNi) has emerged in recent years and attracted the attention of researchers. The novel TFNi membranes are prepared from different nanomaterials and with different loading methods. The choices of intercalated nanomaterials, substrate layers and loading methods are based on the object to be treated. The introduction of nanostructured interlayers improves the formation of the PA separation layer and provides ultrafast water molecule transport channels. In this manner, the TFNi membrane mitigates the trade-off between permeability and selectivity reported for polyamide composite membranes. In addition, TFNi membranes enhance the removal of metal ions and organics and the recovery of organic solvents during nanofiltration and reverse osmosis, which is critical for environmental ecology and industrial applications. This review provides statistics and analyzes the developments in TFNi membranes over the last 5-10 years. The latest research results are reviewed, including the selection of the substrate and interlayer materials, preparation methods, specific application areas and more advanced characterization methods. Mechanistic aspects are analyzed to encourage future research, and potential mechanisms for industrialization are discussed.

Stable Forward Osmosis Nanocomposite Membrane Doped with Sulfonated Graphene Oxide@Metal-Organic Frameworks for Heavy Metal Removal.

A sulfonated graphene oxide@metal-organic framework-modified forward osmosis nanocomposite (SGO@UiO-66-TFN) membrane was developed to improve stability and heavy metal removal performance. An in situ growth method was applied to uniformly distribute UiO-66 nanomaterial with a frame structure on SGO nanosheets to form SGO@UiO-66 composite nanomaterial. This nanomaterial was then added to a polyamide layer using interfacial polymerization. The cross-linking between SGO@UiO-66 and m-phenylenediamine improved the stability of the nanomaterial in the membrane. Additionally, the water permeability was improved because of additional water channels introduced by SGO@UiO-66. SGO, with its lamellar structure, and UiO-66, with its frame structure, made the diffusion path of the solute more circuitous, which improved the heavy metal removal and salt rejection performances. Moreover, the hydrophilic layer of the SGO@UiO-66-TFN membrane could block contaminants and loosen the structure of the pollution layer, ensuring that the membrane maintained a high removal rate. The water flux and reverse solute flux of the SGO@UiO-66-TFN membrane reached 14.77 LMH and 2.95 gMH, and compared with the thin-film composite membrane, these values were increased by 41 and 64%, respectively. The membrane also demonstrated a good heavy metal ion removal performance. In 2 h, the heavy metal ion removal rate (2000 ppm Cu2+ and Pb2+) was greater than 99.4%, and in 10 h the removal rate was greater than 97.5%.

Precisely Tunable Ion Sieving with an Al13-Ti3C2Tx Lamellar Membrane by Controlling Interlayer Spacing.

Two-dimensional (2D) membranes exhibit exceptional properties in molecular separation and transport, which reveals their potential use in various applications. However, ion sieving with 2D membranes is severely restrained due to intercalation-induced swelling. Here, we describe how to efficiently stabilize the lamellar architecture using Keggin Al13 polycations as pillars in a Ti3C2Tx membrane. More importantly, interlayer spacing can be easily adjusted with angstrom precision over a wide range (2.7-11.2 Å) to achieve selective and tunable ion sieving. A membrane with narrow d-spacing demonstrated enhanced selectivity for monovalent ions. When applied in a forward osmosis desalination process, this membrane exhibited high NaCl exclusion (99%) with a fast water flux (0.30 L m-2 h-1 bar-1). A membrane with wide d-spacing showed notable selectivity, which was dependent on the cation valence. When it was applied to acid recovery from iron-based industrial wastewater, the membrane showed good H+/Fe2+ selectivity, which makes it a promising substitute for traditional polymeric membranes. Thus, we introduce a possible route to construct 2D membranes with appropriate structures to satisfy different ion-sieving requirements in diverse environment-, resource-, and energy-related applications.