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The influence of the surface heterogeneity on the plateau length and the origin of the overlimiting current at cation-exchange polymers are investigated. The results have verified the existence of electroconvection as a mechanism destabilizing the laminar boundary layer at the lipid-membrane interface and causing ionic transport above the limiting current density.

The influence of the composition of poly(ethylene oxide)- poly (butylene terephthalate) (PEO-PBT) block copolymers on the stability of water vapor and the thermodynamic quantities governing the solubility of water vapor in these polymers are studied. PEO-PBT copolymers reveal a high solubility for water vapor, which is completely determined by the PEO segment.

Gas diffusion layers (GDLs) are usually coated with a hydrophobic agent to achieve a delicate balance between liquid and gas phases to maximize mass transport. Yet, most GDL numerical models to date have assumed an average contact angle for all materials, thereby eliminating the possibility of studying the role of the polytetrafluoroethylene (PTFE) content. This study introduces two mixed wettability algorithms to predict the mixed wetting behavior of GDLs composed of multiple materials. The algorithms employ contact angle and distance to solid materials to determine the critical capillary pressure for each pore voxel. The application of the algorithms to the estimation of capillary pressure vs saturation curves for two GDLs, namely, a micro-computed tomography (μ-CT) reconstructed SGL 39BA GDL and a stochastically reconstructed Toray 120C GDL, showed that, in agreement with experimental data, the addition of PTFE resulted in a decrease in saturation at a given capillary pressure. For Toray-120C, the mixed wettability model was capable of reproducing experimentally observed features in the intrusion curve at low saturation that could not be reproduced with a single wettability model, providing a clear link between PTFE coverage and intrusion at low saturation. Numerical results also predicted an increased breakthrough pressure and a decrease in saturation with increasing PTFE, in agreement with experimental observations. The decreased saturation at breakthrough improves gas transport through the layer while maintaining the layer's ability to remove water. Diffusivity simulations confirm the increase in diffusivity at breakthrough with increasing PTFE, thereby providing a rationale for the addition of PTFE, as well as for the optimal amount. This study emphasizes the importance of multimaterial wetting models and calls for more detailed investigations into PTFE and ionomer distributions in GDLs and catalyst layers, respectively.

Coupling renewable electricity to reduce carbon dioxide (CO 2 ) electrochemically into carbon feedstocks offers a promising pathway to produce chemical fuels sustainably. While there has been success in developing materials and theory for CO 2 reduction, the widespread deployment of CO 2 electrolyzers has been hindered by challenges in the reactor design and operational stability due to CO 2 crossover and (bi)carbonate salt precipitation. Herein, we design asymmetrical bipolar membranes assembled into a zero-gap CO 2 electrolyzer fed with pure water, solving both challenges. By investigating and optimizing the anion-exchange-layer thickness, cathode differential pressure, and cell temperature, the forward-bias bipolar membrane CO 2 electrolyzer achieves a CO faradic efficiency over 80% with a partial current density over 200 mA cm -2 at less than 3.0 V with negligible CO 2 crossover. In addition, this electrolyzer achieves 0.61 and 2.1 mV h -1 decay rates at 150 and 300 mA cm -2 for 200 and 100 h, respectively. Postmortem analysis indicates that the deterioration of catalyst/polymer-electrolyte interfaces resulted from catalyst structural change, and ionomer degradation at reductive potential shows the decay mechanism. All these results point to the future research direction and show a promising pathway to deploy CO 2 electrolyzers at scale for industrial applications.

In vitro environments that realize biomimetic scaffolds, cellular composition, physiological shear, and strain are integral to developing tissue models of organ-specific functions. In this study, an in vitro pulmonary alveolar capillary barrier model is developed that closely mimics physiological functions by combining a synthetic biofunctionalized nanofibrous membrane system with a novel three-dimensional (3D)-printed bioreactor. The fiber meshes are fabricated from a mixture of polycaprolactone (PCL), 6-armed star-shaped isocyanate-terminated poly(ethylene glycol) (sPEG-NCO), and Arg-Gly-Asp (RGD) peptides by a one-step electrospinning process that offers full control over the fiber surface chemistry. The tunable meshes are mounted within the bioreactor where they support the co-cultivation of pulmonary epithelial (NCI-H441) and endothelial (HPMEC) cell monolayers at air-liquid interface under controlled stimulation by fluid shear stress and cyclic distention. This stimulation, which closely mimics blood circulation and breathing motion, is observed to impact alveolar endothelial cytoskeleton arrangement and improve epithelial tight junction formation as well as surfactant protein B production compared to static models. The results highlight the potential of PCL-sPEG-NCO:RGD nanofibrous scaffolds in combination with a 3D-printed bioreactor system as a platform to reconstruct and enhance in vitro models to bear a close resemblance to in vivo tissues.

In this work, quartz crystal microbalance with dissipation monitoring (QCM-D) was used to develop a new method to evaluate the protein repellency of microgel coatings. Compared to traditional protocols for surface analysis, QCM has the advantage of a real-time quantitative approach with high sensitivity, allowing us to describe variations of the adsorbed mass with unprecedented accuracy. To enable the detectability of the film throughout the whole operational temperature interval, a poly( N -isopropylacrylamide- co -glycidyl methacrylate) p(NIPAm- co -GMA) microgel monolayer with defined thickness and rigidity was designed. Covalent adhesion of the film to the silica surface was achieved by epoxy-thiol click chemistry and tested for repeated temperature cycles, showing substantial reproducibility. Further functionalization of microgel surfaces by grafting polyzwitterionic chains remarkably improved the protein repellence leaving the strong surface adhesion unaltered. Before and after exposure to fluorescein-tagged bovine serum albumin (FITC-BSA), the coatings showed identical responsive behavior, proving the absence of protein deposition. In nonrepellent coatings, QCM monitoring instead displayed a characteristic shift in the volume phase transition (VPT), pointing out the effect of adsorbed proteins on the swelling behavior of pNIPAm. The combination of QCM-D and UV-visible (UV-vis) was used to evaluate the effect of increasing surface coverage, enabling to distinguish between the protein deposition occurring over the coated and the uncoated portion of the sensor.

The electrochemical N 2 reduction reaction (eNRR) represents a carbon-free alternative to the Haber-Bosch process for a sustainable NH 3 synthesis powered by renewable energy under ambient conditions. Despite significant efforts to develop catalyst activity and selectivity toward eNRR, an appropriate electrochemical system to obstruct the drawback of low N 2 solubility remains broadly unexplored. Here, we demonstrate an electrocatalytic system combining a ruthenium/carbon black gas diffusion electrode (Ru/CB GDE) with a three-compartment flow cell, enabling solid-liquid-gas catalytic interfaces for the highly efficient Ru-catalyzed eNRR. The electrolyte optimization and the Ru/CB GDE development through the hydrophobicity, the Ru/CB loading, and the post-treatment have revealed the crucial contribution of interfacial N 2 transportation and local pH environment. The optimized hydrophobic Ru/CB GDE generated excellent eNRR performance, achieving a high NH 3 yield rate of 9.9 × 10 -10 mol/cm 2 s at -0.1 V vs RHE, corresponding to the highest faradaic efficiency of 64.8% and a specific energy efficiency of 40.7%, exceeding the most reported system. This work highlights the critical role of design and optimization of the GDE-flow cell combination and provides a valuable practicable solution to enhance the electrochemical reaction involving gas-phase reactants with low solubility.

Fouling on filtration membranes is induced by the nonspecific interactions between the membrane surface and the foulants, and effectively hinders their efficient use in various applications. Here, we established a facile method for the coating of membrane surface with a dual stimuli-responsive antifouling microgel system enriched with a high polyzwitterion content. Different poly(sulfobetaine) (PSB) zwitterionic polymers with defined molecular weights and narrow dispersities were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and integrated onto poly( N -vinylcaprolactam) (PVCL) microgels via a controlled dosage of a cross-linker, adapting a precipitation polymerization technique to obtain a core-shell microstructure. Increasing the PSB macro-RAFT concentration resulted in a shift of both upper critical solution temperature and lower critical solution temperature toward higher temperatures. Cryogenic transmission electron microscopy at different temperatures suggested the formation of a core-shell morphology with a PVCL-rich core and a PSB-rich shell. On the other hand, the significant variations of different characteristic proton signals and reversible phase transitions of the microgel constituents were confirmed by temperature-dependent 1 H NMR studies. Utilizing a quartz crystal microbalance with dissipation monitoring, we have been able to observe and quantitatively describe the antipolyelectrolyte behavior of the zwitterionic microgels. The oscillation frequency of the sensor proved to change reversibly according to the variations of the NaCl concentration, showing, in fact, the effect of the interaction between the salt and the opposite charges present in the microgel deposited on the sensor. Poly(ethersulfone) membranes, chosen as the model surface, when functionalized with zwitterionic microgel coatings, displayed protein-repelling property, stimulated by different transition temperatures, and showed even better performances at increasing NaCl concentration. These kinds of stimuli-responsive zwitterionic microgel can act as temperature-triggered drug delivery systems and as potential coating materials to prevent bioadhesion and biofouling as well.

A low-energy emulsification process is hollow-fiber emulsification. In this process, the lumen diameter of the membrane mostly determines the droplet size. To gain smaller droplets, approaches for downsizing the inner diameter of membranes have to be carried out. In this work, we describe a new method for the fabrication of parallel microfluidic porous-wall channels of a homogeneous cylindrical shape with lumen diameters down to 7 μm. Parallel and symmetric porous-wall channels are induced into polyvinylidene fluoride membranes during the casting process. The technique comprises liquid-induced phase separation and phase-separation micromolding using thin glass and carbon fibers as molds and an in-house designed tool to position the fibers. The channel positioning and alignment are verified within this work. We show and investigate the droplet formation in these porous-wall channels via hollow-fiber emulsification. The formed droplets are very small in diameter and size distribution. The droplet formation at varying flow rates and channel diameters is examined in detail. Moreover, an area of sufficient operating conditions is given using Weber and capillary numbers. As a numbering-up approach, we show the simultaneous formation of spherical droplets in two parallel channels. With the proposed membrane fabrication using micromolding, we push the downscaling approach of hollow-fiber emulsification to lower micron ranges of the channel diameter. With these small channels, droplets with a diameter down to 25 μm were produced, which are more attractive for most applications.

Efficient operation is crucial for the deployment of photoelectrochemical CO 2 reduction devices for large-scale artificial photosynthesis. In these devices, undesired transport of CO 2 reduction products from the reduction electrode to the oxidation electrode may occur through a liquid electrolyte and an ion exchange membrane, reducing device productivity and increasing the energy required for product purification. Our work investigated the CO 2 reduction product crossover through ion exchange membranes separating the cathode and anode compartments in CO 2 reduction cells. The concentrations of liquid products produced by CO 2 reduction on copper foil were measured. A systematic approach for the investigation of product crossover was developed. The crossover of products was analyzed over a range of working electrode potentials (-1.08 V vs RHE to -0.88 V vs RHE) in cells employing a commercial Selemion AMV membrane and a new poly(vinylimidazolium) family of ion exchange membranes with variable chemical and structural properties. We found that product loss due to electromigration of charged species in the device was more significant than product loss due to diffusion of uncharged species. To reduce the crossover of CO 2 reduction products, the influence of membrane properties such as the ionic conductivity and water volume fraction was investigated for the Selemion AMV membrane and poly(vinylimidazolium) membranes with variable material properties. We show that the water volume fraction and, by extension, ionic conductivity of the membrane may be controlled to reduce product crossover in CO 2 reduction artificial photosynthesis devices.

We investigate soft, temperature-sensitive microgels at fluid interfaces. Though having an isotropic, spherical shape in bulk solution, the microgels become anisotropic upon adsorption. The structure of microgels at interfaces is described by a core-corona morphology. Here, we investigate how changing temperature across the microgel volume phase transition temperature, which leads to swelling/deswelling of the microgels in the aqueous phase, affects the phase behavior within the monolayer. We combine compression isotherms, atomic force microscopy imaging, multiwavelength ellipsometry, and computer simulations. At low compression, the interaction between adsorbed microgels is dominated by their highly stretched corona and the phase behavior of the microgel monolayers is the same. The polymer segments within the interface lose their temperature-sensitivity because of the strong adsorption to the interface. At high compression, however, the portions of the microgels that are located in the aqueous side of the interface become relevant and prevail in the microgel interactions. These portions are able to collapse and, consequently, the isostructural phase transition is altered. Thus, the temperature-dependent swelling perpendicular to the interface ("3D") affects the compressibility parallel to the interface ("2D"). Our results highlight the distinctly different behavior of soft, stimuli-sensitive microgels as compared to rigid nanoparticles.

Recently, activated carbon adsorption for water treatment regained substantial attention due to the emerging task to remove trace organic compounds such as pesticides. In many applications, especially in decentralized water treatment, one major drawback of adsorbents is their limited recyclability due to inadequate logistics or uneconomical reactivation. In this lab-scale study, we present the temperature swing adsorption in the aqueous phase that allows the in situ regeneration of fixed-bed adsorbers, and prove its technical feasibility. Complying with circular water economy principles, we eliminated the pivotal need for regular replacement and consumables by employing only clean water instead of dedicated regeneration solutions. Adsorption of the herbicide amitrole in aqueous solution on granular activated carbon was exothermic (Δ H = -14.4 ± 3.2 kJ mol -1 for T = 20-94 °C) and followed the Freundlich model. The proposed method consisting of a short counterflow flush with liquid water at 125 °C effectively regenerated the adsorbent. Hence, we obtained a cyclic steady state operation with breakthrough after 122 ± 14 bed volumes (at c out / c in = 0.2), cycle-average rejection of 90 ± 1%, and water recovery of up to 78 ± 4%. No thermal aging of adsorbent was observed over the investigated 17 cycles.

Microgels are commonly synthesized in batch experiments, yielding quantities sufficient to perform characterization experiments for physical property studies. With increasing attention on the application potential of microgels, little attention is yet paid to the questions (a) whether they can be produced continuously on a larger scale, (b) whether synthesis routes can be easily transferred from batch to continuous synthesis, and (c) whether their properties can be precisely controlled as a function of synthesis parameters under continuous flow reaction conditions. We present a new continuous synthesis process of two typical but different microgel systems. Their size, size distribution, and temperature-responsive behavior are compared in depth to those of microgels synthesized using batch processes, and the influence of premixing and surfactant is also investigated. For the surfactant-free poly( N-vinylcaprolactam) and poly( N-isopropylacrylamide) systems, microgels are systematically smaller, while the actual size is depending on the premixing of the reaction solutions. However, by the use of a surfactant, the size difference between batch and continuous preparation diminishes, resulting in equal-sized microgels. Temperature-induced swelling-deswelling of microgels synthesized under continuous flow conditions was similar to that of their analogues synthesized using the batch polymerization process. Additionally, investigation of the internal microgel structure using static light scattering showed no significant changes between microgels prepared under batch and continuous conditions. The work encourages synthesis concepts of sequential chemical conditions in continuous flow reactors to prepare precisely tuned new microgel systems.

Ultrathin microporous polymer films are pertinent to the development and further spread of nanotechnology with very promising potential applications in molecular separations, sensors, catalysis, or batteries. Here, we report high-pressure CO 2 sorption in ultrathin films of several chemically different polymers of intrinsic microporosity (PIMs), including the prototypical PIM-1. Films with thicknesses down to 7 nm were studied using interference-enhanced in situ spectroscopic ellipsometry. It was found that all PIMs swell much more than non-microporous polystyrene and other high-performance glassy polymers reported previously. Furthermore, chemical modifications of the parent PIM-1 strongly affected the swelling magnitude. By investigating the behavior of relative refractive index, n rel , it was possible to study the interplay between micropores filling and matrix expansion. Remarkably, all studied PIMs showed a maximum in n rel at swelling of 2-2.5% indicating a threshold point above which the dissolution in the dense matrix started to dominate over sorption in the micropores. At pressures above 25 bar, all PIMs significantly plasticized in compressed CO 2 and for the ones with the highest affinity to the penetrant, a liquidlike mixing typical for rubbery polymers was observed. Reduction of film thickness below 100 nm revealed pronounced nanoconfinement effects and resulted in a large swelling enhancement and a quick loss of the ultrarigid character. On the basis of the partial molar volumes of the dissolved CO 2 , the effective reduction of the T g was estimated to be ∼200 °C going from 128 to 7 nm films.

Mixed-penetrant sorption into ultrathin films of a superglassy polymer of intrinsic microporosity (PIM-1) was studied for the first time by using interference-enhanced in situ spectroscopic ellipsometry. PIM-1 swelling and the concurrent changes in its refractive index were determined in ultrathin (12-14 nm) films exposed to pure and mixed penetrants. The penetrants included water, n-hexane, and ethanol and were chosen on the basis of their significantly different penetrant-penetrant and penetrant-polymer affinities. This allowed studying microporous polymer responses at diverse ternary compositions and revealed effects such as competition for the sorption sites (for water/n-hexane or ethanol/n-hexane) or enhancement in sorption of typically weakly sorbing water in the presence of more highly sorbing ethanol. The results reveal details of the mutual sorption effects which often complicate comprehension of glassy polymers' behavior in applications such as high-performance membranes, adsorbents, or catalysts. Mixed-penetrant effects are typically very challenging to study directly, and their understanding is necessary owing to a broadly recognized inadequacy of simple extrapolations from measurements in a pure component environment.

Dynamic sorption of ethanol and toluene vapor into ultrathin supported films of polymer of intrinsic microporosity PIM-1 down to a thickness of 6 nm are studied with a combination of in situ spectroscopic ellipsometry and in situ X-ray reflectivity. Both ethanol and toluene significantly swell the PIM-1 matrix and, at the same time, induce persistent structural relaxations of the frozen-in glassy PIM-1 morphology. For ethanol below 20 nm, three effects were identified. First, the swelling magnitude at high vapor pressures is reduced by about 30% as compared to that of thicker films. Second, at low penetrant activities (below 0.3p/p 0 ), films below 20 nm are able to absorb slightly more penetrant as compared with thicker films despite a similar swelling magnitude. Third, for the ultrathin films, the onset of the dynamic penetrant-induced glass transition P g has been found to shift to higher values, indicating higher resistance to plasticization. All of these effects are consistent with a view where immobilization of the superglassy PIM-1 at the substrate surface leads to an arrested, even more rigid, and plasticization-resistant, yet still very open, microporous structure. PIM-1 in contact with the larger and more condensable toluene shows very complex, heterogeneous swelling dynamics, and two distinct penetrant-induced relaxation phenomena, probably associated with the film outer surface and the bulk, are detected. Following the direction of the penetrant's diffusion, the surface seems to plasticize earlier than the bulk, and the two relaxations remain well separated down to 6 nm film thickness, where they remarkably merge to form just a single relaxation.

In vitro reconstruction of an alveolar barrier for modeling normal lung functions and pathological events serve as reproducible, high-throughput pharmaceutical platforms for drug discovery, diagnosis, and regenerative medicine. Despite much effort, the reconstruction of organ-level alveolar barrier functions has failed due to the lack of structural similarity to the natural basement membrane, functionalization with specific ligands for alveolar cell function, the use of primary cells and biodegradability. Here we report a bipolar cultured alveolar-capillary barrier model of human primary cells supported by a basement membrane mimics of fully synthetic bifunctional nanofibers. One-step electrospinning process using a bioresorbable polyester and multifunctional star-shaped polyethylene glycols (sPEG) enables the fabrication of an ultrathin nanofiber mesh with interconnected pores. The nanofiber mesh possessed mechanical stability against cyclic expansion as seen in the lung in vivo. The sPEGs as an additive provide biofunctionality to fibers through the conjugation of peptide to the nanofibers and hydrophilization to prevent unspecific protein adsorption. Biofunctionalized nanofiber meshes facilitated bipolar cultivation of endothelial and epithelial cells with fundamental alveolar functionality and showed higher permeability for molecules compared to microporous films. This nanofiber mesh for a bipolar cultured barrier have the potential to promote growth of an organ-level barrier model for modeling pathological conditions and evaluating drug efficacy, environmental pollutants, and nanotoxicology.

As synthetic membrane materials, polymers with intrinsic microporosity (PIMs) have demonstrated unprecedented permeation and molecular-separation properties. Here, we report the swelling characteristics of submicron-thick supported films of spirobisindane-based PIMs, PIM-1 and PIM-6FDA-OH, for six organic solvents and water using in situ spectroscopic ellipsometry. Surprisingly, PIMs swell significantly in most organic solvents, with swelling factors (SF = h swollen /h dry ) as high as 2.5. This leads to the loss of the ultrarigid character of the polymer and produces equilibrated liquid-like swollen films. Filling of the excess frozen-in fractional free volume with liquid was discovered next to swelling-induced polymer matrix dilation. Water hardly swells the polymer matrix, but it penetrates into the intrinsic microporous structure. This study is the first to provide fundamental swelling data for PIMs, leading to better comprehension of their permeation properties. Such an understanding is indispensable for applications such as solvent filtration, natural-gas separation, and ion retention in flow batteries.

A new nanofiltration (NF) hollow fiber membrane is developed by using two oppositely charged polyelectrolytes coagulating into a polyelectrolyte complex (PEC) onto polyether sulfone base polymer. The particular membrane architecture emerges during a single-step procedure, allowing setting both the porous negatively charged support of the hollow fiber and the separation layer containing also the positive polyelectrolyte (PEI/PDADMAC) through a single layer dry-jet wet spinning process. The novelty is two-pronged: the composition of the hollow fiber membrane itself and its fabrication procedure (one-step fabrication of membranes employing polyelectrolytes). These result in highly permeable hollow fiber membranes with a stable separation layer and performance at par with the membranes reported in literature obtained by multistep processes. More importantly, the membranes are obtained through a simple, very fast (one-step), and less expensive procedure. The best performance among these newly obtained hollow-fiber membranes is achieved by PD5% hollow fiber (MWCO of 300 Da), which showed 7.6 L/m(2)·h·bar permeability and ∼90% rejection of MgCl2, MgSO4, and Na2SO4 at 2 bar pressure. Thus, the resulting membranes not only have the advantages of the hollow-fiber configuration, but perform very well at extremely low pressures (the lowest reported in the literature). The broad impact of the results presented in this Article lies in the potential to dramatically reduce both the fabrication (duration and complexity) and the price and desalination costs of highly performing NF hollow fiber membranes. These might result in interesting potential applications and open new directions toward designing efficient functional NF hollow fibers for water desalination.

Sorption of compressed gases into thin polymeric films is essential for applications including gas sensors and membrane based gas separation. For glassy polymers, the sorption behavior is dependent on the nonequilibrium status of the polymer. The uptake of molecules by a polymer is generally accompanied by dilation, or swelling, of the polymer material. In turn, this dilation can result in penetrant induced plasticization and physical aging that affect the nonequilibrium status of the polymer. Here, we investigate the dilation and sorption behavior of ultrathin membrane layers of a hybrid inorganic-organic network material that consists of alternating polyhedral oligomeric silsesquioxane and imide groups, upon exposure to compressed carbon dioxide and methane. The imide precursor contains fluoroalkene groups that provide affinity toward carbon dioxide, while the octa-functionalized silsesquioxane provides a high degree of cross-linking. This combination allows for extremely high sorption capacities, while structural rearrangements of the network are hindered. We study the simultaneous uptake of gases and dilation of the thin films at high pressures using spectroscopic ellipsometry measurements. Ellipsometry provides the changes in both the refractive index and the film thickness, and allows for accurate quantification of sorption and swelling. In contrast, gravimetric and volumetric measurements only provide a single parameter; this does not allow an accurate correction for, for instance, the changes in buoyancy because of the extensive geometrical changes of highly swelling films. The sorption behavior of the ultrathin hybrid layers depends on the fluoroalkene group content. At low pressure, the apparent molar volume of the gases is low compared to the liquid molar volume of carbon dioxide and methane, respectively. At high gas concentrations in the polymer film, the apparent molar volume of carbon dioxide and methane exceeds that of the liquid molar volume, and approaches that of the gas phase. The high sorption capacity and reversible dilation characteristics of the presented materials provide new directions for applications including gas sensors and gas separation membranes.

The present study investigates the possibility of inducing monovalent ion permselectivity on standard cation exchange membranes, by the layer-by-layer (LbL) assembly of poly(ethyleneimine) (PEI)/poly(styrenesulfonate) (PSS) polyelectrolyte multilayers. Coating of the (PEI/PSS)N LbL multilayers on the CMX membrane caused only moderate variation of the ohmic resistance of the membrane systems. Nonetheless, the polyelectrolyte multilayers had a substantial influence on the monovalent ion permselectivity of the membranes. Permselectivity comparable to that of a commercial monovalent-ion-permselective membrane was obtained with only six bilayers of polyelectrolytes, yet with significantly lower energy consumption per mole of Na(+) ions transported through the membranes. The monovalent ion permselectivity stems from an increased Donnan exclusion for divalent ions and hydrophobization of the surface of the membranes concomitant to their modification. Double-layer capacitance obtained from impedance measurements shows a qualitative indication of the divalent ion repulsion of the membranes. At overlimiting current densities, water dissociation occurred at membranes with PEI-terminated layers and increased with the number of layers, while it was nearly absent for the PSS-terminated layers. Hence, LbL layers allow switching on and turning off water splitting at the surface of ion exchange membranes.

Macromolecular networks consisting of homogeneously distributed covalently bonded inorganic and organic precursors are anticipated to show remarkable characteristics, distinct from those of the individual constituents. A novel hyper-cross-linked ultrathin membrane is presented, consisting of a giant molecular network of alternating polyhedral oligomeric silsesquioxanes and aromatic imide bridges. The hybrid characteristics of the membrane are manifested in excellent gas separation performance at elevated temperatures, providing a new and key enabling technology for many important industrial scale applications.

Bipolar membranes are laminated anion and cation exchange membranes that split water at their interface very efficiently upon application of an electric field. This paper investigates the layer-by-layer (LbL) deposition of polyelectrolyte multilayers, as a tool to introduce molecularly thin catalyst groups at this interface of bipolar membranes. The bipolar membranes were prepared by first modifying an anion exchange membrane by consecutive dipping LbL assembly, then casting a thin highly charged intermediate layer followed by casting a cation exchange layer. The results reveal that polyelectrolytes of higher charge density coated on the anion exchange layer yield better performance. Several parameters of the LbL interface deposition were varied. Out of the investigated LbL assembly parameters, ionic strength and number of layers have shown the largest influence on catalytic activity as well as ionic selectivity. The membrane with two bilayers of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) and poly(ethyleneimine) (PEI), where the PEI was prepared in 0.5 M NaCl, gave rise to the best performance. Surprisingly, detailed data analysis at low electrical potential suggests that the interface layers of a bipolar membrane play a major role in its permselectivity. Previously, only the bulk thickness of the anion and cation exchange membrane was assumed to influence the bipolar membrane selectivity.

Exposure of a thin polymer film to a fluid can affect properties of the film such as the density and thickness. In particular in membrane technology, these changes can have important implications for membrane performance. Spectroscopic ellipsometry is a convenient technique for in situ studies of thin films, because of its noninvasive character and very high precision. The applicability of spectroscopic ellipsometry is usually limited to samples with well-defined interfacial regions, whereas in typical composite membranes, often substantial and irregular intrusion of the thin film into the pores of a support exists. In this work, we provide a detailed characterization of a polished porous alumina membrane support, using variable-angle spectroscopic ellipsometry in combination with atomic force microscopy and mercury porosimetry. Two Spectroscopic ellipsometry optical models are presented that can adequately describe the surface roughness of the support. These models consider the surface roughness as a distinct layer in which the porosity gradually increases toward the outer ambient interface. The first model considers the porosity profile to be linear; the second model assumes an exponential profile. It is shown that the models can be extended to account for a composite membrane geometry, by deposition of a thin polysulfone film onto the support. The developed method facilitates practicability for in situ spectroscopic ellipsometry studies of nonequilibrium systems, i.e., membranes under actual permeation conditions.

The fouling behavior of microstructured hollow fibers was investigated in constant flux filtrations of colloidal silica and sodium alginate. It was observed that the fouling resistance increases faster with structured fibers than with round fibers. Reversibility of structured fibers' fouling was similar during silica filtrations and better in sodium alginate filtrations when compared with round fibers. The deposition of two different silica sols on the membranes was observed by NMR imaging. The sols had different particle size and solution ionic strength and showed different deposition behaviors. For the smaller particle-sized sol in deionized solution (Ludox-TMA), there was more deposition within the grooves of the structured fibers and much less on the fins. For the alkali-stabilized sol Bindzil 9950, which had larger particles, the deposition was homogeneous across the surface of the structured fiber, and the thickness of the deposit was similar to that on the round fiber. This difference between the deposition behavior of the two sols is explained by differences in the back diffusion, which creates concentration polarization layers with different resistances. The Ludox sol formed a thick polarization layer with very low resistance. The Bindzil sol formed a slightly thinner polarization layer; however, its resistance was much higher, of similar magnitude as the intrinsic membrane resistance. This high resistance of the polarization layer during the Bindzil sol filtration is considered to lead to quick flow regulation toward equalizing the resistance along the fiber surface. The Ludox particles were trapped at the bottom of the grooves as a result of reduced back diffusion. The fouling behavior in sodium alginate filtrations was explained by considering the size-dependent deposition within the broad alginate size distribution. The better reversibility of fouling in the structured fibers is thought to be the result of a looser deposit within the grooves, which is more easily removed than a compressed deposit on the round fibers.

The permeation properties of a series of block copolymers based on poly(ethylene oxide)-ran-poly(propylene oxide) (PEO-ran-PPO) soft segments and monodisperse tetra-amide (T6T6T) hard segments have been studied. The polyether soft segment used in the current study differs from the commonly used pure poly(ethylene oxide) (PEO) soft segment by the fact that it contains 25 wt % randomly distributed poly(propylene oxide) (PPO). The presence of the methyl group of PPO suppresses crystallization of the soft segment and strongly improves the permeability of these materials, especially at subambient temperatures. In addition, the unique monodisperse character of the hard segment ensures a very well phase-separated morphology, resulting in a very pure soft phase. The soft segment length of these block copolymers was varied between 1000 and 10000 g/mol (62-89 wt %). High soft segment concentrations and flexibility were obtained resulting in high CO(2) permeabilities (up to 570 Barrer at 50 degrees C). Due to the random distribution of PPO in the predominantly PEO based soft segment crystallization of PEO was not observed at temperatures as low as -10 degrees C. CO(2) permeabilities exceeding 200 Barrer could be obtained at this low temperature. The CO(2)/light gas selectivity in these materials is governed by the solubility selectivity and consequently only slightly lowered because of the introduction of PPO in the soft segment. Comparison with literature revealed that this block copolymer system has exceptionally high CO(2) permeabilities combined with reasonable CO(2)/light gas selectivities. It is very interesting in CO(2) separation processes where subambient conditions are present (e.g., separation of CO(2) from natural gas), as at these low temperatures, one can take maximum advantage of the increased separation ability of the polymer materials while maintaining excellent transport characteristics.

Microstructured polymeric films are fabricated by a novel replication method. A polymer solution is applied and contained between two substrates, of which at least one is a patterned PDMS mold. The ensemble is then put in an atmosphere containing water vapor, which diffuses through the PDMS. The absorption of water into the polymer solution causes the precipitation (phase separation) of the polymer while in contact with the microstructured molds. The thickness of the PDMS slab can be exploited to tune the water vapor transport and hence the phase separation kinetics and resulting polymer morphology. Removal of excess polymer solution from between two PDMS slabs, followed by vapor induced phase separation, can also result in microperforated polymer films with great control over the dimensions.

Reverse electrodialysis (RED) is a nonpolluting sustainable technology that converts the free energy of mixing of two solutions with different salinity directly into electrical energy. Although the theoretical potential is high, the practical power output obtained is limited yet due to concentration polarization phenomena and spacer shadow effects. In this work we combinetheoretical calculations with direct current and alternating current experimental stack characterization methods to quantify the contribution of concentration polarization phenomena, spacer shadow effects and stack resistance in RED under different hydrodynamic conditions in a temperature range from 10 to 40 degrees C to show the practical potential of RED. Concentration polarization phenomena play an important role and their influence can be minimized by optimal stack hydrodynamics. Improved spacerdesigns and newspacerconceptsofferextensive room to reduce the spacer shadow effect and to further increase the practical power output Improvement of hydrodynamics and reduction of the spacer shadow effect directly result in a significant increase in power output of the RED process, and values almost double the values currently obtained can be realized, which brings RED close to economical viability.

Porous stamps fabricated by one-step phase separation micromolding were used for microcontact printing of polar inks, in particular aqueous solutions of dendrimers, proteins, and nanoparticles. Permanent hydrophilicity was achieved without any additional treatment by tailored choice of the polymer components. Pores with several hundred nanometers to micrometers were obtained during the phase separation process. These pores can act as ink reservoirs. The porous stamps were thoroughly characterized by SEM, NMR, and contact angle measurement. The versatility of the porous stamps was shown in three printing schemes. First, positive microcontact printing was achieved by printing a polar thioether-modified dendrimer as the ink, followed by backfilling and wet etching. Second, the porous stamps were used for multiple printing of fluorescent proteins without reinking. Third, nanoparticles of about 60 nm in diameter, which cannot be directly transferred by oxidized PDMS stamps, were successfully printed onto substrates by using these porous stamps.

We present a generic concept to create local concentration gradients, based on the absorption of gases or vapors in a liquid. A multilayer microfluidic device with crossing gas and liquid channels is fabricated by micromilling and used to generate multiple gas-liquid contacting regions, separated by a hydrophobic membrane. Each crossing can acts as both a microdosing and microstripping region. Furthermore, the liquid and gas flow rate can be controlled independently of each other. The focus of this conceptual article is on the generation of pH gradients, by locally supplying acidic or basic gases/vapors, such as carbon dioxide, hydrochloric acid, and ammonia, visualized by pH-sensitive dyes. Stationary and moving gradients are presented in devices with 500-microm channel width, depths of 200-400 microm, and lengths of multiple centimeters. It is shown that the method allows for multiple consecutive switching gradients in a single microchannel. Absorption measurements in a microcontactor with the model system CO2/water are presented to indicate the dependence of gas absorption rate on channel depth and residence time. Achievable concentration ranges are ultimately limited by the solubility of used components. The reported devices are easy to fabricate, and their application is not limited to pH gradients. Two proof of principles are demonstrated to indicate new opportunities: (i) local crystallization of NaCl using HCl vapor and (ii) consecutive reactions of ammonia with copper(II) ions in solution.

PPO (poly(2,6-dimethyl-1,4-phenylene oxide)) is a well-known membrane material showing good gas separation properties. The incorporation of nanoparticles can enhance or deteriorate the performance of composite membranes, sometimes depending only on the way of the composite preparation. We have modified the PPO polymer with C60 fullerenes up to a content of 2 wt %. Previous investigations showed a strong dependence of permeability on whether the C60 is simply dispersed in the polymer or chemically bonded to the polymer chains. Free volume effects were suggested as an explanation but not experimentally confirmed. Here, we present free volume studies by positron annihilation lifetime spectroscopy. An additional long positron lifetime shows the increased free volume of composite samples, while the high electron affinity of C60 helps to indicate the homogeneity of the samples. Combining the presented results with permeability measurements refines the understanding of this promising membrane material.

We report on alkaline hydrolysis of tetraethoxysilane (Stöber synthesis) inside a macroporous polymer matrix resulting in a homogeneous coverage of silica onto the polymer surface. The encapsulation of the polymer struts by a continuous silica crust allows further functionalization with hydrophilic and hydrophobic silylating agents. The porous silica polymeric hybrid material combines the morphological control and mechanical flexibility of the polymeric matrix with the convenient surface modifications developed for glass and amorphous silica. This concept is applied to macroporous membranes where alteration in surface functionality allows tuning of hydrophobicity (contact angle and liquid entry pressure), streaming potential, and adsorption capacity of double-stranded DNA.

A fast and reliable method is reported for fabricating superhydrophobic surfaces. The method combines microstructure replication with polymer phase inversion and can be applied to a wide variety of polymers. This method provides a surface that contains roughness on two independently controllable levels, i.e., the microstructure level and the level of porosity stemming from the phase inversion. Both levels were optimized separately, resulting in water contact angles up to 167 degrees.

[structure: see text] Water-soluble models of heme-protein active sites are obtained via the self-assembly of cationic porphyrins 1 and tetrasulfonato calix[4]arene 2 (K(1.2)() = 10(5) M(-)(1)). Selective binding of ligands either outside or inside the cavity of assemblies 1.2 via coordination to the zinc center has been observed. Small ligands such as 4-methylpyridine and 1-methylimidazole are encapsulated, while the bulkier caffeine is bound outside. Assemblies Co-1.2, in which the Zn porphyrin moiety has been replaced by a Co(II) porphyrin, can act as O(2) carriers.