Aqueous Solution Interface Research Articles

Three- and four-electrode EIS analysis of water stable lithium electrode with solid electrolyte plate

The properties of interfaces of water-stable lithium electrode have been investigated by EIS in Li–air batteries and four-electrode test-cells. The water-stable lithium electrode was prepared with the protection of NASICON-type glass–ceramic plate [0.8Li2O·0.25Al2O3·1.5GeO2·1.5P2O5 glass–ceramic (LAGP)]. The glass–ceramic plates are water-stable and 200–500μm thick with ion-conductivity of 4×10−4Scm−1. In Li–air batteries, the AC impedance spectra of LAGP protected lithium electrode contained two semicircles and became three after one week. The composition of impedance of LAGP protected lithium electrode was analyzed, by comparison on the impedance spectra of LAGP protected lithium electrode and bare Li metal electrode in organic electrolyte. Furthermore, in four-electrode test-cell which excluded the LAGP|aqueous-solution interface, the interface impedance of LAGP plate was analyzed. And then by the analysis of impedance, the Li|organic-electrolyte interface caused the main impedance of the water-stable lithium electrode during the discharge. The impedance of water-stable lithium electrode should be decreased by the study of new electrolyte and interface modification.

Reaction of Ferricyanide and Methyl Viologen with Free Radicals Produced by Ultrasound in Aqueous Solutions

The redox reactions of organic radicals, with Fe(CN)63− and methyl viologen, generated from the sonochemical decomposition of aliphatic alcohols in aqueous solutions, have been studied. The number of radicals produced was found to relate to the amount of adsorbed alcohol molecules (Gibbs surface excess) at the gas−aqueous solution interface for any bulk solution concentration of the alcohol. The majority of the radicals produced stem from the thermal degradation of the alcohol molecules that have entered imploding cavitation bubbles. The maximum rate of reduction at 355 kHz, of Fe(CN)63−, was 2.6 ± 0.3 μM min−1, whereas for methyl viologen, it was 1.2 ± 0.3 μM min−1 under the conditions used.The difference in the rates is attributed to the reaction of various pyrolytically produced organic radicals with the methyl viologen radical cation. The possible reactions occurring in the sonolysis of alcohol/water systems are discussed in detail.

Surface charging patterns of stainless alloys – Effect of ageing in conditions of primary cooling circuit of pressurized water reactors

The predominance of electrostatic interactions in the mechanism of particle deposition onto solid surfaces is well documented. Therefore, an electrostatic approach has been used to predict the behavior of activated corrosion products in the primary cooling circuit of a pressurized water reactor (PWR). Only few results have been published on the potential at the interface of metallic alloys and aqueous solutions, even at room temperature. In this study, we present results about the characterization of representative materials such as Inconel 690, stainless steel 304 and Zircaloy 4 at room temperature, for pristine polished samples as well as after an 80-day ageing step in physico-chemical conditions similar to those of a primary circuit (360°C, boron 1gL−1 (as H3BO3), lithium 2mgL−1 (as LiOH), hydrogen 30cm3kg−1). The surface potentials of these alloys have been determined using a streaming current method for pH from 3 to 7. Isoelectric points between 4.1 and 4.6 have been found for all samples and there is no effect of the ageing step. These values have been confirmed by adhesion studies of grafted latex particles either positively charged (amidine surface groups) or negatively charged (carboxylate groups) at pH 3.3 and pH 5.5. The results show that particles deposition is favored only when they carry a charge opposite to the substrate surfaces.

A simple strategy to monitor lipase activity using liquid crystal-based sensors

In this study, we developed a simple label-free technique for monitoring the enzymatic activity of lipase using liquid crystal (LC)-based sensors. The optical response of LCs changed from a bright to dark appearance when an aqueous solution of lipase was in contact with a nematic LC, 4-cyano-4′-pentylbiphenyl (5CB), that was doped with glyceryl trioleate, which is a glyceride that can be enzymatically hydrolyzed by lipase. Since the oleic acid released from the enzymatic reaction could spontaneously form a self-assembled monolayer at the aqueous/LC interface due to its amphiphilic property, the orientation of the LCs transited from a planar to homeotropic state, which induced a change in the optical response of the LCs. We did not observe a bright-to-dark shift in the optical appearance of LCs when pure 5CB was immersed into the lipase solution. Moreover, we further confirmed the specificity of the enzymatic reaction by transferring an aqueous buffer solution not containing an analyte, or with bovine serum albumin (BSA) or trypsin onto the interface of aqueous solutions and the glyceryl trioleate-doped 5CB, which did not produce any distinctive contrast in the optical appearance. These results suggest the feasibility of measuring the enzymatic activity of lipase using the LC-based sensing technique. Furthermore, our strategy could also be used for the preparation of a self-assembled monolayer of carboxylates at the aqueous/LC interface.

Charge transport at the interface of n-GaAs (100) with an aqueous HCl solution: Electrochemical impedance spectroscopy study

Charge transport processes at the interface of n-GaAs (100) with an aqueous HCl solution are studied by electrochemical impedance spectroscopy. It is found that when open-circuit potential and anodic potentials are applied to the semiconductor the impedance spectra contain two capacitive semicircles corresponding to the capacitances of the space charge layer and surface states. In the case of open-circuit potential, semiconductor band bending at the interface with the solution is about 0.7 eV and the density of occupied surface states in the dark and under daylight conditions is 1.6 and 2.8 × 1012 cm2 eV−1, respectively. When cathode potentials are applied to GaAs, hydrogen evolution begins at the semiconductor/electrolyte interface and an additional inductive loop appears in the impedance spectra. At the same time, the density of occupied surface states increases considerably both due to a straightening of the semiconductor bands and to the appearance of As-H bonds. Thus, charge transport through the n-GaAs (100)/aqueous HCl solution interface is always mediated by semiconductor surface states.

Crystal Growth of Clathrate Hydrate at the Interface between Seawater and Hydrophobic-Guest Liquid: Effect of Elevated Salt Concentration

This paper reports the visual observations of the clathrate hydrate crystal growth and morphology at the interface of aqueous NaCl solutions and a guest-substance liquid. The hydrate crystal growth was visually characterized in the systems of a wide range of NaCl concentrations from 0.035 to 0.264 in mass fraction. The mass fraction 0.035 was corresponding to that of ordinary seawater, and the salt concentration tested was extended up to the saturation level, i.e., 0.264. Cyclopentane was used as the guest substance. Formation and growth of hydrate crystals at the cyclopentane-NaCl solution interface were observed. We visually analyzed the individual hydrate crystals and classified the morphology of the crystals according to ΔTsub at atmospheric pressure. It was found that the size of the individual hydrate crystals decreased with increasing ΔTsub. The results showed that the morphology of the individual hydrate crystals in any NaCl concentration is roughly similar at a given ΔTsub. We also measured the l...

In situ imaging of orthoclase–aqueous solution interfaces with x-ray reflection interface microscopy

The use of x-ray reflection interface microscopy (XRIM) to image molecular-scale topography at the aqueous–solid interface, in situ, is described. Specifically, we image interfacial topography of the orthoclase-(001)–aqueous solution interface at room temperature and describe the challenges associated with in situ XRIM imaging. The measurements show that the reflectivity signal for in situ XRIM measurements is substantially smaller than that for ex situ measurements, because of both intrinsic and extrinsic factors. There is also a systematic temporal reduction in the image intensity with increasing x-ray dose, revealing that interaction of the focused x-ray beam with the orthoclase interfaces leads to interfacial perturbations, presumably in the form of surface roughening. This image fading is localized to the x-ray beam footprint, suggesting that the primary damage mechanism is initiated by photoelectrons produced by x-ray beam absorption near the substrate–electrolyte interface. Finally, the role of aqueous solution composition in controlling the sensitivity of the orthoclase surface to x-ray beam-induced effects is explored. A substantial increase in the orthoclase (001) surface stability was observed in solutions having elevated ionic strength, apparently as a result of the reduced lifetime of radiation chemistry products at these conditions.

Calcite growth kinetics: Modeling the effect of solution stoichiometry

Until recently the influence of solution stoichiometry on calcite crystal growth kinetics has attracted little attention, despite the fact that in most aqueous environments calcite precipitates from non-stoichiometric solution. In order to account for the dependence of the calcite crystal growth rate on the cation to anion ratio in solution, we extend the growth model for binary symmetrical electrolyte crystals of Zhang and Nancollas (1998) by combining it with the surface complexation model for the chemical structure of the calcite–aqueous solution interface of Wolthers et al. (2008). To maintain crystal stoichiometry, the rate of attachment of calcium ions to step edges is assumed to equal the rate of attachment of carbonate plus bicarbonate ions. The model parameters are optimized by fitting the model to the step velocities obtained previously by atomic force microscopy (AFM, Teng et al., 2000; Stack and Grantham, 2010). A variable surface roughness factor is introduced in order to reconcile the new process-based growth model with bulk precipitation rates measured in seeded calcite growth experiments. For practical applications, we further present empirical parabolic rate equations fitted to bulk growth rates of calcite in common background electrolytes and in artificial seawater-type solutions. Both the process-based and empirical growth rate equations agree with measured calcite growth rates over broad ranges of ionic strength, pH, solution stoichiometry and degree of supersaturation.

Synthesis and assembly of gold nanoparticle-doped polymer solid foam films at the liquid/liquid interface and their catalytic properties

Gold nanoparticle-doped poly(2-vinylpyridine) (P2VP) microcapsules and foam films were synthesized and assembled at the P2VP chloroform solution/HAuCl4 aqueous solution interface at 25°C. It was found that Au nanoparticles with the average diameter of 2.1nm were homogeneously embedded in and adsorbed on the walls of the capsules and foams, the nanoparticles were composed of Au(0) and Au(III) with the molar ratio of about 75/25, and the mass percent of Au elements was measured to be 19.65%. The formation of the nanostructures was attributed to the self-assembly of P2VP at the liquid/liquid interface, the simultaneous reduction of AuCl4- ions by a small amount of ethanol in the chloroform and adsorption of AuCl4- ions. After irradiated by UV-light for 1h, the average diameter of the nanoparticles was found to be 2.2nm, and the AuCl4- ions were transformed to Au(0) completely. The catalytic performance of these composite nanostructures were evaluated by using the reduction of 4-nitrophenol (4-NP) by potassium borohydride in aqueous solutions. The catalytic activity was very high in the first cycle, decreased rapidly and slightly in the second and third cycles, respectively, due to the aggregation of some nanoparticles, and stabilized after the third cycle.

Effect of solution temperature and ph on adsorption and density of surface charge at aluminum oxyhydroxide /NaF aqueous solution interface

The effect of temperature, pH, and adsorbed fluorine on the density of a surface charge at the aluminum oxyhydroxide /NaF aqueous solution interface is investigated using the method of potentiometric titration. The equilibrium of fluorine ion adsorption in analyzed. Products of electrochemical dimensional machining (ECDM) of an AMG-6 aluminum alloy thermally treated at 200°C are used as an adsorbent. The experiments on the adsorption have been carried out from an acetated buffer with the initial fluorine solution concentrations from 1.0 × 10−3 to 1.5 × 10−1 M/l. The adsorption isotherms were plotted for solution temperatures of 20, 30, and 40°C. Adsorption is shown to obey the Langmuir adsorption model. It is demonstrated that, at all solution temperatures, the pH is 5 for the maximal fluorine adsorption on aluminum oxyhydroxide. It has been revealed that the surface charge at the aluminum oxyhydroxide /NaF aqueous solution interface depends on the solution temperature; i.e., the pH of a point of a zero charge point (pHPZC) of the aluminum oxyhydroxide surface decreases with an increase in temperature. As is the case with temperature, adsorbed fluorine shifts pHPZC toward smaller values, which is typical for specific adsorption. The temperature dependence of pHPZC has made it possible to determine the standard mole enthalpy and entropy of surface-charge formation. The interaction of fluorine with aluminum oxyhydroxide is shown to be the result of the chemical affinity of F with surface centers of AlOH2+ and AlOH and electrostatic attraction.

Aqua Ions–Graphene Interfacial and Confinement Behavior: Insights from Isobaric–Isothermal Molecular Dynamics

We carry out a systematic microstructural characterization of the solid-fluid interface (SFI) of water and simple metal chloride aqueous solutions in contact with a free-standing plate or with two such plates separated by an interplate distance 0 ≤ h (Å) ≤ 30 at ambient conditions via isothermal-isobaric molecular dynamics. With this characterization, we target the interrogation of the system in search for answers to fundamental questions regarding the structure of the "external" and "internal" (confined) SFIs, the effect of the differential hydration behavior among species, and its link to species expulsion from confinement. For water at ambient conditions, we found that the structure of the "external" SFIs is independent of the interplate distance h in the range 0 ≤ h (Å) ≤ 30, that is, the absence of wall-mediated correlation effects between "external" and "internal" SFIs, and that for h < 9 Å the slit-pores dewet. Moreover, we observed a selective expulsion of ions caused by the differential hydration between the anion and the cations with a consequent charging of the slit-pore. All these observations were interpreted in terms of the axial profiles for precisely defined order parameters, including tetrahedral configuration, hydrogen bonding, and species coordination numbers.

Halide Affinity for the Water−Air Interface in Aqueous Solutions of Mixtures of Sodium Salts

The water-air interface plays a critical role in many physical and chemical processes of the Earth's atmosphere. In particular, heavy halide ions are strongly involved in processes of fundamental importance in determining the prevalence of many atmospheric components through heterogeneous reactions at the water-air interface. In this work, molecular dynamics simulations are used to study the halide enhancements at the water-air interface in the case of mixtures of Cl(-), Br(-), and I(-) ions. The results show a pattern of enhancement directly correlated to the anion polarizability. This effect is explained in terms of the charge distribution across the slab resembling an electrical double layer. As a result, the anions with higher polarizability lower the system's potential energy by enhancing their presence at the interface.

Molecular dynamics simulations of aqueous ions at the liquid–vapor interface accelerated using graphics processors

Molecular dynamics (MD) simulations are a vital tool in chemical research, as they are able to provide an atomistic view of chemical systems and processes that is not obtainable through experiment. However, large-scale MD simulations require access to multicore clusters or supercomputers that are not always available to all researchers. Recently, scientists have returned to exploring the power of graphics processing units (GPUs) for various applications, such as MD, enabled by the recent advances in hardware and integrated programming interfaces such as NVIDIA's CUDA platform. One area of particular interest within the context of chemical applications is that of aqueous interfaces, the salt solutions of which have found application as model systems for studying atmospheric process as well as physical behaviors such as the Hoffmeister effect. Here, we present results of GPU-accelerated simulations of the liquid-vapor interface of aqueous sodium iodide solutions. Analysis of various properties, such as density and surface tension, demonstrates that our model is consistent with previous studies of similar systems. In particular, we find that the current combination of water and ion force fields coupled with the ability to simulate surfaces of differing area enabled by GPU hardware is able to reproduce the experimental trend of increasing salt solution surface tension relative to pure water. In terms of performance, our GPU implementation performs equivalent to CHARMM running on 21 CPUs. Finally, we address possible issues with the accuracy of MD simulaions caused by nonstandard single-precision arithmetic implemented on current GPUs.

PLUNC Is a Novel Airway Surfactant Protein with Anti-Biofilm Activity

BackgroundThe PLUNC (“Palate, lung, nasal epithelium clone”) protein is an abundant secretory product of epithelia present throughout the conducting airways of humans and other mammals, which is evolutionarily related to the lipid transfer/lipopolysaccharide binding protein (LT/LBP) family. Two members of this family - the bactericidal/permeability increasing protein (BPI) and the lipopolysaccharide binding protein (LBP) - are innate immune molecules with recognized roles in sensing and responding to Gram negative bacteria, leading many to propose that PLUNC may play a host defense role in the human airways.Methodology/Principal FindingsBased on its marked hydrophobicity, we hypothesized that PLUNC may be an airway surfactant. We found that purified recombinant human PLUNC greatly enhanced the ability of aqueous solutions to spread on a hydrophobic surface. Furthermore, we discovered that PLUNC significantly reduced surface tension at the air-liquid interface in aqueous solutions, indicating novel and biologically relevant surfactant properties. Of note, surface tensions achieved by adding PLUNC to solutions are very similar to measurements of the surface tension in tracheobronchial secretions from humans and animal models. Because surfactants of microbial origin can disperse matrix-encased bacterial clusters known as biofilms [1], we hypothesized that PLUNC may also have anti-biofilm activity. We found that, at a physiologically relevant concentration, PLUNC inhibited biofilm formation by the airway pathogen Pseudomonas aeruginosa in an in vitro model.Conclusions/SignificanceOur data suggest that the PLUNC protein contributes to the surfactant properties of airway secretions, and that this activity may interfere with biofilm formation by an airway pathogen.

Adsorption of adipic acid conjugates at the Au(1 1 1) electrode|aqueous solution interface

The adsorption of adipic acid, an aliphatic dicarboxylic acid, has been studied at the Au(1 1 1) electrode|aqueous solution interface by cyclic voltammetry, chronocoulometry and in situ infrared spectroscopy. The voltammograms recorded at different pH values in adipic acid, biadipate and adipate solutions point to the adsorption of anionic species. A potential dependent order–disorder phase transition is apparent from the voltammetric curves, the transition potential being directly influenced by the solution pH. From infrared spectra it is concluded that as the electrode potential is made more positive, the amount of carboxylic groups in the adsorbed layer increases. The maximum surface excess concentration, Γ = (4.4 ± 0.6) × 10 −10 mol cm −2, and the adsorption free energy, −Δ ads G = 125–190 kJ mol −1, have been determined by a thermodynamic analysis of the chronocoulometric data.

Ion-size effect within the aqueous solution interface at the Pt(111) surface: molecular dynamics studies

All-atom classical force-field based molecular dynamics simulations have been employed to investigate the structure and dynamics of interfacial water in systems of pure water, 1 M LiOH and 1 M KOH aqueous solutions at an uncharged Pt(111) surface. Results indicate that the ordering of water molecules is affected as far as 9 Å from the Pt surface, corresponding to three layers of water molecules. Specific packing geometries of water in electrolyte solutions depend on the ionic radius, and both Li(+) and K(+) ions are found to adsorb directly onto the Pt surface. Significantly higher values of the water-dipole autocorrelation function in the adlayer are found for the system with Li(+) ions compared to the systems with K(+) ions or pure water. Also strongly reduced translational motion is observed in the case of Li(+), both in-plane and perpendicular to the surface. This result suggests a strong stabilizing role of Li(+) ions on water molecules. Decreased mobility of the water adlayer makes it difficult for other compounds in the aqueous solution to access the Pt surface. This implies that the reason for the reduced catalytic activity of Pt(111) surface in the presence of LiOH is due to the freezing effect Li(+) ions have on water.

Silver dendritic nanostructures formed at the solid/liquid interface via electroless deposition

Silver dendritic nanostructures and nanoplates were prepared at the solid/liquid interfaces via electroless deposition. Langmuir monolayers of 5,10,15,20-tetra-4-oxy(2-stearic acid) phenyl porphyrin (TSPP) and arachidic acid (AA) were formed at the air/AgNO 3 aqueous solution interface. These nanostructures were produced when carbon-coated copper grids were covered on the Langmuir monolayers at lower (<20 °C) and higher (20–50 °C) temperature, respectively, and the branches are composed of parallel aligned nanobelts with their (110) face parallel to the interface. The formation of the nanostructures should be attributed to the galvanic reduction of Ag + ions by copper, the electronic conductivity of the carbon layer, the templating effect of the Langmuir monolayer, and the non-equilibrium growth and aggregation of silver nanoparticles at the interface. This is a convenient avenue to produce metal nanostructures.

Voltammetrically Controlled Electron Transfer Reactions from Alkanethiol Modified Gold Electrode Surfaces to Low Molecular Weight Molecules Deposited within Lipid (Lecithin) Bilayers

A procedure was developed for initiating electron transfer from a gold electrode to a low molecular weight electron acceptor present inside supported lipid (lecithin) bilayers, followed by further electron transfer to an electron acceptor present in an aqueous solution. The electron acceptors present in the lecithin bilayers and aqueous phase were 7,7,8,8-tetracyanoquinodimethane (TCNQ) and [Fe(III)(CN)(6)](3-), respectively. A polished planar gold disk electrode was first coated via self-assembly procedures with an alkanethiol monolayer. A phospholipid layer consisting of multiple bilayers of lecithin containing TCNQ was subsequently deposited onto the alkanethiol monolayer. The Au/alkanethiol/lecithin-TCNQ electrode was placed in an aqueous solution containing various amounts of [Fe(III)(CN)(6)](3-) and [Fe(II)(CN)(6)](4-), with 0.5 M KCl as the supporting electrolyte. In the absence of TCNQ inside the alkanethiol/lecithin layers, only a small background current was observed. When TCNQ was included in the alkanethiol/lecithin layers, the voltammetry showed features typical of a catalytic process, due to the TCNQ being reduced to TCNQ(-*) within the lecithin bilayers and then undergoing oxidation back to TCNQ via interaction with [Fe(III)(CN)(6)](3-) at the lecithin-aqueous solution interface. The procedures for preparing the alkanethiol/lecithin-TCNQ coatings were optimized in order to obtain the most reproducible voltammetric response. Experiments were also performed using tetrathiafulvalene (TTF) as an electron donor in the lipid bilayer phase.

Nonequilibrium Phase Transformations at the Air−Liquid Interface

A theoretical model is presented for the formation of an ordered phase close to the air-liquid interface of an open binary aqueous solution. The chemical potential of water in the liquid phase is, in general, not equal to the chemical potential of water in the ambient atmosphere. There are therefore nonequilibrium conditions close to the air-liquid interface. There is also a gradient in the chemical potential of water, which could lead to the formation of a new interfacial phase. The formation of an interfacial phase is analyzed in terms of the equilibrium phase behavior corresponding to the local water chemical potential. The possibility of forming an interfacial phase is strongly dependent on the ambient conditions, bulk composition, and diffusive transport properties of the phases in question. Explicit calculations are presented for the formation of a lamellar liquid-crystalline phase close to the air-liquid interface of an isotropic surfactant solution with parameters chosen from the sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/water system. We consider the relevance of the model to neutron reflectivity studies of the interface between air and surfactant/water systems, as well as to surfactant/polymer/water systems.

On the fluctuations that drive small ions toward, and away from, interfaces between polar liquids and their vapors

Contrary to the expectations from classic theories of ion solvation, spectroscopy and computer simulations of the liquid-vapor interface of aqueous electrolyte solutions suggest that ions little larger than a water molecule can prefer to reside near the liquid's surface. Here we advance the view that such affinity originates in a competition between strong opposing forces, primarily due to volume exclusion and dielectric polarization, that are common to all dense polar liquids. We present evidence for this generic mechanism from computer simulations of (i) water and (ii) a Stockmayer fluid near its triple point. In both cases, we show that strong surface enhancement of small ions, obtained by tuning solutes' size and charge, can be accentuated or suppressed by modest changes in either of those parameters. Statistics of solvent polarization, when the ion is held at and above the Gibbs dividing surface, highlight a basic deficiency in conventional models of dielectric response, namely, the neglect of interfacial flexibility. By distorting the solution's boundary, an ion experiences fluctuations in electrostatic potential and in electric field whose magnitudes attenuate much more gradually (as the ion is removed from the liquid phase) than for a quiescent planar interface. As one consequence, the collective responses that determine free energies of solvation can resolve very differently in nonuniform environments than in bulk. We show that this persistence of electric-field fluctuations additionally shapes the sensitivity of solute distributions to ion polarizability.