Alkali Halides Research Articles

Water, Not Salt, Causes Most of the Seebeck Effect of Nonisothermal Aqueous Electrolytes.

A temperature difference between two electrolyte-immersed electrodes often yields a voltage Δψ between them. This electrolyte Seebeck effect is usually explained by cations and anions flowing differently in thermal gradients. However, using molecular simulations, we found almost the same Δψ for cells filled with pure water as with aqueous alkali halides. Water layering and orientation near polarizable electrodes cause a large temperature-dependent potential drop χ there. The difference in χ of hot and cold electrodes captures most of the thermovoltage, Δψ≈χ_{hot}-χ_{cold}.

Synthesis of 2D Nonlayered α‐Nb2O5 Nanosheets by the Growth Promoter of Sulfur and Alkali Halides

Niobium‐based oxides with wide bandgap and high dielectric constant show great potential in the applications of electronic and optoelectronic devices. Herein, the quasi‐van der Waals epitaxial growth of 2D α‐Nb2O5 nanosheets is reported, in which the growth promoter of sulfur and alkali halides has been utilized to catalyze the ultrathin 2D growth. The relatively low Gibbs free energy of α‐Nb2O5 nanosheets can drive the ultrathin growth down to 30 nm on the c‐Al2O3 substrate by the transformation of T‐Nb2O5 powder sources without any doping effects, demonstrating the diverse α‐Nb2O5 nanostructure morphologies. The as‐grown α‐Nb2O5 nanosheets are characterized with high crystalline quality and specific dominated growth plane, indicating the uniform dielectric properties. The metal–insulator–metal capacitor has confirmed the α‐Nb2O5 nanosheet with a high dielectric constant over 40. The dual promoters’ growth design strategy provides a universal synthesis method for the 2D nonlayered dielectric materials.

A Method for Predicting the Melting Temperature of Ionic Compounds.

Predicting the melting temperature of materials has always been a topic of great concern. This article proposes an alternative model for determining the melting temperature of materials based on the main idea of the Lindemann melting criterion combined with the first-principles calculations of density functional theory. To verify the accuracy of the melting model, this article selected typical ionic crystals of MgO and 10 alkali metal halides as the validation objects. The calculation results indicate that the melting temperature of the MgO crystals and I-VII compounds is in good agreement with the experimental results.

NaI as suitable alkali halide hydrate for domestic thermochemical heat storage

The limits and potentials of alkali (Li - Cs) halides (F - I) as salt hydrate-based thermochemical heat storage materials are studied. Most alkali halides are found unsuitable, and only the hydrates of sodium iodide (NaI) and sodium bromide (NaBr) were investigated experimentally. We confirmed that both have high energy densities of 1.5 GJ/m3 and 1.6 GJ/m3 respectively, based on the crystal structures of the dihydrate phases. NaI demonstrated full cyclic stability at water vapor pressures of 12 and 14.5 mbar, but NaBr did not show rehydration at these conditions. Therefore, NaBr was deemed unsuitable for domestic applications. For the NaI – H2O system, we have measured the p,T equilibrium line between the hydration states and constructed p,T and T,x – phase diagrams. This showed that the hydration temperature is 42 °C for 12 mbar water vapor pressure which is enough for domestic space heating. Additionally, the phase diagrams revealed an incongruent melting point where the NaI·2H2O is in equilibrium with the anhydrate and a saturated aqueous NaI solution. This melting can overlap with dehydration and thereby hinders the cyclability, since in the melting process part of the salt is dissolved which blocks the pores formed during dehydration. Therefore, the performance of NaI can be improved by ensuring dehydration is completed below the incongruent melting point of 68 °C. We also found that pre-cycling can prevent deliquescence which is expected to occur at 25 °C and 12 mbar. Overall, NaI could be a candidate for low temperature heat storage.

Metal‐Free ipso‐Halocyclization of N‐Arylpropynamides Using Hypervalent Iodine(III) Reagents under Aqueous Condition

AbstractWe report, an intramolecular ipso‐halocyclization of N‐arylpropynamides using readily available hypervalent iodine reagent as mild oxidant and alkali halides like KCl, KBr, and KI as the halogen source. Using this method, a broad range of valuable halogenated spiro[4.5]trienones can be obtained in an excellent yield at room temperature. Notably, this protocol doesn't require para‐substituents such as methoxy or fluoro group on the N‐aryl ring. Also, this reaction takes place in the absence of any metal catalyst under aqueous conditions and exhibits a broad substrate scope with high functional group tolerance. A plausible reaction mechanism is proposed based on control experiments.

Effect of XC functionals and dispersion corrections on the DFT‐computed structural and vibrational properties of SrCl2–NaCl and ZrF4–LiF

AbstractDensity functional theory (DFT) calculations were performed to examine the impact of exchange–correlation (XC) functionals and van der Waals corrections (specifically the D3 method) on the structural and vibrational properties of the SrCl2–NaCl and ZrF4–LiF salt systems. Multiple XC functionals, including the local density approximation (LDA), the generalized gradient approximation using the Perdew–Burke–Ernzerhof (PBE) model, and its modified form suitable for solids (PBEsol), the dispersion‐corrected PBE‐D3 and PBEsol‐D3, were considered. Of these functionals, LDA was found to exhibit the highest degree of error, while PBEsol and PBE‐D3 displayed the least error. Underestimated lattice parameters compared with experimental values were observed to result in higher force constants, leading to an overprediction of vibrational frequencies. Conversely, an overestimation of lattice parameters was associated with lower vibrational frequencies. The methodology presented in this study yielded results that are in good agreement with experiment, irrespective of the method (finite differences vs. density functional perturbation theory) employed for calculating infrared and Raman spectra. It was further demonstrated that for alkali halides with weak Raman scattering, utilizing a supercell constructed from primitive cells better predicts Raman features than does the use of conventional cells.

A model evaluation of entropies and related thermal quantities of alkali halides based on a generalised bonding scheme

A model evaluation of entropies and related thermal quantities of alkali halides based on a generalised bonding scheme

Salt-Assisted Vapor-Liquid-Solid Growth of 1D van der Waals Materials.

The method of salt-assisted vapor-liquid-solid (VLS) growth is introduced to synthesize 1D nanostructures of trichalcogenide van der Waals (vdW) materials, exemplified by niobium trisulfide (NbS3). The method uses a unique catalyst consisting of an alloy of Au and an alkali metal halide (NaCl) to enable rapid and directional growth. High yields of two types of NbS3 1D nanostructures, nanowires and nanoribbons, each with sub-ten nanometer diameter, tens of micrometers length, and distinct 1D morphology and growth orientation are demonstrated. Strategies to control the location, size, and morphology of growth, and extend the growth method to synthesize other transition metal trichalcogenides, NbSe3 and TiS3, as nanowires are demonstrated. Finally, the role of the Au-NaCl alloy catalyst in guiding VLS synthesis is described and the growth mechanism based on the relationships measured between structure (growth orientation, morphology, and dimensions) and growth conditions (catalyst volume and growth time) is discussed. These results introduce opportunities to expand the library of emerging 1D vdW materials to make use of their unique properties through controlled growth at nanoscale dimensions.

Estimation of thermodynamic and physicochemical properties of the alkali astatides: On the bond strength of molecular astatine (At2 ) and the hydration enthalpy of astatide (At- ).

The recent accurate and precise determination of the electron affinity (EA) of the astatine atom At0 warrants a re-investigation of the estimated thermodynamic properties of At0 and astatine containing molecules as this EA was found to be much lower (by 0.4 eV) than previous estimated values. In this contribution we estimate, from available data sources, the following thermodynamic and physicochemical properties of the alkali astatides (MAt, M = Li, Na, K, Rb, Cs): their solid and gaseous heats of formation, lattice and gas-phase binding enthalpies, sublimation energies and melting temperatures. Gas-phase charge-transfer dissociation energies for the alkali astatides (the energy requirement for M+ At- ➔ M0 + At0 ) have been obtained and are compared with those for the other alkali halides. Use of Born-Haber cycles together with the new AE (At0 ) value allows the re-evaluation of ΔHf (At0 )g (=56 ± 5 kJ/mol); it is concluded that (At2 )g is a weakly bonded species (bond strength <50 kJ/mol), significantly weaker bonded than previously estimated (116 kJ/mol) and much weaker bonded than I2 (148 kJ/mol), but in agreement with the finding from theory that spin-orbit coupling considerably reduces the bond strength in At2 . The hydration enthalpy (ΔHaq ) of At- is estimated to be -230 ± 2 kJ/mol (using ΔHaq [H+ ] = -1150.1 kJ/mol), in good agreement with molecular dynamics calculations. Arguments are presented that the largest alkali halide, CsAt, like the smallest, LiF, will be only sparingly soluble in water, following the generalization from hard/soft acid/base principles that "small likes small" and "large likes large."

Spectral evidence for irradiated halite on Mars

The proposed chloride salt-bearing deposits on Mars have an enigmatic composition due to the absence of distinct spectral absorptions for the unique mineral at all wavelengths investigated. We report on analyses of remote visible-wavelength spectroscopic observations that exhibit properties indicative of the mineral halite (NaCl) when irradiated. Visible spectra of halite are generally featureless, but when irradiated by high-energy particles they develop readily-identifiable spectral alterations in the form of color centers. Consistent spectral characteristics observed in the reflectance data of the chloride salt-bearing deposits support the presence of radiation-formed color centers of halite on the surface of Mars. We observe a seasonal cycle of color center formation with higher irradiated halite values during winter months, with the colder temperatures interpreted as increasing the formation efficiency and stability. Irradiated halite identified on the surface of Mars suggests that the visible surface is being irradiated to the degree that defects are forming in alkali halide crystal structures.

Comparative study of alkali (Li, Rb and Cs) halide doped KDP single crystals

Comparative study of alkali (Li, Rb and Cs) halide doped KDP single crystals

Induction heating-based pulsed spray drier for dewatering of alkali metal halide salts: Numerical model and its experimental validation

Dewatering of alkali metal halide salts in conventional co-current or counter-current spray driers to obtain low moisture content and agglomeration in resultant dried powders is difficult owing to their hygroscopic nature. Co-current spray driers offer the advantage of good heat transport characteristics in spray zone while counter-current spray driers offer better thermal utilization throughout the drying chamber. In the present work, modified prototype of a conventional counter-current spray drier is developed to obtain both these advantages in the drying chamber by employing induction heating and mechanical pulsation techniques. After carrying out several experiments in this prototype viz. Induction heating-based pulsed spray drier (IH-PSD), the optimal process parameters are obtained which maximize thermal utilization throughout the drying chamber and minimize both moisture content and agglomeration in resultant dried powders of sodium and potassium halide salts. The initial droplet and final particle size distributions are obtained using laser diffraction analyzer and sieve shaker experiments respectively. An experimentally validated numerical model implemented using open-source computational solvers is utilized to obtain average drying rates in IH-PSD. It is observed that the average drying rate lies between 0.03 and 0.18 mg/s and 0.04 and 0.14 mg/s for sodium and potassium metal halide salts respectively.

Isomerism of Cyclodextrin Tetramer Induced by Alkali Halide Cluster Ions Observed by Ion Mobility Spectrometry-Mass Spectrometry.

Cyclodextrins (CDs) exhibit versatile self-assembly properties due to their hydrophilic and hydrophobic components, with applications such as drug delivery and selective binding. While research on CD self-assembly is extensive, limited studies have explored their aggregation behavior, particularly in interactions with small ionic guests. The present work investigates the structure of β-CD tetramers aggregated with alkali metal chloride clusters using ion mobility spectrometry-mass spectrometry (IMS-MS). The results revealed that diverse structures emerge in the tetramer depending on the alkali metal cluster size. Notably, the doubly charged tetramer exhibits distinct aggregation trends with specific numbers of MCl clusters for Na+ and K+ ions. After initially adopting a bucket-wheel structure with two internal cations, the structure transforms into a new isomer with a tetrahedral configuration upon cluster addition. The formation of the new isomer structure is closely linked to filling the cavity volume with MCl clusters and ionic interactions, which possibly compensate for the weakened hydrogen bonds between CDs. Theoretical calculations further support the structures, showing well-matched collision cross-section (CCS) values compared with the experimental CCS values. This study highlights the role of alkali metal chloride clusters as potential templates, leading to the formation of novel CD assemblies.

Ab Initio Study on the Vibrational and Electronic Properties of Radiation-Induced Defects in Potassium Bromide

The vibrational and electronic properties of several basic radiation defects in potassium bromide are computed at the quantum mechanical level using a periodic supercell approach based on hybrid functionals, an all-electron Gaussian-type basis set, and the Crystalcomputer code. The exciton energy in alkali halides is sufficient to create lattice defects, such as F–H Frenkel defect pairs, resulting in a relatively high concentration of single defects and their complexes. Here, we consider eight defects: the electronic F+- and F-centers (bromine vacancy without and with trapped electrons) and their dimers; hole H-center (neutral bromine atom forming the dumbbell ion with a regular Br− ion.); VK-center (Br2− molecular ion consisting of a hole and two regular ions); and two complex Br3− defects, combinations of several simple defects. The local geometry and the charge- and spin-density distributions of all defects are analyzed. Every defect shows its characteristic features in Raman spectra, and their comparison with available experimental data is discussed.

Over 10% Efficient Sb2(S,Se)3 Solar Cells Enabled by CsI-Doping Strategy.

Antimony selenosulfide (Sb2(S,Se)3) is an emerging quasi-1D photovoltaic semiconductor with exceptional photoelectric properties. The low-symmetry chain structure contains complex defects and makes it difficult to improve electrical properties via doping method. This article reports a doping strategy to enhance the efficiency of Sb2(S,Se)3 solar cells by using alkali halide (CsI) as the hydrothermal reaction precursor. It is found that the Cs and I ions are effectively doped and atomically coordinate with Sb ions and S/Se ions. The CsI-doping Sb2(S,Se)3 absorbers exhibit enhanced grain morphologies and reduced trap densities. The consequential CsI-doping Sb2(S,Se)3 based solar cells demonstrate favorable band alignment, suppressed carrier recombination, and improved device performance. An efficiency as high as 10.05% under standard AM1.5 illumination irradiance is achieved. This precursor-based alkali halide doping strategy provides a useful guidance for high-efficiency antimony selenosulfide solar cells.

Ultrafast adsorption of hexavalent chromium from aqueous effluents using covalent triazine frameworks

We have synthesized low-cost high performance covalent triazine framework (CTF) through Schiff base reaction of melamine and terephthalaldehyde with different proportions of the reactants. The synthesized adsorbents showed excellent capacity for adsorption of Cr (VI) at acidic pH while almost negligible adsorption at higher pH. The adsorbent displays excellent reusability, with a little decrease in adsorption capacity with the increasing number of cycles. Moreover, Cr (VI) the adsorption is unaffected by the presence of 50–500 times higher concentration of alkali metal and halide ions in solution, while sulphate ions demonstrate shielding behavior decreasing the adsorption capacity. Mechanistic studies indicate electrostatic attractions, ion exchange and reduction being responsible for the adsorption mediated by abundant nitrogen sites that also imbibes the adsorbent with high capacity. The adsorbent was also utilized to recover chromium from an industrial electroplating effluent, which demonstrates applicability of material for practical applications.

AX·(H2SeO3)n (A = K, Cs; X = Cl, Br; n = 1, 2): A Series of Ionic Cocrystals as Promising UV Birefringent Materials with Large Birefringence and Wide Band Gap.

The design and syntheses of new birefringent crystals will be of great importance in commercial applications and materials science. A series of ultraviolet (UV) birefringent crystals, AX·(H2SeO3)n (A = K, Cs; X = Cl, Br; n = 1, 2), with large sizes up to 23 × 6 × 3 mm3, was successfully synthesized by simple aqueous solution method. These four compounds belong to three different space groups. Isomorphic KCl·(H2SeO3)2 and CsCl·(H2SeO3)2 crystallize in the space group, while CsBr·(H2SeO3)2 and CsCl·H2SeO3 crystallize in the P21/m and P21/c space groups, respectively. They exhibit cocrystal structures composed of [2(H2SeO3)]∞ and [AX]∞ frameworks, ingeniously inheriting the large optical anisotropy of selenite and the wide band gap of alkali metal halide. And it proves that these compounds indeed possess large birefringence (0.1-0.17 at 532 nm) and short UV cutoff edges (227-239 nm), achieving a balance of optical properties. This research affords a simple and viable strategy for the design and syntheses of new UV birefringent crystals. Besides, it is also found that the n value and ionic size (A and X ions) have important influences on the crystal structures and optical properties of AX·(H2SeO3)n. And this will promote further understanding of the alkali metal halide selenite family.

The lithium oxide solubility in molten fluoride system CeF3 - FLiNaK

Molten systems based on alkali metal halides with lithium oxide additives are promising as a working medium on pyrochemical reprocessing of nuclear waste. A mixture of alkali metal fluorides of eutectic composition (FLiNaK) is a suggesting solvent due to the high solubility of actinide oxides, low viscosity, high boiling points, low vapor pressure, and resistance to radiation damage. Thermal analysis, XRD, Raman spectroscopy and thermodynamic simulations were used to obtain evidences on the phase equilibria and liquidus points of the system (0.85 FLiNaK - 0.15 CeF3) - Li2O, containing up to 8.8 mol % lithium oxide. The solubility of lithium oxide in the fluoride melt FLiNaK - CeF3 and the thermodynamic parameters of dissolution were obtained. The eutectic point (the Li2O content is 3.1 mol %, Tm = 489??) and two peritectic points (lithium oxide content are 3.2 and 4.2 mol %, and liquidus points are 497 and 549??, respectively) were found. Thermodynamic simulation results show an exothermic effect due to interaction between lithium oxide and fluoride melt. The interaction product oxyfluoride CeOF was detected by XRD analysis and Raman spectroscopy.

Bright Self-Trapped Exciton Emission in Alkali Iodide Nanocrystals via Sn(II)-Doping

Lead-free alkali halides have gained increasingly attentions due to their desire optoelectronic properties across a variety of light-emitting applications. However, state-of-the art alkali halide emitters commonly are bulky crystals functionalized...

Exotic hexagonal NaCl atom-thin layer on methylammonium lead iodide perovskite: new hints for perovskite solar cells from first-principles calculations.

Alkali halides are simple inorganic compounds extensively used as surface modifiers in optoelectronic devices. In perovskite solar cells (PSCs), they act as interlayers between the light absorber material and the charge selective layers improving their contact quality. They introduce surface dipoles that enable the fine tuning of the relative band alignment and passivate surface defects, a well-known drawback of hybrid organic-inorganic perovskites, that is responsible for most of the issues hampering the long-term performances. Reducing the thickness of such salt-based insulating layer might be beneficial in terms of charge transfer between the perovskite and the electron/hole transport layers. In this context, here we apply density functional theory (DFT) to characterize the structure and the electronic features of atom-thin layers of NaCl adsorbed on the methylammonium lead iodide (MAPI) perovskite. We analyze two different models of MAPI surface terminations and find unexpected structural reconstructions arising at the interface. Unexpectedly, we find an exotic honeycomb-like structuring of the salt, also recently observed in experiments on a diamond substrate. We also investigate how the salt affects the perovskite electronic properties that are key to control the charge dynamics at the interface. Moreover, we also assess the salt ability to improve the defect tolerance of the perovskite surface. With these results, we derive new hints regarding the potential benefits of using an atom-thin layer of alkali halides in PSCs.