Effect Of Ions Research Articles

Electrochromic nickel-oxide-based thin films in KOH electrolyte: Ionic and electronic effects elucidated by impedance spectroscopy

Ni-oxide-based thin films, prepared by sputtering, are investigated by electrochemical impedance spectroscopy in a KOH electrolyte. The films are electrochromic, and an increase of the applied potential leads to a variation from a bleached to a colored state as a result of proton (H+) extraction together with extraction of electrons from the valence band. The complex frequency-dependent impedance displays different features in different potential ranges. At low potentials, where coloration is weak, the spectra give evidence for a constant-phase element in parallel with a leak resistance. At intermediate and high potentials, the impedance spectra indicate the presence of a diffusion process, and a model for anomalous diffusion gives excellent fits to the spectra except in a crossover region. The applicability of this model in a significant part of the studied potential range suggests the presence of a multiple-trapping process for the ions. The potential dependence of the chemical capacitance, as well as the diffusion coefficient of un-trapped ions, are analyzed. The electrochemical density-of-states of the charge-compensating electrons gives indications of the top of the valence band and of a band tail extending into the band gap. Diffusion coefficients are found to increase steeply in the crossover potential region to very high values at high potentials. These features are discussed and related to the electrochromic behavior of Ni-oxide-based thin films.

Double-layered solar evaporator based on polymeric ionic liquid grafted attapulgite and MXene/PPy for efficient desalination and photodegradation

Solar-driven interfacial evaporation (SIE) is a promising fresh water acquisition technology to address the global water resource shortage. Therefore, solar evaporators with efficient photothermal conversion efficiency and multifunctional purification capabilities are still in high demand. At present, a variety of photothermal conversion materials have been explored, however, there are few studies on integrating interfacial evaporation and photocatalytic capabilities into one solar steam generation system collaboratively. In this work, a new double-layered solar interfacial evaporator (MXene/PPy-ACA) was fabricated by using polymeric ionic liquid grafted attapulgite (ATP-PIL) as the matrix and modified the upper surface by MXene and polypyrrole (PPy). The evaporator can not only carry out seawater desalination efficiently, but also has good photocatalytic degradation effect on organic dyes. The MXene/PPy-ACA achieves an evaporation rate of 1.53 kg m−2 h−1 and corresponding to an efficiency of 92.17 % under irradiation of 1 sun. In addition, duing to the ionic repulsion effect of ATP-PIL, the MXene/PPy-ACA possesses good salt resistance. When tested in 20 wt% high brine, the evaporation rate is measured to be 1.40 kg m−2 h−1. Moreover, owing to the superb photocatalytic properties of MXene and PPy, the MXene/PPy-ACA exhibits remarkable photocatalytic efficiency towards organic dyes, achieving degradation rates of 94.9 %, 67.49 %, and 65.11 % for methyl orange (MO), rhodamine B (RhB), and methylene blue (MB), respectively. The prepared interfacial evaporation system can also run stably in acid and alkali solution, and has a good practical application prospect. This study may offer an alternative approach in achieving clean water via SIE of seawater and complex wastewater.

Impact of Ionic Strength (Sodium Chloride Concentration) on Homopolymerization and Copolymerization Kinetics of Acrylamide and 2‐Acrylamido‐2‐Methylpropane Sulfonic Acid

AbstractAnionic polyelectrolytes can be used for a variety of applications, including flocculation and enhanced oil recovery. While it is widely recognized that polyelectrolyte synthesis is impacted by the pre‐polymer formulation and polymerization conditions, the specific relationships between these factors and the subsequent polymer properties are not well understood. Therefore, the current work intends to improve understanding of ionic strength (IS) effects during the copolymerization of 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS) and acrylamide (AAm). The aims of the study are i) to use in situ H1 NMR to study copolymerization kinetics, and ii) to determine how increasing IS impacts copolymerization kinetics (and, by extension copolymer microstructure). It is found that altering IS prior to copolymerization has significant impacts on the reactivity ratios, and therefore impacts the microstructure through multiple mechanisms. Increasing IS causes a crowding effect, where the propagating chain develops a random coil conformation and causes steric hindrance of the large AMPS monomer, decreasing the likelihood of AMPS propagation. When the IS is increased further, the ionic shielding effect is more impactful, increasing the likelihood of AMPS propagation. Ultimately, this work will make it possible to manipulate IS to synthesize AMPS/AAm copolymers with specific desirable properties for target applications.

The Impact of Salinity on Crop Yields and the Confrontational Behavior of Transcriptional Regulators, Nanoparticles, and Antioxidant Defensive Mechanisms under Stressful Conditions: A Review.

One of the most significant environmental challenges to crop growth and yield worldwide is soil salinization. Salinity lowers soil solution water potential, causes ionic disequilibrium and specific ion effects, and increases reactive oxygen species (ROS) buildup, causing several physiological and biochemical issues in plants. Plants have developed biological and molecular methods to combat salt stress. Salt-signaling mechanisms regulated by phytohormones may provide additional defense in salty conditions. That discovery helped identify the molecular pathways that underlie zinc-oxide nanoparticle (ZnO-NP)-based salt tolerance in certain plants. It emphasized the need to study processes like transcriptional regulation that govern plants' many physiological responses to such harsh conditions. ZnO-NPs have shown the capability to reduce salinity stress by working with transcription factors (TFs) like AP2/EREBP, WRKYs, NACs, and bZIPs that are released or triggered to stimulate plant cell osmotic pressure-regulating hormones and chemicals. In addition, ZnO-NPs have been shown to reduce the expression of stress markers such as malondialdehyde (MDA) and hydrogen peroxide (H2O2) while also affecting transcriptional factors. Those systems helped maintain protein integrity, selective permeability, photosynthesis, and other physiological processes in salt-stressed plants. This review examined how salt stress affects crop yield and suggested that ZnO-NPs could reduce plant salinity stress instead of osmolytes and plant hormones.

Modulation of Ionically Generated Space Charge Effects at Hybrid Perovskite and Oxide Interfaces via Surface Modification

AbstractInterfacial space charges significantly influence transport and recombination of charge carriers in optoelectronic devices. Due to the mixed ionic‐electronic conducting properties of halide perovskites, not only electronic effects, but also ionic interactions at their interfaces need to be considered in the analysis of space charges. Understanding of these interactions and their control is currently missing. This study elucidates the ionic effects on space charge formation at the interface between methylammonium lead iodide (MAPI) and alumina, and its modulation through surface modification using organic molecules. Embedding insulating alumina nanoparticles within MAPI films leads to enhancement of the electronic conductivity. This effect is consistent with the formation of an interfacial inversion layer in MAPI and can only be explained on the basis of ionic interactions. Such an effect is attenuated by surface modification of the oxide via the chemisorption of organic molecules. Finally, the same trend is observed in solar cells, where reducing the potential of the distributed space charges within the composite active layer improves device performance. These findings emphasize the necessity of taking into account ionic interactions to control the space charge formation at interfaces involving mixed ionic‐electronic conductors, an essential aspect in the performance optimization of halide perovskite‐based devices.

Effect of Zwitterionic Additives on Solvation and Transport of Sodium and Potassium Cations in (Ethylene Oxide)10: A Molecular Dynamics Simulation Study.

Sodium- (Na+) and potassium- (K+) ion batteries are cost-effective alternatives to lithium-ion (Li+) batteries due to the abundant sodium and potassium resources. Solid polymer electrolytes (SPEs) are essential for safer and more efficient Na+ and K+ batteries because they often exhibit low ionic conductivity at room temperature. While zwitterionic (ZW) materials enhance Li+ battery conductivity, their potential for Na+ and K+ transport in batteries remains unexplored. In this study, we investigated the effect of three ZW molecules (ChoPO4, i.e., 2-methacryloyloxyethyl phosphorylcholine, ImSO3, i.e., sulfobetaine ethylimidazole, and ImCO2, i.e., carboxybetaine ethylimidazole) on the dissociation of Na+ and K+ coordination with ethylene oxide (EO) chains in EO-based electrolytes through molecular dynamics simulations. Our results showed that ChoPO4 possessed the highest cation-EO10 dissociation ability, while ImSO3 exhibited the lowest. Such dissociation ability correlated with the cation-ZW molecule coordination strength: ChoPO4 and ImSO3 showed the strongest and the weakest coordination with cations. However, the cation-ZW molecule coordination could slow the cationic diffusion. The competition of these effects resulted in accelerating or decelerating cationic diffusion. Our simulated results showed that ImCO2 enhanced Na+ diffusion by 20%, while ChoPO4 and ImSO3 led to a 10% reduction. For K+, ChoPO4 reduced its diffusion by 40%, while ImCO2 and ImSO3 caused a similar decrease of 15%. These findings suggest that the ZW structure and the cationic size play an important role in the ionic dissociation effect of ZW materials.

Terahertz ionic Kerr effect: Two-phonon contribution to the nonlinear optical response in insulators

Terahertz ionic Kerr effect: Two-phonon contribution to the nonlinear optical response in insulators

A Gaussian field approach to the solvation of spherical ions in electrolyte solutions.

In this work, the electrostatic response of an electrolyte solution to a spherical ion is studied with a Gaussian field theory. In order to capture the ionic correlation effect in concentrated solutions, the bulk dielectric response function is described by a two-Yukawa response function. The modified response function of the solution is solved analytically in the spherical geometry, from which the induced charge density and the electrostatic energy are also derived analytically. Comparisons with results for small ions in electrolyte solutions from the hyper-netted chain theory demonstrate the validity of the Gaussian field theory.

Specific ions effect on aggregation behaviors and structural changes of amyloid fibrils from rice glutelin

Metal ions have been considered as an important factor on fibrils assembly. Herein, a comprehensive analysis of specific ions effect on fibril formation and structural changes was investigated. The addition of ions (except Zn2+) accelerated the aggregation kinetics of rice glutelin fibrils (RGFs) from 0.93 to 1.28–2.19 h−1. In addition, the fibrillization rate followed the order of NH4+ > Li+ > Na+ > K+ > Cu2+ > Mg2+ > Ca2+ > Zn2+. The highest yield and length of fibrils were observed with Ca2+, probably due to the ionic bridging effect and hydrated capacity of Ca2+. However, Cu2+ reduced the fibrils yield, which was attributable to the fact that Cu2+ disrupted β-sheet structure and inhibited the transition of monomer to fibrils. The polymorphism of fibrils was observed with different salts, and the light metals presented a superior effect on fibrils formation than heavy metals. Overall, this work will provide a further information into how to tune the structure of RGFs using various ions.

Highly-stable gradient poly(anion-π) hydrogels with superior salt-tolerant property for giant osmotic energy harvesting

Harvesting ocean salinity energy has attracted large attentions based on different kinds of asymmetric ionic membranes. Gradient polyelectrolyte hydrogels demonstrated superior power generation capacity due to their abundant charged groups and rectification behaviors. However, they generally suffer from the electrostatic screening and dramatic swelling, leading to unsatisfactory energy conversion performance. Here, an anti-swelling, salt-tolerant gradient polyanion hydrogel is reported for high-efficiency osmotic energy conversion. The gradient polyanion hydrogel is prepared by ultraviolet (UV) induced copolymerization of anionic monomer and aromatic monomer. Benefiting from the mutual electrostatic interaction and π-π conjugation interaction, the gradient polyanion hydrogel presents the outstanding anti-electrostatic screening and anti-swelling performance. As a result, they can maintain excellent cation selectivity and ionic diode effect for providing an ultrahigh power density of 16.4 W/m2 when mixing artificial seawater and river water. This new salt-tolerant gradient polyelectrolyte hydrogel provides a promising way to recover energy from seawater and wastewater.

Dimensionally Stable Anion Exchange Membranes Based on Macromolecular-Cross-Linked Poly(arylene piperidinium) for Water Electrolysis.

The advancement of anion exchange membranes (AEMs) with superior ionic conductivity has been greatly hindered due to the inherent "trade-off" between membrane swelling and ionic conductivity. To resolve this dilemma, macromolecular covalently cross-linked C-FPVBC-x AEMs were fabricated by combining partially functionalized ether-bond-free polystyrene (FPVBC) with poly(arylene piperidinium). The results from atomic force microscopy reveal that an increase in the ratio of FPVBC promotes the fabrication of microphase separation morphology, resulting in a high ionic conductivity of 40.15 mS cm-1 (30 °C) for the C-FPVBC-1.7 membrane. Molecular dynamics simulations further examine the ionic conduction effect of cross-linked AEMs. Besides, the unique cross-linking structure significantly improves mechanical and alkaline stability. After treatment in 1 M KOH at 50 °C for 1200 h, the C-FPVBC-1.7 membrane shows only a 6.9% decrease in conductivity. The C-FPVBC-1.7 AEM-based water electrolyzer achieves a high current density of 890 mA cm-2 at 2.4 V (80 °C) and maintains good stability, enduring over 100 h at 100 mA cm-2 (50 °C). These results demonstrate the significant potential of macromolecularly cross-linked AEMs for practical applications in water electrolysis.

Direct electrochemical synthesis of arenesulfonyl fluorides from nitroarenes: a dramatic ionic liquid effect

A practical electrosynthesis of aryl sulfonyl fluorides from nitroarenes is described. Cheap N-methylimidazolium p-toluenesulfonate has been found to be an effective additive, promoting the desired fluorosulfonylation under very mild conditions.

Unravelling ionic liquid solvent effects for a non-polar Cope rearrangement reaction.

The impact of ionic liquids (ILs) on polar reactions is well recognised, however the impact of ILs on non-polar reactions is less well understood or explored. Pericyclic Cope rearrangements are highly concerted, exhibit minimal charge localisation and pass through an uncharged but well-defined transition state, and thus provide a good mechanism for exploring the impact of IL polarizability on chemical reactivity. Recently, a 10× rate enhancement has been observed for the Cope rearrangement of 3-phenyl-1,5-hexadiene in the IL 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C4C1im][NTf2] compared to benzene. In this work we undertake a DFT based computational study (B3LYP-D3BJ/6-311+G(d,p) and M06-2X-D3/6-311+G(d,p)) of the Cope rearrangement of 3-phenyl-1,5-hexadiene and 3-propyl-hexa-1,5-diene in molecular solvents (acetonitrile, benzene and ethanol) and the IL [C4C1im][NTf2] using the SMD solvation model. The impact of benzene and [C4C1im][NTf2] on the Cope rearrangement of 3-phenyl-1,5-hexadiene is studied in more detail and we provide insight into the reason for the rate enhancement in an IL. The volume of activation is evaluated and the potential impact of 'solvent pressure' is discussed. We identify two potential mechanisms for volume effects to contribute to the rate enhancement. Solvent association energies are evaluated at the DLNPO-CCSD(T) level. Specific solvent interactions are explored through atomic partial charge, molecular orbital and bond critical point analysis, as well as via non-colvalent interaction (NCI) plots, electrostatic potential (ESP) differences and density difference Δρ(r) plots. We find that the cation and anion together form an extensive van der Waals pocket in-which the transition state (TS) sits. Electron density within the TS is anisotropically polarised via a 'push-pull' effect due to the dual cation-anion nature of the IL, stabilising the TS relative to benzene. We also provide experimental evidence that these effects are generalisable to other ILs. Overall, our aim is to provide a deeper moleuclar level understanding of the impact of ILs on non-polar reactions.

LCST ion gels fabricating "all-in-one" smart windows: thermotropic, electrochromic and power-generating.

Smart windows always respond to single stimuli, which cannot satisfy various needs in practical applications. Smart windows that integrate thermotropic, electrochromic and power-generating functions in one device is highly challenging yet important in satisfying on-demand light modulation and energy efficiency in practical applications. Herein, a thermoresponsive lower critical solution temperature (LCST) ion gel was fabricated via a facile in situ polymerization of butyl acrylate in a conventional ionic liquid to explore "all in one" smart windows. The ion gel-assembled smart windows are thermotropic and electrochromic with a reliable adjustment of light transparency as well as power-generating, enabled by the ionic Soret effect of ionic liquids. Additionally, the ion gels demonstrated self-defensive robust mechanical properties, thermal insulating and antifogging properties. With such an interdisciplinary and comprehensive study of the ion gels, the LCST ion gels could fulfil the requirements of genius windows with high energy-saving potential and exceptional climate adaptability, such as shut-down of light transmission in summer, daily solar energy collection, and colour changes on demand. It conceptually updates smart windows from an energy saving to an energy supplier in buildings. It is the first time to explore the "all in one" smart windows based on integrated multifunctional ionic liquids, which could greatly bridge the gap between the materials and buildings to accelerate practical applications of smart windows.

Probing the adsorption configuration of methanol at a charged air/aqueous interface using nonlinear spectroscopy.

Investigating the effects of electrolyte ions on the adsorption configuration of methanol at a charged interface is important for studying the interface structure of electrolyte solutions and the oxidation mechanism of methanol in fuel cells. This study uses sum frequency generation (SFG) and heterodyne-detected second harmonic generation (HD-SHG) to investigate the adsorption configuration of methanol at the air/aqueous interface of 0.1 M NaClO4 solution, 0.1 M HClO4 solution and pure water. The results elucidate that the ion effect in the electrolyte solution affects the interface's charged state and the methanol's adsorption conformation at the interface. The negatively charged surface of the 0.1 M NaClO4 solution and the positively charged surface of the 0.1 M HClO4 solution arise from the corresponding specific ionic effects of the electrolyte solution. The orientation angle of methyl with respect to the surface normal is 43.4° ± 0.1° at the 0.1 M NaClO4 solution surface and 21.5° ± 0.2° at the 0.1 M HClO4 solution surface. Examining these adsorption configurations in detail, we find that at the negatively charged surface the inclined orientation angle (43.4°) of methanol favors the hydroxymethyl production by breaking the C-H bond, while at the positively charged surface the upright orientation angle (21.5°) of methanol promotes the methoxy formation by breaking the O-H bond. These findings not only illuminate the intricate ion effects on small organic molecules but also contribute to a molecular-level comprehension of the oxidation mechanism of methanol at electrode interfaces.

Various Cu+, Mg2+ and S2- ionic concentration effects on a novel Cu2ZnMgS4 quaternary compound synthesis for various scientific applications

Copper zinc magnesium sulfide semiconducting material (Cu2ZnMgS4) compound is slightly new in electronics, opto-electronics and photo emissive field research. So that, we examined the Cu2ZnMgS4 compound formation characteristics step by step using the Copper sulfate (CuSO4.XH2O), Zinc sulfate (ZnSO4.XH2O), Magnesium sulfate (MgSO4.XH2O) and Sodium sulfide Na2S salt solutions. Characterizations such as pH, Electrical conductivity (EC), TDS were carried out for several concentrations. Further its optics properties of Cu2ZnMgS4 compound in liquid form were investigated through photo-colorimeter measurements (at various color λ including mixed band wavelengths), photo-fluorometer (using various primary and secondary filters) and UV-Vis spectrophotometer (at wavelength range of 300 to 900 nm) measurements. The investigated long term results are presented and discussed in this research article.

Ionic substitution effects on the crystal structure and microwave dielectric properties of rutile Zn0.15Nb0.3Ti0.55O2 ceramics

Ionic substitution effects on the crystal structure and microwave dielectric properties of rutile Zn0.15Nb0.3Ti0.55O2 ceramics

Investigation on the Effect of Fluorescence Quenching of Calf Thymus DNA by Piperine: Caspase Activation in the Human Breast Cancer Cell Line Studies.

In this study, we determined the interaction of piperine and calf thymus DNA (ct DNA) in Tris-HCl buffer solution at pH = 6.8 and also evaluated the binding mechanism through the data of multi-spectroscopic techniques along with thermal melting and viscosity measurements. The outcomes of fluorescence quenching confirmed the occurrence of interactions between piperine and ctDNA and pointed out the role of piperine as the quencher. In addition, the KSV values were measured at three different temperatures of 298, 303, and 308 K to be 4.5 × 107 M-1, 5.65 × 107 M-1, and 9.36 × 107 M-1, respectively, which suggested the dominance of dynamic mechanism as the fluorescence quenching of piperine-ctDNA. The thermodynamic parameters revealed the predominance of hydrophobic forces in the interaction of ctDNA with piperine. According to the resonance light scattering data, the formation of a complex between piperine and ctDNA led to the creation of a larger particle. Ethidium bromide (EB) and acridine orange (AO) displacement studies, along with the ionic effects of NaCl and KI assessments, confirmed the interaction of piperine-ctDNA through a groove binding mode. The melting temperature assay of ctDNA upon the addition of piperine concentration indicated the probable groove binding of piperine to ctDNA, which was affirmed by relative viscosity measurement as well. The lack of detecting any alterations in the circular dichroism (CD) spectrum of CD investigation verified as a characteristic sign of groove binding mechanism and also confirmed all the experimental results with regard to the binding of piperine-ctDNA complex. Next to observing a concentration and time-dependent cytotoxicity in MDA-MB-231 cells, the impact of piperine on increasing lipid peroxidation and decreasing the activity of superoxide dismutase was also noticed. Apparently, piperine is capable of inducing caspase-3 activity as well.

Dolomite dissolution and porosity enhancement simulation with acetic acid: Insights into the influence of temperature and ionic effects

Dolostone reservoirs are crucial for global oil and gas storage, holding a significant portion of hydrocarbon reserves within carbonate formations. Understanding the chemical mechanism of dolomite dissolution with organic acids and associated porosity development in these reservoirs is vital for optimizing hydrocarbon recovery. In this work, two sets of simulation experiments are designed to understand the controls of temperature and ionic effects on porosity enhancement during the dissolution of dolomite with acetic acid. In specific, we discovered a three-step reaction process between dolomite and acetic acid, involving acetic acid dissolution in water, acetic acid dissociation, and dolomite dissolution. Burial environments with higher temperatures reduce the degree of acetic acid dissociation, leading to a corresponding decrease in dolomite dissolution in acetic acid solutions. The presence of salt ions in the solution influences the reaction process, with magnesium chloride (MgCl2) having the most significant enhancing effect on dolomite dissolution, followed by sodium chloride (NaCl), while calcium chloride (CaCl2) has a limited impact. Sodium sulfate (Na2SO4) enhances dolomite dissolution at lower temperatures; however, at higher temperatures (>100 °C), it may reduce dolomite dissolution due to the precipitation of CaSO4. Despite a relatively short open-flow time, episodic burial dissolution of dolomite by acetic acid fluids under overburden pressure leads to a "net increase" in the reservoir space and enhances its connectivity attributes. During burial diagenesis, geological forces episodically drive organic acid fluids to the dolomite reservoir, predominantly dissolving dolomite along pre-existing pore development zones and geological interfaces, exhibiting inheritance, episodicity, and localization characteristics. Overall, this study provides insights into the dissolution and diagenetic processes of dolomite in the presence under acetic acids, from the point of dissolution simulation experiments. Collectively, these findings enhance our understanding of pore-system evolution and fluid-rock interactions in deep carbonate reservoirs.

Effect of ionic polarization on the static permittivity of electrolyte aqueous solutions

AbstractWe developed a theoretical model with two separate components for the description of the static permittivity of aqueous electrolytes versus concentration and temperature. The first component is due to the water molecular polarization, whereas the second component is governed by the ionic polarization. We found that the permittivity part due to the ionic polarization effect is comparable to that come from the water molecule polarization for aqueous electrolytes at ambient temperatures. The microdynamic mechanism of the phenomenon, which the static permittivity of sodium chloride aqueous solution with concentration of 2.8 mol/L holds constant with the change of temperature, is clarified. The equilibrium compensation between the decrement of the permittivity part due to the water molecular polarization and the increase of that originated from the ionic polarization as increasing temperature is responsible for this phenomenon. The dipole moment reduction of water molecules as rising temperature is also confirmed by the model.