Editorial for the Special Issue "Preparation and Application of Advanced Functional Membranes".

Membrane science is a discipline that cuts across almost all fields of research and experimentation [...].

Pathway for Water Transport through Breathable Nanocomposite Membranes of PEBAX with Ionic Liquid [C12C1im]Cl.

Water transport through membranes is an attractive topic among the research dedicated to dehydration processes, microenvironment regulation, or more simply, recovery of freshwater. Herein, an atomistic computer simulation is proposed to provide new insights about a water vapor transport mechanism through PEBAX membranes filled with ionic liquid (IL) [C12C1im]Cl. Starting from experimental evidence that indicates an effective increase in water permeation as the IL is added to the polymer matrix (e.g., up to 85·10-3 (g·m)/(m2·day) at 318.15 K for PEBAX@2533 membranes loaded with 70% of IL), molecular dynamics simulations are proposed to explore the key role of IL in water transport inside membranes. The polar region composed of anions and cationic head groups of the IL is demonstrated to serve as the pathway for water transport through the membrane. Water molecules always stay near the pathway, which becomes wider and thus has a larger water-accessible area with increasing IL concentration. Hence, the diffusion coefficients of water molecules and ions increase as the IL concentration increases. The simulation provides useful indications about a microscopic mechanism that regulates the transport of water vapor through a kind of PEBAX/IL membrane, resulting in full agreement with the experimental evidence.

Aliquots of MIL-140 and Graphene in Smart PNIPAM Mixed Hydrogels: A Nanoenvironment for a More Eco-Friendly Treatment of NaCl and Humic Acid Mixtures by Membrane Distillation.

The problem of water scarcity is already serious and risks becoming dramatic in terms of human health as well as environmental safety. Recovery of freshwater by means of eco-friendly technologies is an urgent matter. Membrane distillation (MD) is an accredited green operation for water purification, but a viable and sustainable solution to the problem needs to be concerned with every step of the process, including managed amounts of materials, membrane fabrication procedures, and cleaning practices. Once it is established that MD technology is sustainable, a good strategy would also be concerned with the choice of managing low amounts of functional materials for membrane manufacturing. These materials are to be rearranged in interfaces so as to generate nanoenvironments wherein local events, conceived to be crucial for the success and sustainability of the separation, can take place without endangering the ecosystem. In this work, discrete and random supramolecular complexes based on smart poly(N-isopropyl acrylamide) (PNIPAM) mixed hydrogels with aliquots of ZrO(O2C-C10H6-CO2) (MIL-140) and graphene have been produced on a polyvinylidene fluoride (PVDF) sublayer and have been proven to enhance the performance of PVDF membranes for MD operations. Two-dimensional materials have been adhered to the membrane surface through combined wet solvent (WS) and layer-by-layer (LbL) spray deposition without requiring further subnanometer-scale size adjustment. The creation of a dual responsive nanoenvironment has enabled the cooperative events needed for water purification. According to the MD's rules, a permanent hydrophobic state of the hydrogels together with a great ability of 2D materials to assist water vapor diffusion through the membranes has been targeted. The chance to switch the density of charge at the membrane-aqueous solution interface has further allowed for the choice of greener and more efficient self-cleaning procedures with a full recovery of the permeation properties of the engineered membranes. The experimental evidence of this work confirms the suitability of the proposed approach to obtain distinct effects on a future production of reusable water from hypersaline streams under somewhat soft working conditions and in full respect to environmental sustainability.

Graphene-Coated PVDF Membranes: Effects of Multi-Scale Rough Structure on Membrane Distillation Performance.

Graphene-coated membranes for membrane distillation have been fabricated by using a wet-filtration approach. Graphene nanoplatelets have been deposited onto PVDF membrane surfaces. Morphology and physicochemical properties have been explored to evaluate the changes in the surface topography and related effects on the membrane performance in water desalination. The membranes have been tested in membrane distillation plants by using mixtures of sodium chloride and humic acid. The multi-scale rough structure of the surface has been envisaged to amplify the wetting and fouling resistance of the graphene-coated membranes so that a better flux and full salt rejection have been achieved in comparison with pristine PVDF. Total salt rejection and an increase of 77% in flux have been observed for coated membrane with optimized graphene content when worked with NaCl 0.6 M (DCMD, ΔT ≈ 24 °C) over a test period of 6 h. The experimental findings suggest these novel graphene-coated membranes as promising materials to develop functional membranes for high-performing water desalination.

Performance of PVDF Based Membranes with 2D Materials for Membrane Assisted-Crystallization Process.

Membrane crystallization (MCr) is a promising and innovative process for the recovery of freshwater from seawater and for the production of salt crystals from the brine streams of desalination plants. In the present work, composite polymeric membranes for membrane crystallization were fabricated using graphene and bismuth telluride inks prepared according to the wet-jet milling (WJM) technology. A comparison between PVDF-based membranes containing a few layers of graphene or bismuth telluride and PVDF-pristine membranes was carried out. Among the 2D composite membranes, PVDF with bismuth telluride at higher concentration (7%) exhibited the highest flux (about 3.9 L∙m-2h-1, in MCr experiments performed with 5 M NaCl solution as feed, and at a temperature of 34 ± 0.2 °C at the feed side and 11 ± 0.2 °C at the permeate side). The confinement of graphene and bismuth telluride in PVDF membranes produced more uniform NaCl crystals with respect to the pristine PVDF membrane, especially in the case of few-layer graphene. All the membranes showed rejection equal to or higher than 99.9% (up to 99.99% in the case of the membrane with graphene). The high rejection together with the good trans-membrane flux confirmed the interesting performance of the process, without any wetting phenomena, at least during the performed crystallization tests.

Molecular insights on NaCl crystal formation approaching PVDF membranes functionalized with graphene.

Membrane-assisted crystallization is an emerging technology where microporous hydrophobic membranes are used not as selective barriers but to promote the water vapor transfer between phases inducing supersaturation in solution. This has been successfully tested in the crystallization of ionic salts, low molecular weight organic acids and proteins. In this work, molecular dynamics simulations were used to study the crystal nucleation and growth of sodium chloride in contact with hydrophobic polymer surfaces at a supersaturated concentration of salt. A pristine polyvinylidene fluoride (PVDF) surface and PVDF containing different concentrations of graphene platelets were studied. Membrane crystallization tests were performed in parallel, in order to compare the experimental results with the computational ones. Here, with an integrated experimental-computational approach, we demonstrate that graphene-containing membranes assisted the crystal growth of NaCl, speeding up crystal nucleation in comparison with the pristine PVDF membranes. The computational results agreed with the experimental data, allowing the possibility of exploring the behavior of nanomaterials in membrane processes at a microscopic level.

Controlled Bulk Properties of Composite Polymeric Solutions for Extensive Structural Order of Honeycomb Polysulfone Membranes.

This work provides additional insights into the identification of operating conditions necessary to overcome a current limitation to the scale-up of the breath figure method, which is regarded as an outstanding manufacturing approach for structurally ordered porous films. The major restriction concerns, indeed, uncontrolled touching droplets at the boundary. Herein, the bulk of polymeric solutions are properly managed to generate honeycomb membranes with a long-range structurally ordered texture. Water uptake and dynamics are explored as chemical environments are changed with the intent to modify the hydrophilic/hydrophobic balance and local water floatation. In this context, a model surfactant such as the polyoxyethylene sorbitan monolaurate is used in combination with alcohols at different chain length extents and a traditional polymer such as the polyethersufone. Changes in the interfacial tension and kinematic viscosity taking place in the bulk of composite solutions are explored and examined in relation to competitive droplet nucleation and growth rate. As a result, extensive structurally ordered honeycomb textures are obtained with the rising content of the surfactant while a broad range of well-sized pores is targeted as a function of the hydrophilic-hydrophobic balance and viscosity of the composite polymeric mixture. The experimental findings confirm the consistency of the approach and are expected to give propulsion to the commercially production of breath figures films shortly.

Influence of protein bulk properties on membrane surface coverage during immobilization.

Biomolecules immobilization is a key factor for many biotechnological applications. For this purpose, the covalent immobilization of bovine serum albumin (BSA), lipase from Candida rugosa and protein G on differently functionalized regenerated cellulose membranes was investigated. Dynamic light scattering and electrophoresis measurements carried out on biomolecules in solution indicated the presence of monomers, dimers and trimers for both BSA and protein G, while large aggregates were observed for lipase. The immobilization rate and the surface coverage on functionalized regenerated cellulose membranes were studied as a function of biomolecule concentration. Results indicated that the saturation coverage of BSA and protein G was concentration independent (immobilized protein amount of 2.40±0.03mg/g and 2.65±0.07mg/g, respectively). Otherwise, a different immobilization kinetics trend was obtained for lipase, for which the immobilized amount increases as a function of time without reaching a saturation value. Atomic force microscopy (AFM) micrographs showed the formation of monolayers for both BSA and protein G on the membrane surface, while a multilayer structure is found for lipase, in agreement with the trends observed in the related immobilization kinetics. As a result, the morphology of the proteins layer on the membrane surface seems to be strictly dependent on the proteins behavior in solution. Besides, the surface coverage has been described for BSA and protein G by the pseudo second order models, the results indicating the surface reaction as the controlling step of immobilization kinetics. Finally, enzyme activity and binding capacity studies indicated the preservation of the biomolecule functional properties.

Functional carbon nanotubes for high-quality charge transfer and moisture regulation through membranes: structural and functional insights.

Functional single walled carbon nanotubes (SWCNTs) are assembled onto porous supports by using layer-by-layer (LBL) approaches. Directed nano-assembly of nanotubes is identified as a crucial factor for controlling the combined functions of hybrid-composite membranes, including charge and moisture transport. In both the cases, donor-acceptor interactions are indicated to be responsible for the rearrangement of nanotubes inside the LBL multilayer and their related properties. Aggregation and stratification of the carbon nanotubes along with the availability of selective-site interactions are complementarily investigated by using SEM, Raman and infrared spectroscopy, while high electrical charge and water vapor transfer are achievable, provided that a large number of connections and competitive interactions are allowed. Ohmic behavior is observed for all types of carbon nanotubes, even if better-quality charge transfer pathways are obtained with carboxylated conductive filaments. Likewise, assisted moisture regulation is succeeded when using functional filaments with the capability to establish competitive H-donor-acceptor interactions with water.

Intelligent Membranes: Dream or Reality?

Intelligent materials are claimed to overcome current drawbacks associated with the attainment of high standards of life, health, security and defense. Membrane-based sensors represent a category of smart systems capable of providing a large number of benefits to different markets of textiles, biomedicine, environment, chemistry, agriculture, architecture, transport and energy. Intelligent membranes can be characterized by superior sensitivity, broader dynamic range and highly sophisticated mechanisms of autorecovery. These prerogatives are regarded as the result of multi-compartment arrays, where complementary functions can be accommodated and well-integrated. Based on the mechanism of "sense to act", stimuli-responsive membranes adapt themselves to surrounding environments, producing desired effects such as smart regulation of transport, wetting, transcription, hydrodynamics, separation, and chemical or energy conversion. Hopefully, the design of new smart devices easier to manufacture and assemble can be realized through the integration of sensing membranes with wireless networks, looking at the ambitious challenge to establish long-distance communications. Thus, the transfer of signals to collecting systems could allow continuous and real-time monitoring of data, events and/or processes.

Light responsive polymer membranes: a review.

In recent years, stimuli responsive materials have gained significant attention in membrane separation processes due to their ability to change specific properties in response to small external stimuli, such as light, pH, temperature, ionic strength, pressure, magnetic field, antigen, chemical composition, and so on. In this review, we briefly report recent progresses in light-driven materials and membranes. Photo-switching mechanisms, valved-membrane fabrication and light-driven properties are examined. Advances and perspectives of light responsive polymer membranes in biotechnology, chemistry and biology areas are discussed.

Pure and Modified Co-Poly(amide-12-b-ethylene oxide) Membranes for Gas Separation Studied by Molecular Investigations.

This paper deals with a theoretical investigation of gas transport properties in a pure and modified PEBAX block copolymer membrane with N-ethyl-o/p-toluene sulfonamide (KET) as additive molecules. Molecular dynamics simulations using COMPASS force field, Gusev-Suter Transition State Theory (TST) and Monte Carlo methods were used. Bulk models of PEBAX and PEBAX/KET in different copolymer/additive compositions were assembled and analyzed to evaluate gas permeability and morphology to characterize structure-performance relationships.

High-definition polymeric membranes: construction of 3D lithographed channel arrays through control of natural building blocks dynamics.

The fabrication of well-defined interfaces is in high demand in many fields of biotechnologies. Here, high-definition membrane-like arrays are developed through the self-assembly of water droplets, which work as natural building blocks for the construction of ordered channels. Solution viscosity together with the dynamics of the water droplets can decide the final formation of three-dimensional well-ordered patterns resembling anodic structures, especially because solvents denser than water are used. Particularly, the polymer solution viscosity is demonstrated to be a powerful tool for control of the mobility of submerged droplets during the microfabrication process. The polymeric patterns are structured at very high levels of organization and exhibit well-established transport-surface property relationships, considered basics for any types of advanced biotechnologies.

Water droplets as template for next-generation self-assembled poly-(etheretherketone) with cardo membranes.

Next generation PEEK-WC membranes have been fabricated by using an innovative self-assembly technique. Patterned architectures have been achieved via a solvent-reduced and water-assisted process, resulting in honeycomb packed geometry. The membranes exhibit monodisperse pores with size and shape comparable to those left by templating water droplets. Influencing factors for the formation of self-assembled poly-(etheretherketone) with Cardo [PEEK-WC] membranes have been evaluated, identifying the critical parameters for nucleation, growth, and propagation of the droplet-mobile arrays through the overall films. Structure-transport relationships have been discussed according to the results achieved from the implementation of membrane distillation processes, yielding indication about the suitability of self-assembled PEEK-WC films to work as interfaces in contactor operations.