Ion Coupling, Bonding, and Transfer in Narrow Carbon Nanotubes.

Narrow carbon nanotubes (nCNT) are unique mimics of biological channels with water-ion selectivity attractive for applications such as water purification and osmotic energy harvesting, yet their understanding is still incomplete. Here, an ab initio computation is employed to develop the full picture of ion transfer in nCNT including specificity and coupling between ions. The thermodynamic costs of ion transfer are computed for single ions and ion pairs and used to evaluate different local coupling scenarios including strong (pairing) and weak (free-ion) coupling as well as "electroneutrality breakdown" (EB), possible for cations only due to their chemisorption-like interaction with nCNT. The results also indicate that nCNT behaves as a highly polarizable metal-like shell, which eliminates the dielectric energy when CNT accommodates coupled cation and anion. This allows facile computation and comparison of the full transfer costs, including translation entropy, for different ions in different coupling modes to identify the dominant regime. EB transfer appears most favorable for K+, while anions strongly favor transfer as pairs, except for chloride which favors weak coupling and, at neutral pH, transfers as a trace ion coupled to both cation and OH-. The results demonstrate that, in general, observed ion permeation and conduction in nCNT, especially for anions, reflect a complex ion-specific and composition-dependent interplay between different ions.

Pseudo-bottle-brush decorated thin-film composite desalination membranes with ultrahigh mineral scale resistance.

High water recovery is crucial to inland desalination but is impeded by mineral scaling of the membrane. This work presents a two-step modification approach for grafting high-density zwitterionic pseudo-bottle-brushes to polyamide reverse osmosis membranes to prevent scaling during high-recovery desalination of brackish water. Increasing brush density, induced by increasing reaction time, correlated with reduced scaling. High-density grafting eliminated gypsum scaling and almost completely prevented silica scaling during desalination of synthetic brackish water at a recovery ratio of 80%. Moreover, scaling was effectively mitigated during long-term desalination of real brackish water at a recovery ratio of 90% without pretreatment or antiscalants. Molecular dynamics simulations reveal the critical dependence of the membrane's silica antiscaling ability on the degree to which the coating screens the membrane surface from readily forming silica aggregates. This finding highlights the importance of maximizing grafting density for optimal performance and advanced antiscaling properties to allow high-recovery desalination of complex salt solutions.

Dielectric exclusion, an éminence grise.

Dielectric exclusion has long been well-established as the key mechanism in membrane desalination, critical for delivering the required levels of salt rejection, also playing important role in electro-membrane processes, nanofluidics, and biomimetics. Unfortunately, its elusive nature and many features, such as dependence on the pore size, membrane hydration, and ion size and charge, make it deceivingly similar to the other ion exclusions mechanisms, steric and Donnan, which has led to much controversy and misconceptions. Starting from the Born model and the concept of self-energy, the present paper reviews and highlights the physical basis of dielectric exclusion, its main features and the ways it may be looked at. It discusses what makes the dielectric exclusion both similar and distinctly different from the other mechanism and its synergy and intimate connection with other phenomena, such as Donnan exclusion, permeability-selectivity upper-bound, and selectivity of charged membranes towards uncharged solutes. The paper also addresses subjects that still cause much controversy at present, such as appropriate measures of ionic radii and the subtle distinction between the dielectric exclusion and primary ion hydration. It also points to gaps that need to be bridged towards more complete theory. The points addressed here are important for understanding, modeling and development of various next-generation separation technologies including water purification, resource recovery and reuse, and green energy generation and storage.

Dynamics of underwater microparticle adhesion to soft hydrated surfaces: Modeling and analysis by time-dependent AFM force spectroscopy.

HYPOTHESIS: Understanding the attachment and detachment of microparticles and living cells to surfaces is crucial for developing antifouling strategies. Hydrogel coatings have shown promise in reducing fouling and particle adhesion due to their softness and high water content, yet the mechanisms involved are dynamic and complex, and relevant parameters are not easily accessible. AFM-based force spectroscopy (FS) experiments with colloidal probe particles is a direct way of evaluating adhesive and mechanical relaxational dynamics, yet their interpretation and modeling has been challenging. The present study proposes and examines several dynamic models, suitable for quantitative analysis of FS results with model probe particle on hydrogels surfaces. EXPERIMENTS: FS were performed using polyethylene glycol (PEG) hydrogels and polystyrene microspheres including particle attachement to the hydrogel surface (loading), holding the particle on the surface with a constant force for variable times (dwell) and pulling the particle away from the surface (unloading) FINDINGS: It was found that a viscoelastic extension of the classical JKR model with energy of adhesion unevenly distributed over the contact area and vanishing at its circumferences accurately described all FS experiments and yielded physically consistent viscoelastic and adhesive dynamic parameters, steadily changing with dwell time and applied force. The observed time evolution and force dependence were rationalized as combination of osmotic and osmo-mechnical relaxation in the contact region.

Polystyrene Sulfonate Particles as Building Blocks for Nanofiltration Membranes.

Today the standard treatment for wastewater is secondary treatment. This procedure cannot remove salinity or some organic micropollutants from water. In the future, a tertiary cleaning step may be required. An attractive solution is membrane processes, especially nanofiltration (NF). However, currently available NF membranes strongly reject multivalent ions, mainly due to the dielectric effect. In this work, we present a new method for preparing NF membranes, which contain negatively and positively charged domains, obtained by the combination of two polyelectrolytes with opposite charge. The negatively charged polyelectrolyte is provided in the form of particles (polystyrene sulfonate (PSSA), d ~300 nm). As a positively charged polyelectrolyte, polyethyleneimine (PEI) is used. Both buildings blocks and glycerol diglycidyl ether as crosslinker for PEI are applied to an UF membrane support in a simple one-step coating process. The membrane charge (zeta potential) and salt rejection can be adjusted using the particle concentration in the coating solution/dispersion that determine the selective layer composition. The approach reported here leads to NF membranes with a selectivity that may be controlled by a different mechanism compared to state-of-the-art membranes.

Ambipolar blend-based organic electrochemical transistors and inverters.

CMOS-like circuits in bioelectronics translate biological to electronic signals using organic electrochemical transistors (OECTs) based on organic mixed ionic-electronic conductors (OMIECs). Ambipolar OECTs can reduce the complexity of circuit fabrication, and in bioelectronics have the major advantage of detecting both cations and anions in one device, which further expands the prospects for diagnosis and sensing. Ambipolar OMIECs however, are scarce, limited by intricate materials design and complex synthesis. Here we demonstrate that judicious selection of p- and n-type materials for blend-based OMIECs offers a simple and tunable approach for the fabrication of ambipolar OECTs and corresponding circuits. These OECTs show high transconductance and excellent stability over multiple alternating polarity cycles, with ON/OFF ratios exceeding 103 and high gains in corresponding inverters. This work presents a simple and versatile new paradigm for the fabrication of ambipolar OMIECs and circuits with little constraints on materials design and synthesis and numerous possibilities for tunability and optimization towards higher performing bioelectronic applications.

Putting together the puzzle of ion transfer in single-digit carbon nanotubes: mean-field meets ab initio.

Nature employs channel proteins to selectively pass water across cell membranes, which inspires the search for bio-mimetic analogues. Carbon nanotube porins (CNTPs) are intriguing mimics of water channels, yet ion transport in CNTPs still poses questions. As an alternative to continuum models, here we present a molecular mean-field model that transparently describes ion coupling, yet unlike continuum models, computes ab initio all required thermodynamic quantities for the KCl salt and H+ and OH- ions present in water. Starting from water transfer, the model considers the transfer of free ions, along with ion-pair formation as a proxy of non-mean-field ion-ion interactions. High affinity to hydroxide, suggested by experiments, making it a dominant charge carrier in CNTPs, is revealed as an exceptionally favorable transfer of KOH pairs. Nevertheless, free ions, coexisting with less mobile ion-pairs, apparently control ion transport. The model well explains the observed effects of salt concentration and pH on conductivity, transport numbers, anion permeation and its activation energies, and current rectification. The proposed approach is extendable to other sub-nanochannels and helps design novel osmotic materials and devices.

Elucidating the Effect of Aliphatic Molecular Plugs on Ion-Rejecting Properties of Polyamide Membranes.

Polyamide RO membranes are widely used for seawater desalination owing to their high salt rejection and water permeability; however, improved selectivity-permeability trade-off is still desired. "Molecular plugs," small molecules immobilized within the polyamide structure, offer an attractive approach; however, their overall effect on polyamide physicochemical properties poses many questions. Here, we analyze the effect of decylamine, a promising plug, and a few charged and uncharged mimics on polyamide films using several in situ techniques. Electrochemical impedance spectroscopy (EIS) reveals a complex pH-dependent response, whereby, upon exposure to amine solution, conductivity first rapidly drops; however, under alkaline conditions, when amine is uncharged, the trend subsequently slowly reverses, and conductivity increases. This slow reversal was observed for noncharged alcohols of similar size as well, but not for larger surfactant molecules. The reversal was assigned to the uptake of plug molecules within polyamide, as opposed to the fast initial drop assigned to surface adsorption. EIS and quartz-crystal microbalance (QCM) results showed that exposure to decylamine under alkaline conditions ultimately led to an irreversible decrease in conductivity, that is, stronger ion rejection, remaining after re-exposure of polyamide to amine-free buffer. This suggests that plug uptake within polyamide resulted in polymer stress, indeed observed in surface stress measurements, and subsequent relaxation. The results indicate that the moderate size of decylamine and conditions minimizing its charge were optimal for irreversible change; however, charge interactions helped maximize its binding within polymer and induce the desired sustained change in selectivity. The results have many potential implications for improving current membrane desalination technology and increasing inherent membrane selectivity toward hard-to-remove species.

Electrospun Ion-Conducting Composite Membrane with Buckling-Induced Anisotropic Through-Plane Conductivity.

Fuel cell (FC) is an attractive green alternative for today's fuel combustion systems. In common FCs, a polymer electrolyte membrane selectively conducts protons but blocks the passage of electrons and fuel. Nafion, the current benchmark membrane material, has a superior conductivity owing to unique morphology comprising randomly oriented elongated ionic nanochannels within its Teflon-like matrix. Channel orientation enhances Nafion conductivity, yet there has been no facile method to induce a stable alignment in the desired through-plane (TP) direction. Here, we report an approach based on dual electrospun Nafion-PVDF nanofiber composites that yields a stable TP alignment. It utilizes extreme thinness and strong inherent orientation within electrospun nanofibers, which is readily converted to TP alignment by plunging an electrospun nanofiber mat into a thin slit, resulting in nanofiber buckling and subsequent consolidation. Using TEM and SAXS, we demonstrate a pronounced and sustained TP ion channel orientation in prepared membranes, yielding a highly anisotropic swelling and conductivity exceeding that of bulk Nafion when normalized to Nafion content. The analysis also highlights the importance of PVDF as a stabilizing component, preserving orientation upon annealing, while a similarly prepared pure Nafion membrane loses anisotropy. The approach holds potential to advance the FC technology by overcoming current limitations of ionomeric membranes.

Water and Ion Transfer to Narrow Carbon Nanotubes: Roles of Exterior and Interior.

Narrow carbon nanotubes (CNTs) desalinate water, mimicking water channels of biological membranes, yet the physics behind selectivity, especially the effect of the membrane embedding CNTs on water and ion transfer, is still unclear. Here, we report ab initio analysis of the energies involved in transfer of water and K+ and Cl- ions from solution to empty and water-filled 0.68 nm CNTs for different dielectric constants (ϵ) of the surrounding matrix. The transfer energies computed for 1 ≤ ϵ < ∞ permit a transparent breakdown of the transfer energy to three main contributions: binding to CNT, intra-CNT hydration, and dielectric polarization of the matrix. The latter scales inversely with ϵ and is of the order 102/ϵ kJ/mol for both ions, which may change ion transfer from favorable to unfavorable, depending on ion, ϵ, and CNT diameter. This may have broad implications for designing and tuning selectivity of nanochannel-based devices.

Spatial pattern and surface-specificity of particle and microorganism deposition and attachment: Modeling, analytic solution and experimental test.

HYPOTHESIS: Understanding microparticle and living cell deposition and attachment on surfaces from a flow is a long-standing surface-science problem, pivotal to developing antifouling strategies. Recent studies indicate a complex non-conservative and surface-specific nature of adhesion and mechanical contact forces that determine attachment kinetics. This requires new models and kinetic data, however, observed deposition rates (e.g., in parallel-plate flow chamber, PPFC) represent a superposition of attachment and bulk transport. Here, we propose to deduce attachment rates (as an appropriate rate constant) from spatial deposition profiles along PPFC and develop an analytical solution for the full problem, suitable for deposition data analysis and parameter fitting. EXPERIMENTS: Analytical solution, validated by numerical simulations, reveals relation between the deposition profile along PPFC and key model parameter B, the ratio of sedimentation and attachment rates. Its use is demonstrated on experimental data obtained in a PPFC for particles and bacteria on various surfaces. FINDINGS: Fitted B values highlight correlation with the particle/substrate nature and consistently explain the observed trends along PPFC, both decreasing and increasing. Thus derived attachment rates will serve as basis for future microscopic modelling that would relate attachment to appropriate surface and contact-mechanical characteristics of particles and substrate and flow conditions.

Ion partitioning and permeation in charged low-T* membranes.

Understanding ion transport in membrane materials is key to engineering and development of desalination and water purification technologies as well as electro-membrane applications. To date, modeling of ion transport has mainly relied on mean-field approaches, originally intended for weak inter-ionic interactions, i.e., high reduced temperature T*. This condition is violated in many membranes, which could explain disagreement between predicted trends and experiments. The paper highlights observed discrepancies and develops a new approach based on the concept of ion association, more adequate in the low-T⁎ limit. The new model addresses ion binding and mobility consistently within the same physical picture, applied to different types of single and mixed salts. The resulting relations show a significantly weaker connection between ion partitioning and permeability than the standard ones. Estimates using primitive model (PM) of ions in a homogeneous dielectric suggest that non-PM mechanisms, originating from the molecular structure of the ion-solvating environment, might enhance ion association in membranes. PM analysis also predicts that ion solvation and association must be rigidly related, yet non-PM effects may decouple these phenomena and allow a crossover to non-trivial regimes consistent with experiments and simulations. Despite the crude nature of the presented approach and some questions remaining open, it appears to explain most available experimental data and presents a step towards predictive modeling of ion-selective membrane separations in water-, environment- and energy-related applications.

Effect of the membrane exclusion mechanism on phosphate scaling during synthetic effluent desalination.

Calcium phosphate scaling is one of the main limitations in effluent desalination using membranes. This may be overcome by tailoring membranes with lower rejection of the scalant ions. In this study, we systematically examined the use of negatively and positively charged membranes, rejecting ions mainly based on Donnan exclusion, as a low-scaling alternative to dielectric-exclusion-dominated polyamide NF membranes for effluent desalination. The two charged membranes exhibited a lower calcium and especially phosphate rejection than the polyamide membrane. Consequently, the calcium phosphate supersaturation and then the propensity to scaling of the charged membranes were much lower than the polyamide membrane. This also allowed filtering at a much higher recovery ratio with the charged membranes. It was also found that, despite the fact that the charged membranes had an opposite fixed charge, their scaling behavior was similar. Apparently, although these membranes showed opposite selectivity towards scalant ions (phosphate and calcium) in single salt solutions, the rejection pattern in mixed salt solutions resulted in similar saturation indices, much lower than for polyamide membrane. The scale formed on all three membranes was identified as amorphous calcium phosphate (ACP), although its saturation index was lower than its solubility factor. This was explained by concentration polarization which increases the saturation index in the solution adjacent to the membrane surface. Tests in absence of permeate flux showed a much slower precipitation that took a few days compared with filtration conditions (few hours). In addition, under these conditions, the effect of the scaling on the membrane permeability was generally reduced and the scale contained crystalline calcium phosphate products, different from ACP. The results indicate that the ion rejection and resulting polarization next to the membrane surface plays a crucial role in scaling. Thus, tuning ion selectivity of NF membranes towards scalant ions presents a promising alternative for scaling mitigation during effluent desalination.

In Situ Modification of Reverse Osmosis Membrane Elements for Enhanced Removal of Multiple Micropollutants.

Reverse osmosis (RO) membranes are widely used for desalination and water treatment. However, they insufficiently reject some small uncharged micropollutants, such as certain endocrine-disrupting, pharmaceutically active compounds and boric acid, increasingly present in water sources and wastewater. This study examines the feasibility of improving rejection of multiple micropollutants in commercial low-pressure RO membrane elements using concentration polarization- and surfactant-enhanced surface polymerization. Low-pressure membrane elements modified by grafting poly(glycidyl methacrylate) showed enhanced rejection of all tested solutes (model organic micropollutants, boric acid, and NaCl), with permeability somewhat reduced, but comparable with commercial brackish water RO membranes. The study demonstrates the potential and up-scalability of grafting as an in situ method for improving removal of various classes of organic and inorganic micropollutants and tuning performance in RO and other dense composite membranes for water purification.

Degradation of Polyamide Membranes Exposed to Chlorine: An Impedance Spectroscopy Study.

Polyamide is the key material in modern membrane desalination; however, its well-known and incompletely understood drawback is its low tolerance to chlorine, the most efficient in-line disinfectant. Here we report a first investigation of the mechanism and kinetics of chlorine attack using electrochemical impedance spectroscopy (EIS) that directly probes changes in ion permeation upon chlorination at different pH values, focusing on its early stages and low chlorine concentrations (15-197 ppm). EIS results partly conform to an established two-stage mechanism that proceeds as N-chlorination followed by either C-chlorination in acidic conditions or amide bond scission in alkaline conditions. However, early time kinetics in acidic conditions shows inconsistencies with this model, explained by possible effects of direct ring chlorination and finite polymer relaxation rates. The findings indicate that (a) N-chlorination reduces membrane polarity and ion permeability, while C-chlorination has an opposite effect; (b) chlorination in acidic conditions must involve other reactions, such as direct ring chlorination, in addition to N-chlorination and Orton rearrangement; and (c) the ultimate chemical transformations (C-chlorination or amide bond scission) result in an irreversible increase in membrane polarity and loss of ion rejection. The results highlight the potential of EIS as a powerful and sensitive tool for studying chemical degradation of ion-selective materials that may assist in developing new chlorine-resistant membranes.

Modeling QCM-D Response to Deposition and Attachment of Microparticles and Living Cells.

Quartz crystal microbalance with dissipation monitoring (QCM-D) is a powerful tool for studying adhesion, yet its use for analyzing the deposition of microparticles and living cells on surfaces has been hampered by difficulties in interpretation. Here we report a new quantitative model of QCM-D response, presented as an equivalent acoustic impedance circuit. As an essential feature, the particle interaction with surrounding fluid is modeled by relations for a freely oscillating rotating and translating sphere in an unbounded fluid, which is a valid approximation for microparticles. This helps deduce from the measured reponse the parameters pertinent to the contact mechanics. We use the model to analyze deposition of different microparticles as well as Pseudomonas fluorescens bacteria on several substrates using QCM-D combined with real-time microscopy. The parameter space is increased by varying particle type and size, substrate surface chemistry and rigidity, and ionic strength of the solution, which allows observation of diverse responses and transition from inertial to elastic loading, including rarely observed resonant regimes. Ultimately, we find that the model describes reasonably well the observed response for different microparticles and substrates, as well as for bacteria, and enables extraction of the contact characteristics in elastic and mixed loading regimes. It also reveals discrepancies between measured and anticipated parameters for large particles. The new model can be a useful tool for interpreting and quantifying QCM-D data on the adhesion of particles and living cells to surfaces, including time-dependent adhesion phenomena.