Trivalent Ions Research Articles

Anomalous Water Penetration in Al3+ Dissolution.

The physicochemical characterization of trivalent ions is limited due to a lack of accurate force fields. By leveraging the latest machine learning force field to model aqueous AlCl3, we discover that upon dissolution of Al3+, water molecules beyond the second hydration shell are involved in the hydration process. A combination of scissoring of coordinating water is followed by synchronized secondary motion of water in the second solvation shell due to hydrogen bonding. Consequently, the water beyond the second solvation penetrates through the second solvation shell and coordinates to the Al3+. Our study reveals a novel microscopic understanding of solvation dynamics for the trivalent ion.

Features of isomorphism of post-spinel phases: result of computer simulation of the composition of inclusions in lower mantle diamonds

The mixing properties of solid solutions of post-spinel phases of the composition CaCr2O4–CaAl2O4, CaCr2O4–CaFe2O4, MgCr2O4–MgAl2O4 and MgCr2O4–MgFe2O4 in the temperature range 1873– 2223 K and pressures 18–25 GPa were studied using the method of semi-empirical modeling. With these PT parameters, the energies of formation of impurity defects of trivalent metal ions (aluminum and iron) in isomorphic sites were estimated. It is shown that (1) the studied binary solid solutions are characterized by complete miscibility, (2) the incorporation of the Fe3+ impurity ion into the post-spinel phases of MgCr2O4 and CaCr2O4 is less favorable in terms of energy than the incorporation of Al3+ ions over the entire range of pressures and temperatures under study. The results obtained were used to interpret the composition of post-spinel phases forming inclusions in lower mantle diamonds.

A Hexanuclear Gallium(III) Complex with a {GaIII6(μ‐OH)10} Core Supported by two Naphthalenediolate‐Based Ligands

We have developed a family of 2,7‐disubstituted 1,8‐naphthalenediol ligands to pre‐organize two metal ions to the distance of two neighboring phosphate diesters of 6‐7 Å in the DNA backbone by a rigid backbone. As complexes with divalent ions (CuII and NiII) bind to DNA, interferes DNA synthesis via PCR, and kills human cancer cells more efficiently than human stem cells of the same proliferation rate, we intended to increase the binding affinity by going from divalent to trivalent ions ‐ especially FeIII. Here, we apply GaIII as redox inactive model for FeIII and obtain for the first time a complex with trivalent ions. However, the structural characterization provides not a dinuclear GaIII complex, but a hexanuclear GaIII complex with a central {GaIII6(m‐OH)10} core, that is yet unprecedented.

Stabilization effect of trivalent chromium on a Cu-based metal-organic framework: Strengthen the original O–Cu–O metal-ligand bond

Cu-BTC materials are widely used because of the high specific surface areas and special pore structures, but the water instability has also been proven. With the adsorption of trivalent chromium, the long-time stability of Cu-based metal-organic frameworks Cu-BTC was got improved in water treatments. A strategy to improve the framework stability in water by the adsorption of trivalent chromium ions into Cu-BTC has been developed. The results showed that the treated Cu-BTC-Cr material has much better water stability and alkaline resistance than the original Cu-BTC.

Spectroscopic Properties of TmF3-Doped CaF2 Crystals.

In this study, we report the growth and comprehensive spectroscopic analysis of TmF3-doped CaF2 crystals, grown using the vertical Bridgman method. The optical absorption and photoluminescence properties of both trivalent (Tm3+) and divalent (Tm2+) thulium ions were investigated. Optical absorption spectra in the UV-VIS-NIR range reveal characteristic transitions of Tm3+ ions, as well as weaker absorption bands corresponding to Tm2+ ions. The Judd-Ofelt (JO) formalism was applied to determine the intensity parameters Ω2, Ω4, and Ω6, which were used to calculate radiative transition probabilities, branching ratios, and radiative lifetimes for the Tm3+ ions. The emission spectra showed concentration-dependent quenching effects, with significant emissions observed for the concentration of 0.1 mol% TmF3 under excitation at 260 nm and 353 nm for Tm3+ ions and at 305 nm for Tm2+ ions. A new UV emission associated with divalent Thulium is reported. The results indicate that higher TmF3 concentrations lead to increased non-radiative energy transfer, which reduces luminescence efficiency. These findings contribute to the understanding of the optical behavior of Tm-doped fluoride crystals, with implications for their application in laser technologies and radiation dosimetry.

Effect of branching in the alkyl chain of diglycolamide on the sequestration of tetravalent actinides: solvent extraction and theoretical studies.

DGA (diglycolamide) ligands show a different extraction behavior of trivalent metal ions by changing the branching alkyl chain length as well as the branching at the methylene position. There are no studies of these factors on the extraction efficiency of these DGA derivatives for the extraction of tetravalent actinides. We have evaluated four different DGA derivatives for the extraction of Np, Pu, and Th from molecular diluents. The n-butyl derivative shows enhanced extraction efficiency and branching gives rise to a reduction in the extraction efficiency of tetravalent ions. The distribution ratios are higher in pure octanol than in a mixture of 30% octanol and 70% n-dodecane. This behavior is in marked difference to that of the extraction of trivalent ions where the addition of an alcohol generally decreases the distribution ratio of trivalent ions due to the ligand-modifier intercation, poor aggregation or micelle formation tendency of DGAs in polar solvents. This suggests that micelle-mediated extraction may not be the dominating factor for the extraction of tetravalent metal ions. Slope analysis suggests the involvement of only two DGA molecules in the extracted species suggesting no/poor possibility of micelle formation in the present system. The higher extraction in pure octanol may be due to a better solubility of the extracted complexes in this polar medium compared to the mixture of octanol and n-dodecane. The water and acid uptake, the back extraction, and the radiation stability of the solvent systems were also investigated. DFT studies were performed to get a better insight into the extraction and complexation of the different DGA solvent systems.

Features of cavitation wear of chrome electrolytic coatings

Cavitation wear is a pervasive phenomenon on water transport. The parts of ship propulsion system as well as the water-cooled surface of cylinder liners of high-speed ship diesels are subjected to cavitation attack. Bright chromium deposits are used to protect the water-cooled surface of liners. Nevertheless, the effect of cracks appearing in the electrolytic chrome coating upon depositing on the cavitation resistance of coating is still an open relevant problem. The goal of the study is to analyze the kinetics and mechanism of the destruction of the bright chrome electrolytic deposit under cavitation attack. The cavitation resistance of chrome electrolytic coatings after grinding and after polishing was studied. The chrome electrolytic coatings were obtained on the plates (90 × 30 × 7 mm in size) made of cast iron SCh21. The chrome was deposited on one side (90 × 30 mm) of the plate placed vertically by flow anodic jet chrome plating in standard electrolyte (kg/m3): chrome anhydride — 250; sulfuric acid — 2.5; trivalent chrome — no more than 5; trivalent iron ions — no more than 10. The electrolyte was prepared using distilled water of a single distillation. The parameters of depositing: electrolyte temperature is 50°C; the current density amounts to 60 A/dm2. Four samples cut from the same plate were used. The coatings on the first two samples were ground using the abrasive paper number 320. The coatings on the second pair of samples were first ground successively on the abrasive paper of different grit: 320, 500, 800, 1000, and 1200, and then polished on the cloth with GOI paste. The cavitation wear tests were carried out on a magnetostrictive vibratory rig in fresh water, the frequency and amplitude of the rig horn vibration was equal to 22 kHz and 28 μm, respectively. The spacing between the chrome-plated sample surface and the horn butt was 0.5 mm. The wear of the samples was evaluated by periodical weighing during testing. The wear of the ground samples turned to be significantly higher, than that of polished samples. The photographs of the surface after different duration of the cavitation attack show that the initial cracks formed on the coating during chrome plating are the centers of cavitation destruction. To reduce the negative impact of initial cracks on the cavitation resistance of the bright chrome electrolytic coatings deposited on the water-cooled surface of the cylinder liners of diesels it is shown expedient to include polishing in the technological process of depositing chrome coatings.

Spectroscopic analysis of La2(WO4)3:Tb3+ phosphor and the delayed concentration quenching of 5D4 →7FJ emission

Trivalent terbium ion doped lanthanum tungstate (La2-xTbx(WO4)3; x = 0.6,1.0,1.4) and terbium tungstate (Tb2(WO4)3) phosphors were successfully synthesized via optimized microwave-assisted co-precipitation technique. The phase purity and crystallinity of the prepared samples were confirmed using the powder XRD technique. The photoluminescence studies revealed a quenching-free emission up to 70 % of Tb3+ doping concentration, even though the emission intensity slightly decreases under host excitation since it becomes less relevant at higher doping concentrations. The experimental and calculated oscillator strengths were evaluated using absorption data and further used to quantify the Judd - Ofelt (JO) intensity parameters, which appeared in a trend of Ω2>Ω4>Ω6 for all samples. As a theoretical approach to assure the excellency of the tungstate host, the radiative parameters were calculated from the emission data using the JO analysis technique. The dominance in the values of stimulated emission cross section and gain bandwidth corresponding to 5D4→7F5 transition of Tb3+ ion of lanthanum tungstate proclaims it as an excellent green phosphor. Hence, the less susceptibility of the tungstate host towards concentration quenching is confirmed in the present work.

Crystal and thermodynamic properties of [formula omitted], (X = Al, Ga)

The crystal and thermodynamic properties of Tb2Ni2X (X = Al, Ga) are reported through measurements of X-ray diffraction (XRD), magnetic susceptibility, χ(T), magnetization, M(μ0H) and heat capacity, Cp(T). XRD pattern analysis confirms the orthorhombic W2CoB2-type structure with the space group of Immm. χ(T) at high temperature for both compounds follows the Curie – Weiss relationship giving an effective magnetic moment close to that expected for the trivalent Tb ion. The low-temperature χ(Cp) data indicate that both compounds order antiferromagnetically at TN = 41 K (40.4 K) and 41.5 K (41.4 K) for Al and Ga compounds, respectively. Cp(T) data of the nonmagnetic counterparts Y2Ni2X (X = Al, Ga) are well described by the Debye model giving a Debye temperature, θD = 236.9(4) K and 225.3(2) K for Al and Ga compounds, respectively. The low-temperature part of the 4f-magnetic contribution to the total heat capacity, C4f(T) can be described by the antiferromagnetic spin-wave dispersion, giving an energy gap Δsw = 47(3) K and 26(2) K for Al and Ga compounds, respectively. The 4f – magnetic entropy S4f(T) for both compounds reaches the value of 2Rln(2) close to their respective TN values.

Photoluminescence and scintillation properties of rare earth doped Lu2O3 single crystal grown by floating zone method

A series of Lu2O3 single crystals doped with rare earth (RE) ions (RE = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb, dopant concentrations are 1 %) was synthesized by the floating zone method. Their photoluminescence (PL) and scintillation properties were evaluated. In PL, emissions due to 4f-4f transitions of trivalent rare earth ions were observed, and those doped with Nd3+, Eu3+, Tb3+ and Er3+ showed the highest emission intensities among the samples. As a scintillation property, those doped with Eu, Gd, and Dy showed a clear photoabsorption peak under 137Cs 662 keV γ-ray irradiation. Among them, the Eu3+-doped Lu2O3 showed the highest scintillation light yield of 67000 photons/MeV. The current work conducted the first systematic study of rare earth doped Lu2O3 single crystals grown by the floating zone method.

Efficient separation of Chromium(III) from Lanthanide(III) via reductive boronization in molten chloride

It is an easy way to recover metals in molten salt by the precipitation-based method, but the selectivity yet remains challenging. Herein, a new separation method employing reductive boronization is proposed, and it is validated by the separation of trivalent chromium and lanthanide ions in molten LiCl-KCl. Although no Cr(III) and La(III) separation was achieved by using NaBH4, Cr(III) was successfully removed via the formation of insoluble CrB2 when B powder was used as the boronization reagent with La(III) remaining entirely in the melt. More than 97% Cr(III) can be removed from the CrCl3-LaCl3-LiCl-KCl melt after a reaction time of 300 min, and the removal rate was retained when the La/Cr ratio varied from 0.1:1 to 10:1. Such reductive boronization method is also valid in other Ln(III)/Cr(III) systems. The boronization process involves the reduction of Cr(III) and the reaction between zero valent metal and boron rather than the simple combination of anions and cations to give precipitates as evidenced by the XPS analyses. The difference in reactivity between Cr(III) and La(III) toward B can be rationalized in terms of their significant difference in the ΔG values of the boronization reactions that mainly correlates with the much lower reduction potential of La(III)/La(0), which makes B an ideal boronization reagent for the separation of trivalent chromium and lanthanide ions in molten chloride.

Selective adsorption of divalent and trivalent cations in porous electrodes.

The capacitive deionization technology uses the electrochemical adsorption of ions in porous electrodes to desalinate seawater or brackish water. Recently, capacitive deionization has gained significant attention as a technology for selective adsorption of ionic species from multicomponent aqueous electrolytes. To investigate the mechanism of selective adsorption at the molecular level, we performed molecular dynamics simulations of aqueous electrolytes and porous electrodes with different divalent or trivalent ions, electrode pore sizes, and applied voltages. We calculated the free energy barriers preventing ions from entering the pores of the electrode and the structure of the water molecules near the ions and the electrode surface under various conditions. Our results suggest that, when the pore and ion sizes are comparable, the steric and electrostatic interactions between the hydrated ions and electrode pores are comparable in magnitude. Moreover, the relative importance of the two interactions can be reversed by slight changes in the external conditions, such as the ion size, valence of the ions, electrode pore size, and applied voltage. Thus, by finely tuning the electrode pore size and the applied voltage, it may be possible to selectively adsorb a particular ionic species from a multicomponent electrolyte through capacitive deionization using a porous electrode.

Fluorescence/colorimetric dual-signal sensor based on carbon dots and gold nanoparticles for visual quantification of Cr3.

A convenient and sensitive dual-signal visualization method is constructed for detection of trivalent chromium ions (Cr3+) based on fluorescent carbon dots (CDs) and glutathione-modified gold nanoparticles (GSH-Au NPs). The fluorescence of CDs can be quenched by GSH-Au NPs due to the inner filter effect. Cr3+ induces aggregation of GSH-Au NPs because of the coordination with GSH on the surface of Au NPs, leading to the red shift of surface plasmon resonance absorption of Au NPs that provides a "turn-on" fluorescence and colorimetric assay for Cr3+. The fluorescence/colorimetric dual signal detection shows high sensitivity for Cr3+ with wide detection linear ranges (0.5-70μM for fluorescence detection and 2-50μM for colorimetric detection) and low detection limits (0.31μM for fluorescence detection and 0.30μM for colorimetric detection). Besides, the method has high selectivity for Cr3+ and can be used for detection of Cr3+ in lake water and tap water samples, showing great potential for visual detection of environmental Cr3+.

Biomass Derived Self-Doped Carbon Nanosheets Enable Robust Hole Transport Layers with Ion Buffer for Perovskite Solar Cells.

The diffusion of iodine species and lead leakage during device degradation represent the main obstacles restricting the commercial application of perovskite solar cells (PSCs). Cobalt loaded ultrathin carbon nanosheets (Co(III)-CNS) derived from biomass are prepared as ion buffer material to construct robust hole transport layers (HTLs). The carbon nanosheets containing trivalent cobalt ions can facilitate the oxidation of the hole transport material while preserving the structural integrity and electrical properties of HTLs under thermal stress, thereby ensuring efficient carrier transport. The two-dimensional ultrathin graphitized lamellar structure of Co(III)-CNS is conducive to alleviate the corrosive effects of the outward diffusion of iodine species on HTLs and silver electrodes, while avoiding irreversible degradation of PSCs. With the improvement of HTL composition and the related interfaces, Co(III)-CNS doped devices can maintain intact device structure under thermal stress and remain above 80% of the original power conversion efficiency (PCE) after thermal aging at 85 oC for 720 h. Notably, the chemical interactions between heteroatoms of self-doped carbon nanosheets and the mobile lead ions can effectively alleviate lead leakage and avoid the potential impacts of device degradation on ecosystem. Ultimately, the Co(III)-CNS doped PSCs with enhanced thermal stability exhibit a champion PCE of 22.32%.

Wide Range Near-Zero Thermal Quenching of Orange-Yellow Phosphor via Impeding Self-Oxidation of Eu2+ for Versatile Optoelectronic Applications.

Li2SrSiO4:Eu2+ is a promising substitute for traditional Y3Al5O12:Ce3+ (YAG:Ce3+) owing to its strong orange-yellow emission of 4f-5d transition originating from Eu2+ dopant, covering the more red-light region. However, its inevitable luminescence thermal quenching at high temperatures and the self-oxidation of Eu2+ strongly impede their applications. Their remediation remains highly challenging. Herein, an anti-self-oxidation(ASO) concept of Eu2+ in Li2SrSiO4 substrate by adding trivalent rare-earth ions (A3+: A = La, Gd, Y, Lu) for highly efficient and stable orange-yellow light emission have been proposed. A significantly increased orange-yellow emission (202% improvement) from Li2Sr0.95A0.05SiO4:Eu2+ with a wide range near-zero thermal quenching is obtained, superior to other Eu2+ activated phosphors. The presence of A3+ ions with various radii modifies the ASO degree of Eu2+ ions, achieving the tunable chemical state, composition, electronic configuration, crystal-field strength, and luminescent characteristics of the developed phosphors. For the proof of the concept, a W-LED device and a PDMS (Polydimethylsiloxane) luminescent film are fabricated, endowing excellent luminescence performance and thermal stability and the huge application prospects of Li2SrSiO4:Eu2+ in lighting and display fields.

The Solid‐State Battery Applicational Technology: Material Characteristics and Charge–Discharge Mechanisms of Iron Chloride Electrodes

ABSTRACTThis study delves into the unique characteristics of an iron chloride cathode with a solid‐state electrolyte (SSE) and the construction of a button cell battery (BT cell) for its evaluation. The iron ions in this system can provide either divalent or trivalent ions, which possess a higher electrical capacity (~200 mAh/g) and competitive advantages. The solid‐state electrolyte materials, iron compounds (chloride, oxide), exhibit high activation in electrochemistry. After the cycle test, the ferric chloride electrolyte transforms into another iron hydroxide compound due to its high activation. The study examines iron, ferric oxide (Fe2O3), and ferrous chloride (FeCl2) as cathode materials and evaluates their impact on the battery. Cyclic voltammetry compares the potential and current values of the redox reactions among the three. Finally, transmission electron microscopy (TEM) explores the ferric chloride layer and iron hydroxide in ferrous chloride. The study focuses on the high electrochemical activity of the iron chloride layer and explores the crystal structure and composition for electrochemical analysis. The findings of this study are crucial for understanding the potential of iron‐ion batteries and the role of iron compounds in improving battery performance.

Transforming contaminant ligands at water–solid interfaces via trivalent metal coordination

In environmental matrices, the migration and distribution of contaminants at water–solid interfaces play a crucial role in their capture or dissemination. Scientists working in environmental remediation and wastewater treatment are increasingly aware of metal–contaminant coordination; however, interfacial behaviors remain underexplored. Here, we show that trivalent metal ions (e.g. Al3+ and Fe3+) mediate the migration of pollutant ligands (e.g. tetracycline (TC) and ofloxacin) to the organic solid interface. In the absence of Al3+, humic acid (HA) colloids (50 mg/L) capture 26.1 % of the TC in water (initial concentration: 10 mg/L) via weak intermolecular interactions (binding energy: −5.71 kcal/mol). Adding Al3+ (2.5 mg/L) significantly enhances the binding of TC to an impressive 94.2 % via Al3+ mediated coordination (binding energy: −84.89 kcal/mol). The significant increase in binding energy results in superior interfacial immobilization. However, excess free Al3+ competes for TC binding via direct binary coordination, as confirmed based on the unique fluorescence of Al3+–TC complexes. Density functional theory calculations reveal the intricate process of HA–Al3+ binding via carboxyl and phenolic hydroxyl sites. The HA–Al3+ flocs then leverage the remaining coordination capacity of Al3+ to chelate with TC. As well as providing insights into the pivotal role of metal ion on the self-purification of natural water bodies, our findings on the interfacial behavior of metal–contaminant coordination will propel coagulation technology to the capture of microscale pollutants.

Metal-organic framework-based off-on fluorescent probe for highly selective and sensitive phosphate detection

The escalating demand for versatile and precise diagnostic tools across various biomedical applications has led to the development of an advanced assay utilizing a fluorescent metal-organic framework (MOF). Our novel approach centers on the synthesis of a controlled-explosive NH2-MIL-53(Fe) MOF, composed of trivalent iron ions and 2-aminoterephthalic acid. This framework possesses the unique capability to produce explosively enhanced fluorescence upon environmental triggers such as phosphate conditions, where it disintegrates to release intensely fluorescent molecules. The surface of NH2-MIL-53(Fe) MOF was further functionalized with poly(acrylic acid-co-maleic acid) polymers (PAAcoMA) to form PAAcoMA@MIL-53(Fe) MOF, thereby enhancing its stability. The presence of phosphate ions is detected by the degree of fluorescence resulting from the unquenching of PAAcoMA@MIL-53(Fe) MOF. This system demonstrates not only high sensitivity but also a broad dynamic range, making it suitable for phosphate ion detection. This innovative technology holds promise for significant advancements in the field of phosphate indicator-based biosensing, with potential applications in the development of PCR kits, thereby supporting a wide range of diagnostic and therapeutic applications.

A novel organic chromo-fluorogenic optical sensor for detecting chromium ions

Sensing trivalent chromium ion (Cr(III)) is widely applied in different areas, such as clinical analysis, marine, environmental monitoring, or even chemical industry applications. Cr(III) has a significant role in the physiological process of human life. It is classified as an essential micronutrient for living organisms. Herein, we developed and designed a novel optical Cr(III) ions sensor film. The investigated sensor has a relatively small dynamic range of 1.24 × 10−3 to 0.5 μM. We report a highly sensitive optical sensor film for Cr(III) ions based on diethyl 3,4-diaminothieno[2,3-b]thiophene-2,5-dicarboxylate (3D) probe. The optical characteristics of the chemical probe exhibit substantial emission at 460 nm under 354 nm excitation. Besides, the interaction of the Cr(III) ions with 3D involves a complex formation with a 2:1 (metal: ligand) ratio, which is convoyed by the main peak enhancement that centered at 460 nm of 3D, and the main peak is red-shifted to 480 nm. The easily discernible fluorescence enhancement effect is a defining characteristic of the complexation reaction between the 3D probe and Cr(III). On the basis of the substantial fluorescence mechanism caused by the formation of a (Cr(III)-3D complex, which inhibits the photo-induced electron transfer (PET) process, the devised optical sensor was proposed. This film exhibits exceptional sensitivity and selectivity due to its notable fluorescence properties, stock shift of less than 106 nm, and detection capabilities at a significantly low detection limit of 0.37 × 10−3 μM. The detection procedure is executed by utilizing a physiological pH medium (pH = 7.4) with a relative standard deviation RSDr (1 %, n = 3). In addition, the 3D sensor demonstrates a high degree of affinity for Cr(III), as determined by the calculation of its binding constant to be 1.40 × 106. We present an impressive optical sensor that is constructed upon a three-dimensional molecule.

Hydrothermal Synthesis of a Valence State Constant High-Entropy Perovskite Sr(TiZrHfVNb)O3 with Improved Photoresponsiveness.

A vanadium ion valence state constant high-entropy perovskite system was synthesized using the hydrothermal method with a trivalent vanadium ion as the vanadium source. The B-site of the perovskite crystal lattice was loaded with five atoms in equal proportions. We tried to synthesize the Sr(TiZrHfVNb)O3 high-entropy system using different methods. However, the valence state of the vanadium ion could only be kept constant using the hydrothermal process in the valence balanced high-entropy composition system. There was significant vanadium element segregation and second phase in the Sr(TiZrHfVNb)O3 system prepared using the solid-state reaction process. Also, obvious vanadium ion valence state ascending from V3+ to V5+ appeared in this high-entropy system with an increase in calcination temperature. Inconspicuous vanadium element segregation appeared at 900 °C, the significant segregation phenomenon and second phase appeared at 1200 °C, and the particle size increased with the temperature. This meant that the high-entropy value could not only stabilize the crystal phase, but also stabilize the ionic valence state. Moreover, the constant trivalent vanadium ion valence state could provide coordinated performance with a wide optical response range and a low band gap for the high-entropy system. This suggests that the system might grow a potential ceramic material for optical applications.