Search Results (101)

Aza-crown ether structures have been proven to be effective in constructing fluorescent biosensors for selectively detecting and imaging alkali metal ions in biological environments. However, choosing the right aza-crown ether for a specific alkali metal ion remains challenging for synthetic chemists because theoretical guidance on the chelating activities between aza-crown ethers and alkali metal ions has not been available up to now. Predicting the physical properties of the chelator–metal complexations poses a greater challenge due to the numerous quantum mechanical functionals and basis sets to be used in any theoretical investigation. In this study, we report a theoretical investigation of different aza-crown ether structures and their selectivities to alkali metal ions via a novel relationship between the binding energy and charge transfer calculated using twelve different quantum mechanical methods, using a myriad of bases, within the Jacob’s Ladder of Chemical Accuracies. Furthermore, this report represents a guide for the synthetic chemist in the selection of aza-crown ethers in the capturing of specific alkali metal ions, primary objectives, while benchmarking different quantum mechanical calculations, as a secondary objective. Full article

¹³⁷Cs is a persistent β/γ-emitter (t_1/2 = 30.1 years) generated from ²³⁵U and ²³⁹Pu fission. It is a critical challenge to efficiently capture ¹³⁷Cs⁺ for nuclear waste management due to its high solubility, environmental mobility, and propensity for biological accumulation. Herein, we prepare a two-dimensional (2D) thiotitanate Rb_0.32TiS₂·0.75H₂O (denoted Rb-TiS₂) using a special molten salt synthesis method, “Mg + RbCl”. Rb-TiS₂ can selectively capture Cs⁺ from aqueous solutions. Its structure features a flexible anionic thiotitanate layer with Rb⁺ as counter ions located at the interlayer spaces. As an ion exchanger, it possesses high adsorption capacity (q_m^Cs = 232.70 mg·g⁻¹), rapid kinetics (the removal rate R > 72% within 10 min), and a wide pH tolerance range (pH = 4–12) for Cs⁺ adsorption. Through a single-crystal X-ray structural analysis, we elucidated the mechanism of Cs⁺ capture, revealing the ion exchange pathways between Cs⁺ and Rb⁺ in Rb-TiS₂. This work not only provides an important reference for the synthesis of transition metal sulfides with alkali metal cations but also proves the application prospect of transition metal sulfides in radionuclide remediation. Full article

Solid-state electrolytes are currently receiving increasing interest due to their high mechanical strength and chemical stability for safe battery construction. However, their poor ion conduction and unclear conduction mechanism need further improvement and exploration. This study focuses on a hybrid solid-state electrolyte containing MOF-based scaffolds, using metal salts as the conductor. In this paper, we employ an ion substitution strategy to manipulate the scaffold structure at the lattice level by replacing hydrogen with larger alkali cations. The research systematically presents how changes in the lattice affect the physical and chemical properties of MOFs and emphasizes the role of scaffold–salt interactions in the evolution of ion conduction. The results reveal that long range-ordered structural distortion can enhance permittivity at 1 Hz, from 58 ohms to more than 10 M ohms, which can boost ion pairs dissociation and improve the transference number from 4.7% to 22.6%. Defects in the lattice can help stabilize the intermediate state in the charge transfer process and lower the corresponding impedance from 2.6 MΩ to 559 Ω. Full article

Modern research technology’s goal is to produce multifunctional materials that require low energy. In this work, we have applied polypyrrole (PPy) doped with dodecyl benzenesulfonate (DBS-) with the addition of polyoxometalates (POM) such as phosphotungstic acid (PTA) forming PPyDBS-PT composites. Two different PTA concentrations (4 mM and 8 mM) were used to form PPyDBS-PT4 and PPyDBS-PT8. The higher concentration of PTA created a highly dense and compact film which can be observed from scanning electron microscopy (SEM cross-section image), and also contains fewer phosphotungstate anions (PT³⁻) inclusion (via energy-dispersive X-ray spectroscopy, EDX). Three different aqueous electrolytes, LiCl (lithium chloride), NaCl (sodium chloride), and KCl (potassium chloride), were applied to investigate how those alkali metal ions perform as typical cation-driven actuators. Cyclic voltammetry with linear actuation revealed the tendency LiCl > NaCl > KCl in view of better strain, charge density, electronic conductivity, and Young’s modulus of PPyDBS-PT4 outperformed PPyDBS-PT8. Chronopotentiometric measurements showed high specific capacitance for PPyDBS-PT4 at 260.6 ± 21 F g⁻¹ with capacity retention after 5000 cycles of 88.5%. The sensor calibration of PPyDBS-PT4 revealed that the alkali cations (Li⁺, Na⁺, and K⁺) can be differentiated from each other. The PPyDBS-PT4 has multifunctional applications such as actuators, sensors, and energy storage. Full article

As a large-volume industrial solid waste generated during the production of wet-process phosphoric acid, the primary disposal method for phosphogypsum (PG) currently involves centralized stockpiling, which requires substantial land use. Additionally, PG contains impurities, such as phosphorus, fluorine, and alkali metals, that may pose potential pollution risks to the surrounding environment. However, the mechanisms governing the co-release of phosphorus and fluorine impurities alongside valuable metal cations during leaching remain unclear, posing challenges to efficient disposal and utilization. This study compares the leaching characteristics of cations and anions in PG of different particle sizes through static pH leaching experiments. Using Visual MINTEQ simulation combined with XRD, XPS, and FT-IR characterization methods, we analyzed the leaching mechanisms and key controlling factors for various metal elements and inorganic elements, like phosphorus and fluorine, under different pH conditions. The experimental results show that Ca, Al, Fe, Ti, Ba, Sr, Y, and PO₄³⁻ in PG are more easily released under acidic conditions, while Si, Zn, Co, and F are primarily influenced by the content of soluble components. The dynamic “dissolution–crystallization” reaction of CaSO₄·H₂O significantly impacts the leaching of fluorine, and the XRD, XPS, and FT-IR characterization results confirm the presence of this reaction during the leaching process. This research provides theoretical guidance for the environmental risk assessment of stockpiled PG and the recovery of phosphorus, fluorine, and valuable metal resources from PG. Full article

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. Full article

The electroanalytical behavior of SnS_x (x = 1, 2) encapsulated into a carbon phase was studied using the galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS). These techniques are widely utilized in battery systems to investigate the diffusion of alkali metal cations in anode and cathode materials depending on the concentration of ions in the host material. Here, we report different calculation methods showing how the applied model affects the derived diffusion coefficient. The calculated value of the apparent chemical diffusion coefficient of sodium ions ($D_{{\mathrm{N}\mathrm{a}}^{+}}$) is in the range of 1 × 10⁻¹⁰ to 1 × 10⁻¹⁵ cm²/s depending on the technique, mathematical protocol, geometry of the electrode material, and applied potential. Full article

Owing to the important role of and increasing demand for lithium resources, lithium extraction is crucial. The use of molecular extractants is a promising strategy for selective lithium recovery, in which the interaction between lithium and the designed extractant can be manipulated at the molecular level. Herein, we demonstrate that anion receptors of tripodal hexaureas can selectively extract Li₂SO₄ solids into water containing DMSO (0.8% water) compared to other alkali metal sulfates. The hexaurea receptor with terminal hexyl chains displays the best Li⁺ extraction selectivity at 2-fold over Na⁺ and 12.5-fold over K⁺. The driving force underpinning selective lithium extraction is due to the combined interactions of Li⁺-SO₄²⁻ electrostatics and the ion–dipole interaction of the lithium–receptor (carbonyl groups and N atoms); the latter was found to be cation size dependent, as supported by computational calculations. This work indicates that anion binding receptors could drive selective cation extraction, thus providing new insights into the design of receptors for ion recognition and separation. Full article

The paper presented delivers the proof for one of the possible solutions to the so-called medium-temperature gap—the lack of electrolytic systems able to efficiently work in a temperature range spanning from 200 to 450 °C. Regardless of the progress made in this field, the commercially available systems are still operating either at close to ambient temperatures, where hydrogen purity requirements are a significant limit, or above ca. 600 °C, where they suffer from increased corrosion and excessive thermal stresses occurring during startup and shutdown. Alkali metal orthoborates (M₃BO₃ M = Li, Na, K, or the mixture of these), in contrast to commercially used tetra-(M₂B₄O₇) and meta-(MBO₂) borates of these metals, are compounds with relatively poorly understood structure and physicochemical properties. The possibility of their application as an electrolyte in a fuel cell is a relatively new idea and has been preliminary reported. Therefore, an extended phase-focused analysis of the materials applied was needed to re-optimize both the synthetic strategy and the application route. Results of PXRD and FT-IR investigations showed, on the one hand, a complicated multi-phase structure, including the main orthoborate phase, as well as the presence of additional borate-based phases, including boric oxoacid. On the other hand, DTA tests proved not only that their melting temperatures are lower than these characteristics for the tetra- and meta-counterparts, but also that cation mixing leads to a subsequent decrease in this important functional parameter of the materials studied. Full article

A systematic study has been conducted on barbiturate complexes of all five alkali metals, Li–Cs, prepared from metal carbonates or hydroxides in an aqueous solution without other potential ligands present, varying the stoichiometric ratio of metal ion to barbituric acid (BAH). Eight polymeric coordination compounds (two each for Na, K, and Rb and one each for Li and Cs) have been characterised by single-crystal X-ray diffraction. All contain some combination of barbiturate anion BA⁻ (necessarily in a 1:1 ratio with the metal cation M⁺), barbituric acid, and water. All organic species and water molecules are coordinated to the metal centres via oxygen atoms as either terminal or bridging ligands. Coordination numbers range from 4 (for the Li complex) to 8 (for the Cs complex). Extensive hydrogen bonding plays a significant role in all the crystal structures, almost all of which include pairs of N–H···O hydrogen bonds linking BA⁻ and/or BAH components into ribbons extending in one dimension. Factors influencing the structure adopted by each compound include cation size and reaction stoichiometry as well as hydrogen bonding. Full article

This study addresses the escalating demand for clean water resources driven by population growth and water quality deterioration. The research focuses on evaluating the efficacy of a nanocomposite material, incorporating zero valent iron nanoparticles into a chelating cation exchange resin matrix, for selectively removing heavy metals from polluted aquatic environments. The selected resin, featuring iminodiacetic acid functional groups, demonstrates notable selectivity for heavy metal cations over alkali earth metals. Column experiments were conducted to assess the nanocomposite’s performance, utilizing a feed solution spiked with heavy metals at concentrations ten times higher than Greek legislation limits for wastewater effluent recycling. The nanocomposite exhibited significant effectiveness for Cu, Cr(VI), and Pb, consistently maintaining Cu levels below detection limits and demonstrating limited breakthrough of Cr(VI) and Pb depending on experimental conditions. However, the removal efficiency was lower for Ni and insufficient for Cd, Zn, and As in this complex multicomponent solution. This research contributes valuable insights into the potential application of the developed nanocomposite for targeted removal of specific heavy metals in contaminated water sources, providing a foundation for further exploration and application in water remediation technologies. Full article

Elevated concentrations of heavy metals in natural waters can cause significant ecological problems. It is therefore essential to ensure their removal from any water discharged into the environment immediately, especially in case of an accident, where there is a risk of releasing large quantities or high concentrations. The aim of this paper is to test a newly developed adsorbent for the removal of heavy metals from aqueous solutions—in particular, it is very fast adsorption, and thus efficiency, during clean-ups. The alkali-activated foamed zeolite adsorbent was laboratory-prepared and -tested in both batch and flow-through arrangements on single and multi-component solutions and compared with natural zeolite. The experimental setup for batch adsorption consisted of a set of samples and solutions containing iron, cobalt, manganese, zinc and nickel. The samples were put on a horizontal shaker with a 500 mg adsorbent loading in a 50 mL solution. The column adsorption experimental setup consisted of a glass column with an inside diameter of 15 mm and a bed length of 165 mm. A measured amount of each adsorbent was added to the column to achieve a filter fixed-bed height of 160 mm. The high efficiency of the tested adsorbent on various heavy metals was confirmed. The adsorbent has a high potential for use in decontamination processes, water protection and landscape revitalization. Due to its rapid precipitation and subsequent fixation of metal cations in the form of insoluble oxide or hydroxide, it can be used as an emergency adsorbent, the great advantage of which is its low production cost and natural origin. Full article

Argillaceous limestone (AL) is comprised of carbonate minerals and clay minerals and is widely distributed throughout the Earth’s crust. However, owing to its low surface area and poorly active sites, AL has been largely neglected. Herein, manganic manganous oxide (Mn₃O₄) was used to modify AL by an in-situ deposition strategy through manganese chloride and alkali stepwise treatment to improve the surface area of AL and enable its utilization as an efficient adsorbent for heavy metals removal. The surface area and cation exchange capacity (CEC) were enhanced from 3.49 to 24.5 m²/g and 5.87 to 31.5 cmoL(+)/kg with modification, respectively. The maximum adsorption capacities of lead (Pb²⁺), copper (Cu²⁺), and nickel (Ni²⁺) ions on Mn₃O₄-modified argillaceous limestone (Mn₃O₄–AL) in mono-metal systems were 148.73, 41.30, and 60.87 mg/g, respectively. In addition, the adsorption selectivity in multi-metal systems was Pb²⁺ > Cu²⁺ > Ni²⁺ in order. The adsorption process conforms to the pseudo-second-order model. In the multi-metal system, the adsorption reaches equilibrium at about 360 min. The adsorption mechanisms may involve ion exchange, precipitation, electrostatic interaction, and complexation by hydroxyl groups. These results demonstrate that Mn₃O₄ modification realized argillaceous limestone resourcization as an ideal adsorbent. Mn₃O₄-modified argillaceous limestone was promising for heavy metal-polluted water and soil treatment. Full article

Perovskites have been recognized as a class of promising materials for optoelectronic devices. We intentionally include excessive Cs⁺ cations in precursors in the synthesis of perovskite CsPbBr₃ nanocrystals and investigate how the Cs⁺ cations influence the lattice strain in these perovskite nanocrystals. Upon light illumination, the lattice strain due to the addition of alkali metal Cs⁺ cations can be compensated by light–induced lattice expansion. When the Cs⁺ cation in precursors is about 10% excessive, the electron–phonon coupling strength can be reduced by about 70%, and the carrier cooling can be slowed down about 3.5 times in lead halide perovskite CsPbBr₃ nanocrystals. This work reveals a new understanding of the role of Cs⁺ cations, which take the A–site in ABX₃ perovskite and provide a new way to improve the performance of perovskites and their practical devices further. Full article

CAN-zeolite was synthesized with a high purity from natural kaolinite via alkali fusion by hydrothermal treatment at a pressure of 1 kbar H₂O. It was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy and nitrogen adsorption at 77 K. The results show that after AK hydrothermal treatment (under specific conditions), the SBET increases from 5.8 m²g⁻¹ to 30.07 m²g⁻¹ which is six times greater. The AK which was a non-porous or macroporous solid (the nitrogen adsorption/desorption of AK is of type II) became mesoporous (N₂ adsorption–desorption isotherms exhibit typical hysteresis of type IV) with a pore size of 5.9 Å. XRD of AK shows the presence of quartz (Q) as impurities, and illite and kaolinite as major fractions; after hydrothermal treatment, the XRD diffractogram shows only fine pics related to CAN-zeolite (with a good crystallinity), confirming the success of the synthesized process. These results suggest that the synthesized CAN-zeolite has the potential to be tested in the removal of heavy metals from waste water as part of a remediation process. Batch reactors were used to evaluate the adsorption isotherms and kinetic studies of heavy metals, cadmium, and lead, by natural kaolinite clay (AK) and synthesized cancrinite zeolite (CAN-zeolite). The results show that the adsorption kinetics of the bivalent heavy metals cadmium and lead are extremely fast with either AK or CAN-zeolite. Equilibrium was reached within 2 min. Adsorption isotherms show that the synthesized CAN-zeolite has a higher adsorption capacity; the retention capacity of lead and cadmium was three times greater than that presented by the natural clay mineral. According to the findings, CAN-zeolite has a higher affinity for PbII (192 mg/g) compared to CdII (68 mg/g). The negative reactive surface sites interacting with these cationic heavy metals resulted in a higher amount of heavy metals adsorption than the cation exchange capacity (CEC). The adsorption information was analyzed using the Langmuir and Freundlich equations. The Langmuir model provided a good fit to the equilibrium data, indicating a monolayer adsorption mechanism. Full article