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A classical non-polarizable force field for the common halide (F−, Cl−, Br−, and I−) and alkali (Li+, Na+, K+, and Cs+) ions in SPC/E water is presented. This is an extension of the force field developed by Loche et al. for Na+, K+, Cl−, and Br− (JPCB 125, 8581–8587, 2021): in the present work, we additionally optimize Lennard-Jones parameters for Li+, I−, Cs+, and F− ions. Li+ and F− are particularly challenging ions to model due to their small size. The force field is optimized with respect to experimental solvation free energies and activity coefficients, which are the necessary and sufficient quantities to accurately reproduce the electrolyte thermodynamics. Good agreement with experimental reference data is achieved for a wide range of concentrations (up to 4 mol/l). We find that standard Lorentz–Berthelot combination rules are sufficient for all ions except F−, for which modified combination rules are necessary. With the optimized parameters, we show that, although the force field is only optimized based on thermodynamic properties, structural properties are reproduced quantitatively, while ion diffusion coefficients are in qualitative agreement with experimental values. [ABSTRACT FROM AUTHOR]

The isomerization of azobenzo-13-crown ether can be expected to be hindered due to the polyoxyethylene linkage connecting the 2,2′-positions of azobenzene. The mixed reference spin-flip time-dependent density functional theory results reveal that the planar and rotational minima of the first photo-excited singlet state (S1) of the trans-isomer pass through a barrier (2.5–5.0 kcal/mol) as it goes toward the torsional conical intersection (S0/S1) geometry (

The sinking of alkali cations in superfluid 4He nanodroplets is investigated theoretically using liquid 4He time-dependent density functional theory at zero temperature. The simulations illustrate the dynamics of the buildup of the first solvation shell around the ions. The number of helium atoms in this shell is found to linearly increase with time during the first stages of the dynamics. This points to a Poissonian capture process, as concluded in the work of Albrechtsen et al. on the primary steps of Na+ solvation in helium droplets [Albrechtsen et al., Nature 623, 319 (2023)]. The energy dissipation rate by helium atom ejection is found to be quite similar between all alkalis, the main difference being a larger energy dissipated per atom for the lighter alkalis at the beginning of the dynamics. In addition, the number of helium atoms in the first solvation shell is found to be lower at the end of the dynamics than at equilibrium for both Li+ and Na+, pointing to a kinetic rather than thermodynamical control of the snowball size for small and strongly attractive ions. [ABSTRACT FROM AUTHOR]

Graphene oxide (GO) is a two-dimensional, mechanically strong, and chemically tunable material for separations. Elucidating GO–ion–water interactions at the molecular scale is highly important for predictive understanding of separation systems. However, direct observations of the nanometer region by GO surfaces under operando conditions are not trivial. Therefore, thin films of GO at the air/water interface can be used as model systems. With this approach, we study the effects of alkali metal ions on water organization near graphene oxide films at the air/water interface using vibrational sum frequency generation (SFG) spectroscopy. We also use an arachidic acid Langmuir monolayer as a benchmark for a pure carboxylic acid surface. Theoretical modeling of the concentration-dependent sum frequency signal from graphene oxide and arachidic acid surfaces reveals that the adsorption of monovalent ions is mainly controlled by the carboxylic acid groups on graphene oxide. An in-depth analysis of sum frequency spectra reveals at least three distinct water populations with different hydrogen bonding strengths. The origin of each population can be identified from concentration dependent variations of their SFG signal. Interestingly, an interfacial water structure seemed mostly insensitive to the character of the alkali cation, in contrast to similar studies conducted at the silica/water interface. However, we observed an ion-specific effect with lithium, whose strong hydration prevented direct interactions with the graphene oxide film. [ABSTRACT FROM AUTHOR]

The efflorescence problem is always an intractable problem for geopolymer. Silica fume (SF), nano-silica (NS), 5A zeolite (ZL) and nano-silica treated with silane (NST), were used to mitigate the efflorescence of fly ash (FA) - granulated blast furnace slag (GBFS) - steel slag (SS) based geopolymer. The effect of their dosages on the efflorescence was evaluated through accelerated efflorescing, leaching and unconfined compressive strength (UCS) tests. The inhibition mechanisms were explored by XRD, SEM, FTIR and MIP characterization. It revealed that SF and NS presented the most effective mitigating effect on efflorescence, with 9 % of SF and 2 % of NS totally inhibiting efflorescence and improving the compressive strength, and ZL and NST also alleviated the efflorescence at appropriate contents. Optimizing pore network and stabilizing free alkali were found to be the most important aspects for inhibiting efflorescence. The SF and NS worked efficiently in both two ways, which contained a large amount of dissolvable silicate that reacted with the excessive alkali to form C(N)-A-S-H and C-S-H gels. This filled and reduced the pores from 26 nm to less than 10 nm, and stabilized alkali with reduce the free w (Na+) by more than 50.45 %. On the other hand, ZL can solidify free alkali through the ion exchange property and fill pores due to its microaggregate nature, and NST reduced the efflorescence through blocking free alkali migration paths by hydrophobicity of the pores. These findings would guide the selection of appropriate methods to solve the efflorescence problem of geopolymers. • Reactive silicates in SF and NS can consume free alkalis to improve efflorescence resistance. • The NS inhibited free alkalis migration through optimized pore structure. • The ZL and NST mitigated efflorescence by reducing alkali leaching. [ABSTRACT FROM AUTHOR]

The development of lead-free primary explosives is urgent from industrial and military aspects. Herein, a typical energetic molecule with the dinitromethyl group and tetrazole ring was selected as the ligand for different alkali metals (Na, K, Rb, and Cs) to achieve a series of energetic coordination polymers (ECPs), namely, ECP 1 to ECP 4. The DNMT molecule showed outstanding coordination ability with metal ions to form diverse metal complexes and coordination frameworks. It was found that the conformation of the energetic ligand as well as the framework structure can be tuned by the deprotonation of DNMT and the corresponding metal centers. Interestingly, a rare metal–π(tetrazole) coordinate bond was also observed in ECP 3, which is valuable for designing new ECPs and energetic metal complexes (EMCs). A new method has been developed for predicting the energetic properties of EMCs and ECPs. The calculation results indicate that the DNMT-based ECPs have good detonation performance and can be used as lead-free primary explosives. Moreover, the perforated lead plate test reveals the extensive application of the DNMT-based ECPs in emerging laser-initiated explosives. Compared to pure DNMT, the DNMT-based ECPs show significantly enhanced thermal stability. The mechanisms behind different detonation performances and thermal stabilities among the DNMT-based ECPs were also discussed. All the results will be valuable for the future development of ECPs in the applications of lead-free primary explosives. [ABSTRACT FROM AUTHOR]

Benzoate substituted with a cationic quaternary ammonium group at the para‐position, [4‐(CH3)3N(C6H4)CO2], forms mononuclear alkali metal ion complexes, [4‐(CH3)3N(C6H4)CO2M]+ (M=Li, Na, K, Rb and Cs), which are observed by electrospray‐ionisation mass spectrometry. When mass selected and subjected to collision‐induced dissociation each of these complexes undergoes decarboxylation to produce the mononuclear arylalkali complex cations, [4‐(CH3)3N(C6H4)M]+, which subsequently react with water via hydrolysis to yield the quaternary ammonium cation, (CH3)3NC6H5+. The unexpected product ions, [M((CH3)2NC6H5)]+, [M(CH3OH)]+, and M+, which are associated with the hydrolysis pathway, suggest an unusual reaction occurring within the exit channel ion‐molecule complex, [(CH3)3NC6H5+MOH]+. DFT calculations were used to examine the: decarboxylation reaction of [4‐(CH3)3N(C6H4)CO2M]+, which readily proceeds via a four‐centred transition state; the hydrolysis and SN2 reactions accounting for formation of products in the exit channel, which are connected via a roaming mechanism in which the metal hydroxide moiety migrates from the para‐hydrogen of (CH3)3NC6H5+ to one of the methyl groups. [ABSTRACT FROM AUTHOR]

A series of red-emitting phosphors, Na3.6Y1.8−x(PO4)3:xEu3+, have been synthesized by a high-temperature solid-phase method. The impact of the partial Li+/K+ ion substitution on the crystal structure and photoluminescence (PL) performance of Na3.6Y1.05(PO4)3:0.75Eu3+ phosphor have been investigated. Various techniques have been used for characterization of the as-obtained materials. X-ray diffraction (XRD) analysis was utilized to confirm the composites of these samples, and the morphology and element distribution were examined by scanning electron microscope (SEM) and transmission electron microscope (TEM). This study found that the developed Na3.6Y1.8−x(PO4)3:xEu3+ phosphors exhibited a prominent emission peak at ~620 nm when excited at 393 nm, which corresponded to 5D0 → 7F2 transitions of Eu3+ ions. Furthermore, the robust emission peak at ~705 nm (5D0 → 7F4) of these phosphors enables a better match with plant pigment absorption. Beyond that, the partial substitution of Li+/K+ ions probably changed the crystal structure, and reduces the symmetry around Eu3+, leading to significantly enhanced luminous intensities by 23.24% and 18.29%, with the highest quantum yields (QYs) reaching 99.85% and 96.29%, respectively. Additionally, the prepared phosphors show non-thermal quenching and superior thermal stability at elevated temperatures from 298 to 473 K. These findings and results suggest that Li⁺/K⁺-substituted Na3.6Y1.05(PO₄)₃:0.75Eu3⁺ phosphors can serve as promising red-emitting phosphors for plant lighting applications. [ABSTRACT FROM AUTHOR]

The rapid progress of urbanization and industrialization has led to the accumulation of large amounts of metal ions in the environment. These metal ions are adsorbed onto the negatively charged surfaces of clay particles, altering the total surface charge, double-layer thickness, and chemical bonds between the particles, which in turn affects the interactions between them. This causes changes in the microstructure, such as particle rearrangement and pore morphology adjustments, ultimately altering the mechanical behavior of the soil and reducing its stability. This study explores the effects of four common metal ions, including monovalent alkali metal ions (Na+, K+) and divalent heavy metal ions (Pb2+, Zn2+), with a focus on how ion valence and concentration impact the soil's microstructure and mechanical properties. Microstructural tests show that metal ion incorporation reduces particle size, increases clay content, and transforms the structure from layered to honeycomb-like. Small pores decrease while large pores dominate, reducing the specific surface area and pore volume, while the average pore size increases. Although cation exchange capacity decreases, cation adsorption density per unit surface area increases. Monovalent ions primarily disperse the soil structure, while divalent ions induce coagulation. Macro-mechanical tests reveal that metal ion contamination reduces porosity under loading, with compressibility rises as the ion concentration increases. Soils contaminated with alkali metal ions shows higher compression coefficients at all loads, while heavy metal ions cause higher compression under lower loads. Shear strength, the internal friction angle, and cohesion in metal-ion-contaminated clay decrease compared to uncontaminated field-state clay, with greater declines at higher ion concentrations. The Micropore Morphology Index and hydro-pore structural parameter effectively characterize both micro- and macrostructural properties, establishing a quantitative relationship between HPSP and the engineering properties of metal-ion-contaminated clay. [ABSTRACT FROM AUTHOR]

The Rubik's cube PBA frameworks with infinite structural variations have been obtained by a simple coprecipitation method and exhibits enhanced cycling and rate performance when tested as the anode materials in alkali-ion batteries (LIBs, SIBs, and KIBs). More importantly, the storage mechanism of the Co-Zn PBA frameworks have also been explored by DFT, in-situ XRD, and XPS measurements. [Display omitted] • Successfully synthesized Rubik's Co-M PBAs and explored the storage mechanism of the anode in alkali-metal-ion batteries. PBA frameworks have stood out among metal–organic frameworks because of their easy preparation, excellent stability, porous structures, and rich redox properties. Unfortunately, their non-ideal conductivity and significant volume expansion during cycling prevent more widespread application in alkali-metal-ion (Li+, Na+, and K+) batteries. By changing the type and molar ratio of metal ions, Rubik's PBA frameworks with infinite structural variations were obtained in this study, just like the Rubik's cube undergoes infinite changes during the rotation. X-ray adsorption fine structure measurements have documented the existence and determined the coordination environment of the metal ions in the Rubik's PBA framework. Benefiting from the more stable Rubik's cube structures with diverse composition, enhanced conductivity, and greater adsorption capacity, the obtained Rubik's cubes CoM-PBA anodes, especially CoZn-PBA deliver the enhanced cycling and rate performance in all the alkali-metal-ion batteries. The findings are supported by density functional theory calculations. Ex-situ X-ray photoelectron spectroscopy, and in-situ X-ray diffraction measurements were undertaken to explore the storage mechanism of CoZn-PBA anodes. Our results further demonstrate that the Rubik's cube PBA framework-based materials could be widely applied in the field of alkali-metal-ion batteries. [ABSTRACT FROM AUTHOR]

Designable molecular structures, unique ion‐coordination charge storage mechanisms, and resource sustainability enable organic electrode materials to become potential candidates for alkali metal‐ion batteries (AMIBs). Herein, integrating the excellent π–π stacking ability of Hexaazatriphenylene units and strong electron‐withdrawing properties of cyano (C≡N) groups into one moleuce, a π‐conjugated organic compound 1,4,5,8,9,11‐Hexaazatriphenylenehexacarbonitrile (HAT‐CN) is synthesized and systematically investigated as electrodes in Li/Na/K‐ion batteries. Explored by mechanism characterizations and density functional theory calculations, HAT‐CN can provide nine redox‐active sites for Na/K‐ions to intercalate/de‐intercalate, among which six Na/K‐ions are distributed evenly to both sides of conjugated skeletons through intermolecular intercalation and three Na/K‐ions are stored with the synergistic effect of C≡N groups. Employing HAT‐CN as electrodes, AMIBs are found to exhibit high reversible capacities, excellent rate capabilities, and stable cycle performances. After 100 cycles at the current density of 100 mA g−1, Na‐ion batteries present 415.6 mAh g−1 with a capacity fading rate of 1.2% per cycle. Meanwhile, K‐ion batteries maintain 345 mAh g−1 with a coulombic efficiency ≈100%. Li‐ion batteries display superlithiation performances with ultra‐high reversible capacity. This work emphasizes the necessity of comprehensively studying the electrochemical performance of organic electrodes in different secondary battery systems and is conducive to maximizing electrode functionality. [ABSTRACT FROM AUTHOR]

Covalent organic framework (COF) membranes feature with well‐developed 1D in‐plane pores and parallelly arranged 2D interlayer gallery, presenting promising platform for precise separations. However, it remains a formidable challenge to construct and regulate membrane channels at angstrom scale. Herein, pH‐sensitive dopamine is taken advantage to elaborately engineer the spatial size of 1D/2D channels in COF membranes for the separations of alkali metal ions. Acid treatment allows monomolecular dopamine to segment 1D in‐plane pores of COF membrane, achieving ultramicroporous regulation from 1.25 nm to 0.71 nm, which enables high selectivity of 18.7 for K+/Li+ separation. Molecular dynamics simulations reveal the higher dehydration degree, weaker channel‐cation interaction and faster diffusion coefficient of K+ than Li+. For alkaline treatment, dopamine self‐polymerizes to form nanoparticles between COF layers, which enlarges the 2D interlayer channels from 0.33 nm to 0.45 nm in COF membrane, enabling high‐permeance ion/molecule separations. The water permeance increases 86.7% to 404 L m−2 h−1 bar−1, without the sacrifice of membrane sieving ability. Both cation separation and ion/molecule separation performances outperform the current state‐of‐the‐art membranes. This dopamine‐mediated channel engineering strategy may provide the new insights for the design of membrane channels in precise separations. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal "Dalton Transactions: An International Journal of Inorganic Chemistry." It includes the titles and authors of various articles published in the journal, covering topics such as crystal engineering, nonmetallic ion storage, nitrate reduction, and catalytic activity of metal complexes. The journal is published by The Royal Society of Chemistry, a leading chemistry community. [Extracted from the article]

FeS2 is a promising electrode material for alkali metal ion storage due to its high theoretical capacity. However, it still faces critical issues such as suboptimal rate and cycling performances owing to sluggish charge transport and significant volume variations. Herein, we constructed FeS2 (m-FeS2) and pyrite FeS2 (p-FeS2) nanocomposites embedded in N,S-doped carbon nanoboxes (m/p-FeS2@NSCN) to conquer such challenges. The microstructure design of nanoboxes effectively alleviates the stress caused by the volume expansion of FeS2 during lithiation processes, thereby improving the cycling stability of the FeS2 electrode. The marcasite/pyrite compositing design further increases the electronic conductivity of FeS2 and optimizes ion migration. As expected, the target m/p-FeS2@NSCN exhibits improved rate capability (595.5 mA h g−1 at 5.0 A g−1) and robust cycling stability (500 cycles without significant capacity decay at 0.1 A g−1) in lithium-ion batteries. Furthermore, m/p-FeS2@NSCN also shows excellent battery performances and potential application prospects in the field of sodium-ion batteries. It achieves a capacity of 355 mA h g−1 at 10.0 A g−1 and sustains 800 cycles without noticeable capacity decay at 0.5 A g−1. This work offers valuable guidance for rationally designing high-performance energy storage materials for alkali metal ion storage. [ABSTRACT FROM AUTHOR]

Synthetic membrane technology plays an increasingly dominant role in modern industry, boasting remarkable efficiency and low carbon attributes. The ever-growing demand for molecular-level separation necessitates precise structures at the angstrom range with a concomitant low transport resistance, but it still remains a great challenge. Here, we demonstrate an enhanced separation performance towards monovalent cations of two-dimensional (2D) conjugated polymeric carbon nitride (PCN) membranes with angstrom pores, achieved through the strategic incorporation of multivalent ions. Based on the additional ions, the energy barrier of transmembrane transport for individual alkali metal ions could be effectively manipulated. Remarkably, the presence of LaCl3 substantially improves monovalent cation selectivity ratios, improving from 7 to 22 for K+/Li+ in mixtures. More importantly, under an initial concentration gradient, the transport rate of K+ was further enhanced over 1 kmol m−2 h−1, primarily attributed to the low ion transfer barrier. [ABSTRACT FROM AUTHOR]

A series of MgAl 2 O 4 : Cr, Mn, M (M = Li, Na, K) red phosphors were prepared by solution combustion combined with subsequently annealing treatment. The influence of Cr3+ or Mn4+ single-doping, Cr3+ and Mn4+ double-doping and alkali metal ions co-doping on the luminescence performance of MgAl 2 O 4 phosphors were systematically investigated. XRD and SEM were used to characterize the composition and morphology of the phosphors, and the optical absorption, photoluminescent excitation, photoluminescent emission, fluorescence lifetime and chromaticity coordinate were performed to characterize their luminescence properties. Compared with Cr3+ or Mn4+ single-doped MgAl 2 O 4 phosphors, Cr3+ and Mn4+ double-doped ones can achieve red light emission under a wide range of excitation from ultraviolet to visible light. Co doping with alkali metal ion Li enhances the fluorescence intensity and lifetime of MgAl 2 O 4 : Cr, Mn phosphors. [ABSTRACT FROM AUTHOR]

Among the alkali metals, potassium is known to significantly shift selectivity toward value-added, heavier alkanes and olefins in iron-based Fischer–Tropsch synthesis catalysts. The aim of the present contribution is to shed light on the mechanism of action of alkaline promoters through a systematic study of the structure–reactivity relationships of a series of Fe oxide FTS catalysts promoted with Group I (Li, Na, K, Cs) alkali elements. Reactivity data are compared to structural data based on in situ, synchrotron-based XRD and XPS, as well as temperature-programmed studies (TPR-H2, TPC-CO, TPD-CO2, and TPD-H). It has been observed that the alkali elements induced higher carburization rates, higher basicities, and lower adsorbed hydrogen coverages. Catalyst stability followed the trend Na-Fe > unpromoted > Li-Fe > K-Fe > Cs-Fe, being consistent with the ability of the alkali (Na) to prevent active site loss by catalyst reoxidation. Potassium was the most active in promoting high α hydrocarbon formation. It is active enough to promote CO dissociative adsorption (and the formation of FeCx active phases) and decrease the surface coverage of H-adsorbed species, but it is not so active as to cause premature catalyst deactivation by the formation of a carbon layer resulting in the blocking active sites. [ABSTRACT FROM AUTHOR]

To monitor radioactivity and its emissions in retired nuclear facilities, this study established an analytical method for 63 Ni and 55 Fe in mixed soil samples from a decommissioning reactor. After ashing at 400 °C for 4 hours, the sample was dissolved in a mixture of concentrated hydrochloric acid, nitric acid, and hydrofluoric acid, and then heated to dryness and dissolved in 9 mol/L hydrochloric acid. Subsequently, 63Ni and 63Fe were separated and purified using sodium hydroxide precipitation, anon exchange chromatography, and nickel specific rein extraction, and then measured by the liquid scintillation method. The results showed that the final stable recovery rates of Ni and Fe were 98.8% and 95.8%, respectively. The minimum detection limit and minimum detectable activity for 63Ni and 55Fe were 208 (counting) and 0.041 Bq,208 (counting) and 0.144 Bq, respectively. The actual activity concentrations of 63Ni and 55Fe in the samples were 76.9 Bq/g and 30.4 Bq/g, respectively. The recovery simulation experiment was conducted using standard soil substances, achieving a recovery of over 95%. Experiments were conducted on the separation of Ni and Fe from various elements using alkali precipitation and anon exchange chromatography, respectively. Among them, the sodium hydroxide precipitation method effectively coprecipitated Ni and Fe, and removed most of Re,Sr, and all Cs at pH value between 8.7 and 11.1. The decontamination factors for Co,Fe, and Zn in the nickel fraction of anion exchange chromatography were all above 660, wide the decontamination factors for Co,Eu,Mn,Ni, Sr,Zn, and Zr in the iron fraction were all above 2 000. This work also investigated the purification effects of DMG precipitation method and nickel specific resin method on Ni, respectively. The recovery of Ni by DMG precipitation method was 87.14%, and the recovery of Ni by nickel resin method was close to 100% when the nickel interference element ratio was above 10:1. Moreover, the purification effect of interference elements such as Ba, Eu, Fe, Mn, and Sr was the best. Therefore, before using nickel resin, other methods such as alkali precipitation and ion exchange resin should be used for preliminary separation. This method is simple to operate and has a high recovery, which can meet the needs of monitoring 63Ni and 55Fe in retired nuclear facilities. [ABSTRACT FROM AUTHOR]

To decipher the effects of replacing alkali with zinc on thermo-mechanical properties, a series of borosilicate glasses with the molar compositions of 70.65SiO 2 ·21.09B 2 O 3 ·1.88Al 2 O 3 ·1Li 2 O·(5.38- x)R 2 O· x ZnO (x = 0, 0.34, 0.67, 1, 1.34, 2.69, 4.04, and 5.38) were prepared. Upon adding a slight quantity of ZnO, a local extreme point for glass transition temperature (T g) appears. This behavior is deciphered to be originated from two opposite factors. On one hand, T g reduces as a characteristic of the colligative properties for a dilute solution; in addition, T g rises due to the higher field strength, bond energy and covalent characteristic of zinc cations compared to that of alkali ions. Otherwise, based on the evolution of intermediate-range clusters revealed by infrared, Raman and NMR spectra, we elucidate the atomic-scale structural origin, which leads to the nonlinear evolution of elastic moduli and coefficient of thermal expansion with the molar ratio of [ZnO]/([R 2 O]+[ZnO]). [ABSTRACT FROM AUTHOR]

[Display omitted] Interlayer intercalation engineering shows great feasibility to improve the structure stability of the layered oxides. Although high Zn-storage capability has been attained based on the pillar effect of multifarious intercalants, an in-depth understanding the synergistic effect of intercalated multiple metal ions is still in deficiency. Herein, alkali metal ion K+, alkaline earth metal ion Mg2+ and trivalent metal ion Al3+ are introduced into the VO interlayer of V 2 O 5. Due to the different electronegativity and hydrated ion radius of K+, Mg2+ and Al3+, adjusting the relative proportions of these metal ions can achieve an appropriate interlayer spacing, stable layer structure and regular morphology, which facilitates the transport kinetics of Zn2+. Under the synergistic effect of pre-intercalated multi-metal ion, the optimal tri-metal ion intercalated hydrated V 2 O 5 cathode exhibits a high specific capacity of 382.4 mAh g−1 at 0.5 A g−1, and long-term cycling stability with capacity retention of 86 % after 2000 cycles at the high current density of 10 A g−1. Ex-situ and kinetic characterizations reveal the fast charge transfer and reversible Zn2+ intercalation mechanism. The multi-ion engineering strategy provides an effective way to design desirable layered cathode materials for aqueous zinc-ion batteries. [ABSTRACT FROM AUTHOR]

Single ion conducting gel polymer electrolytes (GPEs) are characterized as having a certain amount of ionic liquid or solvent incorporated into a single ion-conducting polymer matrix and may afford the advantages of high conductivity and low electrolyte polarization under battery operation. Single ion conducting polymers often suffer from low conductivity due to their reliance on polymer segmental motion to achieve sufficient ion mobility. However, by incorporating specific solvents into a single ion conducting matrix, mobility of the polymer can be enhanced while still maintaining the advantages of single ion conduction. Although many of the solvents used to swell GPEs are mixtures of flammable organic solvents (such as dimethyl carbonate), there are many potential non-reactive, low vapor pressure solvents that could effectively solvate alkali-ion based GPEs and plasticize the polymer matrix to enhance ion conductivity. Adipate-based solvents are a group of non-volatile plasticizers with low viscosities and low vapor pressures at room temperature derived from adipic acid. The ester groups in these solvents may effectively solvate alkali ions such as Na+, leading to higher conductivity, while circumventing issues of flammability found in current alkali-ion conducting electrolytes. This study investigates the properties of sodium-ion conducting GPEs that have been swollen with varying adipate-based solvents and the subsequent dielectric response from the solvent addition. Dielectric relaxation spectroscopy was used to characterize the Na+ conductivity, static dielectric constant, ion-conducting content, and mobility of the membranes before and after the non-volatile solvent uptake. Understanding this relationship will pave the path toward safer, more efff cient solid-state polymer electrolytes for battery applications. [ABSTRACT FROM AUTHOR]

A facile room-temperature synthetic method is presented to produce alkali metal salts of tert-butyl phosphonic acid. The reaction between equimolar amounts of alkali metal carbonates and tert-butyl phosphonic acid in methanol results in the formation of [(tBuPO3H)Li(H2O)3•(H2O)] (1), [(tBuPO3)Na2(H2O)4]n (2), and [(tBuPO3H)K(H2O)]n (3). Solid-state structures of these compounds have been confirmed by single-crystal X-ray diffraction studies and further validated using numerous spectroscopic and analytical techniques. Compounds 1--3 are polymeric solids that are predominantly made up of a 1-D polymeric metal phosphonate chain. This synthetic approach leads to the formation of network structures/polymers in the solid state that otherwise are absent in solution due to the ionic nature of the interaction between the alkali metal ions and phosphonate anions. Apart from the multidentate nature of the phosphonate ligands, additional hydrogen bonding interactions involving water molecules, free P--OH groups, and P O moieties allow these chains to be propagated into 2-D sheets. We have further utilized the completely metalated sodium phosphonate 2 to synthesize layered metal phosphonates [(tBuPO3)Ca(H2O)]n (4), [(tBuPO3)Mn(H2O)]n (5) and [(tBuPO3)Co(H2O)]n (6) via a simple metathesis reaction. [ABSTRACT FROM AUTHOR]

Layered honeycomb iridates receive significant attention in the materials chemistry and physics fields due to the relevance of their crystal structures to the Kitaev model of a quantum spin liquid (QSL). In quest of liquid‐like magnetic ground state signatures, first‐generation alkali metal iridates A2IrO3 ≡ A3[AIr2]O6 (A = Li, Na) and second‐generation iridates T3[AIr2]O6 (T = Cu, Ag, H) are developed. T3[AIr2]O6 is synthesized from A3[AIr2]O6 via metathesis reactions replacing alkali ions located between honeycomb layers. Herein, the next level of chemical and structural complexity is introduced by synthesizing the honeycomb iridate, Cu3ZnIr2O6, in which alkali ions between and within the honeycomb layers are both selectively exchanged with two different transition metals. Analysis of powder X‐Ray diffraction data reveals corrugation of the honeycomb layers in Cu3ZnIr2O6 that hinders complete magnetic frustration and results in a spin glass behavior observed from magnetization and specific heat data. Thus, Cu3ZnIr2O6 represents yet another model, which broadens understanding of intricate relationships between intralayer distortions and magnetism of prospective Kitaev QSL compounds. [ABSTRACT FROM AUTHOR]

Radiative cooling pigments offer new opportunities for sustainable carbon neutrality as zero‐energy and zero‐pollution functional materials. However, it is a challenge to prepare inorganic yellow pigments simultaneously with environmentally friendly, high color value, and weather resistance. In this study, a series of alkali metal‐doped γ‐Sm2S3 yellow pigments with near‐infrared reflectance were synthesized. The doping of alkali metal ions reduced synthesis temperature of Sm2S3 from 1300°C to 1000°C. The change in energy band structure induced by alkali metal doping allows the products to exhibit modifiable colors. Typical γ‐[Na]‐Sm2S3 pigment powders have a high near‐infrared reflectance and impressive colors (b* = 78.6, C* = 77.6). Furthermore, colored films made by prepared yellow powders with polyvinylidene fluoride in certain ratios had high near‐infrared reflectance and excellent environmental weathering, resulting in an effective cooling of 4–8°C in outdoor experiments. This work expands the range of options for energy‐efficient building and yellow colorant. [ABSTRACT FROM AUTHOR]

Fluorinated carbon cathode materials have extremely high theoretical specific energy among known cathode materials of lithium primary batteries. Nevertheless, current fluorinated carbon cannot meet the performance demands of future applications due to the rate performance. This work innovatively applies hollow carbon spheres with a porous structure as carbon sources to prepare fluorinated hollow porous carbon spheres (FHPCS) with high energy density and power density. The porous structure provides more reaction sites for the fluorination process and also shortens the diffusion path of lithium ions during the discharge. Additionally, the hollow porous structure offers more interfacial contact areas and reduces volumetric expansion during discharge reactions. The Li/CFx primary battery has a maximum specific energy of 2007 Wh kg−1 and a maximum power density of 30,400 W kg−1 and can have a capacity retention rate of 80.8% at a current density of 16 A g−1. In addition, FHPCS also has the highest specific energy of 1999 Wh kg−1 and 1711 Wh kg−1 in Na/CFx and K/CFx primary batteries, respectively. The diffusion efficiency of an alkali metal ion is analyzed by the different discharge depths with electrochemical impedance spectroscopy and galvanostatic intermittent titration technique. This effort introduces a new high-performance fluorinated carbon featuring a hollow porous structure and puts forward an innovative approach to designing fluorinated carbon materials. [ABSTRACT FROM AUTHOR]

Using large-scale molecular dynamics simulations, we investigate the surface properties of lithium, sodium, and potassium silicate glasses containing 25 mol % of alkali oxide. The comparison of two types of surfaces, a melt-formed surface (MS) and a fracture surface (FS), demonstrates that the influence of the alkali modifier on the surface properties depends strongly on the nature of the surface. The FS exhibits a monotonic increase of modifier concentration with increasing alkali size while the MS shows a saturation of alkali concentration when going from Na to K glasses, indicating the presence of competing mechanisms that influence the properties of a MS. For the FS, we find that larger alkali ions reduce the concentration of under-coordinated Si atoms and increase the fraction of two-membered rings, implying an enhanced chemical reactivity of the surface. For both types of surfaces, the roughness is found to increase with alkali size, with the effect being more pronounced for the FS than for the MS. The height–height correlation functions of the surfaces show a scaling behavior that is independent of the alkali species considered: The ones for the MS are compatible with the prediction of the frozen capillary wave theory while the ones for the FS show a logarithmic growth, i.e., on the nanoscale these surfaces are not self-affine fractals. The influence of the modifier on the surface properties are rationalized in terms of the interplay between multiple factors involving the size of the ions, bond strength, and charge balance on the surface. [ABSTRACT FROM AUTHOR]

Ultraviolet (UV) photolysis of nitrite ions (NO2−) in aqueous solutions produces a suite of radicals, viz., NO·, O−, ·OH, and ·NO2. The O− and NO· radicals are initially formed from the dissociation of photoexcited NO2−. The O− radical undergoes reversible proton transfer with water to generate ·OH. Both ·OH and O− oxidize the NO2− to ·NO2 radicals. The reactions of ·OH occur at solution diffusion limits, which are influenced by the nature of the dissolved cations and anions. Here, we systematically varied the alkali metal cation, spanning the range from strongly to weakly hydrating ions, and measured the production of NO·, ·OH, and ·NO2 radicals during UV photolysis of alkaline nitrite solutions using electron paramagnetic resonance spectroscopy with nitromethane spin trapping. Comparing the data for the different alkali cations revealed that the nature of the cation had a significant effect on production of all three radical species. Radical production was inhibited in solutions with high charge density cations, e.g., lithium, and promoted in solutions containing low charge density cations, e.g., cesium. Through complementary investigations with multinuclear single pulse direct excitation nuclear magnetic resonance (NMR) spectroscopy and pulsed field gradient NMR diffusometry, cation-controlled solution structures and extent of NO2− solvation were determined to alter the initial yields of ·NO and ·OH radicals as well as alter the reactivity of NO2− toward ·OH, impacting the production of ·NO2. The implications of these results for the retrieval and processing of low-water, highly alkaline solutions that comprise legacy radioactive waste are discussed. [ABSTRACT FROM AUTHOR]

The photocatalytic hydrogen evolution performance of ZnIn 2 S 4 is significantly enhanced by the synergy of Na doping and loading CoSe 2 cocatalyst. [Display omitted] • ZnIn 2 S 4 was modified by doping alkali metal ions and loading CoSe 2 cocatalyst for photocatalytic hydrogen production. • Alkali metal ions doping regulate the band gap and electronic structure of ZnIn 2 S 4 , thereby improving light absorption and charge separation. • Loading CoSe 2 cocatalyst further improves the charge separation and prolongs the lifetime of charge. • CoSe 2 /Na-ZnIn 2 S 4 shows much higher H 2 evolution activity than that of pure ZnIn 2 S 4. Element doping has been demonstrated as a useful strategy to regulate the band gap and electronic structure of photocatalyst for improving photocatalytic activity. Herein, ZnIn 2 S 4 (ZIS) nanosheets were doped with alkali metal ions (Li+, Na+ or K+) by a simple solution method. Experimental characterizations reveal that alkali metal ions doping reduce the band gap, raise the conduction band position, and improve surface hydrophilicity of ZIS. In addition, theoretical calculations show that Na doping increases the electron density at valence band maximum and surrounding S atom, which is conducive to produce more electrons and effective utilization of electrons, respectively. Benefited from above factors, Na-doped ZIS (Na-ZIS) shows the highest photocatalytic hydrogen evolution performance. Furthermore, CoSe 2 cocatalyst is loaded on the surface of Na-ZIS (CS/Na-ZIS), which further improve the charge separation and prolong the lifetime of charges. As a result, the optimized CS/Na-ZIS shows a H 2 evolution rate of 4525 μmol·g−1·h−1 with an apparent quantum efficiency of 27.5 % at 420 nm, which are much higher than that of pure ZIS. This study provides an in-depth understanding of the synergistic effect of Na doping and CoSe 2 cocatalyst in ameliorating photocatalytic activity. [ABSTRACT FROM AUTHOR]

Borosilicate glasses possess excellent melting properties and high stability against chemical attack by aqueous solutions, enabling this glass family to be used in various fields. In this article, we design a novel glass network in order to achieve a chemically robust glass with a low melting temperature. Therefore, the substitution effect of Na2O by MgO, Al2O3, Li2O, and K2O on the chemical durability and melting properties of sodium aluminosilicate glass (i.e., 80SiO2‒5Al2O3‒15Na2O [mol%]) was examined using a standard hydrolytic resistance test and viscosity measurement. Interestingly, we found that the partial replacement of Na2O by Al2O3, Li2O, and K2O (i.e., 80SiO2‒5Al2O3‒15Na2O → 80SiO2‒6.5Al2O3‒9Li2O‒2.25Na2O‒2.25K2O) makes the glass network with chemical durability and melting properties comparable to those of the commercial borosilicate network, resulting in a low HCl consumption of 0.04 mL/g and working temperature of 1238°C (i.e., temperature at viscosity 104 dPa s). The structural characterizations indicate that the high chemical stability of this glass composition originates from the abundance of SiO4 tetrahedrons with three and four bridging oxygen in the glass network as well as the increase in cationic field strength of mixed alkali ions. These excellent melting properties and superior chemical durability of glass imply the possibility of using the mixed alkali metal oxides aluminosilicate glass together with the commercial borosilicate glass in the markets for numerous practical applications. [ABSTRACT FROM AUTHOR]

Sodium‐ion batteries (SIBs) offer excellent potential for meeting the urgent need to develop low‐cost and durable large‐scale electrical energy storage systems. However, the electrochemical performance of currently available SIBs requires substantial improvement to enable their practical deployment. The cathode material is one of the greatest factors impacting SIB performance. The recent development of cathodes with core–shell structures and concentration gradients offers considerable promise for addressing these issues limiting the implementation of SIBs. Therefore, this review presents the primary factors affecting the development of these advanced cathode materials. First, the study discusses recently developed methods for preparing these materials, including precipitation reactions, ion‐exchange reactions, and doping induction. The study further summarizes recent advances in developing layered transition‐metal oxides, poly‐anionic compounds, Prussian blue analogs, organic molecules, and other cathodes with core–shell structures and concentration gradients. Moreover, the state of understanding regarding the Na storage mechanisms of these heterogeneous cathodes is also presented. Finally, the remaining major challenges restricting the development of these cathode structures are discussed and possible solutions are provided. This review also enables the heterogeneous concepts to be expanded to high‐capacity anodes employed in alkali metal ion batteries. [ABSTRACT FROM AUTHOR]

In alkali metal‐doped optical temperature measurement materials, the influence of the electronegativity difference of alkali metal ions on optical temperature measurement performance is rarely reported. This study investigates and analyzes the performance of optical temperature measurement of Na0.5Gd0.5TiO3: Yb, Er doped with Li+ and K+ ions, utilizing the Judd‐Ofelt theory and the first‐principles method. The results reveal that the sensitivities increase with the increase of atomic number of doped alkali metal ions. The reason is that a difference in ionic radius between the dopant and the replaced ion decreases the symmetry of the crystal field and increases the value of Ω2. The doping K+ with low electronegativity leads to an increase in the s orbital electron density of rare earth ions, thereby repelling the d orbital electrons, reducing the d electron density, and decreasing the value of Ω6. Based on the Judd‐Ofelt theory, a combination of a large Ω2 and a small Ω6 is expected to enhance the absolute sensitivity of optical temperature‐measuring materials doped with rare earth ions. Therefore, it can be concluded that doping an ion with low electronegativity and a significant radius difference from the substitution site is beneficial for enhancing the optical temperature sensitivity. [ABSTRACT FROM AUTHOR]

Hard carbon (HC) is a promising anode material in alkali metal ion batteries owing to its cost‐effectiveness, abundant sources, and low working voltage. However, challenges persist in achiving prolonged cycling stability and consistent capacity, and the sodium storage mechanism in HC is still debated. Herein, an unreported biomass precursor, “sisal,” for deriving hard carbon is developed. A series of sisal hemp‐derived hard carbon with natural 3D porous channels are prepared. Through phase characterization and electrochemical testing, the relationship between microstructure and sodium storage capacity is elucidated, further confirming the suitability of the “adsorption‐insertion‐filling” mechanism for sodium storage properties in hard carbon materials. Without the need for any additional modification strategies, this biomass‐derived hard carbon demonstrates excellent electrochemical performance in both sodium‐ion and potassium‐ion batteries (SIBs and PIBs). The as‐prepared HC‐1300 demonstrates excellent ion storage capability, delivering a high reversible capacity of 345.2 mAh g−1 in SIBs and 310 mAh g−1 in PIBs at 0.1 C. Moreover, it maintains a specific capacity of 237.3 mAh g−1 over 1200 cycles at 1 C when used in SIBs. The excellent cycling stability and superior rate performance are also presented in full cells, highlighting its potential for practical applications. [ABSTRACT FROM AUTHOR]

Mixed‐halide perovskites are emerging as excellent photovoltaic candidates because of their tunable bandgaps for semitransparent and tandem perovskite solar cells. However, the notorious film quality originated from the rapidly downward crystallization process susceptibly propagates enormous detrimental defects, which deteriorate the photovoltaic performance and accelerate halide segregation. To address this issue, herein, a multilayer alkalis‐intercalated‐vermiculite is employed as pre‐buried interface modifier to regulate the perovskite lattice property. The matchable lattice structure between perovskite and vermiculite by forming Pb─O bond not only releases the interfacial strain during the film growth but also the embedded alkalis ions can gradually diffuse into perovskite lattice to form a favorable vertical gradient owing to the weak interlamellar van der Waals interaction, playing bis‐roles of atomical lubricant and ion‐reservoir to eliminate detrimental defects. As a result, the film quality and lattice stability is significantly improved with suppressed phase segregation for mixed‐halide perovskites, accompanying a champion efficiency of 11.42% for carbon‐based CsPbIBr2 device, 15.25% for carbon‐based CsPbI2Br device and 23.17% for p‐i‐n inverted (Cs0.05MA0.05FA0.9)Pb(I0.93Br0.07)3 cell. This work provides a new strategy on buried interface engineering for making high‐efficiency and stable perovskite platforms. [ABSTRACT FROM AUTHOR]

Borosilicate glasses are widely used for radioactive waste disposal due to their ability to incorporate a variety of contaminants and radionuclides while exhibiting high durability in various disposal scenarios. This research evaluated the dissolution of borosilicate glass using both single-pass-flow-through (ASTM C1662-18) and product consistency test (ASTM C1285-21) methods with different solutions, including a cementitious-contacted water (called grout-contacted, GC, from this point) and solutions with varying levels of dissolved cementitious species such as Si, Ca, Al. The results indicated that the presence of Ca plays a crucial role in suppressing glass corrosion, as evidenced by the slower normalized dissolution rates, which were one order of magnitude lower for boron and two orders of magnitude lower for rhenium, observed in both Ca-amended and GC solutions compared to the pH 12 buffer solution. This effect is attributed to the formation of a dense, low-porosity, and strongly bonded calcium silicate hydrate (CSH) layer on the glass surface, which implies that a glass corrosion process is influenced by ion exchange involving alkali ions Na+, K+, Ca2+, and hydrogen-containing species. A small number of glass particles treated in the GC solution showed minor corrosion pits in the form of shallow craters with an average diameter of approximately 500 μm. This observation is correlated with a significant reduction, 2000 to 3000 times lower, in the cumulative volume of glass pores, indicating that smaller pore voids were "sealed" in the presence of Ca2+ ions, likely attributed to the formation of CSH precipitation or other corrosion products such as calcium carbonate saturated from the grout solution. These findings suggest that the presence of dissolved Ca in the GC solution can slow down the dissolution of borosilicate glass, contrary to the expected trend of higher dissolution rates resulting from exposure to high alkaline and thus higher pH solutions. [ABSTRACT FROM AUTHOR]

A density functional theory method was employed to conduct theoretical calculations on the pyrolysis reaction pathways of lignin monomer model compounds with an aldehyde or carboxyl group under the catalytic effect of alkali metal ions Na+ and K+, exploring their influence on the formation of the small molecular gaseous products CO and CO2. The results indicate that Na+ and K+ can easily bind with the oxygen-containing functional groups of the lignin monomer model compounds to form stable and low-energy complexes. Except for benzaldehyde and p-hydroxybenzaldehyde, Na+ and K+ can facilitate the decarbonylation reactions of other benzaldehyde-based and phenylacetaldehyde-based lignin monomer model compounds during the pyrolysis process, thereby enhancing the generation of CO. When the characteristic functional groups on the benzene rings of benzaldehyde-based and phenylacetaldehyde-based lignin monomer model compounds are the same, the phenylacetaldehyde-based ones are more prone to undergo decarbonylation than the benzaldehyde-based ones. Additionally, both Na+ and K+ can inhibit the decarboxylation reactions of benzoic acid-based and phenylacetic acid-based lignin monomer model compounds, thereby restraining the formation of CO2. When the characteristic functional groups on the benzene rings of benzoic acid-based and phenylacetic acid-based lignin monomer model compounds are the same, the phenylacetic acid-based ones are more difficult to undergo decarboxylation than the benzoic acid-based ones. [ABSTRACT FROM AUTHOR]

Single-layer blue phosphorus (SLBP) has displayed charming photoelectric performances, but its property in hydrogen storage is not outstanding due to the weak interactions. To expand the application of SLBP in hydrogen storage, we attempt to screen SLBP-based materials with stable structures and strong polarity using density functional theory by doping lightweight elements and grafting alkali metal atoms. The simulation results indicate that the lightweight elements (B, C, N, O and F) doped SLBP systems have more stable structures due to the strong orbital interaction than pure SLBP, and exhibit electron deficient characteristics. Compared to the pure SLBP, the H 2 adsorption energies of the doped systems improve and range from 0.05 to 0.09 eV, but it still cannot meet the requirements of ideal hydrogen storage. Therefore, the lightweight element doped SLBP systems are further grafted by Li atom. Under the synergistic effect of doping lightweight elements and grafting Li atoms, H 2 molecules are strongly polarized, and the corresponding adsorption energies of H 2 reach to 0.16, 0.26, 0.28, 0.30, and 0.10 eV, respectively. It is worth emphasizing in the C-doped SLBP system that the hydrogen storage capacity of reaches 5.53 wt% for each Li atom adsorbs one hydrogen molecule and the corresponding adsorption energy is 0.23 eV/H 2 when the ratio of C to P atoms increases to 6:26. For each Li atom adsorbs two hydrogen molecules in the same hydrogen storage system, the hydrogen storage capacity reaches 10.48 wt% with 0.18 eV/H 2 adsorption energy. We hope these results can provide theoretical basis and scientific guidance for searching for SLBP-based materials with excellent hydrogen storage performances at ambient temperature. [ABSTRACT FROM AUTHOR]

The carbon dioxide reduction reaction (CO2RR) is one of the most promising solutions for realizing carbon neutralization via converting the emitted CO2 into value‐added chemicals. The CC coupling step for CO dimerization is the rate‐determining step for C2 pathways, which have not been thoroughly investigated. Herein, the direct cation stabilization effects on CO dimerization for *OCCO formation on the representative Cu(100) and Pt(100) surfaces are investigated. Density functional theory calculations show that the presence of alkali metal ions plays a vital role in promoting the coupling of *CO monomers on both metal surfaces, where Cu shows a stronger stabilization effect. More importantly, a strong linear correlation (R2 ≈ 0.9) between the dimer stabilization energy and the reaction energy is revealed for the first time, which is a promising indicator for the selectivity of C2 pathways. Further investigations on electronic structures reveal that the promoting effect on *OCCO formation is strongly related to the negative charges of the molecules, in which the negative charge accumulation is favored by the directional electron transfer due to the chemisorption of *OCCO on Cu(100) surface. This work offers insights into the understanding of CC coupling reactions for CO2RR mechanisms. [ABSTRACT FROM AUTHOR]

The high-pressure structure and physical properties of RbNO3 at zero temperature was systematically explored using first-principles calculations based on density generalized theory combined with CALYPSO crystal structure predictions. The accuracy of four different functionals was compared based on experimental data of the RbNO3-IV phase, and the revised PBE for solids (PBEsol) functional was found to be the most reliable. The zero-temperature phase transition sequence of RbNO3 predicted is R3m→Pnma→Pmmn (experimental phase V) based on the PBEsol functional, and the two phase transition pressures are 1.7 and 8.2 GPa. The two phase transitions are first-order phase transitions, and the volume collapse rates reach 3.73% and 2.54%, respectively. This suggests that RbNO3 at low pressure may have new low-temperature phases those are different from P31 structure given by experiment in the room temperature and ambient pressure. In the energy-stabilized pressure interval, all three phases satisfy the "Born-Huangkun" elastic stability criteria, and there is no phonon virtual frequency phenomenon in the whole Brillouin zone, which indicates that they are dynamically stable structures. The electronic property analysis showed that the three phases are semiconductors, and the band gap changes caused by the phase transition are generally small, but the pressure generally inhibits the charge transfer from alkali metal ions to nitrate ions. The high-pressure phase transition sequence predicted in this paper and the elasticity, lattice dynamics, and electronic structure properties of the individual phases can provide a reference for subsequent experimental and theoretical studies. [ABSTRACT FROM AUTHOR]

The electrochemical CO2 reduction reaction (CO2RR) has been widely studied as a promising means to convert anthropogenic CO2 into valuable chemicals and fuels. In this process, the alkali metal ions present in the electrolyte are known to significantly influence the CO2RR activity and selectivity. In this study, we report a strategy for preparing efficient electrocatalysts by introducing a cation‐relaying ligand, namely 6‐mercaptohexanoic acid (MHA), into atom‐precise Au25 nanoclusters (NCs). The CO2RR activity of the synthesized Au25(MHA)18 NCs was compared with that of Au25(HT)18 NCs (HT=1‐hexanethiolate). While both NCs selectively produced CO over H2, the CO2‐to‐CO conversion activity of the Au25(MHA)18 NCs was significantly higher than that of the Au25(HT)18 NCs when the catholyte pH was higher than the pKa of MHA, demonstrating the cation‐relaying effect of the anionic terminal group. Mechanistic investigations into the CO2RR occurring on the Au25 NCs in the presence of different catholyte cations and concentrations revealed that the CO2‐to‐CO conversion activities of these Au25 NCs increased in the order Li+

To date, superconductivity in fullerides has been almost exclusively tuned by (chemical or physical) pressure control of the conduction bandwidth, W at half filling. This contrasts sharply with the extensive control of the superconducting transition temperature, T c in atom-based superconductors such as the cuprates and iron pnictides and chalcogenides via changes in valence (bandfilling). Here, we investigate the effect of doping away from the exactly half-filled C 6 0 3 − level in quaternary face-centered-cubic (fcc) — structured fulleride solids with nominal composition ( Rb 2. 5 − x Csx) Ba 0. 5 C 6 0 (0 ≤ x ≤ 2. 5), in which divalent Ba 2 + ions partially replace monovalent alkali Rb + / Cs + ions. The resulting charged-modified fullerides in which the t 1 u bandwidth is also varied with changing x show a dome-shaped dependence of T c on interfullerene separation in analogy with their half-filled antecedents. However, following electron injection beyond half-filling, the superconductivity dome is found to shift towards shorter interfullerene separations, i.e. towards increased conduction bandwidths. [ABSTRACT FROM AUTHOR]

Summary: Plant yields heavily depend on proper macro‐ and micronutrient supply from the soil. In the leaf cells, nutrient ions fulfill specific roles in biochemical reactions, especially photosynthesis housed in the chloroplast. Here, a well‐balanced ion homeostasis is maintained by a number of ion transport proteins embedded in the envelope and thylakoid membranes. Ten years ago, the first alkali metal transporters from the K+ EFFLUX ANTIPORTER family were discovered in the model plant Arabidopsis. Since then, our knowledge about the physiological importance of these carriers and their substrates has greatly expanded. New insights into the role of alkali ions in plastid gene expression and photoprotective mechanisms, both prerequisites for plant productivity in natural environments, were gained. The discovery of a Cl− channel in the thylakoid and several additional plastid alkali and alkali metal transport proteins have advanced the field further. Nevertheless, scientists still have long ways to go before a complete systemic understanding of the chloroplast's ion transportome will emerge. In this Tansley review, we highlight and discuss the achievements of the last decade. More importantly, we make recommendations on what areas to prioritize, so the field can reach the next milestones. One area, laid bare by our similarity‐based comparisons among phototrophs is our lack of knowledge what ion transporters are used by cyanobacteria to buffer photosynthesis fluctuations. See also the Commentary on this article by Kuang & Romand, 243: 506–508. [ABSTRACT FROM AUTHOR]

[Display omitted] The construction of heterostructure materials has been demonstrated as the promising approach to design high-performance anode materials for sodium ion batteries (SIBs). Herein, micro-mesoporous cobalt phosphosulfide nanowires (Co 3 S 4 /CoP/NC) with Co 3 S 4 /CoP hetero-nanocrystals encapsulating into N -doped carbon frameworks were successfully synthesized via hydrothermal reaction and subsequent phosphosulfidation process. The obtained micro-mesoporous nanowires greatly improve the charge transport kinetics from the facilitation of the charge transport into the inner part of nanowire. When evaluated as SIBs anode material, the Co 3 S 4 /CoP/NC presents outstanding electrochemical performance and battery properties owing to the synergistic effect between Co 3 S 4 and CoP nanocrystals and the conductive carbon frameworks. The electrode material delivers outstanding reversible rate capacity (722.33 mAh/g at 0.1 A/g) and excellent cycle stability with 522.22 mAh/g after 570 cycles at 5.0 A/g. Besides, the Ex-situ characterizations including XRD, XPS, and EIS further revealed and demonstrated the outstanding sodium ion storage mechanism of Co 3 S 4 /CoP/NC electrode. These findings pave a promising way for the development of novel metal phosphosulfide anodes with unexpected performance for SIBs and other alkali ion batteries. [ABSTRACT FROM AUTHOR]

This article provides a comprehensive review of various methods for synthesizing silyl anions, which are important in synthetic organic chemistry. The article discusses different approaches for generating silylboranes, silylaluminum compounds, and disilanes. It highlights the challenges and limitations of each method and presents recent advancements in the field. The authors emphasize the need for further development and improvement in the synthesis of silyl anions to enhance their properties and expand their applications in organic chemistry. The article is written by a group of researchers who have expertise in the field and provides valuable insights for library patrons conducting research on silyl anions. [Extracted from the article]

The harsh geological conditions in the northwest region of China, characterized by widespread saline-alkali soil rich in alkali ions, pose a high risk of Alkali-Silica reaction (ASR) in concrete, particularly due to the presence of ASR-active natural river sands. To address ASR hazards, locally applied concrete often employs High-Performance concrete (HPC) prepared with high proportions of mineral admixtures. In this paper, the alkali content is controlled by adding mixed water with NaOH to the initial configuration of concrete, and three different alkali content states are set up. A 1 mol/L NaOH solution was used to simulate alkaline conditions, and HPC specimens were immersed for an extended period to investigate the effects of equivalent alkali content, immersion time, concrete strength, and admixture on the flexural mechanical properties of HPC under the condition of long-term alkali immersion. Results indicate that, the strength grade was positively correlated with the flexural strength of HPC, but the alkali content was negatively. Initial immersion significantly enhances strength, followed by a gradual decline after long-term immersion. Among three types of admixture addition methods, the impact on flexural strength of HPC immersed in alkaline solution for 10 years follows the order: Double doped air entraining agent and rust inhibitor is greater than single doped air entraining agent is greater than single doped rust inhibitor. In the process of macroscopic test, it is difficult to observe the variation rule of stress and strain in detail, only the final aggregate failure mode can be analyzed. In order to analyze the strain change of the specimen and the failure process of the aggregates more accurately, a three-dimensional random aggregate concrete mesoscopic model was established, and equations relating microhardness to the mechanical properties of concrete components were derived from statistical analysis, providing a basis for parameter selection in the model. Results demonstrate that with increasing strength, the occurrence time of initial cracks is delayed, and the ratio of cracks bypassing aggregates (cracks develop along the ITZ between aggregate and mortar until complete failure) decreases, and the ratio of cracks penetrating aggregates (cracks develop directly through aggregates in an almost vertical direction) increases. [ABSTRACT FROM AUTHOR]

Two inorganic–organic hybrid polyoxotantalates, H4[Na(H2O)5]2[CoII(en)3]2{[CoIII(en)]2(Ta6O19)2}·22H2O (1) and H2K2Na6 (H2O)24{[CoIII(en)]2(Ta6O19)2}·33H2O (2) have been constructed from {[CoIII(en)(Ta6O19)]2}10− ({Co2Ta12}) dimers. Compound 1 has a three-dimensional supramolecular framework with a pcu-type topology. Compound 2 possesses a three-dimensional structure composed of {Co2Ta12} dimers and alkali metal ions (Na+/K+) via coordination bonds. Polyoxotantalates 1 and 2 have been used as active materials for ITO/1/Ag and ITO/2/Ag RRAM devices. These devices exhibit stable non-volatile storage behavior and rewritable resistive switching with high ON/OFF ratios of 1.43 × 103 and 2.17 × 104 for 1-based and 2-based RRAM devices, respectively, and stable cyclic performance during 100-cycle stability tests. This discovery opens up new opportunities for the development of electrical bistability materials. [ABSTRACT FROM AUTHOR]

The discovery of novel electrode materials based on two-dimensional (2D) structures is critical for alkali metal-ion batteries. Herein, we performed first-principles computations to investigate functionalized MXenes, Mo2BT2 (T = O, S), which are also regarded as B-based MXenes, or named as MBenes, as potential anode materials for Li-ion batteries and beyond. The pristine and T-terminated Mo2BT2 (T = O, S) monolayers reveal metallic character with higher electronic conductivity and are thermodynamically stable with an intrinsic dipole moment. Both Mo2BO2 and Mo2BS2 monolayers exhibit high theoretical Li/Na/K storage capacity and low ion diffusion barriers. These findings suggest that functionalized Mo2BT2 (T = O, S) monolayers are promising for designing viable anode materials for high-performance alkali-ion batteries. [ABSTRACT FROM AUTHOR]

The separation of chloride and chlorate ions in the case of a significant excess of chloride ions in a sample is studied by capillary electrophoresis. It is found that under standard separation conditions using a chromate background electrolyte, the signal-to-noise ratio for the chlorate ion peak at c() = 0.1 mM sharply decreases at the concentration ratio c(Cl–)/c() > 100. A number of approaches are considered to eliminate this phenomenon. The most effective approach was to introduce a solution containing acetate ions into the capillary after the sample zone to create conditions for transient isotachophoresis. Optimal parameters for the electrophoretic separation of chloride and chlorate ions are selected at a chloride ion content of 35 mM in the sample. The limit of detection is 0.01 mM chlorate ions (0.03−0.06% based on the mass of dry potassium, sodium, or lithium chlorides). The calibration curve is linear in the range of 0.01−1 mM . The selected conditions allow the determination of chlorate ions at a molar ratio of chloride to chlorate ions of 35−3500. The stacking efficiency factors are 10−70. Perchlorate ions do not interfere with the determination of chlorate ions at the concentrations of both ions of 0.1 mM or lower. The procedure is tested by analysis of table salt. [ABSTRACT FROM AUTHOR]

The dehydrocoupling reaction between alcohols and hydrosilanes is considered to be one of the most atom-economical ways to produce Si–O coupling compounds because its byproduct is only hydrogen (H2), which make it extremely environmentally friendly. In past decades, various kinds of homogeneous catalysts for the dehydrocoupling of alcohols and hydrosilanes, such as transition metal complexes, alkaline earth metals, alkali metals, and noble metal complexes, have been reported for their good activity and selectivity. Nevertheless, the practical applications of these catalysts still remain unsatisfactory, which is mainly restricted by environmental impact and non-reusability. A facile and recyclable heterogeneous catalyst, ultra-small Ag nanoparticles supported on porous carbon (Ag/C) for the etherification of silanes, has been developed. It has high catalytic activity for the Si–O coupling reaction, and the apparent activation energy of the reaction is about 30 kJ/mol. The ultra-small Ag nanoparticles dispersed in the catalyst through the carrier C have an enrichment effect on all reactants, which makes the reactants reach the adsorption saturation state on the surface of Ag nanoparticles, thus accelerating the coupling reaction process and verifying that the kinetics of the reaction of the catalyst indicate a zero-grade reaction. [ABSTRACT FROM AUTHOR]

[Display omitted] In this paper, we have developed a simple and efficient sulfur-amine chemistry strategy to prepare a three-dimensional (3D) porous Ti 3 C 2 T x composite with large amounts of N and S terminal groups. The well-designed 3D macroporous architecture presents enlarged interlayer spacing, large specific surface area, and unique porous structure, which successfully solves the re-stacking issue of MXene during storage and electrode fabrication. It is the amount of concentrated hydrochloric acid added to the S-EDA (ethylenediamine)/MXene colloidal suspension that is critical to the formation of 3D morphology. In addition, N and S terminals on MXene could improve the adsorption ability of K+. Owing to the synergistic effect of the structure design and terminal modification, the N, S codoped three-dimensional porous Ti 3 C 2 T x (3D-NSPM) material shows a high surface capacitive contribution and rapid diffusion kinetics for K+ and Na+. As a result, the as-prepared 3D-NSPM delivers high reversible capacity (237 and 273 mAh g−1 at 0.1 A g−1 for PIBs and SIBs, respectively), superb cycling stability (84.9% capacity retention after 10,000 cycles at 1 A g−1 in PIBs and 74.0% capacity retention after 2200 cycles at 1 A g−1 in SIBs), and excellent rate capability (111 and 196 mAh g−1 at 5 A g−1 for PIBs and SIBs, respectively), which are superior to other MXene-based anodes for PIBs and SIBs. Moreover, the described strategy provides a new insight for constructing the 3D porous structure from 2D building blocks beyond MXene. [ABSTRACT FROM AUTHOR]