Trivalent Ions Research Articles

Cadmium-treatment efficiency and membrane fouling during electrodialysis of wastewater discharged from zinc smelting

Zinc smelting wastewater contains high concentrations of Cd. Here, the treatment efficiency of Cd using electrodialysis was evaluated. In addition, scale accumulation of ion-exchange membrane (IEM) was analyzed, and fouling control was studied. The results showed that spacers effectively improved the limiting current density but accelerated foulant accumulation. The Cd-treatment efficiency improved to 85.4% without a spacer. Dissolved organic carbon (DOC) and hydrophobic DOC levels in diluted water decreased by 0.65 mg L−1 and 2.1 mg L−1, respectively; in contrast, hydrophilic DOC level increased by 1.45 mg L−1. Some of the hydrophobic DOC in the diluted water was converted to hydrophilic DOC and subsequently to low-molecular-weight (LMW) DOC. DOC level in the concentrated water did not change substantially, but the LMW fraction of the hydrophilic DOC increased. In the cation-exchange membrane, a material composed of calcium sulfate accumulated in the bottom layer, and hydroxides of divalent and trivalent ions accumulated on top of it. In contrast, the anion-exchange membrane was fouled by humic substances. In terms of fouling control, physical and acid cleaning of IEMs was more effective than the reversal operation.

Spectrophotometric and colorimetric trivalent chromium ions detection in aqueous solution based on citrate-capped gold nanoparticles

Spectrophotometric and colorimetric trivalent chromium ions detection in aqueous solution based on citrate-capped gold nanoparticles

Multi-functional bio-film based on sisal cellulose nanofibres and carboxymethyl chitosan with flame retardancy, water resistance, and self-cleaning for fire alarm sensors

Flexible and environmentally friendly bio-based films have attracted significant attention as next-generation fire-responsive sensors. However, the low structural stability, durability, and flame retardancy of pure bio-based films limit their application in outdoor and extreme environments. Here, we report the design of a sustainable bio-based composite film assembled from carboxymethyl-modified sisal fibre microcrystals (C-MSF), carboxymethyl chitosan (CMC), graphene nanosheets (GNs), phytic acid (PA), and trivalent iron ions (Fe3+). Cross-linking between Fe3+ and the C-MSF/CMC matrix and the formation of PA–Fe3+ complexes on the surface of the film imparted excellent mechanical properties, chemical stability, self-cleaning ability, and flame retardancy to the bio-film. Furthermore, the bio-film produced a reversible and sensitive response to temperature at 55.3–214.1 °C, and a fire alarm system made from the bio-film had a fire-response time of 4.6 s. In addition, the char layer of the bio-film retained a stable cyclic response to temperature, enabling it to serve as a fire resurgence sensor with a response time of 2.3 s and recovery time of 11.2 s. This work provides a simple pathway for the fabrication of self-cleaning, flame retardant, and water-resistant bio-films that can be assembled into fire alarm systems for the real-time monitoring of fire accidents and resurgence.

Photoluminescence Properties of Ho3+-doped Fluoroborate Optical Glasses

A trivalent rare earth ion Holmium doped zinc magnesium lithium fluoroborate (ZMLB) glasses with the composition of 10ZnO-10MgO-20LiF-(60-x)B2O3-xHo2O3 (where x = 0, 0.1, 0.3, 0.5 and 1 mol%) were prepared by a well-known melt quenching procedure. The produced glass samples structural, optical, emission and decay curve characteristics have been investigated. From the X-ray diffraction investigation, it is confirmed all the produced glasses possess amorphous nature. The borate-oxygen and vibration bonds were noticed by using Fourier transform infrared analysis. From the ultraviolet-visible absorption studies, the produced glasses absorption peaks were noticed and optical energy band gap values also identified by using Tauc’s relation. Under excitation with 456 nm, the Ho3+ activated ZMLB glasses luminescence spectra consist of three luminescence bands positioned at 550, 677 and 764 nm were corresponding electronic transitions are 5S2 + 5F4 → 5I8, 5F5→ 5I8 and 5F4→ 5I7, respectively. From all these emission bands the prominent emission band observed at 550 nm (green). For the Ho3+ activated ZMLB glasses, the lifetimes were decreased with the enhance of Ho3+ doping content owing to energy transfer in resonance form in between Ho3+ ions. From emission spectra, the CCT and CIE coordinates were estimated, and the CIE values are pointed greenish-yellow area in CIE image. Therefore, all these findings convey that the current zinc magnesium lithium fluoroborate glasses conceivably significant candidate for green display and lighting applications.

Periodicity of the Affinity of Lanmodulin for Trivalent Lanthanides and Actinides: Structural and Electronic Insights from Quantum Chemical Calculations.

Lanmodulin (LanM) is the first identified macrochelator that has naturally evolved to sequester ions of rare earth elements (REEs) such as Y and all lanthanides, reversibly. This natural protein showed a 106 times better affinity for lanthanide cations than for Ca, which is a naturally abundant and biologically relevant element. Recent experiments have shown that its metal ion binding activity can be further extended to some actinides, like Np, Pu, and Am. For this reason, it was thought that LanM could be adopted for the separation of REE ions and actinides, thus increasing the interest in its potential use for industry-oriented applications. In this work, a systematic study of the affinity of LanM for lanthanides and actinides has been carried out, taking into account all trivalent ions belonging to the 4f (from La to Lu) and 5f (from Ac to Lr) series, starting from their chemistry in solution. On the basis of a recently published nuclear magnetic resonance structure, a model of the LanM-binding site was built and a detailed structural and electronic description of initial aquo- and LanM-metal ion complexes was provided. The obtained binding energies are in agreement with the available experimental data. A possible reason that could explain the origin of the affinity of LanM for these metal ions is also discussed.

Dynamics of the Ligand Excited States Relaxation in Novel β-Diketonates of Non-Luminescent Trivalent Metal Ions.

Complexes emitting in the blue spectral region are attractive materials for developing white-colored light sources. Here, we report the luminescence properties of novel coordination compounds based on the trivalent group 3, 13 metals, and the 1-phenyl-3-methyl-4-cyclohexylcarbonyl-pyrazol-5-onate (QCH) ligand. [M(QCH)3] (M = Al, Ga, and In), [M(QCH)3(H2O)] (M = Sc, Gd, and Lu), [Lu(QCH)3(DMSO)], and [La(QCH)3(H2O)(EtOH)] complexes were synthesized and structurally characterized by a single-crystal X-ray diffraction study. It has been found that the luminescence quantum yields of the ligand increase by one order of magnitude upon metal coordination. A significant correspondence between the energies of the ligand's excited states and the luminescence quantum yields to the metal ion's atomic numbers was found using molecular spectroscopy techniques. The replacement of the central ion with the heavier one leads to a monotonic increase in singlet state energy, while the energy of the triplet state is similar for all the complexes. Time-resolved measurements allowed us to estimate the intersystem crossing (ISC) rate constants. It was shown that replacing the Al3+ ion with the heavier diamagnetic Ga3+ and In3+ ions decreased the ISC rate, while the replacement with the paramagnetic Gd3+ ion increased the ISC rate, which resulted in a remarkably bright and room-temperature phosphorescence of [Gd(QCH)3(H2O)].

Strong luminescence intensity and high temperature sensitivity of Er3+-doped KYb(MoO4)2 phosphors optimized by codoping trivalent ions

Strong luminescence intensity and high temperature sensitivity of Er3+-doped KYb(MoO4)2 phosphors optimized by codoping trivalent ions

Rhodamine B-Quinoline based schiff base as fluorescent ‘turn on’ sensor of Al3+, Cr3+, HSO4− and its cytotoxicity and cell imaging application on TPC-1 and HtH-7 cell lines

A designed Rhodamine-B-quinoline based Schiff base chemosensor (RhBQ) has been synthesized and characterized using various spectroscopic techniques. It shows ‘turn on’ fluorescence emission and also colorimetric sensitivity and selectivity towards trivalent metal ions (Al3+ and Cr3+) and anion (HSO4−) present in aqueous medium. Stoichiometry of both metal (Al3+ & Cr3+) - RhBQ complexes are found to be 1:1 using Job’s plot. A notable enhancement in emission intensity for RhBQ-Al3+ (∼341 fold), RhBQ-Cr3+ (∼292 fold), and RhBQ-HSO4− (∼136 fold) complexes compare to RhBQ are observed. Sensing mechanism i.e. opening of spirolactam ring of RhBQ has been confirmed through various spectroscopic techniques such as; 1H NMR, 13C NMR, ESI-MS, TRPL, FT-IR, and DFT based computational study. The limit of detection (LOD) for Al3+, Cr3+, and HSO4− are found to be 2.2 × 10−8 M, 2.12 × 10−8 M and 8.63 × 10−7 M respectively. An advanced level 3 input OR–INHIBIT logic gate are constructed using chelating ligand EDTA. For onsite detection, TLC paper strip spot of the probe, RhBQ is prepared and the detection of Al3+ in few antacid drug are presented. In addition, cell-imaging analysis of Al3+, Cr3+, and HSO4− ions in the Human papillary thyroid carcinoma cell line (TPC-1) & Human anaplastic thyroid cancer cell lines (HtH-7) are presented and shows promising concentration and time-dependent detection results.

Combined recovery of valuable metals from LiFePO4–LiCoO2 system without adding oxidant and reductant

AbstractBased on the oxidation of ferrous ions in lithium iron phosphate and reduction of trivalent cobalt ions in lithium cobaltate, an innovative combined recovery process of lithium iron phosphate and lithium cobaltate powders is proposed. The effects of leaching conditions on leaching performance are studied and the optimal leaching conditions are obtained. Under these conditions, the leaching efficiencies of lithium and cobalt ions reach up to 99.92% and 81.11%, respectively. After removing ferric ions from leachate, the cobalt and lithium ions are separately recovered from the leaching solution. The final precipitation rate of cobalt ions is up to 97.71% with the purity of cobalt oxalate as 99.94%. In addition, the precipitation rate of lithium ions is 78.54% and the purity of lithium carbonate reaches up to 99.94%. Finally, the reaction path and mechanism for the combined recovery of lithium iron phosphate–lithium cobaltate system are preliminary investigated.

Application of TEMPO‐Oxidized Cellulose Nanofibrils/Lanthanide Hybrid Materials TOCN/Eu(III) as Luminescent Sensor

AbstractThis study prepares lanthanide rare earth ion‐doped optical materials TOCN/Eu(III) based on the simple blending reaction of TEMPO‐oxidized cellulose nanofiber (TOCN) with trivalent lanthanide ions (Eu3+). The carboxyl groups on the surface of TOCN are adopted to generate solid ionic bonds with rare earth ions (Eu3+) so that TOCN/Eu(III) emits solid red light under UV irradiation. TOCN/Eu(III) composites are synthesized and proved to selectively detect Fe3+. This finding suggests that the cellulose‐based lanthanide hybrid material, TOCN/Eu(III), holds promising application potential as a fluorescent probe for the selective detection of Fe3+ ions.

Structural and functional properties of a plant NRAMP-related aluminum transporter.

The transport of transition metal ions by members of the SLC11/NRAMP family constitutes a ubiquitous mechanism for the uptake of Fe2+ and Mn2+ across all kingdoms of life. Despite the strong conservation of the family, two of its branches have evolved a distinct substrate preference with one mediating Mg2+ uptake in prokaryotes and another the transport of Al3+ into plant cells. Our previous work on the SLC11 transporter from Eggerthella lenta revealed the basis for its Mg2+ selectivity (Ramanadane et al., 2022). Here, we have addressed the structural and functional properties of a putative Al3+ transporter from Setaria italica. We show that the protein transports diverse divalent metal ions and binds the trivalent ions Al3+ and Ga3+, which are both presumable substrates. Its cryo-electron microscopy (cryo-EM) structure displays an occluded conformation that is closer to an inward- than an outward-facing state, with a binding site that is remodeled to accommodate the increased charge density of its transported substrate.

Electrostatic Interactions in the Formation of DNA Complexes with Cis- and Trans-Isomers of Azobenzene-Containing Surfactants in Solutions with Di- and Trivalent Metal Ions.

The effect of the presence of divalent and trivalent metal ions in solutions upon DNA packaging induced by the photosensitive azobenzene-containing surfactant is considered. It has been shown that the addition of divalent and trivalent metal ions does not affect the DNA-surfactant interaction for both the cis- and the trans-isomers of the surfactant. At the same time, the ionic strength of the solution, which is provided by a certain concentration of the salt, has a huge impact. It affects the association of surfactant molecules with each other and their binding to DNA. It has been shown by computer simulation that cobalt hexamine is attracted to the N7 atom of guanine in the major groove of DNA and does not penetrate into grooves near the AT base pairs.

Downconverted significant luminescence enhancement and structural confinement of a dichromatic nanophosphor for potential applications in NUV-triggered cool pc-WLEDs

Trivalent rare-earth ions activated phosphor-converted near ultraviolet (NUV) triggered white light-emitting diodes (WLEDs) are nowadays being explored as a prominent light source, in the field of lighting. Herein, we prepared a sequence of single-phase Gd2O3:Dy3+,Li+nanophosphor via chemical co-precipitation techniques for the applications in cool pc-WLEDs. To examine the crystal structure, luminescent characteristics, and potential applications of WLEDs, a systematic and comprehensive analysis was conducted. This study extensively investigated the effect of Li+ on the Gd2O3:Dy3+white-emitting nanophosphor. The phase purity and crystal structure of nanophosphors were characterized via powder X-ray diffraction (XRD) analysis. Rietveld refinement clearly quantified that the Gd2O3 host possesses two non-equivalent cationic sites that are coordinated sixfold. The interior morphology and elemental composition were illustrated by high-resolution transmission electron microscopy (HR-TEM) and energy dispersive spectroscopy (EDS). These nanophosphors effectively exhibit dichromatic significant photoluminescence (PL) emission bands of Dy3+ ion for blue and yellow color at 486 and 574 nm, while triggered in the NUV range. The blending of blue and yellow color lights yields a broad spectrum of light that appears white color to the human eye. Besides, it has been observed that the incorporation of Li+ significantly enhances the PL-emission intensity. The critical distance between Gd3+ and Dy3+ was determined, and it showed that the electric multipolar interaction was responsible for the energy transfer quenching mechanism. The colorimetric performance reveals that the CIE coordinates fall within the white region of the color space and that the correlated color temperature (CCT) is substantially higher than 4000 K. The lowest color purity (CP) was found to be 4.0% for x = 2 at.%Li+ ion concentration under excitation wavelength 350 nm. These findings suggest that the prepared nanophosphors are a suitable candidate for application in NUV-triggered cool-WLEDs.

Role of dual doping in zinc oxide for optimizing thermoelectric performance

In this study, we have investigated the effect of dual doping on the thermoelectric performance of zinc oxide (ZnO). Pure ZnO is a wide band-gap semiconductor with a very low carrier concentration in its intrinsic form. Doping ZnO by trivalent impurity ions is considered a viable approach to improve its electrical conductivity by enhancing the concentration of charge carriers in the material. However, the above enhancement in the carrier concentration can also increase the electronic component of the system's thermal conductivity, thereby limiting its thermoelectric performance. It is expected that the dual doping of ZnO can decrease its thermal conductivity without adversely affecting its electrical conductivity. To test the above hypothesis, we doped ZnO with four different pairs of dopants (In/B, In/Al, In/Ga, and In/Bi) and compared the thermoelectric performance of the resulting materials over the temperature range of 350 K–773 K. For the above comparison, Seebeck coefficient, electrical conductivity, and thermal conductivity of the samples were measured, and corresponding power factors (PF) and figure of merits (ZT) were determined. Among all the samples investigated in the study, the In/Bi-doped ZnO exhibited the highest ZT value of 0.37 at 773 K.

Elucidating Trivalent Ion Adsorption at Floating Carboxylic Acid Monolayers: Charge Reversal or Water Reorganization?

We study the adsorption of trivalent neodymium on floating arachidic acid films at the air-water interface by two complementary surface specific probes, sum frequency generation spectroscopy and X-ray fluorescence near total reflection. In the absence of background ions, neodymium ions compensate for the surface charge of the arachidic acid film at a bulk concentration of 50 μM without any charge reversal. Increasing the bulk concentration to 1 mM does not change the neodymium surface coverage but affects the interfacial water structure significantly. In the presence of a high concentration of NaCl, there is overcharging at 1 mM Nd3+, i.e., 30% more Nd3+ than needed to compensate for the surface charge. These results show that the total coverage of neodymium ions is not enough to describe the complete picture at the interface, and interfacial water and ion coverage needs to be considered together to understand more complex ion adsorption and transport processes.

Mechanisms of photoluminescence in cerium oxide pellets with different types of defects

We systematically investigated the photoluminescence (PL) spectra of sintered pellets of cerium oxide, CeO2. The crystal defects were controlled by commonly used techniques in the field of solid-state ionics. We observed the transitions between the O-2p and Ce-4f energy levels in intrinsic CeO2. By doping with trivalent lanthanide ions, which results in oxygen vacancies by charge compensation, a new transition band appears. It involves electronic levels that are similar to those of Ce2O3 clusters, rather than to those of oxygen vacancies. In reduced cerium oxide CeO2-δ, where the number of Ce3+ ions is larger, electrons partially fill the energy levels of defects similar to Ce2O3 clusters, and thus an optical response derived from the Ce-4f–Ce-5d transition appears.

Enhancing multi-state programming and synaptic plasticity through optical stimulation in Bi-alloyed Cs2AgInCl6 double perovskite based memristor

Long-term stability and toxicity issue of the halide perovskite based electronic devices have been aimed to resolve. Considering the requirement of miniaturization without compromising the scaling limit, it is possible to witness, having double halide perovskite as the material of interest. In this work, we have partially substituted the trivalent indium ion with bismuth ion having higher ionic radius in lead-free double perovskite Cs2AgInCl6 by simple solution process. The purpose was novel as it diversified the application of this material in memristor device by initiating optically stimulated response of device conductance. The Au/Cs2AgIn0.8Bi0.2Cl6/ITO device was found to be superior to the Au/Cs2AgInCl6/ITO device in terms of switching window, high-density storage and synaptic plasticity. The improvement in device credibility is attributed to the shift in optical absorption and structural distortion upon bismuth inclusion. Moreover, the film topography of the double perovskite has also enhanced significantly in this process. Bismuth incorporation not only promotes the optical phenomenon in the device but also increases the concentration of bromide vacancies, which is beneficial for the memory and artificial learning performance. Since, the activation energy of bromide ions/vacancies is comparatively low; so, it immensely impacted the device performance due to higher migration rate.

DEHP- extractant binding to trivalent lanthanide Er3+: Fast binding accompanied by concerted angular motions of hydration water.

Solvent extraction of trivalent rare earth metal ions by organophosphorus extractants proceeds via binding of phosphoric acid headgroups to the metal ion. Water molecules in the tightly bound first hydration shell of the metal ions must be displaced by oxygen atoms from phosphoric acid headgroups. Here, we use classical molecular dynamics simulations to explore the event in which a fully hydrated Er3+ binds to its first phosphoric acid headgroup. Approach of the headgroup into the region between the first and second hydration shells leads to a fast ejection of a water molecule that is accompanied by reordering of the hydration water molecules, including discretization of their angular positions and collective rotation about the metal ion. The water molecule ejected from the first shell is located diametrically opposite from the binding oxygen. Headgroup binding places a headgroup oxygen closer to Er3+ than its first hydration shell and creates a loosely bound water that subsequently exchanges between the first shell and its environment. This second exchange of water also occurs at discrete angular positions. This geometrical aspect of binding may be of relevance to understanding the binding and transport of ion-extractant complexes that are expected to occur at the organic-aqueous liquid-liquid interface used in solvent extraction processes.

Radiation synthesis of chitosan/poly(acrylamide-co-maleic acid) hydrogel for the removal of 152+154Eu (III) ions

Using gamma radiation, a chitosan-poly (acrylamide-co-maleic acid) hydrogel was created by copolymerizing acrylamide and maleic acid onto the surface of chitosan. The shape, thermal stability, and structure of the hydrogel were confirmed by Fourier transform infrared analysis, scanning electron microscopy, thermogravimetric analysis, and differential thermal analysis. The batch adsorption of 152+154Eu(III) ions from an aqueous solution showed a rapid initial uptake with an equilibrium time of 24 h at pH (∼4). The Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm models were used to study the adsorption equilibrium data. The adsorption behavior of 152+154Eu(III) ions closely followed the Langmuir isotherm, exhibiting a maximum adsorption capacity of 144.96 mg/g. The adsorption kinetics of 152+154Eu(III) ions are best described by the pseudo-second order model. The thermodynamic parameters were studied and revealed that the adsorption process was spontaneous, exothermic, and favorable at a lower temperature. 0.1 M HCl and AlCl3 desorbed 152+154Eu(III) ions with 97.09% and 88.63%, respectively. Hence, the hydrogel will serve as a starting point for the adsorption of trivalent lanthanide ions in the future.

Luminescence properties of Ln3+ doped BaMoO4 (Ln3+ = Sm3+ and Dy3+) phosphors under UV excitation

Ln3+ doped BaMoO4 (Ln 3+ = Sm3+ and Dy3+) nanoparticles have been synthesized successfully using ethylene glycol as a solvent. All the prepared samples are well indexed into the pure scheelite-type tetragonal structure of BaMoO4, the doping of trivalent ions (Ln3+) in to the bivalent host ions (Ba2+) sites of the BaMoO4 do not change the pure tetragonal structure of BaMoO4 although there is a charge difference between Ba2+ and Ln3+. The SEM image of the prepared BaMoO4 samples shows a number of uniform shuttle-like nanocrystalline with protrusion in the middle. The doping of Ln3+ ions do not change the morphology of the BaMoO4. The photoluminescence study has been carried in detail by measuring the excitation and emission spectra of the prepared samples. The excitation spectrum consists of a broad band with a maximum at about 268 nm thereby demonstrating the transfer of energy from MoO2-4 groups to the doped Ln3+ ions. Yellow emission is dominated over blue in case of Dy3+ doped BaMoO4 and in Sm3+ doped BaMoO4 red emission dominated over other lights under UV excitation. The luminescence intensity is highest at 10 at.% Ln3+ under the UV excitation. Under this UV excitation BaMoO4:Sm3+ exhibits strong orange-red and BaMoO4:Dy3+ greenish-yellow emissions. Excitation of Dy3+ in thin film of BaMoO4 emits an intense yellow color which could be applicable in the field of biological assays and biological fluorescence labeling.