Search Results (127)

Rationally designing and synthesizing chemosensors capable of simultaneously detecting both anions and cations via water content modulation is challenging. In this study, we synthesized and characterized a novel triazine calixarene derivative-based iodide and copper ion-selective fluorescent “turn-off” sensor. This dual-channeled fluorescent probe is able to recognize Cu²⁺ and I⁻ ions simultaneously in aqueous systems. The fluorescent sensor s4 was synthesized by displacement reaction of acridine with 1, 3-bis (dichloro-mono-triazinoxy) benzene in acetonitrile. Mass spectrometry (MS), UV-vis, and fluorescence spectra were acquired to characterize the fluorescence response of s4 to different cations and anions, while infrared (IR) spectroscopy and isothermal titration calorimetry (ITC) were employed to study the underlying selectivity mechanism of s4 to Cu²⁺ and I⁻. In detail, s4 displayed extremely high sensitivity to Cu²⁺ with over 80% fluorescence decrement caused by the paramagnetic nature of Cu²⁺ in the aqueous media. The reversible fluorescence response to Cu²⁺ and the responses to Cu²⁺ in the solution of other potential interferent cations, such as Li⁺, Na⁺, K⁺, Ca²⁺, Cd²⁺, Zn²⁺, Sr²⁺, Ni²⁺, Co²⁺ were also investigated. Probe s4 also exhibited very good fluorescence selectivity to iodide ions under various anion (F⁻, Cl⁻, Br⁻, NO₃⁻, HSO₄⁻, ClO₄⁻, PF₆⁻, AcO⁻, H₂PO₄⁻) interferences. In addition to the fluorescent response to I⁻, s4 showed a highly selective naked-eye-detectable color change from colorless to yellow with the other tested anions. Full article

Pyrometallurgical recycling of lithium-ion batteries presents distinct advantages including streamlined processing, simplified pretreatment requirements, and high throughput capacity. However, its industrial implementation faces challenges associated with high energy demands and lithium loss into slag phases. This investigation develops an integrated reduction smelting–chloridizing volatilization process for the comprehensive recovery of strategic metals (Li, Mn, Cu, Co, Ni) from spent ternary lithium-ion batteries; calcium chloride was selected as the chlorinating agent for this purpose. Thermodynamic analysis was performed to understand the phase evolution during reduction smelting and to design an appropriate slag composition. Preliminary experiments compared carbon and aluminum powder as reducing agents to identify optimal operational parameters: a smelting temperature of 1450 °C, 2.5 times theoretical CaCl₂ dosage, and duration of 120 min. The process achieved effective element partitioning with lithium and manganese volatilizing as chloride species, while transition metals (Cu, Ni, Co) were concentrated into an alloy phase. Process validation in an induction furnace with N₂-O₂ top blowing demonstrated enhanced recovery efficiency through optimized oxygen supplementation (four times the theoretical oxygen requirement). The recovery rates of Li, Mn, Cu, Co, and Ni reached 94.1%, 93.5%, 97.6%, 94.4%, and 96.4%, respectively. This synergistic approach establishes an energy-efficient pathway for simultaneous multi-metal recovery, demonstrating industrial viability for large-scale lithium-ion battery recycling through minimized processing steps and maximized resource utilization. Full article

Next-generation recycling technologies must be urgently innovated to tackle huge volumes of spent batteries, photovoltaic panels or printed circuit boards (WPCBs). Current e-waste recycling industrial technology is dominated by traditional recycling technologies. Herein, ionic liquids (ILs), deep eutectic solvents (DESs) and promising oxidizing additives that can overcome some traditional recycling methods of metal ions from e-waste, used in our works from last year, are presented. The unique chemical environments of ILs and DESs, with the application of low-temperature extraction procedures, are important environmental aspects known as “Green Methods”. A closed-loop system for recycling zinc and manganese from the “black mass” (BM) of waste, Zn-MnO₂ batteries, is presented. The leaching process achieves a high efficiency and distribution ratio using the composition of two solvents (Cyanex 272 + diethyl phosphite (DPh)) for Zn(II) extraction. High extraction efficiency with 100% zinc and manganese recovery is also achieved using DESs (cholinum chloride/lactic acid, 1:2, DES 1, and cholinum chloride/malonic acid, 1:1, DES 2). New, greener recycling approaches to metal extraction from the BM of spent Li-ion batteries are presented with ILs ([N_8,8,8,1][Cl], (Aliquat 336), [P_6,6,6,14][Cl], [P_6,6,6,14][SCN] and [Benzet][TCM]) eight DESs, Cyanex 272 and D2EHPA. A high extraction efficiency of Li(I) (41–92 wt%) and Ni(II) (37–52 wt%) using (Cyanex 272 + DPh) is obtained. The recovery of Ni(II) and Cd(II) from the BM of spent Ni-Cd batteries is also demonstrated. The extraction efficiency of DES 1 and DES 2, contrary to ILs ([P_6,6,6,14][Cl] and [P_6,6,6,14][SCN]), is at the level of 30 wt% for Ni(II) and 100 wt% for Cd(II). In this mini-review, the option to use ILs, DESs and Cyanex 272 for the recovery of valuable metals from end-of-life WPCBs is presented. Next-generation recycling technologies, in contrast to the extraction of metals from acidic leachate preceded by thermal pre-treatment or from solid material only after thermal pre-treatment, have been developed with ILs and DESs using the ABS method, as well as Cyanex 272 (only after the thermal pre-treatment of WPCBs), with a process efficiency of 60–100 wt%. In this process, four new ILs are used: didecyldimethylammonium propionate, [N_10,10,1,1][C₂H₅COO], didecylmethylammonium hydrogen sulphate, [N_10,10,1,H][HSO₄], didecyldimethylammonium dihydrogen phosphate, [N_10,10,1,1][H₂PO₄], and tetrabutylphosphonium dihydrogen phosphate, [P_4,4,4,4][H₂PO₄]. The extraction of Cu(II), Ag(I) and other metals such as Al(III), Fe(II) and Zn(II) from solid WPCBs is demonstrated. Various additives are used during the extraction processes. The Analyst 800 atomic absorption spectrometer (FAAS) is used for the determination of metal content in the solid BM. The ICP-OES method is used for metal analysis. The obtained results describe the possible application of ILs and DESs as environmental media for upcycling spent electronic wastes. Full article

Since 2010, BiCuSeO has emerged as a captivating subject of investigation within the realm of thermoelectric materials. Its allure lies in a remarkable confluence of characteristics: a distinctive natural super-lattice structure, an elevated Seebeck coefficient, and a low thermal conductivity, all of which have collectively piqued the intense interest of scientists worldwide. Over the subsequent eight-year period, an extensive array of research endeavors has been meticulously carried out, delving deep into the multifaceted properties of BiCuSeO and exploring avenues for performance enhancement. In this comprehensive review, we embark on a detailed exploration of the fundamental properties of BiCuSeO, encompassing its preparation methodologies, as well as its thermoelectric and mechanical attributes. A thorough synthesis of diverse strategies for optimizing the composition and structure of BiCuSeO is presented, elucidating how these modifications contribute to the enhancement of its thermoelectric and mechanical performance. Finally, the current state of research on N-type BiCuSeO is systematically summarized, offering a panoramic view of the advancements and challenges in this particular area. Full article

Na-layered Li-containing Mn-based cathodes (Na_xLi_yMn_1-yO₂, NLMOs) with additional Na⁺ storage ability resulting from the anionic redox reaction (ARR) hold great promise for sodium-ion batteries (NIBs). However, practical applications of NLMOs encounter challenges, such as migration of transition metal Mn, loss of lattice oxygen, and voltage decay during cycling. Here, we show that Cu plays an important role in enhancing the ARR via the reductive coupling mechanism (RCM). Results shows that a Cu²⁺/Fe³⁺ modified NLMO sample delivers a Na⁺ storage capacity as high as 174 mA h g⁻¹ at 0.2C, higher than that of a Zn²⁺/Fe³⁺ modified NLMO sample (130 mA h g⁻¹) and NLMO (154 mA h g⁻¹). Both in situ and ex situ characterization results indicate that the obvious improvement in the electrochemical performance of the Cu²⁺/Fe³⁺ modified NLMO is due to the additional overlaps between the Cu 3d and O 2p orbitals, which is beneficial for the RCM. As a result, the ARR is enhanced so as to increase the Na⁺ storage capacity. Full article

High-temperature adsorption is a promising technology for carbon mitigation, and it can be applied in direct carbon capture and the integration with utilization. Lithium-based adsorbents, known for their high CO₂ uptake and rapid kinetics, have garnered significant interest. However, adsorption performance, cycling stability, and degradation behavior of this type of adsorbent are rarely reported and compared under comparable conditions. In this work, nine lithium-based adsorbents were synthesized and characterized for their physicochemical properties. Dynamic and isothermal thermogravimetric analysis were conducted to determine adsorption/desorption equilibrium temperatures, evaluate CO₂ adsorption characteristics under varying thermal conditions, and assess cycling stability over 20 adsorption–desorption cycles. The results reveal exceptional initial CO₂ capacities for α-Li₅AlO₄, Li₅GaO₄, Li₅FeO₄, and Li₆ZnO₄; however, these values decline to 30.2 wt.%, 24.3 wt.%, 41.6 wt.%, and 44.2 wt.% after cycling. In contrast, Li₂CuO₂ and Li₄SiO₄ exhibit lower initial capacities but possess superior cycling stability with final values of 21 wt.% and 21.6 wt.%. Phase composition and microstructural analysis identify lithium carbonate and metal oxides as primary products, and microstructural sintering was observed during cycling. This study could provide insights into the trade-offs between the initial capacity and cycling stability of lithium-based adsorbents, offering guidelines for adsorbent optimization through doping or pore engineering to advance high-temperature CO₂ capture technologies. Full article

This study evaluates the wear and corrosion resistance of the Cu-50Ni-5Al alloy reinforced with CeO₂ nanoparticles for potential use as anodes in molten carbonate fuel cells (MCFCs). Cu–50Ni–5Al alloys were synthesized, with and without the incorporation of 1% CeO₂ nanoparticles, by the mechanical alloying method and spark plasma sintering (SPS). The samples were evaluated using a single scratch test with a cone-spherical diamond indenter under progressive normal loading conditions. A non-contact 3D surface profiler characterized the scratched surfaces to support the analysis. Progressive loading tests indicated a reduction of up to 50% in COF with 1% NPs, with specific values drop-ping from 0.48 in the unreinforced alloy to 0.25 in the CeO₂-doped composite at 15 N of applied load. Furthermore, the introduction of CeO₂ decreased scratch depths by 25%, indicating enhanced wear resistance. The electrochemical behavior of the samples was evaluated by electrochemical impedance spectroscopy (EIS) in a molten carbonate medium under a H₂/N₂ atmosphere at 550 °C for 120 h. Subsequently, the corrosion products were characterized using X-ray diffraction (XRD), scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the CeO₂-reinforced alloy exhibits superior electro-chemical stability in molten carbonate environments (Li₂CO₃-K₂CO₃) under an H₂/N₂ atmosphere at 550 °C for 120 h. A marked reduction in polarization resistance and a pronounced re-passivation effect were observed, suggesting enhanced anodic protection. This effect is attributed to the formation of aluminum and copper oxides in both compositions, together with the appearance of NiO as the predominant phase in the materials reinforced with nanoparticles in a hydrogen-reducing atmosphere. The addition of CeO₂ nanoparticles significantly improves wear resistance and corrosion performance. Recognizing this effect is vital for creating strategies to enhance the material’s durability in challenging environments like MCFC. Full article

We have investigated for the first time the temperature, size, and ion-doping concentration dependence of the magnetic properties, band-gap energy, and specific heat of CuFeO₂ in both bulk materials and nanoparticles using a microscopic model (the s-d model) and Green’s function theory. Variations in the ionic radii of the dopant elements compared to those of the host ions introduce strain effects, which alter the exchange-interaction constants. Consequently, the influence of ion doping on the various properties of CuFeO₂ nanoparticles has been elucidated at a microscopic level. The magnetization exhibits an increase when CuFeO₂ is doped with Mn at the Fe site or Li and Ca at the Cu site, whereas doping with Sc or Mg at the Fe site leads to a decrease in magnetization. Regarding the band-gap energy, it increases upon doping with Mg and Sc at the Fe site, while doping with Mn at the Fe site or with Li and Ca at the Cu site results in a decrease. The temperature dependence of the specific heat reveals two distinct peaks, corresponding to the two magnetic phase-transition temperatures. The theoretical results show good qualitative agreement with experimental data, confirming the validity of the proposed model. Full article

Typical greisen-type ore samples from northeastern Tasmania were investigated for their critical metal potential. The samples contain zinnwaldite (KLiFe²⁺Al(AlSi₃O₁₀)(F,OH)₂), a lithium-bearing mica that is prone to excessive breakage during conventional processing, leading to the generation of very-fine-sized particles (i.e., slimes, <20 µm), eventually ending up in tailings and resulting in lithium (Li) loss. To assess whether the natural grain size of valuable minerals could be preserved, the samples were processed using electric pulse fragmentation (EPF). The results indicate that EPF preferentially fragmented along mica-rich veins, maintaining coarse grain sizes, although a lower degree of liberation was observed in fine-grained, massive samples. In addition, the critical metal distribution within zinnwaldite was examined using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) techniques. The results reveal differences in Li content between groundmass zinnwaldite and vein-hosted zinnwaldite and that the zinnwaldite contains the critical elements rubidium (Rb), cesium (Cs), and rare earth elements (REEs: La, Ce, Pr, and Nd). Vein-hosted zinnwaldite has a higher average Li content, whereas groundmass mica contains higher concentrations of Rb, Cs, and REEs. Both mica types host inclusions of bismuth–copper–thorium–arsenic (Bi-Cu-Th-As), which are more abundant in vein-hosted mica. In some of the samples, Bi, Cu, Th, and REEs also occur along the mica cleavage planes, as well as in mineral inclusions. The Li, Rb, and Cs grades are comparable to those of European deposits, such as Cínovec and the Zinnwald Lithium Project. Full article

Boron Neutron Capture Therapy is a re-emerging therapy for the treatment of cancer, and the development of new neutron-reactive nuclei carriers with enhanced efficiency is of great importance. In this work we propose three new boron-based solid compounds, of formulas [Ca(H₂O)₆](C₁₄H₈O₆B)₂ (CaSB), [Cu(C₁₄H₈O₆B)] (CuSB), and [Li(C₁₄H₈O₆B)(H₂O)] (LiSB), usable as nanoparticles for the carriage of the ¹⁰B isotope. The copper atom in CuSB was introduced because it is known that its presence magnifies the effect of the radiation on cells. Furthermore, the lithium atom in LiSB also allows us to include the ⁶Li isotope, which can take part in the nuclear reactions, enhancing the efficiency of the anti-cancer treatment. The compounds were characterized with single-crystal X-ray diffraction to compare the densities of the reactive isotopes in the materials, a key parameter related to the efficiency of the materials. In this work, we used a computational method to calculate the dose absorbed by a tumor mass treated with nanoparticles of the compounds in order to select the most efficient one for the therapy. The results reported in this work are encouraging. Full article

We report a facile galvanic oxidation corrosion method for the preparation of cuprite nanocrystals (Cu₂O) with controllable oxygen vacancies. The Cu₂O microspheres have been employed as active anode materials in lithium-ion batteries (LIBs), exhibiting excellent electrochemical performance. The effect of oxygen vacancies on the electrochemical properties was studied. The oxygen vacancy-rich Cu₂O electrodes exhibited a high specific discharge capacity (1002.3 mAh g⁻¹ at 0.1 C) and remarkable reversibility. Oxygen vacancies in Cu₂O not only promote high electronic conductivity but also provide additional active sites for lithiation/delithiation, further enhancing electrochemical performance. Furthermore, the formation mechanism of Cu₂O during the galvanic oxidation–corrosion process has been proposed. Full article

Lithium niobate (LiNbO₃), a multifunctional crystalline material, has critical importance in advancing holographic storage systems. However, persistent challenges such as optical damage, limited diffraction efficiency, and slow response kinetics hinder its practical implementation. This work systematically examines the correlation between the Zn²⁺ dopant concentration and the defect architecture, photodamage resistance, and holographic storage properties of Zn:Cu:Fe:LiNbO₃ crystals, employing advanced characterization techniques to elucidate structure–property relationships and optimize performance metrics. The experimental data reveal a pronounced Zn²⁺ doping concentration dependence in both photodamage resistance and holographic storage capabilities. Notably, Zn:Cu:Fe:LiNbO₃ crystals doped with 7 mol% Zn²⁺ achieve a substantial 416-fold improvement in photodamage resistance (786.55 J/cm²) relative to the 1 mol% doped variant. Concurrently, these optimally doped crystals demonstrate superior holographic storage performance, characterized by a response time of 196.4 s, a dynamic range of 9.81, a diffraction efficiency of 66.7%, and a sensitivity of 1.04. The observed performance enhancement is fundamentally attributed to Zn²⁺ doping, which concomitantly suppresses intrinsic defect formation and tailors the spatial distribution of Fe³⁺/Cu²⁺ photorefractive centers within the crystal lattice. These mechanistic insights establish critical guidelines for the rational design of next-generation holographic storage materials with optimized photorefractive response and defect engineering capabilities. Full article

A straightforward chemical polymerization process was used to create the polyaniline/LiClO₄/CuO nanoparticle (PLC) nanocomposite, which was then exposed to varying doses of electron beam (EB) radiation and studied. The FESEM, XRD, FTIR, DSC, TG/DTA, and electrochemical measurements with higher EB doses showed clear changes. The FTIR spectra of the PLC nanocomposite showed variations in the C-N and carbonyl groups at 1341 cm⁻¹ and 1621 cm⁻¹, respectively. After a 120 kGy EB dose, the shape changed from a smooth, uneven surface to a well-connected, nanofiber-like structure, creating pathways for electricity to flow through the polymer matrix. The EB irradiation improved the thermal stability by decreasing the melting temperature, and the XRD and DSC studies reveal that the decrease in crystallinity is attributed to the dominant chain scission mechanism. The enhanced absorption and red shift in the wavelength (from 374 nm to 400 nm) observed in the UV-Visible spectroscopy were caused by electrons transitioning from a lower to a higher energy state, with a progressive drop in the band gaps (E_g) from 2.15 to 1.77 eV following irradiation. The dielectric parameters increased with the temperature and electron beam doses because of the dissociation of the ion aggregates and the emergence of defects and/or disorders in the polymer band gaps. This was triggered by chain scission, discontinuity, and bond breaking in the molecular chains at elevated levels of radiation energy, leading to an augmented charge carrier density and, subsequently, enhanced conductivity. The cyclic voltammetry study revealed an enhanced electrochemical stability at a high scan rate of about 600 mV/s for the PLC nanocomposite with the increase in the EB doses. The I-V characteristics measured at room temperature exhibited nonohmic behavior with an expanded current range, and the electrical conductivity was estimated, using the I-V curve, to be around 1.05 × 10⁻⁴ S/cm post 20 kGy EB irradiation. Full article

The copper(II) complexes of general formula [Cu(^GL2^H,H)(Cl)] (A4–A6, G = NO₂, H and OMe, respectively), bearing NNO tridentate Schiff base ligands (^GL2^H,H)⁻ derived from the mono-condensation of 1,3-diaminopropane and G-substituted salicylaldehydes, are here reported. The elongation of the diamine with one additional carbon atom with respect to the triad derived from ethylenediamine [Cu(^GL1^H,H)(Cl)] (A1–A3, G = NO₂, H and OMe, respectively) led to different synthetic procedures, with the difficult isolation of A6 that could be obtained only in few crystals suitable for X-ray diffractions. Operating in acidic conditions to promote the coordination of chloride and expulsion of pyridine from the complex [Cu(^GL2^H,H)(py)](ClO₄) (G = NO₂) allows for obtaining A4. On the other hand, structural rearrangement occurs when G = H, yielding the dinuclear species [Cu₂(μ-saltn)(^HL2^H,H)](ClO₄)⋅0.5MeOH (D5⋅0.5MeOH) instead of the desired A5, which can be obtained by avoiding the use of HCl and operating in the excess of LiCl. Finally, A4 and A5 were investigated as cytotoxic agents against malignant (MDA-MB-231 and 22-Rv1) and healthy (HaCaT) cell lines, and the ability of the most promising A5 to be internalized and interact with cellular targets was studied. Full article

Critical metals in coal-bearing strata have recently emerged as a frontier hotspot in both coal geology and ore deposit research. In the Upper Carboniferous coal-bearing “Si–Al–Fe” strata (Benxi Formation) of the North China Craton (NCC), several critical metals, including Li, Ga, Sc, V, and rare earth elements and Y (REY or REE + Y), have been discovered, with notable mineralization anomalies observed across northern, central, and southern Shanxi Province. However, despite the widespread occurrence of outcrops of the “Si–Al–Fe” strata in the northeastern Qinshui Basin of eastern Shanxi, there has been no prior report on the critical metal content in this region. Traditionally, the “Si–Al–Fe” strata have been regarded as a primary source of clastic material for the surrounding coal seams of the Carboniferous–Permian Taiyuan and Shanxi Formations, which are known to display critical metal anomalies (e.g., Li and Ga). Given these observations, it is hypothesized that the “Si–Al–Fe” strata in the northeastern Qinshui Basin may also contain critical metal mineralization. To evaluate this hypothesis, new outcrop samples from the “Si–Al–Fe” strata of the Benxi Formation in the Yangquan area of the northeastern Qinshui Basin were collected. Detailed studies on critical metal enrichment were assessed using petrographic observations, mineralogy (XRD, X-ray diffractometer), and geochemistry (XRF, X-ray fluorescence spectrometer, and ICP-MS, inductively coupled plasma mass spectrometer). The results indicate that the siliceous, ferruginous, and aluminous rocks within the study strata exhibit varying degrees of critical metal mineralization, mainly consisting of Li and REY, with minor associated Nb, Zr, and Ga. The Al₂O₃/TiO₂, Nb/Y vs. Zr/TiO₂, and Nb/Yb vs. Al₂O₃/TiO₂ diagrams suggest that these critical metal-enriched layers likely have a mixed origin, comprising both intermediate–felsic magmatic rocks and metamorphic rocks derived from the NCC, as well as alkaline volcaniclastics associated with the Tarim Large Igneous Province (TLIP). Furthermore, combined geochemical parameters, such as the CIA (chemical index of alteration), Sr/Cu vs. Ga/Rb, Th/U, and Ni/Co vs. V/(V + Ni), indicate that the “Si–Al–Fe” strata in the northeastern Qinshui Basin were deposited under warm-to-hot, humid climate conditions, likely in suboxic-to-anoxic environments. Additionally, an economic evaluation suggests that the “Si–Al–Fe” strata in the northeastern Qinshui Basin hold considerable potential as a resource for the industrial extraction of Li, REY, Nb, Zr, and Ga. Full article