Behavior Of Aqueous Solutions Research Articles

Potential-Dependent ATR-SEIRAS and EQCM-D Analysis of Interphase Formation in Zinc Battery Electrolytes.

With the heightening interest in bivalent battery technology, there arises a necessity for a thorough investigation into zinc-ion battery (ZIB) electrolytes, accommodating their chemical attributes and potential-dependent structural dynamics. While the phenomenon of in situ solid electrolyte interphase formation is extensively documented in lithium-ion batteries, its analogous occurrences in ZIBs remain limited. Herein is a comparative study of three zinc electrolytes of interest: ZnSO4, ZnOTF, and Zn(TFSI)2/LiTFSI hybrid water-in-salt electrolyte. Additionally, the impact of an acetonitrile additive is scrutinized, with a comparative assessment of the interfacial behavior in aqueous solutions. Utilizing ATR-SEIRAS, potential-dependent alterations in the composition of the electrolyte/electrode interface were monitored, while EQCM-D facilitated a comprehensive understanding of variations in the mass and structural properties of the adsorbed layer. Aqueous ZnSO4 demonstrated the accumulation of porous Zn4SO4(OH)6·xH2O at negative potentials, leading to a mass of 1.47 μg cm-2 after five cycles. Bisulfate formation was observed at positive potentials. SEIRAS measurements for ZnOTF demonstrated reorientation and surface adsorption of CF3SO3- to favor CF3 at the surface for positive potentials, and acetonitrile showed increased stability for the electrode at negative potentials. The additive was also reported to lead to the accumulation of a substantial passivation layer with viscoelastic properties. The zinc water-in-salt showed exceptional surface stability at negative potentials and a widened potential window. A thin rigid zinc SEI layer is reported with a mass of 0.7 μg cm-2. The compositional intricacies of these surface structures are discussed in relation to their solvent conditions. This investigation not only sheds light on the initial charge/discharge cycles in ZIBs but also underscores their pivotal role in instigating enduring transformations that can significantly influence their long-term cycling performance.

Alkyl polyglycosides derived from α-olefins via Fisher glycosidation and their adsorption and aggregation behavior in aqueous solution

The effective and stable use of α-olefins is a topic of great research interest due to their abundant reserves, and the fact that the hydrolysis and epoxidation reaction of these substances produces hydroxyl group as a key linking group plays an important role in the synthesis of surfactants. Consequently, a series of alkyl polyglycosides (DC08PG, DC10PG, and DC12PG) were synthesized as non-ionic surfactants via the glycosidation reaction of long-chain 1, 2-vicinal diol with different carbon numbers and glucose. The results showed that 1, 2-vicinal diol exhibited increased reactivity in glycosidation due to their unique molecular structure. Furthermore, it was observed that the degree of polymerization (DP) achieved was notably elevated, registering at 1.63, surpassing the DP of 1.37 typically prepared using conventional methods. This enhancement was paralleled by a demonstrable increase in hydrophilicity, as evidenced by the hydrophile-lipophile balance number (HLB), resulting in a substantial improvement in the water solubility of the product, the transmission rate > 90 %. For adsorption and aggregation behavior, DC12PG showed a smaller cross-sectional area (Amin), larger saturation adsorption (Γmax), and could aggregate to form micelles at low concentrations, and short-term dynamic adsorption properties (DST) was prominent. At the same concentration, for foam properties, DC12PG with longer alkyl chains produced higher and more stable foam; for emulsification properties, the emulsification time was 298 s; for wetting properties, the contact angle was 61.59° in 30 s. This analysis will help to reveal the intrinsic connection between the molecular structure and properties of surfactants.

Adsorption, Aggregation, and Application Properties of Green Pluronic Aliphatic Alcohol Ether Carboxylic Acids and Nonionic/Amphoteric Surfactants in Water.

In the realm of colloid and interface science, new types of green surfactants, including anionic Pluronic alcohol ether carboxylate (AEC), branched alkyl glucoside (IG), and zwitterionic coconut oil amide propyl betaine (CAB), have been identified and merit further exploration. AEC, characterized by its inclusion of 5 EO and 3.5 PO units, was synthesized, and its behavior in aqueous solutions with IG and CAB was meticulously examined. Their performance in applications such as foam generation, wetting, and the dispersion and stabilization of graphene was also evaluated. At αAE5P3C = 0.5, AE5P3C/CAB exhibited superior surface and interfacial properties compared to AE5P3C/IG. In these hybrid systems, the self-assembly of micelles is predominantly influenced by hydrogen bonding, electrostatic interactions, and hydrophobic forces. Kinetic analysis further confirmed that the driving force for micelle formation in these hybrid systems is enthalpy, with the adsorption process involving a mixed diffusion-kinetic adsorption mechanism. AE5P3C/CAB demonstrated enhanced foaming ability, foam stability, and wetting properties compared to AE5P3C/IG. Intriguingly, the optimal dispersion and stabilization of graphene were achieved with AE5P3C/IG at αAE5P3C = 0.2, providing a foundational basis for its potential application in graphene-based systems. A thorough examination of the synergistic mechanisms and application potential of these three distinct surfactants in aqueous solutions was presented, taking into account various charged ions and the specific hydrophilic and hydrophobic groups of EO and PO. This study not only provides fundamental insights into their intrinsic properties but also offers a fresh perspective for the ongoing exploration of green surfactants.

High-temperature anodization route to nanoporous niobium oxides with enhanced supercapacitive properties in aqueous electrolytes

Relatively little work has been done on Nb2O5 pseudocapacitive behaviors in aqueous solutions. Here, the galvanostatic anodization of niobium in K2HPO4-containing glycerol electrolyte at high temperature is fully explored. The anodically grown films on niobium have ordered nanoporous morphology and are composed of a low-crystalline orthorhombic Nb2O5, which can be directly employed as supercapacitor electrodes without any posttreatment process. To further improve their supercapacitive performances, a facile technique to generate Fe-doped Nb2O5 films is developed, where the as-anodized films are treated by an electrochemical doping in FeCl3 ethylene glycol solution. The Fe-doped Nb2O5 films show a wider potential window and higher capacitance than that of the as-anodized films in aqueous electrolytes. They present a maximum areal capacitance of 168.1 mF cm−2 at 1 mV s−1 and excellent cycling stability with 85.8 % capacitance retention after 10,000 cycles. The charge storage in the Fe-doped Nb2O5 is believed to occur by the incorporation of Li+ ions with concomitant reduction of Nb5+ to Nb4+ in aqueous lithium-containing solutions. Unlike nonaqueous media, Li+ intercalation/deintercalation in aqueous media is a diffusion-controlled process, leading to the comparatively slower pseudocapacitive processes. Nevertheless, in terms of an industrial applicability the Fe-doped Nb2O5 films deserve special attention.

Capillary wave-assisted collapse of non-Newtonian droplets

Understanding the peripheral capillary wave propagation during droplet impact is crucial for comprehending the physics of wetting onset and droplet fragmentation. Although Newtonian droplets have been extensively studied, we show how capillary waves deform non-Newtonian droplets in such a way that rheological features, such as the critical concentrations for the overlap (c*) and entangled polymer molecules (c**), may be directly obtained from the deformation history. Determining these critical concentrations is essential as they mark transitions in the rheological behavior of aqueous polymeric solutions, influencing viscosity, elasticity, and associated fluid dynamics. We have also compared capillary waves among Newtonian, shear-thinning, and Boger fluid droplets and found that although the fluid kinematics appear to be purely biaxial extensional flow, the infinite-shear properties of the droplets dominate the physics of capillary wave formation and propagation.

Multiscale Computational Study of Cellulose Acetate-Water Miscibility: Insights from Molecularly Informed Field-Theoretic Modeling.

Cellulose acetate (CA), a prominent water-soluble derivative of cellulose, is a promising biodegradable ingredient that has applications in films, membranes, fibers, drug delivery, and more. In this work, we present a molecularly informed field-theoretic model for CA to explore its phase behavior in aqueous solutions. By integrating atomistic details into large-scale field-theoretic simulations via the relative entropy coarse-graining framework, our approach enables efficient calculations of CA's miscibility window as a function of the degree of substitution (DS) of cellulose hydroxyl groups with acetate side chains. This allows us to capture the intricate phase behavior of CA, particularly its unique miscibility at intermediate substitution, without relying on experimental input. Additionally, the model directly probes CA solution behavior specific to the relative DS at C2, C3, and C6 alcohol sites, providing insights for the rational design of water-soluble CA for diverse applications. This work demonstrates a promising integration of molecularly informed field theories, complementing wet-lab experimentation, for engineering the next-generation polymeric materials with precisely tailored properties.

Structural and dynamic behaviour of concentrated aqueous solutions of (poly)ethylene glycols: Insight into the impact of hydrophobicity, hydrogen bonding and chain length

Understanding the delicate interplay between hydrophobicity/hydrophilicity, hydrogen bonding ability and solute size in modulating the chemico-physical properties of aqueous solutions with increasing solute concentration is a challenging task. Here, we focus on how bulk properties, such as diffusion and aggregation behaviour, are affected by the different hydration patterns observed for differently concentrated aqueous solutions of (poly)ethylene glycols, and their corresponding methoxyethers, of various lengths. Using a combined experimental and computational approach, we analyse solutions of ethylene glycol (EG), dimethoxyethane (DME), polyethylene glycol with 4 repeating units capped with either hydroxyl (PEG200) or methoxyl (PEG250DME) tails, and polyethylene glycol with 9 repeating units (PEG400). By disentangling the contributions of hydrophobicity, hydrogen bonding ability, and chain length, we observe that for the smaller solutes electristriction and hydrophobic hydration are the main phenomena occurring. Instead, as the solute becomes larger, these effects give way to the non-trivial conformational flexibility that can either favour or disfavour intermolecular interactions which lead to the formation of water-rich regions excluded from the solute.

Exploring Mucoadhesive and Toxicological Characteristics Following Modification of Linear Polyethylenimine with Various Anhydrides.

Linear polyethylenimine (L-PEI) has numerous applications, such as in pharmaceutical formulations, gene delivery, and water treatment. However, due to the presence of secondary amine groups, L-PEI shows a relatively high toxicity and low biocompatibility. Here, various organic anhydrides were used to modify L-PEI to reduce its toxicity and enhance its functionality. We selected methacrylic anhydride, crotonic anhydride, maleic anhydride, and succinic anhydride to modify L-PEI. The structure of the resulting derivatives was characterized using 1H NMR and FTIR spectroscopies, and their behavior in aqueous solutions was studied using turbidimetric and electrophoretic mobility measurements over a broad range of pHs. A fluorescence flow through method determined the mucoadhesive properties of the polymers to the bovine palpebral conjunctiva. Methacrylated L-PEI and crotonylated L-PEI showed strong mucoadhesive properties at pH 7.4, likely due to covalent bonding with mucin thiol groups. In contrast, maleylated and succinylated L-PEI were poorly mucoadhesive as the pH was above their isoelectric point, resulting in electrostatic repulsion between the polymers and mucin. The toxicity of these polymers was evaluated using in vivo assays with planaria and the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) cell viability assay in human alveolar epithelial cells. Moreover, the irritancy of polymers was assessed using a slug mucosa irritation assay. The results demonstrated that anhydride modification mitigated the adverse toxicity effects seen for parent L-PEI.

Two-Dimensional Cu-Based MOF for Selective Staining of the Cellular Nucleus through Fluorescence Imaging and Selective Sorption of Dye Molecules in Aqueous Medium.

A two-dimensional copper-based metal-organic framework, [Cu(C23H14O6)(C10H8N2)2]·H2O·DMSO, 1, was synthesized using pamoic acid (C23H16O6) and 4,4'-bipyridine (C10H8N2) as an organic ligand and Cu(II) as a metal ion. Single-crystal structure X-ray diffraction studies of the as-synthesized compound showed a two- dimensional structure with free hydroxyl groups. Upon excitation at 370 nm, the aqueous dispersion of [Cu(C23H14O6)(C10H8N2)2]·H2O·DMSO, 1, showed emission centered at 525 nm resulting from the intraligand energy transfer. Fluorescence microscopic experiments using a human epithelioid cervix carcinoma HeLa cell line were carried out, clearly showing that our compound selectively stained the cellular nucleus. To utilize the porous nature of [Cu(C23H14O6)(C10H8N2)2]·H2O·DMSO, 1, its dye sorption behavior in aqueous solution was determined, and a high affinity for methylene blue (MB) dye was confirmed. Our synthesized compound sorbed 88% MB dye with an initial concentration of 32 mg L-1, and its sorption capacity for MB was found to be 29.79 mg g-1. The possible mechanism of the dye sorption behavior was discussed in terms of the size and charge of dye molecules with respect to molecular-level interactions between the framework and the dye molecules.

Electrical conductivity behaviour of aqueous solutions of methylene blue at different temperatures using impedance spectroscopy

Electrical conductivity behaviour of aqueous solutions of methylene blue at different temperatures using impedance spectroscopy

Synthesis by design and application to desalination of VO2/CTAB-Ti3C2 capacitive deionization electrode

As an emerging technology in capacitive deionization (CDI), flow-electrode capacitive deionization (FCDI) has attracted much attention due to its unlimited electrosorption capacity and continuous operation. Like CDI, carbon is generally chosen as the electrode material for FCDI at this stage, but conventional carbon materials have limited desalination capacity due to the double electric layer. The two-dimensional layered material MXene has been gradually applied to CDI due to its unique structure and physicochemical properties. However, the van der Waals forces exist between the MXene layers, and the layered structure of MXene is susceptible to stacking, while exhibiting an obvious swelling behavior in aqueous solution, thus affecting its desalination performance. Herein, we report a designed VO2/CTAB-Ti3C2 heterostructure synthesised by a simple hydrothermal method. The addition of VO2 can alleviate the lamellar structure buildup of Ti3C2 and improve the desalination performance of Ti3C2. On the other hand, Ti3C2 can be used as a conductive substrate for VO2, which improves the charge transfer rate of VO2, prevents VO2 agglomeration, and provides more contact surfaces for ion intercalation. Compared with the pure VO2 and Ti3C2 electrodes, the composite electrode has a good desalination performance, and its desalination reaches 1041.5 mg g−1 at 1.2 V. Therefore, this VO2/CTAB-Ti3C2 hybrid material is expected to be used as an electrode material for flow capacitive deionization.

Integrating low salinity water, surfactant solution, and functionalized magnetite nanoparticles with natural acidic groups for enhanced oil recovery: Interfacial tension study

In recent years, nanoparticles (NPs) have become a popular choice for improving oil recovery through enhanced oil recovery (EOR) methods. NPs can enhance oil recovery by reducing interfacial tension (IFT), altering wettability, and decreasing the mobility ratio. In this study, magnetic NPs with acidic groups (tartaric acid and malic acid), which are natural acids found in fruits such as grapes and apples, were synthesized and functionalized to reduce the IFT between oil and water. Various characterizations tests, including zeta potential (ZP), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), dynamic light scattering (DLS), field emission scanning electron microscopy (FE-SEM), and energy dispersive X-ray analysis (EDAX), were used to determine the properties of NPs. Afterwards, the IFT behaviour of crude oil and aqueous solutions, containing surfactant sodium dodecyl sulfate (SDS), two types of salts namely sodium chloride (NaCl) and sodium sulfate (Na2SO4), and functionalized magnetite NPs with tartaric acid and malic acid were investigated. Two crude oils were used in this study: light (A) and heavy (B). The results showed that increasing salt concentration decreases the IFT for crude oils down to an optimum point (20000 ppm for both salts), after which the IFT increases with increasing salt concentration. The presence of functionalized Fe3O4@Tartaric acid NPs (300 ppm) in the aqueous solutions containing salts at their optimum concentration (20000 ppm) and SDS (300 ppm) can decrease the IFT more significantly than that of Fe3O4 and Fe3O4@Malic acid for both crude oils. This is due to higher stability and higher ZP of functionalized Fe3O4@Tartaric acid NPs compared to Fe3O4@Malic. The IFT for oil A decreases from 20.8 mN/m to 2.87 mN/m for light crude oil and from 32.96 mN/m to 1.91 mN/m for heavy crude oil. The IFT for heavy crude oil was more reduced than that of light crude oil, which was due to the presence of asphaltene, resin, and other surface-active agents in heavy crude oil, which can act as a natural surfactant in oil and help reducing the IFT.

Four-Component Statistical Copolymers by RAFT Polymerization.

This manuscript serves as the starting point for in-depth research of multicomponent, statistical, methacrylate-based copolymers that potentially mimic the behavior of proteins in aqueous solutions. These synthetic macromolecules are composed of specially chosen comonomers: methacrylic acid (MAA), oligoethylene glycol methyl ether methacrylate (OEGMA475), 2-(dimethylamino)ethyl methacrylate (DMAEMA) and benzyl methacrylate (BzMA). Monomer choice was based on factors such as the chemical nature of pendant functional groups, the polyelectrolyte/polyampholyte and amphiphilic character and the overall hydrophobic-hydrophilic balance (HLB) of the obtained quaterpolymers. Their synthesis was achieved via a one-pot reversible addition fragmentation chain transfer (RAFT) polymerization in two distinct compositions and molecular architectures, linear and hyperbranched, respectively, in order to explore the effects of macromolecular topology. The resulting statistical quaterpolymers were characterized via 1H-NMR and ATR-FTIR spectroscopies. Their behavior in aqueous solutions was studied by dynamic (DLS) and electrophoretic light scattering (ELS) and fluorescence spectroscopy (FS), producing vital information concerning their self-assembly and the structure of the formed aggregates. The physicochemical studies were extended by tuning parameters such as the solution pH and ionic strength. Finally, the quaterpolymer behavior in FBS/PBS solutions was investigated to test their colloid stability and biocompatibility in an in vivo-mimicking, biological fluid environment.

Range and sensitivity of 17O nuclear spin-lattice relaxation as a probe of aqueous electrolyte dynamics.

The study of electrolytic solutions is of relevance in many research fields, ranging from biophysics, materials, and colloid science to catalysis and electrochemistry. The dependence of solution dynamics on the nature of electrolytes and their concentrations has been the subject of many experimental and computational studies, yet it remains challenging to obtain a full understanding of the factors that govern solution behavior. Here, we provide additional insights into the behavior of aqueous solutions of alkali chlorides by combining 17O relaxation data with diffusion and viscosity data and contrast their behavior with 1H nuclear magnetic resonance relaxation data. The main findings are that 17O relaxation correlates well with viscosity data but not with diffusion data, while 1H relaxation correlates with neither. Certain ionic trends match known ion-specific series behavior, especially at high concentrations. Notably, we also examine the ranges of the interactions and conclude that the majority of the effects are tied to local water reorientation dynamics.

The Use of an Advanced Intelligent-Responsive Polymer for the Study of Dynamic Water-Carbon Dioxide Alternating Displacement.

Addressing the issue of inadequate temperature tolerance in traditional polymers, in this study, we successfully executed a one-step synthesis of intelligent-responsive polymers which have excellent adaptability in water-gas alternating displacement scenarios. Utilizing the fatty acid method, we produced OANND from oleic acid (OA) and N,N-dimethyl-1,3-propanediamine (NND). Upon testing the average particle size in the aqueous solution both prior and subsequent to CO2 passage, it became evident that OANND assumes the form of a small-molecule particle in the aqueous phase, minimizing damage during formation. Notably, upon CO2 exposure, it promptly organizes into stable micelles with an average size of 88 nm and a relatively uniform particle distribution. This unique characteristic endows it with a rapid CO2 response mechanism and the ability to form a highly resilient gel. In the exploration of viscoelastic fluids, we observed the remarkable behavior of the AONND aqueous solution when CO2/N2 was introduced. This system displayed repeatable transitions between aqueous and gel states, with the highest viscosity peaking at approximately 3895 mPa·s, highlighting its viscosity reversibility and reusability properties. The rheological property results that we obtained indicate that an elongated micellar structure is present in the solution system, with the optimal concentration ratio for its formation determined as 0.8, which is the molar ratio of the OANND-NaOA system. In the sealing performance tests, a 1.0 wt% concentration of the gel system exhibited excellent injectability properties. At 80 °C, this gel effectively reduced the permeability of a sand-filled model to 94.5% of its initial value, effectively sealing potential leakage paths or gas fluxes. This remarkable ability to block leakage paths and reduce seepage capacity highlights the material's superior blocking effect and erosion resistance properties. Furthermore, even at a temperature of 90 °C and an injection pore volume (PV) of 3, this plugging system could reduce the permeability of a high-permeability sand-filled model to over 90% of its initial value.

Adsorption Layer Properties and Foam Behavior of Aqueous Solutions of Whey Protein Isolate (WPI) Modified by Vacuum Cold Plasma (VCP)

For years, cold plasma processing has been used as a non-thermal technology in industries such as food. As interfacial properties of protein play a remarkable role in many processes, this study investigates the effect of cold plasma on the foaming and interfacial behavior of WPI. The objective of this study is to evaluate the effect of different gases (air, 1:1 argon–air mixture, and sulfur hexafluoride (SF6)) used in low-pressure cold plasma (VCP) treatments of whey protein isolate (WPI) on the surface and foaming behavior of aqueous WPI solutions. Dynamic surface dilational elasticity, surface tension isotherms, surface layer thickness, and the foamability and foam stability were investigated in this study. VCP treatment did not significantly affect the adsorption layer thickness. However, an increase in induction time, surface pressure equilibrium value, and aggregated size is observed after SF6VCP treatment, which can be attributed to the reaction of WPI with the reactive SF6 species of the cold plasma. The surface dilational elastic modulus increased after VCP treatment, which can be related to the increased mechanical strength of the protein layer via sulfonation and aggregate formation. VCP treatment of WPI increases the foam stability, while the average diameter of foam bubbles and liquid drainage in the foam depends on the gas used for the cold plasma.

Self-Assembly of Amphiphilic PDI and NDI Derivatives with Opposite Thermoresponsive Fluorescent Behaviors in Aqueous Solution.

This work presents a study of the thermally induced aggregation of perylene diimide (PDI) and naphthalene diimide (NDI) derivatives modified with oligo ethylene glycol (OEG) chains in aqueous solution. Water-soluble and flexible OEG side chains were introduced into the π-core of glutamate-modified NDI and PDI structures, and the aggregation process was modulated by heating or cooling in water. Interestingly, a rare opposite temperature response of fluorescent behavior from the two amphiphilic chromophores was revealed, in which the PDI exhibited fluorescent enhancement, while fluorescent quenching upon temperature increase was observed from the NDI assembly. The mechanism of thermally induced aggregation is clearly explained by studies with various spectroscopic techniques including UV-visible, fluorescence, 1H NMR, 2D NMR spectroscopy, and SEM observation as well as control experiments operated in DMSO solution. It is found that although similar J-aggregates were formed by both amphiphilic chromophores in aqueous solution, the temperature response of the aggregates to temperature was opposite. The degree of PDI aggregation decreased, while that of NDI increased upon temperature rising. This research paves a valuable way for understanding the complicated supramolecular behaviors of amphiphilic chromophores.

Water-soluble dye – ZnII octacarboxy substituted tetrapyrazinoporphyrazine: Spectral-luminescence study of behavior in aqueous solutions

ZnII complex of octacarboxy substituted tetrapyrazinoporohyrazine, ZnTPyzPA(COOH)8, was prepared by mild alkaline hydrolysis of the corresponding octaethyl ester, ZnTPyzPA(COOEt)8, which was synthesized by template cycloteramerization of 5,6-di(ethoxycarbonyl)pyrazine-2,3-dicarbonitrile in the presence zinc(II) acetate in o-dichlorobenzene. Both complexes were characterized by IR, UV–vis, NMR spectroscopy (1H, 13C). Conformational analysis performed by DFT method in agreement with spectral study indicates that one of COOH group in each pyrazine ring participates in intramolecular hydrogen bonding with the adjacent pyrazine nitrogen atom. Unlike octacarboxy substituted ZnII phthalocyanine, ZnTPyzPA(COOH)8 remains non-aggregated not only in the octaanionic form present in the basic medium but also in tetraanioinic form existing in acid aqueous solutions since intramolecular H-bonding prevents intermolecular interactions. However, the fluorescence is almost completely quenched for tetraanion which can be related to the proton transfer in the excited state from carboxylic group to the pyrazine nitrogen. Aggregation is observed only for non-ionized form of ZnTPyzPA(COOH)8 existing in strongly acidic medium (1 M HCl solution, pH < 1).

Structure and self-diffusivity of mixed-cation electrolytes between neutral and charged graphene sheets.

Graphene-based applications, such as supercapacitors or capacitive deionization, take place in an aqueous environment, and they benefit from molecular-level insights into the behavior of aqueous electrolyte solutions in single-digit graphene nanopores with a size comparable to a few molecular diameters. Under single-digit graphene nanoconfinement (smallest dimension <2nm), water and ions behave drastically different than in the bulk. Most aqueous electrolytes in the graphene-based applications as well as in nature contain a mix of electrolytes. We study several prototypical aqueous mixed alkali-chloride electrolytes containing an equimolar fraction of Li/Na, Li/K, or Na/K cations confined between neutral and positively or negatively charged parallel graphene sheets. The strong hydration shell of small Li+ vs a larger Na+ or large K+ with weaker or weak hydration shells affects the interplay between the ions's propensity to hydrate or dehydrate under the graphene nanoconfinement and the strength of the ion-graphene interactions mediated by confinement-induced layered water. We perform molecular dynamics simulations of the confined mixed-cation electrolytes using the effectively polarizable force field for electrolyte-graphene systems and focused on a relation between the electrochemical adsorption and structural properties of the water molecules and ions and their diffusion behavior. The simulations show that the one-layer nanoslits have the biggest impact on the ions' adsorption and the water and ions' diffusion. The positively charged one-layer nanoslits only allow for Cl- adsorption and strengthen the intermolecular bonding, which along with the ultrathin confinement substantially reduces the water and Cl- diffusion. In contrast, the negatively charged one-layer nanoslits only allow for adsorption of weakly hydrated Na+ or K+ and substantially break up the non-covalent bond network, which leads to the enhancement of the water and Na+ or K+ diffusion up to or even above the bulk diffusion. In wider nanoslits, cations adsorb closer to the graphene surfaces than Cl-'s with preferential adsorption of a weakly hydrated cation over a strongly hydrated cation. The positive graphene charge has an intuitive effect on the adsorption of weakly hydrated Na+'s or K+'s and Cl-'s and a counterintuitive effect on the adsorption of strongly hydrated Li+'s. On the other hand, the negative surface charge has an intuitive effect on the adsorption of both types of cations and only mild intuitive or counterintuitive effects on the Cl- adsorption. The diffusion of water molecules and ions confined in the wider nanoslits is reduced with respect to the bulk diffusion, more for the positive graphene charge, which strengthened the intermolecular bonding, and less for the negative surface charge, which weakened the non-covalent bond network.

Hydration numbers of biologically relevant divalent metal cations from abinitio molecular dynamics and continuum solvation methods.

Hydration and, in particular, the coordination number of a metal ion is of paramount importance as it defines many of its (bio)physicochemical properties. It is not only essential for understanding its behavior in aqueous solutions but also determines the metal ion reference state and its binding energy to (bio)molecules. In this paper, for divalent metal cations Ca2+, Cd2+, Cu2+, Fe2+, Hg2+, Mg2+, Ni2+, Pb2+, and Zn2+, we compare two approaches for predicting hydration numbers: (1) a mixed explicit/continuum DFT-D3//COSMO-RS solvation model and (2) density functional theory based abinitio molecular dynamics. The former approach is employed to calculate the Gibbs free energy change for the sequential hydration reactions, starting from [M(H2O)2]2+ aqua complexes to [M(H2O)9]2+, allowing explicit water molecules to bind in the first or second coordination sphere and determining the most stable [M(H2O)n]2+ structure. In the latter approach, the hydration number is obtained by integrating the ion-water radial distribution function. With a couple of exceptions, the metal ion hydration numbers predicted by the two approaches are in mutual agreement, as well as in agreement with the experimental data.