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1.
Environ Sci Technol ; 58(14): 6435-6443, 2024 Apr 09.
Artículo en Inglés | MEDLINE | ID: mdl-38551393

RESUMEN

Nanovoids within a polyamide layer play an important role in the separation performance of thin-film composite (TFC) reverse osmosis (RO) membranes. To form more extensive nanovoids for enhanced performance, one commonly used method is to incorporate sacrificial nanofillers in the polyamide layer during the exothermic interfacial polymerization (IP) reaction, followed by some post-etching processes. However, these post-treatments could harm the membrane integrity, thereby leading to reduced selectivity. In this study, we applied in situ self-etchable sacrificial nanofillers by taking advantage of the strong acid and heat generated in IP. CaCO3 nanoparticles (nCaCO3) were used as the model nanofillers, which can be in situ etched by reacting with H+ to leave void nanostructures behind. This reaction can further degas CO2 nanobubbles assisted by heat in IP to form more nanovoids in the polyamide layer. These nanovoids can facilitate water transport by enlarging the effective surface filtration area of the polyamide and reducing hydraulic resistance to significantly enhance water permeance. The correlations between the nanovoid properties and membrane performance were systematically analyzed. We further demonstrate that the nCaCO3-tailored membrane can improve membrane antifouling propensity and rejections to boron and As(III) compared with the control. This study investigated a novel strategy of applying self-etchable gas precursors to engrave the polyamide layer for enhanced membrane performance, which provides new insights into the design and synthesis of TFC membranes.


Asunto(s)
Incrustaciones Biológicas , Nanopartículas , Ósmosis , Nylons/química , Grabado y Grabaciones , Membranas Artificiales , Agua/química
2.
Nano Lett ; 23(16): 7470-7476, 2023 Aug 23.
Artículo en Inglés | MEDLINE | ID: mdl-37540493

RESUMEN

Hydrogen separation membranes are a critical component in the emerging hydrogen economy, offering an energy-efficient solution for the purification and production of hydrogen gas. Inspired by the recent discovery of monolayer covalent fullerene networks, here we show from concentration-gradient-driven molecular dynamics that quasi-square-latticed monolayer fullerene membranes provide the best pore size match, a unique funnel-shaped pore, and entropic selectivity. The integration of these attributes renders these membranes promising for separating H2 from larger gases such as CO2 and O2. The ultrathin membranes exhibit excellent hydrogen permeance as well as high selectivity for H2/CO2 and H2/O2 separations, surpassing the 2008 Robeson upper bounds by a large margin. The present work points toward a promising direction of using monolayer fullerene networks as membranes for high-permeance, selective hydrogen separation for processes such as water splitting.

3.
Environ Sci Technol ; 56(22): 15220-15237, 2022 11 15.
Artículo en Inglés | MEDLINE | ID: mdl-36330774

RESUMEN

In view of the high risks brought about by organic micropollutants (OMPs), nanofiltration (NF) processes have been playing a vital role in advanced water and wastewater treatment, owing to the high membrane performance in rejection of OMPs, permeation of water, and passage of mineral salts. Though numerous studies have been devoted to evaluating and technically enhancing membrane performance in removing various OMPs, the trade-off effect between water permeance and water/OMP selectivity for state-of-the-art membranes remains far from being understood. Knowledge of this effect is significant for comparing and guiding membrane development works toward cost-efficient OMP removal. In this work, we comprehensively assessed the performance of 88 NF membranes, commercialized or newly developed, based on their water permeance and OMP rejection data published in the literature. The effectiveness and underlying mechanisms of various modification methods in tailoring properties and in turn performance of the mainstream polyamide (PA) thin-film composite (TFC) membranes were quantitatively analyzed. The trade-off effect was demonstrated by the abundant data from both experimental measurements and machine learning-based prediction. On this basis, the advancement of novel membranes was benchmarked by the performance upper-bound revealed by commercial membranes and lab-made PA membranes. We also assessed the potentials of current NF membranes in selectively separating OMPs from inorganic salts and identified the future research perspectives to achieve further enhancement in OMP removal and salt/OMP selectivity of NF membranes.


Asunto(s)
Membranas Artificiales , Purificación del Agua , Estudios Prospectivos , Sales (Química) , Purificación del Agua/métodos , Nylons , Agua
4.
J Memb Sci ; 6602022 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-36186741

RESUMEN

A primary goal in the design of reverse osmosis (RO) membranes is to improve water-solute selectivity and water permeance. These transport properties are commonly calculated in the literature using the solution-diffusion model with selectivity (A/B, bar-1) defined as the ratio between water permeance (A, L.m-2.h-1.bar-1) and solute permeance (B, L.m-2.h-1). In calculating transport properties, researchers often use simplifying assumptions about concentration polarization (CP; i.e., assuming negligible CP or a certain extent of CP) and solute rejection (i.e., assuming solute rejection is approximately 1 to enable the explicit use of the CP modulus in solute permeance calculations). Although using these assumptions to calculate transport properties is common practice, we could not find a study that evaluated the errors associated with using them. The uncertainty in these errors could impede unequivocally identifying manufacturing approaches that break through the commonly plotted trade-off frontier between selectivity and water permeance (A/B vs. A); however, we did not find in the literature a study that quantified such errors. Accordingly, we aimed to: (1) quantify the error in transport properties (A, B, and A/B) calculated using common simplifying assumptions about CP and rejection; and (2) determine if using simplifying assumptions affects conclusions drawn about membrane performance or trends concerning the trade-off frontier. Results show that compared with the case where no simplifying assumptions were made, simplified calculations were least accurate at low pressures for water permeance (up to 78% overestimation) and high pressures for solute permeance (up to 188% overestimation). Accordingly, the corresponding selectivities were least accurate at low pressure (up to 111% overestimation) and high pressure (up to 66% underestimation), and conclusions drawn about membrane performance and trade-off trends were pressure-dependent. Importantly, even in the absence of simplifying assumptions, selectivity results were pressure-dependent, indicating the importance of standardizing test conditions for the continued use of current performance metrics (i.e., A/B and A). We propose a two-pressure approach-collecting data for A and B at a high and a low pressure, respectively-combined with simplifying assumptions for more accurate simplified estimations of selectivity (< 10% absolute error). Our work contributes to a better understanding of the effects of operating pressure and key simplifying assumptions commonly used in calculating RO membrane performance metrics and interpretation of corresponding results.

5.
J Chem Technol Biotechnol ; 97(8): 1966-1977, 2022 May 21.
Artículo en Inglés | MEDLINE | ID: mdl-37941567

RESUMEN

BACKGROUND: Many organic solvents form difficult-to-separate mixtures with water and have an affinity for water, making drying a potential reuse prerequisite. Pervaporation (PV) and vapor permeation (VP) membrane technologies hold promise for energy-efficient solvent drying. Several water-selective membrane materials are commercially available, but performance data is limited, particularly for two recently commercialized membrane materials: chabazite (CHA) and T-type zeolites. In this work, commercial-grade samples of CHA and T-type membranes, along with a NaA zeolite membrane, were evaluated for the removal of water from ethanol. RESULTS: The CHA sample had the highest initial PV water permeance (6820 GPU) and water permselectivity (3430) with 5 wt% water in ethanol at 50 °C. Initial NaA membrane performance was slightly lower (6060 GPU and 3260), while the T-type membrane had the lowest initial permeance and selectivity (4260 GPU and 1090). Performance declined over time, most notably for the NaA membrane, for which water permeance fell over 50% through 39 days of testing. The T-type membrane exhibited the steadiest PV water permeance, but the most variable ethanol permeance. CONCLUSION: The PV performance of the three membranes largely overlapped the predicted range for T-type membranes. That performance generally exceeds the anticipated ethanol drying performance of non-zeolitic PV membranes but is less than that predicted for NaA and CHA membranes. The present CHA membrane results, along with other recent reports, refine earlier predictions of the ethanol dehydration performance of that type of zeolite. The changing performance with time should be understood to properly design a solvent dehydration system.

6.
Molecules ; 27(23)2022 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-36500475

RESUMEN

Most researchers focused on developing highly selective membranes for CO2/CH4 separation, but their developed membranes often suffered from low permeance. In this present work, we aimed to develop an ultrahigh permeance membrane using a simple coating technique to overcome the trade-off between membrane permeance and selectivity. A commercial silicone membrane with superior permeance but low CO2/CH4 selectivity (in the range of 2-3) was selected as the host for surface modification. Our results revealed that out of the three silane agents tested, only tetraethyl orthosilicate (TEOS) improved the control membrane's permeance and selectivity. This can be due to its short structural chain and better compatibility with the silicone substrate. Further investigation revealed that higher CO2 permeance and selectivity could be attained by coating the membrane with two layers of TEOS. The surface integrity of the TEOS-coated membrane was further improved when an additional polyether block amide (Pebax) layer was established atop the TEOS layer. This additional layer sealed the pin holes of the TEOS layer and enhanced the resultant membrane's performance, achieving CO2/CH4 selectivity of ~19 at CO2 permeance of ~2.3 × 105 barrer. This performance placed our developed membrane to surpass the 2008 Robeson Upper Boundary.


Asunto(s)
Amidas , Dióxido de Carbono , Humanos , Investigadores , Silanos , Siliconas
7.
Small ; 17(46): e2102975, 2021 11.
Artículo en Inglés | MEDLINE | ID: mdl-34643032

RESUMEN

Filtration through membranes with nanopores is typically associated with high transmembrane pressures and high energy consumption. This problem can be addressed by reducing the respective membrane thickness. Here, a simple procedure is described to prepare ultrathin membranes based on protein nanopores, which exhibit excellent water permeance, two orders of magnitude superior to comparable, industrially applied membranes. Furthermore, incorporation of either closed or open protein nanopores allows tailoring the membrane's ion permeability. To form such membranes, the transmembrane protein ferric hydroxamate uptake protein component A (FhuA) or its open-pore variant are assembled at the air-water interface of a Langmuir trough, compressed to a dense film, crosslinked by glutaraldehyde, and transferred to various support materials. This approach allows to prepare monolayer or multilayer membranes with a very high density of protein nanopores. Freestanding membranes covering holes up to 5 µm in diameter are visualized by atomic force microscopy (AFM), helium ion microscopy, and transmission electron microscopy. AFM PeakForce quantitative nanomechanical property mapping (PeakForce QNM)  demonstrates remarkable mechanical stability and elastic properties of freestanding monolayer membranes with a thickness of only 5 nm. The new protein membrane can pave the way to energy-efficient nanofiltration.


Asunto(s)
Nanoporos , Membranas Artificiales , Microscopía de Fuerza Atómica , Microscopía Electrónica de Transmisión
8.
New Phytol ; 229(3): 1415-1430, 2021 02.
Artículo en Inglés | MEDLINE | ID: mdl-32964437

RESUMEN

Plants continue to lose water from their leaves even after complete stomatal closure. Although this minimum conductance (gleaf-res ) has substantial impacts on strategies of water use and conservation, little is known about the potential drivers underlying the variability of this trait across species. We thus untangled the relative contribution of water leaks from the cuticle and stomata in order to investigate how the variability in leaf morphological and anatomical traits is related to the variation in gleaf-res and carbon assimilation capacity across 30 diverse species from the Brazilian Cerrado. In addition to cuticle permeance, water leaks from stomata had a significant impact on gleaf-res . The differential pattern of stomata distribution in the epidermis was a key factor driving this variation, suggesting the existence of a trade-off between carbon assimilation and water loss through gleaf-res . For instance, higher gleaf-res , observed in fast-growing species, was associated with the investment in small and numerous stomata, which allowed higher carbon assimilation rates but also increased water leaks, with negative impacts on leaf survival under drought. Variation in cuticle structural properties was not linked to gleaf-res . Our results therefore suggest the existence of a trade-off between carbon assimilation efficiency and dehydration tolerance at foliar level.


Asunto(s)
Pradera , Estomas de Plantas , Brasil , Hojas de la Planta , Transpiración de Plantas , Agua
9.
Nano Lett ; 20(8): 5821-5829, 2020 08 12.
Artículo en Inglés | MEDLINE | ID: mdl-32628856

RESUMEN

Despite the commercial success of thin film composite polyamide membranes, further improvements to the water permeation of polyamide membranes without degradation in product water quality remain a great challenge. Herein, we report the fabrication of an interfacially polymerized polyamide nanofiltration membrane with a novel 3D honeycomb-like spatial structure, which is formed from a tobacco mosaic virus (TMV) porous protein nanosheet-coated microfiltration membrane support. TMV nanosheets with uniform pores and appropriate hydrophilicity deposited inside the support membrane pores facilitate the construction of a localized water-oil reaction interface with evenly distributed monomers and guide the formation of a defect-free polyamide layer with a spatial structure that copies the geometry of the membrane cavities. Such a 3D morphology possesses ultrahigh specific surface area, leading to unprecedented membrane water permeance as high as 84 L m-2 h-1 bar-1, high MgSO4 rejection of 98%, and monovalent/divalent ion sieving selectivity up to 89.


Asunto(s)
Membranas Artificiales , Nylons , Polimerizacion , Porinas , Porosidad
10.
J Food Sci Technol ; 57(8): 3060-3070, 2020 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-32624608

RESUMEN

The infusion kinetics of tea bags containing black tea or green tea has been studied in detail in the past. However, the tea bag papers have never been characterized and evaluated earlier to understand their contribution towards tea bag infusion. In the present work, papers used for making tea bags were characterized for thickness, wettability, surface topography, pore size, porosity and permeance to understand their influence on infusion kinetics of tea bags. Scanning electron microscopy studies highlighted the pore structure and porous nature of tea bag papers. The porosity of tea bag paper was quantified using image processing and permeance was determined experimentally. Besides, a relationship between porosity and permeance of tea bag papers has been perceived. A general trend of increase in permeance with increasing porosity was observed. Woven nylon paper showed the highest permeance (23.9 × 10-5 m/s) when compared with other tea bag papers. Furthermore, an initial infusion rate was determined using initial infusion data of tea bag infusion for different tea bag papers. The influence of permeance on the initial infusion rate of tea bag papers has also been investigated.

11.
Angew Chem Int Ed Engl ; 57(23): 6814-6818, 2018 06 04.
Artículo en Inglés | MEDLINE | ID: mdl-29508511

RESUMEN

Lamellar membranes show exceptional molecular permeation properties of key importance for many applications. However, their design and development need the construction of regular and straight interlayer channels and the establishment of corresponding transport rate equation. The fabrication of a uniformly lamellar membrane is reported using double-layered Ti3 C2 Tx MXenes as rigid building blocks. This membrane possesses ordered and straight 2 nm channels formed via a direct self-stacking, in contrast to the conventional irregular ones from flexible sheets. Such channels permit precise molecular rejection and unparalleled molecular permeation. The permeance of water and organics by this membrane reached 2300 and 5000 L m-2 h-1 bar-1 , respectively. The molecular transfer mechanism in confined nanochannels, and the corresponding model equation are established, paving a way to nanoscale design of highly efficient channeled membranes for transport and separation applications.

12.
Biochim Biophys Acta ; 1861(9 Pt B): 1336-1344, 2016 09.
Artículo en Inglés | MEDLINE | ID: mdl-26965486

RESUMEN

Using (14)C-labeled epoxiconazole as a tracer, cuticular permeability of Arabidopsis thaliana leaves was quantitatively measured in order to compare different wax and cutin mutants (wax2, cut1, cer5, att1, bdg, shn3 and shn1) to the corresponding wild types (Col-0 and Ws). Mutants were characterized by decreases or increases in wax and/or cutin amounts. Permeances [ms(-1)] of Arabidopsis cuticles either increased in the mutants compared to wild type or were not affected. Thus, genetic changes in wax and cutin biosynthesis in some of the investigated Arabidopsis mutants obviously impaired the coordinated cutin and wax deposition at the outer leaf epidermal cell wall. As a consequence, barrier properties of cuticles were significantly decreased. However, increasing cutin and wax amounts by genetic modifications, did not automatically lead to improved cuticular barrier properties. As an alternative approach to the radioactive transport assay, changes in chlorophyll fluorescence were monitored after foliar application of metribuzine, an herbicide inhibiting electron transport in chloroplasts. Since both, half-times of photosynthesis inhibition as well as times of complete inhibition, in fact correlated with (14)C-epoxiconazole permeances, different rates of decline of photosynthetic yield between mutants and wild type must be a function of foliar uptake of the herbicide across the cuticle. Thus, monitoring changes in chlorophyll fluorescence, instead of conducting radioactive transport assays, represents an easy-to-handle and fast alternative evaluating cuticular barrier properties of different genotypes. This article is part of a Special Issue entitled: Plant Lipid Biology edited by Kent D. Chapman and Ivo Feussner.


Asunto(s)
Arabidopsis/genética , Cloroplastos/genética , Mutación/genética , Hojas de la Planta/genética , Transportadoras de Casetes de Unión a ATP/genética , Aciltransferasas/genética , Arabidopsis/crecimiento & desarrollo , Proteínas de Arabidopsis/genética , Radioisótopos de Carbono/química , Compuestos Epoxi/química , Regulación de la Expresión Génica de las Plantas , Genotipo , Lípidos de la Membrana/genética , Hojas de la Planta/crecimiento & desarrollo , Factores de Transcripción/genética , Triazoles/química
13.
J Exp Bot ; 68(19): 5281-5291, 2017 Nov 09.
Artículo en Inglés | MEDLINE | ID: mdl-28992330

RESUMEN

The interface between the atmosphere and leaves and fruits is formed by the lipophilic plant cuticle, which seals the outer epidermal cell walls, thus significantly reducing water loss and uptake of dissolved solutes deposited on the cuticle surface. Different experimental and theoretical approaches for quantifying barrier properties of cutinized leaf and fruit surfaces are presented and discussed in this review. Quantitative characterization of cuticle barrier properties requires (i) the measurement of diffusion kinetics, namely the amount diffusing versus time, (ii) accurate knowledge of driving forces, namely concentration gradients, acting across the barrier, and (iii) the calculation of permeances, namely diffusion velocity. We suggest that on the basis of permeances, which are independent from experimental boundary conditions such as driving forces, the time period of measurement, and area, cuticle barrier properties of different plant organs, different plant species, and different lines, as well as barrier properties of suberized root tissue or synthetic membranes, can be directly compared. This review provides a short and easy to understand manual on what should be kept in mind when quantifying barrier properties of cutinized and suberized transport barriers. This could be helpful for scientists working on cuticle biosynthesis and its regulation.


Asunto(s)
Botánica/métodos , Frutas/fisiología , Fisiología/métodos , Epidermis de la Planta/fisiología , Hojas de la Planta/fisiología , Agua/metabolismo , Difusión , Transpiración de Plantas
14.
J Exp Bot ; 68(19): 5271-5279, 2017 Nov 09.
Artículo en Inglés | MEDLINE | ID: mdl-29036342

RESUMEN

When the stomata are closed under drought, the only route for water loss from the leaf interior to the atmosphere is across the cuticle. Thus, the extent of cuticular transpiration in relation to the reservoirs of water in the plant and the water acquisition from the soil determines the fitness and survival of the plant. It is, therefore, widely assumed that the cuticular water permeability of plants regularly experiencing drought is comparatively low and, thus, adapted to the environment. To test this hypothesis, 382 measurements of cuticular permeability from 160 species were extracted from the literature published between 1996 and 2017. The data had been produced either by using isolated cuticles and astomatous leaf sides or by measuring the minimum leaf conductance under conditions assumed to induce maximum stomatal closure. The species were assigned to 11 life form groups. Except for two particular cases (epiphytes, and climbers and lianas), the cuticular permeabilities of all groups either did not differ significantly or the available data did not allow a statistical test. In conclusion, present knowledge either does not support the hypothesis that ecological adaptions of cuticular water permeability exist or the available data are insufficient to test it.


Asunto(s)
Epidermis de la Planta/fisiología , Hojas de la Planta/fisiología , Fenómenos Fisiológicos de las Plantas , Transpiración de Plantas/fisiología , Agua/metabolismo , Permeabilidad
15.
Artículo en Inglés | MEDLINE | ID: mdl-26761276

RESUMEN

Zeolite-NaA membranes were synthesized from an extract of fused South African fly ash on a porous titanium support by a secondary growth method. The influence of the synthesis molar regime on the formation of zeolite NaA membrane layer was investigated. Two synthesis mixtures were generated by adding either aluminium hydroxide or sodium aluminate to the fused fly ash extract. The feedstock material and the synthesized membranes were characterized by X-diffraction (XRD), scanning electron microscopy (SEM) and X-ray fluorescence spectroscopy (XRF). It was found by XRD and SEM that the cubic crystals of a typical zeolite NaA with a dense intergrown layer was formed on the porous Ti support. The study shows that the source of Al used had an effect on the membrane integrity as sodium aluminate provided the appropriate amount of Na(+) to form a coherent membrane of zeolite NaA, whereas aluminium hydroxide did not. Morphological, the single hydrothermal stage seeded support formed an interlocked array of zeolite NaA particles with neighbouring crystals. Also, a robust, continuous and well-intergrown zeolite NaA membrane was formed with neighbouring crystals of zeolite fused to each other after the multiple stage synthesis. The synthesized membrane was permeable to He (6.0 × 10(6) L m(-2)h(-1) atm(-1)) and CO2 (5.6 × 10(6) L m(-2)h(-1) atm(-1)), which indicate that the layer of the membrane was firmly attached to the porous Ti support. Membrane selectivity was maintained showing membrane integrity with permselectivity of 1.1, showing that a waste feedstock, fly ash, could be utilized for preparing robust zeolite NaA membranes on Ti support.


Asunto(s)
Compuestos de Aluminio/química , Hidróxido de Aluminio/química , Ceniza del Carbón/química , Membranas Artificiales , Compuestos de Sodio/química , Zeolitas/química , Microscopía Electrónica de Rastreo , Porosidad , Sudáfrica , Propiedades de Superficie
16.
Membranes (Basel) ; 14(2)2024 Jan 24.
Artículo en Inglés | MEDLINE | ID: mdl-38392657

RESUMEN

Direct air capture (DAC) is an emerging negative CO2 emission technology that aims to introduce a feasible method for CO2 capture from the atmosphere. Unlike carbon capture from point sources, which deals with flue gas at high CO2 concentrations, carbon capture directly from the atmosphere has proved difficult due to the low CO2 concentration in ambient air. Current DAC technologies mainly consider sorbent-based systems; however, membrane technology can be considered a promising DAC approach since it provides several advantages, e.g., lower energy and operational costs, less environmental footprint, and more potential for small-scale ubiquitous installations. Several recent advancements in validating the feasibility of highly permeable gas separation membrane fabrication and system design show that membrane-based direct air capture (m-DAC) could be a complementary approach to sorbent-based DAC, e.g., as part of a hybrid system design that incorporates other DAC technologies (e.g., solvent or sorbent-based DAC). In this article, the ongoing research and DAC application attempts via membrane separation have been reviewed. The reported membrane materials that could potentially be used for m-DAC are summarized. In addition, the future direction of m-DAC development is discussed, which could provide perspective and encourage new researchers' further work in the field of m-DAC.

17.
Adv Sci (Weinh) ; : e2404001, 2024 Jul 08.
Artículo en Inglés | MEDLINE | ID: mdl-38973254

RESUMEN

Nanographene oxide (nGO) flakes-graphene oxide with a lateral size of ≈100 nm or less-hold great promise for superior flux and energy-efficient nanofiltration membranes for desalination and precise ionic sieving owing to their unique high-density water channels with less tortuousness. However, their potential usage is currently limited by several challenges, including the tricky self-assembly of nano-sized flakes on substrates with micron-sized pores, severe swelling in aqueous solutions, and mechanical instability. Herein, the successful fabrication of a robust membrane stacked with nGO flakes on a substrate with a pore size of 0.22 µm by vacuum filtration is reported. This membrane achieved an unprecedented water permeance above 819.1 LMH bar-1, with a high rejection rate of 99.7% for multivalent metal ions. The nGO flakes prepared using an electron beam irradiation method, have uniquely pure hydroxyl groups and abundant aromatic regions. The calculations revealed the strong hydrogen bonds between two nGO flakes, which arise from hydroxyl groups, coupled with hydrophobic aromatic regions, greatly enhance the stability of stacked flakes in aqueous solutions and increase their effective lateral size. The research presents a simple yet effective approach toward the fabrication of advanced 2D nanographene membranes with superior performance for ion sieving applications.

18.
Adv Mater ; : e2404164, 2024 Aug 01.
Artículo en Inglés | MEDLINE | ID: mdl-39091057

RESUMEN

The precise manipulation of the porous structure of the nanofiltration membrane is critical for unlocking enhanced separation efficiencies across various liquids and solutes. Ultrathin films of crosslinked macrocycles, specifically cyclodextrins (CDs), have drawn considerable attention in this area owing to their ability to facilitate precise molecular separation with high liquid permeance for both polar and non-polar liquids, resembling Janus membranes. However, the functional role of the intrinsic cavity of CD in liquid transport remains inadequately understood, demanding immediate attention in designing nanofiltration membranes. Here, the synthesis of polyester nanofilms derived from crosslinked ß-CD, demonstrating remarkable Na2SO4 rejection (≈92 - 99.5%), high water permeance (≈4.4 - 37.4 Lm-2h-1bar-1), extremely low hexane permeance (<1 Lm-2h-1bar-1), and extremely high ratio (α > 500) of permeances for polar and non-polar liquids, is reported. Molecular simulations support the findings, indicating that neither the polar nor the non-polar liquids flow through the ß-CD cavity in the nanofilm. Instead, liquid transport predominantly occurs through the 2.2 nm hydrophilic aggregate pores. This challenges the presumed functional role of macrocyclic cavities in liquid transport and raises questions about the existence of the Janus structure in nanofiltration membranes produced from the macrocyclic monomers.

19.
Membranes (Basel) ; 14(3)2024 Mar 06.
Artículo en Inglés | MEDLINE | ID: mdl-38535285

RESUMEN

The gas transport properties of thin film composite membranes (TFCMs) with selective layers of PolyActive™, polydimethylsiloxane (PDMS), and polyoctylmethylsiloxane (POMS) were investigated over a range of temperatures (10-34 °C; temperature increments of 2 °C) and pressures (1-65 bar abs; 38 pressure increments). The variation in the feed pressure of condensable gases CO2 and C2H6 enabled the observation of peaks of permeance in dependence on the feed pressure and temperature. For PDMS and POMS, the permeance peak was reproduced at the same feed gas activity as when the feed temperature was changed. PolyActive™ TFCM showed a more complex behaviour, most probably due to a higher CO2 affinity towards the poly(ethylene glycol) domains of this block copolymer. A significant decrease in the permeate temperature associated with the Joule-Thomson effect was observed for all TFCMs. The stepwise permeance drop was observed at a feed gas activity of p/po ≥ 1, clearly indicating that a penetrant transfer through the selective layer occurs only according to the conditions on the feed side of the membrane. The permeate side gas temperature has no influence on the state of the selective layer or penetrant diffusing through it. The most likely cause of the observed TFCM behaviour is capillary condensation of the penetrant in the swollen selective layer material, which can be provoked by the clustering of penetrant molecules.

20.
Membranes (Basel) ; 13(7)2023 Jun 28.
Artículo en Inglés | MEDLINE | ID: mdl-37504993

RESUMEN

The adhesion enhancement of a graphene oxide (GO) layer on porous ceramic substrates is a crucial step towards developing a high-performance membrane for many applications. In this work, we have achieved the chemical anchoring of GO layers on custom-made macroporous disks, fabricated in the lab by pressing α-Al2O3 powder. To this end, three different linkers, polydopamine (PDA), 3-Glycidoxypropyltrimethoxysilane (GPTMS) and (3-Aminopropyl) triethoxysilane (APTMS), were elaborated for their capacity to tightly bind the GO laminate on the ceramic membrane surface. The same procedure was replicated on cylindrical porous commercial ZrO2 substrates because of their potentiality for applications on a large scale. The gas permeance properties of the membranes were studied using helium at 25 °C as a probe molecule and further scrutinized in conjunction with water permeance results. Measurements with helium at 25 °C were chosen to avoid gas adsorption and surface diffusion mechanisms. This approach allowed us to draw conclusions on the deposition morphology of the GO sheets on the ceramic support, the mode of chemical bonding with the linker and the stability of the deposited GO laminate. Specifically, considering that He permeance is mostly affected by the pore structural characteristics, an estimation was initially made of the relative change in the pore size of the developed membranes compared to the bare substrate. This was achieved by interpreting the results via the Knudsen equation, which describes the gas permeance as being analogous to the third power of the pore radius. Subsequently, the calculated relative change in the pore size was inserted into the Hagen-Poiseuille equation to predict the respective water permeance ratio of the GO membranes to the bare substrate. The reason that the experimental water permeance values may deviate from the predicted ones is related to the different surface chemistry, i.e., the hydrophilicity or hydrophobicity that the composite membranes acquire after the chemical modification. Various characterization techniques were applied to study the morphological and physicochemical properties of the materials, like FESEM, XRD, DLS and Contact Angle.

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