Robust ultrathin nanoporous MOF membrane with intra-crystalline defects for fast water transport

Rational design of high-performance stable metal–organic framework (MOF) membranes is challenging, especially for the sustainable treatment of hypersaline waters to address critical global environmental issues. Herein, a molecular-level intra-crystalline defect strategy combined with a selective layer thinning protocol is proposed to fabricate robust ultrathin missing-linker UiO-66 (ML-UiO-66) membrane to enable fast water permeation. Besides almost complete salt rejection, high and stable water flux is achieved even under long-term pervaporation operation in hash environments, which effectively addresses challenging stability issues. Then, detailed structural characterizations are employed to identify the type, chemical functionality, and density of intra-crystalline missing-linker defects. Moreover, molecular dynamics simulations shed light on the positive atomistic role of these defects, which are responsible for substantially enhancing structural hydrophilicity and enlarging pore window, consequently allowing ultra-fast water transport via a lower-energy-barrier pathway across three-dimensional sub-nanochannels during pervaporation. Unlike common unfavorable defect effects, the present positive intra-crystalline defect engineering concept at the molecular level is expected to pave a promising way toward not only rational design of next-generation MOF membranes with enhanced permeation performance, but additional water treatment applications.

Excavated farmland with plastic mulching as a strategy in saving water and controlling soil salinization in dryland agricultural areas

Water shortage and soil salinization in gully farmland comprising sediment deposited farmland (SF) and excavated farmland (EF) have become a widespread concern in the loess hilly region. A two-year field experiment was conducted to assess the soil water content (SWC) and salt content (SSC) and their effect on the spring maize yield and water use efficiency in SF and EF. Eight treatments comprising flat cropping without mulching (1), ridge planting without mulching (2), ridge planting with plastic mulching (3), and ridge planting with straw mulching (4) were tested in the SF and EF plots, respectively. The results showed that the yield was higher in SF than EF, whereas the water use efficiency was significantly higher in EF because the bottom water flux was 117.4% higher in SF than EF (P < 0.01). A significant positive correlation was found between the average SWC and yield (P < 0.01), thereby indicating that the yield was severely limited by the SWC. Thus, the higher water use efficiency in EF has important implications for alleviating water scarcity during agricultural production in this region. The risk of soil salinization was decreased greatly by treatment 3 where the SSC was decreased in EF and SF were 0.09 g kg–1 and 0.08 g kg–1, respectively. In addition, treatment 3 had the most significant impacts on the yield and water use efficiency. Our study provided appropriate land type and effective tillage measure for the sustainable development in dryland agricultural areas.

Fabrication of Polyvinylidene Difluoride Membrane with Enhanced Pore and Filtration Properties by Using Tannic Acid as an Additive

Potential use of tannic acid (TA) as an additive for fabrication of polyvinylidene difluoride (PVDF) membrane was investigated. The TA was introduced by blending into the dope solution with varying concentrations of 0, 1, 1.5, and 2 wt%. The prepared membranes were characterized and evaluated for filtration of humic acid (HA) solution. The stability of the membrane under harsh treatment was also evaluated by one-week exposure to acid and alkaline conditions. The results show that TA loadings enhanced the resulting membrane properties. It increased the bulk porosity, water uptake, and hydrophilicity, which translated into improved clean water flux from 15.4 L/m2.h for the pristine PVDF membrane up to 3.3× for the TA-modified membranes with the 2 wt% TA loading. The flux recovery ratio (FRR) of the TA-modified membranes (FRRs = 78–83%) was higher than the pristine one (FRR = 58.54%), with suitable chemical stability too. The improved antifouling property for the TA-modified membranes was attributed to their enhanced hydrophilicity thanks to improved morphology and residual TA in the membrane matric.

Water Recovery from Bioreactor Mixed Liquors Using Forward Osmosis with Polyelectrolyte Draw Solutions

This paper reports on the use of forward osmosis (FO) with polyelectrolyte draw solutions to recover water from bioreactor mixed liquors. The work was motivated by the need for new regenerative water purification technologies to enable long-duration space missions. Osmotic membrane bioreactors may be an option for water and nutrient recovery in space if they can attain high water flux and reverse solute flux selectivity (RSFS), which quantifies the mass of permeated water per mass of draw solute that has diffused from the draw solution into a bioreactor. Water flux was measured in a direct flow system using wastewater from a municipal wastewater treatment plant and draw solutions prepared with two polyelectrolytes at different concentrations. The direct flow tests displayed a high initial flux (>10 L/m2/h) that decreased rapidly as solids accumulated on the feed side of the membrane. A test with deionized water as the feed revealed a small mass of polyelectrolyte crossover from the draw solution to the feed, yielding an RSFS of 80. Crossflow filtration experiments demonstrated that steady state flux above 2 L/m2·h could be maintained for 70 h following an initial flux decline due to the formation of a foulant cake layer. This study established that FO could be feasible for regenerative water purification from bioreactors. By utilizing a polyelectrolyte draw solute with high RSFS, we expect to overcome the need for draw solute replenishment. This would be a major step towards sustainable operation in long-duration space missions.

Excellent hydrophilicity of polyurethane modified polyvinylidene fluoride

Polyvinylidene fluoride (PVDF) is a promising membrane material in ultrafiltration (UF) applications; its extensive application however is limited due to the disadvantage in hydrophilicity and low surface energy. Herein, a sort of TPU-modified PVDF membrane is prepared by blending method and its hydrophilicity is compared with a series of pure/modified PVDF membranes. The contact angle and pure water flux (PWF) results demonstrate that the hydrophilicity of the TPU-modified PVDF membrane is enhanced, and the performance is not inferior to that of traditional pore-modified PVDF membranes. SEM image shows that the TPU-modified PVDF membrane maintains morphology of the pure PVDF membrane, indicating that TPU molecules have excellent compatibility with PVDF molecules and can maintain the mechanical property of PVDF membrane to a certain extent. Finally, we explore the effects of TPU molecules and PVDF molecules on water molecules, respectively, from a microscopic perspective involving first principles. This investigation not only establishes that PVDF membrane has been prepared with enhanced hydrophilicity, but also provides a novel avenue for the modification of membrane properties.

Cellulose Blended Membranes for High-Salinity Water Pervaporation Desalination

In the current study, cellulose acetate (CA)/cellulose triacetate (CTA) nanocomposite membranes blended with zirconium dioxide (ZrO2) are prepared via phase inversion for pervaporation desalination performance. ZrO2 nanoparticles are added to enhance the hydrophilicity and porosity of the nanocomposite membranes. The fabricated nanocomposite membranes are characterized by SEM, FTIR, TGA, and DSC to study the surface morphology, chemical composition, thermal stability and strength. Nanocomposite membranes’ performance for pervaporation desalination is assessed as a function of feed concentration. Pervaporation results revealed that the nanocomposite membrane consisting of 2% ZrO2 achieved a maximum water flux of 6.5 kg/m2h, whereas the salt rejection was about 99.8%.

Statistical Analysis of Synthesis Parameters to Fabricate PVDF/PVP/TiO2 Membranes via Phase-Inversion with Enhanced Filtration Performance and Photocatalytic Properties

Non-solvent induced phase-inversion is one of the most used methods to fabricate membranes. However, there are only a few studies supported by statistical analysis on how the different fabrication conditions affect the formation and performance of membranes. In this paper, a central composite design was employed to analyze how different fabrication conditions affect the pure water flux, pore size, and photocatalytic activity of polyvinylidene fluoride (PVDF) membranes. Polyvinylpyrrolidone (PVP) was used to form pores, and titanium dioxide (TiO2) to ensure the photocatalytic activity of the membranes. The studied bath temperatures (15 to 25 °C) and evaporation times (0 to 60 s) did not significantly affect the pore size and pure water flux of the membranes. The concentration of PVDF (12.5 to 17.5%) affected the viscosity, formation capability, and pore sizes. PVDF at high concentrations resulted in membranes with small pore sizes. PVP affected the pore size and should be used to a limited extent to avoid possible hole formation. TiO2 contents were responsible for the decolorization of a methyl orange solution (10−5 M) up to 90% over the period studied (30 h). A higher content of TiO2 did not increase the decolorization rate. Acidic conditions increased the photocatalytic activity of the TiO2-membranes.

Embedded three spinel ferrite nanoparticles in PES-based nano filtration membranes with enhanced separation properties

In this study, three types of ferrites nanoparticles including CoFe2O4, NiFe2O4, and ZnFe2O4 were synthesized by microwave-assisted hydrothermal method. The X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR), and field emission scanning electron microscopy (FESEM) were employed to analyze synthesized nanoparticles and fabricated membranes. The morphology of membrane surface was investigated by surface images. The ability of ferrite nanoparticles was evaluated to the separation of sodium salt and heavy metals such as Cr2+, Pb2+, and Cu2+ from aqueous solutions. The modified membrane showed the enhancement of membrane surface hydrophilicity, porosity, and mean pore size. The results revealed a significant increase in pure water flux: 152.27, 178, and 172.68 L·m−2·h−1 for PES/0.001 wt% of CoFe2O4, PES/0.001 wt% NiFe2O4, and PES/0.001 wt% ZnFe2O4 NPs, respectively. Moreover, Na2SO4 rejection was reached 78% at 0.1 wt% of CoFe2O4 NPs. The highest Cr (II) rejection obtained 72% for PES/0.001 wt% of NiFe2O4 NPs while it was 46% for the neat PES membrane. The Pb(II) rejection reached above 75% at 0.1 wt% of CoFe2O4 NPs. The Cu(II) rejection was obtained 75% at 0.1 wt% of CoFe2O4 NPs. The ferrite NPs revealed the high potential of heavy metal removal in the filtration membranes.