Range Of Electrolyte Concentrations Research Articles

Cation-induced morphological transitions and aggregation of thermoresponsive PNIPAM nanogels

Poly(N-isopropylacrylamide) (PNIPAM) nanogels are promising responsive colloidal particles that can be used in pharmaceutical applications as drug carriers. This work investigates the temperature-dependent morphological changes and agglomeration of PNIPAM nanogels in the presence of mono- and multi-valent cationic electrolytes. We described the deswelling, flocculation, thermal reversibility behaviour and aggregated morphology of PNIPAM nanogels over a range of electrolyte concentrations and temperatures revealing the critical transition points from stable suspension to spontaneous agglomeration. We demonstrated that the flocculating ability and the rate of aggregate formation follow the order of deswelling behaviour. Transmission electron microscopy and atomic force microscopy analysis revealed the presence of a shell-like layer with varying density in the multivalent electrolyte solutions when compared to those in aqueous medium. We identified a concentration threshold of the thermally induced reversible aggregation/dispersion for the PNIPAM nanogels in the presence of Na+ and K+ ions at 10 mM, for Mg2+ and Ca2+ ions at 1 mM and for Al3+ ions at 0.1 mM concentrations. Such concentration thresholds indicated the effective destabilization of the electrolyte system with multivalency following the Schulze–Hardy rule. Our findings were supported by applying a Debye screening model that accounts for the shielding effect of multivalent cationic electrolytes on these nanogel systems. Our experiments and the models confirmed the compression of the electric double layer as the valency and ionic strength increased, except for Al3+ at higher concentrations which seemed to disrupt the electrical double layer and cause reversal of zeta potential. Our work highlights the significant impact the presence of multivalent cations can impose on the stability and morphology of nanogels, and this understanding will help in designing responsive nanogel systems based on PNIPAM nanogels.

Advanced approach of forming cutting edge radii on cemented carbide cutting tools using plasma discharges in electrolyte

The paper deals with the task of preparing cutting edge microgeometry. Unconventional methods for edge preparation are presented, and an overview of articles, patents, and reports that deal with modern and advanced approaches are stated. Moreover, an innovative cutting edge preparation method using plasma discharges in an electrolyte was examined. The main aim was to determine the effect of the process parameters, namely electrolyte concentration, the temperature of the electrolyte, the voltage between electrodes and the operating time, on the shape and size of the cutting edge rounding as well as surface roughness and topography. The tested type of cutting tool was cutting insert. The cutting inserts were made of cemented carbide (WC + Co). It was examined that cutting edge radius sizes were strongly affected by the process parameter of plasma discharges in electrolyte as well as the shape of rounding. However, specific types of defects can occur on the cutting edge after edge preparation using plasma discharges in electrolyte. These defects can be avoided by correctly setting the process parameters. From the results of the experimental research, it was confirmed that cutting edges can be rounded without defects in the entire range of electrolyte concentration, but the setting of voltage and temperature of the electrolyte must be simultaneously considered. Furthermore, decreasing the electrolyte concentration, the temperature of the electrolyte and the voltage between electrodes resulted in a larger cutting edge radius. Cutting edge preparation using plasma discharges in electrolyte takes only a few seconds, depending on the cutting edge radius sizes. Cutting edge radii with a value of 20 μm were manufactured in 30 s. This innovative advanced edge preparation method is one of the most productive edge preparation methods. An even more important aspect is not to burden the environment with hazardous waste such as acids because this electrolyte solution can be prepared by dissolving a small amount of salt in tap water. The issue of the topography of the surface of cemented carbides after PDE treatment should be expecially heeded.

Surface tension of aqueous electrolyte solutions. A thermomechanical approach.

We determine the surface tension of aqueous electrolyte solutions in contact with non-polar dielectric media using a thermomechanical approach, which involves deriving the stress tensor from the thermodynamic potential of an inhomogeneous fluid. To obtain the surface tension, we calculate both the normal and tangential pressures using the components of the stress tensor, recently derived by us [Y. A. Budkov and P. E. Brandyshev, J. Chem. Phys. 159, 174103 (2023)] within the framework of Wang's variational field theory. Using this approach, we derive an analytical expression for the surface tension in the linear approximation. At low ionic concentrations, this expression represents the classical Onsager-Samaras limiting law. By utilizing only one fitting parameter, which is related to the affinity of anions to the dielectric boundary, we successfully approximated experimental data on the surface tension of several aqueous electrolyte solutions. This approximation applies to both the solution-air and solution-dodecane interfaces, covering a wide range of electrolyte concentrations.

Relation between Double Layer Structure, Capacitance, and Surface Tension in Electrowetting of Graphene and Aqueous Electrolytes.

Deciphering the mechanisms of charge storage on carbon-based materials is pivotal for the development of next-generation electrochemical energy storage systems. Graphene, the building block of graphitic electrodes, is an ideal model for probing such processes on a fundamental level. Herein, we investigate the thermodynamics of the graphene/aqueous electrolyte interface by utilizing a multiscale quantum mechanics-classical molecular dynamics (QM/MD) approach to provide insights into the effect of alkali metal ion (Li+) concentration on the interfacial tension (γSL) of the charged graphene/electrolyte interface. We demonstrate that the dependence of γSL on the applied surface charge exhibits an asymmetric behavior relative to the neutral surface. At the positively charged graphene sheet, the electrowetting response is amplified by electrolyte concentration, resulting in a strongly hydrophilic surface. On the contrary, at negative potential bias, γSL shows a weaker response to the charging of the electrode. Changes in γSL greatly affect the total areal capacitance predicted by the Young-Lippmann equation but have a negligible impact on the simulated total areal capacitance, indicating that the EDL structure is not directly correlated with the wettability of the surface and different interfacial mechanisms drive the two phenomena. The proposed model is validated experimentally by studying the electrowetting response of highly oriented pyrolytic graphite over a wide range of electrolyte concentrations. Our work presents the first combined theoretical and experimental study on electrowetting using carbon surfaces, introducing new conceptual routes for the investigation of wetting phenomena under potential bias.

Optimized synthesis of cysteine-functionalized nanocrystalline hydroxyapatite for synchronous decontamination of Cd(II) and Pb(II)

The synchronous removal of toxic heavy metals (e.g., cadmium (Cd), lead (Pb), and etc.) from the contaminated water environment is an urgent demand in the pollution control field. Herein, an innovative adsorbent synthesis idea was proposed and a series of cysteine-functionalized nanohydroxyapatite (CysHAP) composites were prepared by adopting different reaction temperatures, cysteine/HAP ratios, and synthesis methods. According to the single factor tests, a co-precipitation temperature of 25 °C with a molar cysteine/HAP ratio of 2.0 was selected to synthesize the optimum CysHAP2.0–25 composite. Multiple characterization results showed that cysteine markedly altered the morphology, crystallinity, and crystal structure of HAP, leading to the formation of CysHAP2.0–25 composite with a superior dispersity, a smaller crystal size, a higher specific surface area, and a greater number of binding sites. Compared with HAP-25, the CysHAP2.0–25 composite exhibited a better Cd(II) sorption performance and a 100% Pb(II) removal in a wide range of solution pH and background electrolyte concentration. The removal performance of CysHAP2.0–25 composite towards Cd(II) was suppressed by the coexisting aqueous components with an obviously stronger inhibiting action of humic acid (HA) than low molecular weight organic acids (LMWOAs) and mixed inorganic components (IC). Pb(II) slightly reduced the sorption ratio of Cd(II) and forced Cd(II) to bind on the -SOx sites derived from sulfhydryl oxidation. In contrast, Cd(II) had no impact on the sorption behaviors of Pb(II). Overall, the synthesized CysHAP2.0–25 composite could be potential applied for the purification of Cd- and Pb-bearing water systems.

EFFECT OF ELECTROCHEMICAL PROCESS PARAMETERS ON THE HASTELLOY C-276 ALLOY FOR MACHINING SPEED AND SURFACE-CORROSION FACTOR

Electrochemical micromachining (ECMM) is a well know for manufacturing hard-to-cut materials, e.g., nickel-based alloys, titanium alloys and metal-matrix composites. For this reason it finds application in aerospace, automobile and biomedical industries. In this research Hastelloy C-276 is used as a workpiece and stainless-steel electrode coated with polytetrafluoroethylene (PTFE) to avoid stray current. The effect of process parameters such as voltage, duty cycle and electrolyte concentration on the machining speed and the surface-corrosion factor were studied. The range of 9–11 V has an impact on the machining speed. The electrolyte concentration range of 25–35 g/L shows a linear increase in the machining speed and the surface-corrosion factor is found to be highest at 1.1449 for an electrolyte concentration of 15g/L. The surface roughness depth profile depicts the values of Rz, Rt, Ra are 16.3 µm, 99.1 µm and 1.90 µm, and 15.4 µm, 50.6 µm and 1.49 µm, respectively.

Measurement Compensation Method for Wearable Microfluidic Sweat Sensors Toward Monitoring a Wide Range of Local Sweat Rates and Electrolyte Concentration

Measurement Compensation Method for Wearable Microfluidic Sweat Sensors Toward Monitoring a Wide Range of Local Sweat Rates and Electrolyte Concentration

A switchable ionic diode membrane enabled by sub-3 nm covalent organic framework channels

Various efforts have been made to mimic the regulatory properties of biological channels that exist in cell membranes of living organisms. Such ion channels are able to tune electric signals in response to changes in surrounding environments (e.g., pH or ions). Here, we report the design and fabrication of a novel pH-switchable ionic diode membrane (IDM), TFP-EB COF@PET, composed of a thin layer of sub-3 nm covalent organic framework (COF) channels and a polyethylene terephthalate (PET) membrane having conical nanochannels with tip size of 20–40 nm. The designed IDM is found to exhibit ion current rectification (ICR) over a wide range of electrolyte concentrations, attributable to its structural and charge asymmetries. Interestingly, the TFP-EB COF@PET can exhibit pH-switchable ion transport behaviors even though the surface charge natures of TFP-EB COF and PET channels remain unchanged. The mechanisms for the pH-switchable ICR properties are proposed to explain the inversion phenomenon. This work highlights the pH-switchable ionic transport properties of the sub-3 nm-scale COF-based IDM, as well as its potential for long-term operation under high salinity conditions.

Response Mechanism of Polymeric Liquid Junction-Free Reference Electrodes Based on Organic Electrolytes.

To achieve a transition from conventional liquid-junction reference electrodes (LJF REs) to their all-solid-state alternatives, organic electrolytes are often introduced into the polymeric electrode membranes. In this article, we implement a theoretical approach to the explanation and quantification of the boundary potential stabilization phenomenon for the electrodes modified with organic electrolytes (Q+B-). For the first time, stabilization of the phase boundary potential due to the partition of lipophilic ions of the Q+B- electrolyte between the polymeric and aqueous phases is numerically simulated to predict the LJF electrodes behavior. The impact of the hydrophilic electrolyte on the potential stabilization is demonstrated both numerically and experimentally. The developed model predicted that the small additions of a traditional ion-exchanger enhance performance of the Q+B--based reference electrodes. For some specific cases, the optimal concentrations of Q+B- and ion-exchanger in the polymeric phase are suggested to provide stable electrode potential in a broad range of aqueous electrolyte concentrations. In addition, the efficiency of the stabilization was shown to be dependent on the overall Q+B- load in the polymeric membrane rather than on the closeness of the partition coefficients of the Q+ and B- ions; and on the volume of the aqueous phase. The model results are verified experimentally with poly(vinyl chloride) membranes containing ion-exchanger or hydrophilic electrolyte and Q+B- in various proportions. A good agreement between the measured electrode response and the theoretical results is observed in a broad range of solution concentrations. In particular, the cationic function of membranes containing KTpClPB is suppressed, and the electrodes begin to behave as REs starting from 50-60 mol. % of ETH500 electrolyte added to the membrane, relative to the total amount of salt.

Gating ion and fluid transport with chiral solvent.

The development of modern membranes for ionic separations and energy-storage devices such as supercapacitors depends on the description of ions at solid interfaces, as is often provided by the electrical double layer (EDL) model. The classical EDL model ignores, however, important factors such as possible spatial organization of solvent at the interface and the influence of the solvent on the spatial dependence of the electrochemical potential; these effects in turn govern electrokinetic phenomena. Here we provide a molecular-level understanding of how solvent structure can dictate ionic distributions at interfaces using a model system of a polar, aprotic solvent, propylene carbonate, in its enantiomerically pure and racemic forms, at a silica interface. We link the interfacial structure to the tuning of ionic and fluid transport by the chirality of the solvent and the salt concentration. The results of nonlinear spectroscopic experiments and electrochemical measurements suggest that the solvent exhibits lipid-bilayer-like interfacial organization, with a structure that is dependent on the solvent chirality. The racemic form creates highly ordered layered structure that dictates local ionic concentrations, such that the effective surface potential becomes positive in a wide range of electrolyte concentrations. The enantiomerically pure form exhibits weaker ordering at the silica surface, which leads to a lower effective surface charge induced by ions partitioning into the layered structure. The surface charge in silicon nitride and polymer pores is probed through the direction of electroosmosis that the surface charges induce. Our findings add a new dimension to the nascent field of chiral electrochemistry, and emphasize the importance of including solvent molecules in descriptions of solid-liquid interfaces.

A New Force Field for OH- for Computing Thermodynamic and Transport Properties of H2 and O2 in Aqueous NaOH and KOH Solutions.

The thermophysical properties of aqueous electrolyte solutions are of interest for applications such as water electrolyzers and fuel cells. Molecular dynamics (MD) and continuous fractional component Monte Carlo (CFCMC) simulations are used to calculate densities, transport properties (i.e., self-diffusivities and dynamic viscosities), and solubilities of H2 and O2 in aqueous sodium and potassium hydroxide (NaOH and KOH) solutions for a wide electrolyte concentration range (0-8 mol/kg). Simulations are carried out for a temperature and pressure range of 298-353 K and 1-100 bar, respectively. The TIP4P/2005 water model is used in combination with a newly parametrized OH- force field for NaOH and KOH. The computed dynamic viscosities at 298 K for NaOH and KOH solutions are within 5% from the reported experimental data up to an electrolyte concentration of 6 mol/kg. For most of the thermodynamic conditions (especially at high concentrations, pressures, and temperatures) experimental data are largely lacking. We present an extensive collection of new data and engineering equations for H2 and O2 self-diffusivities and solubilities in NaOH and KOH solutions, which can be used for process design and optimization of efficient alkaline electrolyzers and fuel cells.

Modeling on the phase equilibrium of gas hydrate in electrolytes containing system

The phase equilibrium of gas hydrate is fundamental for flow assurance, energy exploitation, and hydrate concerning technique. In this study, the electrolyte NRTL equation coupled with the two-step hydrate model of Chen and Guo was successfully applied to predict the phase equilibrium of gas hydrate in the presence of single and binary mixed electrolytes. The predicted results were in good agreement with the available experimental data over a wide range of electrolyte concentrations when taking into account the contributions of long-range and short-range interactions in saline solution. Validated with 943 hydrate experimental data of pure gas and gas mixture formed in single and mixed electrolytes, the average absolute deviations in pressure are 5.42 % and 4.71 %, respectively. More importantly, it is further investigated that the proposed model shows a better performance for the high-concentration saline solution with concentration up to the near-saturation, with an average deviation of 0.59 K for methane hydrate. Therefore, the proposed model in this work is significant for comprehending gas hydrate phase behavior in saline solution, and provides better guidance for hydrate exploitation and industrial applications.

Electrolyte adsorption in graphene and hexagonal boron nitride nanochannels

Understanding the dynamics of confined electrolytes through graphene-based channels is essential in multiple fields of science including: (a) developing novel artificial membranes for drug delivery, DNA sequencing and water desalination and (b) developing quantum nanoelectronic devices. In this work, All-Atom molecular dynamics simulations are used to study the adsorption of confined NaCl electrolyte solutions in graphene (GR), hexagonal boron nitride (hBN) and combined GR-hBN-GR nano-channels over a wide range of electrolyte concentrations c∈(0.1,2) M. The behavior of electrolytes confined between these surfaces is analyzed by evaluating the ionic density profiles, Potential of Mean Force (PMF), net charge density and integrated charge. Although neither graphene nor hBN has net electric charge, we observed significant changes in the ionic structure including the enhanced accumulation of sodium and the depletion in chloride density close to the hBN interfaces at low salt concentration. However, increasing the salt concentration leads to accumulation of chloride close to hBN surfaces. Two different types of hBN-GR junctions are considered in this study: a) shuffle (zigzag bonds) and (b) glide (parallel bonds). High adsorption of sodium and chloride ions near shuffle GR-hBN-GR surfaces is observed due to electrostatic attraction forces between the sodium and nitrogen atoms and between chloride and boron atoms at hBN–graphene junctions across zigzag bonds. This study reveals that GR-hBN-GR with shuffle interface is highly advantageous in adsorbing sodium and chloride ions than graphene and hBN alone. To the best of our knowledge, this is the first study that elucidates the interaction between monovalent electrolytes and GR-hBN-GR heterostructures in a confined medium.

Entropy of electrolytes with off-centre charge cations. Monte Carlo studies

Monte Carlo techniques including Inverse Grand Canonical Monte Carlo simulations are utilized to calculate the entropy of a restricted primitive model electrolyte with the caveat that the cation charge centre is displaced from the geographical centre of the cation sphere towards the surface of the sphere. Calculations have been performed for symmetric valency (1:1) and asymmetric valency (2:1) electrolytes at 298.15 K for a range of electrolyte concentrations. The cation charge centre displacement accompanied by an increase of temperature leads to an increase of entropy. For the 2:1 valency system the entropy as a function of the square root of concentration reveals a broad inflexion region that separates the domains of deformation due to the electrostatic and steric interactions. When the central ion is an anion, and the charge centres of the surrounding cations are oriented towards the anion then the electrostatic interactions are stronger than in the standard restricted primitive model and the entropy decreases, while a central cation deforms the ionic atmosphere surrounding it and the entropy increases. In the low concentration regime good agreement is seen between the results from the Debye-Hückel limiting law and the corresponding simulations.

An Anode-Free Zn-Graphite Battery.

The anode-free battery concept isproposed to pursue the aspiration of energy-dense, rechargeable metal batteries, but this has not been achieved with dual-ion batteries. Herein, the first anode-free Zn-graphite battery enabled by efficient Zn plating-stripping onto a silver-coated Cu substrate is demonstrated. The silver coating guides uniform Zn deposition without dendrite formation or side reaction over a wide range of electrolyte concentrations, enabling the construction of anode-free Zn cells. In addition, the graphite cathode operates efficiently under reversible bis(trifluoromethanesulfonyl)imide anion (TFSI- ) intercalation without anodic corrosion. An extra high-potential TFSI- intercalation plateau is recognized at 2.75V, contributing to the high capacity of graphite cathode. Thanks to efficient Zn plating-stripping and TFSI- intercalation-deintercalation, an anode-free Zn-graphite dual-ion battery that exhibits impressive cycling stability with 82% capacity retention after 1000 cycles is constructed. At the same time, a specific energy of 79Whkg-1 based on the mass of cathode and electrolyte is achieved, which is over two times higher than conventional Zn-graphite batteries (<30Whkg-1 ).

Electric-Field-Induced Spatially Dynamic Heterogeneity of Solvent Motion and Cation Transference in Electrolytes

While electric fields primarily result in migration of charged species in electrolytic solutions, the solutions are dynamically heterogeneous. Solvent molecules within the solvation shells of the cation will be dragged by the field while free solvent molecules will not. We combine electrophoretic NMR measurements of ion and solvent velocities under applied electric fields with molecular dynamics simulations to interrogate different solvation motifs in a model liquid electrolyte. Measured values of the cation transference number (t_{+}^{0}) agree quantitatively with simulation-based predictions over a range of electrolyte concentrations. Solvent-cation interactions strongly influence the concentration-dependent behavior of t_{+}^{0}. We identify a critical concentration at which most of the solvent molecules lie within solvation shells of the cations. The dynamic heterogeneity of solvent molecules is minimized at this concentration where t_{+}^{0} is approximately equal to zero.

A new model for the relative viscosity of aqueous electrolyte solutions

In this work, taking into account the hydration of ions, a new model of the relative viscosity of aqueous electrolyte solutions is proposed. The predictions of the proposed model were compared with experimental data and the results of other models, and a good correlation was achieved over a wide range of electrolyte concentrations for aqueous solutions of a number of chlorides and hydroxides. According to this model, a decrease in the ionic radius and an increase in both the ion effective hydration number and the electrolyte concentration increase the viscosity of the aqueous electrolyte solution. Using the proposed model and experimental data on the relative viscosity of these aqueous solutions, the total effective hydration numbers of the considered electrolytes were determined for various electrolyte concentrations at 25 °C.

Near Infrared Spectroscopy As an Effective Way of Studying Hydrogen Bonding in a LiCl–H2O–CO2 Ternary Mixture

Abstract The possibility of using near IR spectroscopy to analyze the effect isobaric heating has on hydrogen bonding in an aqueous solution of LiCl in equilibrium with supercritical carbon dioxide (a LiCl–H2O–scCO2 ternary mixture) is demonstrated in a wide range of electrolyte concentrations. It is shown that this approach is highly efficient when studying ion and molecular systems with different types of interparticle interactions. The use of near IR spectroscopy allows distinguishing spectral contributions from hydrogen bonded n-mers of bulk water and water molecules in the solvation shells of ions or in ion–water chains like those formed in solutions with extremely high electrolyte concentrations that do not contain bulk water. It is shown for the studied ternary mixture that raising the concentration of electrolyte completely neutralizes the destructive effect of carbon dioxide on the formation of a hydrogen bonded structure of water. The latter is stabilized under the influence of an ion field, which also substantially weakens the temperature effect.

Modeling electrochemical [formula omitted] reduction at silver gas diffusion electrodes using a TFFA approach

A spatially resolved mathematical model for low temperature electrochemical CO2 reduction (eCO2R) at silver gas diffusion electrodes is presented and validated using flow cell measurements. The combination of experimental and model results provides novel insights regarding an inhibition of the catalyst performance by the product carbon monoxide. The developed model shows good agreement with experimental results concerning the overpotential and the Faradaic efficiency in dependence of the current density over a range of KHCO3 electrolyte concentrations (0.75–1.25M) and CO2 fractions in the gas feed (25–100vol.%). The model results highlight two main problems that have to be overcome to achieve a more efficient eCO2R process at high current densities: Firstly, the electrode performance becomes strongly limited by CO2 mass transport at higher current densities. Secondly, only around 50% of the CO2 consumed is converted electrochemically, while the remainder chemically absorbs in the electrolyte in form of carbonate and bicarbonate, resulting in a low carbon efficiency. Addressing these issues will be crucial to make eCO2R feasible for industrial application.

Synthesis and characterization of triazole stabilized silver nanoparticles as colorimetric probe for mercury

This study reports the synthesis and characterization of triazole stabilized silver nanoparticles and their investigation as a colorimetric sensor for Hg2+ in tap water. Benzotriazole conjugated silver nanoparticles (BT-AgNPs) were synthesized using the chemical reduction method. Techniques such as UV–visible, Zetasizer, FTIR, SEM, and AFM were used for the characterization of the nanoparticles. The nanoparticles were highly monodispersed and revealed a mean size of 40–50 nm. Further, they were found highly stable at elevated temperatures and over a wide range of electrolyte concentrations and pH. The nanoparticles were then investigated as a colorimetric sensor for Hg2+. The addition of mercury significantly suppressed nanoparticles' absorption intensity and the color change from yellow to colorless. They were found highly selective towards Hg2+in the presence of other interfering metal ions. The binding ratio between the nanoparticles and Hg2+ was found to be 1:1 as determined by the jobs plot experiment. The nanoparticles demonstrated sensitivity towards a wide concentration of Hg2+ with a limit of detection of 0.33 µM. The synthesized nanoparticles were finally used as a sensing probe for Hg2+ detection in water. The limit of detection of the current sensor is lower than most of the reported methods. These findings reveal the triazole stabilized nanoparticles as an easy, selective, and sensitive sensing probe for Hg2+.