g-C3N4 modified natural low-grade dolomite-palygorskite: Removal capacity and adsorption mechanism for Gd3.

Rare earth elements (REEs) pose significant environmental challenges due to the wastewater generated during their extraction. Developing efficient adsorbents with simple, economical and eco-friendly methods for removing and recovering REEs from wastewater is highly demanded but full of challenges. This study creates a novel adsorbent (g-C3N4/0.5DPal) for efficient REEs removal and recovery by integrating the low-grade mineral dolomite-palygorskite with g-C3N4 through a "one-pot" calcination method. Characterization techniques including SEM, XRD, FT-IR, XPS, etc., were employed to analyze the structure of the g-C3N4/0.5DPal composite. Batch adsorption experiments focusing on Gd3+ from among the REEs were conducted to evaluate the adsorption performance. The results reveal a remarkable 3.34 times increase in Gd3+ adsorption capacity of g-C3N4/0.5DPal (192.46 mg/g) compared to raw dolomite-palygorskite (57.62 mg/g) at 298 K, highlighting the effectiveness of the modification. The adsorption mechanism involves electrostatic interactions, surface complexation, and cation-π interactions. It is worth noting that g-C3N4 facilitates the conversion of dolomite to calcite during the preparation process, enhancing the Gd3+ adsorption of g-C3N4/0.5DPal. This work offers a promising solution for the removal and recovery of REEs and the high-value utilization of low-grade minerals, addressing both environmental concerns and resource sustainability.

Mixed rare earth metals production from surface soil in Idaho, USA: Techno-economic analysis and greenhouse gas emission assessment.

Rare earth elements are crucial for the development of cutting-edge technologies in various sectors, such as energy, transportation, and health care. Traditional extraction of rare earth elements from soil and ore deposits primarily involves chemical leaching and solvent extraction. Environmental-based biological rare earth element extraction, such as bioleaching, can be a promising alternative to mitigate pollution and hazardous wastes. We investigated the sustainability aspects (techno-economic and environmental impact) of mixed rare earth metals production from soil in Idaho, USA. We focused on the bioleaching of surface soil using techno-economic analysis and "cradle-to-gate" life cycle assessment. The system boundary included collection, transportation, bioleaching, and molten salt electrolysis. Our results revealed that the mixed rare earth metals (including Nd, Ce, and La) production costs approximately $10,851 per metric ton and generates 1.9 × 106 kg CO2 eq./ton. Our results showed that most emissions are due to energy consumption during bioleaching. Over a 100-year time horizon ultrasound-assisted bioleaching can reduce greenhouse gas emissions by approximately 91 % compared to the traditional bioleaching process by decreasing the organic acid leaching process time and energy consumption. Our work demonstrates that higher solids loading in leaching with biological reactions can promote economic feasibility and reduce chemical wastes.

Crystal structure of tetra-phenyl phosphate tetra-kis-[dimethyl (2,2,2-tri-chloro-acet-yl)phos-pho-ramidato]lutetium(III), PPh4[LuL4].

A lutetium(III) complex based on the anion of the ligand dimethyl (2,2,2-tri-chloro-acet-yl)phospho-ramidate (HL) and tetra-phenylphosphonium, of composition PPh4[LuL 4] (L = CAPh = carbacyl-amido-phosphate), or (C24H20)[Lu(C4H6Cl3NO4P)4], has been synthesized and structurally characterized. The X-ray diffraction study of the compound revealed that the lutetium ion is surrounded by four bis-chelating CAPh ligands, forming the complex anion [LuL 4]- with a coordination number of 8[O] for LuIII, while PPh4 + serves as a counter-ion. The coordination geometry around the Lu3+ ion was determined to be a nearly perfect triangular dodeca-hedron. The complex crystallizes in the monoclinic crystal system, space group P21/c, with four mol-ecules in the unit cell. Weak hydrogen bonds O⋯HC(Ph), Cl⋯HC(Ph) and N⋯HC(Ph) are formed between the cations and anions. For a comparative study, HL-based structures were retrieved from the Cambridge Structural Database (CSD) and their geometries and conformations are discussed. A Hirshfeld surface analysis was also performed.

A monodispersed metal-complexing peptide-based polymer for mass cytometry enabling spectral applications.

We report the synthesis of a novel class of metal-complexing peptide-based polymers, which we name HyperMAPs (Hyper-loaded MetAl-complexed Polymers). The controlled solid-phase synthesis of HyperMAPs' scaffold peptide provides our polymer with a well-defined molecular structure that allows for an accurate on-design assembly of a wide variety of metals. The peptide-scaffold features a handle for direct conjugation to antibodies or any other biomolecules by means of a thiol-maleimide-click or aldehyde-oxime reaction, a fluorogenic moiety for biomolecule conjugation tracking, and a well-defined number of functional groups for direct incorporation of metal-chelator complexes. Since metal-chelator complexes are prepared in a separate reaction prior to incorporation to the peptide scaffold, polymers can be designed to contain specific ratios of metal isotopes, providing each polymer with a unique CyTOF spectral fingerprint. We demonstrate the complexing of 21 different metals using two different chelators and provide evidence of the application of HyperMAPs on a 13 parameter CyTOF panel and compare its performance to monoisotopic metal-conjugated antibodies.

Dual Stabilization of a Tri-Metallofullerene Radical Er3@C80: Exohedral Derivatization and Endohedral Three-Center Bonding.

The enclosed space within fullerene molecules, capable of trapping metal clusters, offers an opportunity to investigate the behavior of metal atoms in a highly confined sub-nanometer environment. However, the studies on trimetallofullerenes M3@C80 have been very limited due to their difficult obtainability. In this paper, we present a new method for obtaining a tri-metallofullerene Er3@C80 through exohedral modification of the fullerene cage. Our findings reveal that Er3@C80 exhibits a radical character and can react with the dichlorobenzene radical to generate a stable derivative Er3@C80PhCl2. Theoretical calculations demonstrate the presence of a three-center two-electron metal-metal bond in the center of the fullerene cage. This bond serves to counterbalance the Coulomb repulsion between the Er ions. Consequently, both exohedral derivatization and endohedral three-center bonding contribute to the substantial stability of Er3@C80PhCl2. Furthermore, molecular dynamics simulations indicate that the Er3 cluster within the molecule possesses a rigid triangle structure. The availability of M3@C80 derivatives opens avenues for future investigations into interactions among metal atoms, such as magnetic coupling, within fullerene cages.

2D Ionic Liquid-Like State of Charged Rare-Earth Clusters on a Metal Surface.

Rare-earth complexes are vital for separation chemistry and useful in many advanced applications including emission and energy upconversion. Here, 2D rare-earth clusters having net charges are formed on a metal surface, enabling investigations of their structural and electronic properties on a one-cluster-at-a-time basis using scanning tunneling microscopy. While these ionic complexes are highly mobile on the surface at ≈100 K, their mobility is greatly reduced at 5 K and reveals stable and self-limiting clusters. In each cluster, a pair of charged rare-earth complexes formed by electrostatic and dispersive interactions act as a basic unit, and the clusters are chiral. Unlike other non-ionic molecular clusters formed on the surfaces, these rare-earth clusters show mechanical stability. Moreover, their high mobility on the surface suggests that they are in a 2D liquid-like state.

Modulated Electronic Structure of Co3O4 by Single Atoms for Efficient Anodic Oxygen Evolution in Acid.

The challenge of the practical application of a water electrolyzer system lies in the development of low-manufacturing cost, highly active, and stable electrocatalysts to replace the noble metal ones, in order to enable environmentally friendly hydrogen production on a large scale. Herein, a facile method is proposed for boosting the performance of Co3O4 through the incorporation of large-sized single atoms. Due to the larger ionic radius of rare earth metals than that of Co, the incorporation elongates the bond length of Co─O, resulting in the narrowed d-p band centers and the high spin configuration, which is favorable for the interaction and charge transfer with absorbent (*OH). As a result, the Ce-incorporated Co3O4 with the longest Co─O bond length exhibits the best oxygen evolution reaction (OER) performance, specifically, the turnover frequency is over 17 times higher than that of pristine Co3O4 nanosheet under an overpotential of 400 mV. Powered by a commercial Si solar cell, a two-electrode solar water-splitting device combining Ce-incorporated Co3O4 and Pt delivers a solar-to-hydrogen conversion efficiency of 13.53%. The strategy could provide a new insight for improving the performance of OER electrocatalysts in acid toward practical applications.

Rice Husk-Based Adsorbents for Removal of Metals from Aqueous Solutions.

Adsorption is one of the main methods of water purification. Novel advanced, eco-friendly, cost-effective adsorbents with high adsorption capacity and selectivity are required to remove pollutants from aqueous solutions. Plant polymers are viewed as both prospective adsorbents and as raw materials to produce them instead of conventional adsorption materials. There is widespread interest in using rice husk as a universal sorbent to remove different contaminants from aqueous media because of its surplus availability, low cost, and high content of oxygen containing functional and silanol groups as active sites for adsorptive extraction. Different methods of heat and chemical treatments have been developed to improve the sorption properties of raw rice husk. Unmodified rice husk and rice-husk-based sorbents have been tested to uptake non-ferrous, ferrous, minor, precious, rare, and rare-earth metals and radionuclides from artificial and industrial solutions, natural contaminated water, and industrial wastewater. This review summarizes the results of numerous studies and characterizes the current state of work in this area, with recommendations for further development.

The Effect of Linker-to-Metal Energy Transfer on the Photooxidation Performance of an Isostructural Series of Pyrene-Based Rare-Earth Metal-Organic Frameworks.

The tetratopic linker, 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4 TBAPy) along with rare-earth (RE) ions is used for the synthesis of 9 isostructures of a metal-organic framework (MOF) with shp topology, named RE-CU-10 (RE = Y(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), and Lu(III)). The synthesis of each RE-CU-10 analogue requires different reaction conditions to achieve phase pure products. Single crystal X-ray diffraction indicates the presence of a RE9 -cluster in Y- to Tm-CU-10, while a RE11 -cluster is observed for Yb- and Lu-CU-10. The photooxidation performance of RE-CU-10 analogues is evaluated, observing competition between linker-to-metal energy transfer versus the generation of singlet oxygen. The singlet oxygen produced is used to detoxify a mustard gas simulant 2-chloroethylethyl sulfide, with half-lives ranging from 4.0 to 5.8 min, some of the fastest reported to date using UV-irradiation and < 1 mol% catalyst, in methanol under O2 saturation.

Composition and recycling of smartphones: A mini-review on gaps and opportunities.

After more than a decade since smartphones became consolidated in the market, many recycling solutions have been proposed to deal with them. To continue developing useful solutions and enable adjustment of routes, this mini-review aims to analyse the current research scenario, presenting relevant gaps, trends and opportunities. From a structured searching and screening procedure, a vast source of data was arranged and is available to extract useful information (43 studies on composition and 93 studies on recycling). The study provides discussions about the history of smartphone development, constituent materials and recycling methods for different components, comparisons between feature phones and smartphones and others. Among some conclusions, the authors highlight the lack of studies on pre-extractive methods, green chemistry, recovery of critical and precious metals, determination of priority materials for recovery and solutions for entire devices. In the end, a list containing six research gaps for composition studies and seven research gaps for recycling studies is provided and may be seen as opportunities for future research.

Kaolinite clay as a raw material for erbium extraction.

Currently, due to the high rate of development of the rare-earth industry, new sources of raw materials are being mastered and new technologies for obtaining rare-earth metals (REM) are being developed. Studies have shown that REM in kaolinite clays of Alexeevskoe deposit in Kazakhstan and Egypt deposits in Sinai Peninsula (K-Watt, K-Tech) and in Aswan region (KB,KPL) are mainly represented by erbium (Er). Production of Er concentrate is considered as a by-product in a comprehensive middlings processing of kaolinite clays to produce alumina and building materials. The possibility of obtaining Er concentrate by sulfuric acid leaching and sorption concentration methods has been determined. Optimal technological conditions of kaolinite clays leaching is the use of 5% solution of H2SO4, at temperature 50 °C, duration 60 min and L:S ratio = 5. Under these conditions the separation of REM from the main components Fe2O3, Al2O3, SiO2 is achieved. Concentrates were obtained with the content of the sum of REM oxides from 91.3 to 93.4%, in which the relative content of Er was from 64.89 to 90.82%. The results showed that the developed technology can be used for processing of erbium-containing kaolinite clays of various deposits.

Influence of rare earth metals on volumetric characteristics of Al-Ni-Co-R alloys in crystalline and liquid states.

Density of Al-Ni-Co-R (R = Nd, Sm, Gd, Tb, Yb) glass-forming alloys is studied experimentally by gamma-absorption method in a wide temperature range including crystalline and liquid states. Molar volumes and thermal expansion coefficients are calculated from the experimental data. It is shown that these melts remain strongly microheterogeneous systems at small overheatings above liquidus. Some regimes of melt heat treatment before quenching are discussed.

Application of Molecular Imprinting for Creation of Highly Selective Sorbents for Extraction and Separation of Rare-Earth Elements.

The aim of the work is to study the effectiveness of a molecular imprinting technique application for the creation of highly selective macromolecular sorbents for selective sorption of light and heavy rare-earth metals (for example, samarium and gadolinium, respectively) with subsequent separation from each other. These sorbents seem to be promising due to the fact that only the target rare-earth metal will be sorbed owing to the fact that complementary cavities are formed during the synthesis of molecularly imprinted polymers. In other words, the advantage of the proposed macromolecules is the absence of accompanying sorption of metals with close chemical properties. Two types of molecularly imprinted polymers (MIP) were synthetized based on methacrylic acid (MAA) and 4-vinylpyridine (4VP) functional monomers. The sorption properties (extraction degree, exchange capacity) of the MIPs were studied. The impact of template removal cycle count (from 20 to 35) on the sorption effectivity was studied. Laboratory experiments on selective sorption and separation of samarium and gadolinium from a model solution were carried out.

Expanding the Structural Topologies of Rare-Earth Porphyrinic Metal-Organic Frameworks through Ligand Modulation.

Expanding the structural diversity of porphyrinic metal-organic frameworks (PMOFs) is essential to develop functional materials with novel properties or enhanced performance in different applications. Herein, we establish a strategy to construct rare-earth (RE) PMOFs with unprecedented topology via rational functionalization of porphyrinic ligands. By introducing phenyl/pyridyl groups to the meso-positions of the porphyrin core, the symmetries and connectivities of the ligands are tuned, and three RE-PMOFs (BUT-224/-225/-226) with new topologies are successfully obtained. In addition, BUT-225(Co), with both the Lewis basic and acidic sites, exhibits enhanced CO2 uptake and higher catalytic activity for the cycloaddition of CO2 and epoxides under mild conditions. This work reveals that the RE-PMOFs with novel topologies can be rationally designed and constructed through ligand functionalization, which provides insights into the construction of tailored PMOFs for various applications.

Reviving Oxygen Evolution Electrocatalysis of Bulk La-Ni Intermetallics via Gaseous Hydrogen Engineering.

A hydrogen processing strategy is developed to enable bulk LaNi5 to attain high activity and long-term stability toward the electrocatalytic oxygen evolution reaction (OER). By a combination of in situ Raman and quasi in situ X-ray absorption (XAS) spectra, secondary-electron-excited scanning transmission electron microscopy (STEM) patterns as well as the Rietveld method and density functional theory (DFT) calculations, it is discovered that hydrogen-induced lattice distortion, grain refinement, and particle cracks dictate the effective reconstruction of the LaNi5 surface into a porous hetero-nanoarchitecture composed of uniformly confined active γ-NiOOH nanocrystals by La(OH)3 layer in the alkaline OER process. This significantly optimizes the charge transfer, structural integrity, active-site exposure, and adsorption energy toward the reaction intermediates. Benefiting from these merits, the overpotential (322 mV) at 100 mA cm-2 for the hydrogen-processed OER catalyst deposited on nickel foam is reduced by 104 mV as compared to the original phase. Notably, it exhibits remarkable stability for 10 days at an industrial-grade current density of more than 560 mA cm-2 in alkaline media.

The Phosphinate Group in the Formation of 2D Coordination Polymer with Sm(III) Nodes: X-ray Structural, Electrochemical and Mössbauer Study.

A coordination polymer has been synthesized using ferrocene-based ligand-bearing phosphinic groups of 1,1'-ferrocene-diyl-bis(H-phosphinic acid)), and samarium (III). The coordination polymer's structure was studied by both single-crystal and powder XRD, TG, IR, and Raman analyses. For the first time, the Mössbauer effect studies were performed on ferrocenyl phosphinate and the polymer based on it. Additionally, the obtained polymer was studied by the method of cyclic and differential pulse voltammetry. It is shown that it has the most positive potential known among ferrocenyl phosphinate-based coordination polymers and metal-organic frameworks. Using the values of the oxidation potential, the polymer was oxidized and the ESR method verified the oxidized Fe(III) form in the solid state. Additionally, the effect of the size of the phosphorus atom substituent of the phosphinate group on the dimension of the resulting coordination compounds is shown.

Selective Confinement of Rare-Earth-Metal Hydrates by a Capped Metallo-Cage under Aqueous Conditions.

The properties of rare-earth-metal ions in aqueous media often depend on their various hydration modes, which allow them to exist as monomeric or oligomeric species with different coordination numbers. Capturing rare-earth-metal ions in a confined cavity can fix their hydration modes and thus enable their intrinsic properties to be distinguished. However, the isolation of ionic species from bulk aqueous media is not an easy task due to competitive interaction with bulk water. Here, we report the encapsulation of hydrated rare-earth-metal ions in a hydrophobic cavity of a synthetic cage. Cap-like counter anions located at the cage's portals play an important role in capturing the rare-earth metals at a fixed position via electrostatic interactions. Preferential encapsulation of early lanthanoid (III) ions was observed even though all the rare-earth metals have the same hydration number and geometry, as visualized by the competitive inclusion of a dye molecule. Accordingly, the early lanthanoid ion was selectively extracted from a mixture of two rare-earth-metal ions.

Synthesizing and Optimizing Rutile TiO2 Nanoparticles for Magnetically Guided Drug Delivery.

Introduction: Titanium dioxide nanoparticles (TiO2 NPs) have shown tremendous potential in targeted drug-delivery applications. Among various mechanisms, magnetically guided transport of drugs is one such technique for the said purpose. TiO2 NPs being diamagnetic or sometimes exhibiting very weak ferromagnetism can be modified by treating them with suitable magnetic materials. Methods: Rutile TiO2 NPs were synthesized and doped with Iron Supplement FericipXT and rare-earth metals like cerium, erbium and neodymium via sol-gel technique. FericipXT-coated rutile TiO2 NPs were synthesized in three different core-shell ratios (1:3, 1:1 and 3:1). The resulting samples were characterized via X-ray Diffraction (XRD), Vibrating Sample Magnetometer (VSM) and High-Resolution Transmission Electron Microscopy (HR-TEM). Results: XRD of FericipXT-doped TiO2 NPs showed a rutile phase for 1% and 3% doping; however, only a small fraction of the maghemite phase was obtained for 5% doping. The XRD plots of Ce-doped, Er-doped and Nd-doped TiO2 NPs showed a variety of phases of TiO2 NPs (such as anatase/rutile/mixed) along with the oxide phases of the corresponding rare-earth metal. The presence of various iron titanium oxides and iron oxides was found in core-shell NPs. HR-TEM images confirmed the formation of 1:3, 1:1 and 3:1 core-shell TiO2 NPs. VSM studies showed that the resulting NPs depicted magnetism in the form of superparamagnetism, ferromagnetism and even paramagnetism. Discussion: The doping to 3% does not affect the original phase of the resulting TiO2 NPs as depicted from the XRD; however, a doping of 5% and more resulted in extra phases corresponding to the dopant added. FericipXT was loaded over TiO2 NPs in amorphous form. Among all the samples synthesized, FericipXT-coated TiO2 NPs demonstrated the best magnetic ability. It was deduced that coating with a magnetic material drastically improves the magnetic character of the host NPs.

Electrochemical Reduction of La2O3, Nd2O3, and CeO2 in LiCl-Li2O Melt.

The reduction of pellets composed of individual CeO2, Nd2O3 and a La2O3-Nd2O3-CeO2 mixture by lithium extracted on a cathode during lithium chloride electrolysis at 650 °C was studied. The methods of cyclic voltammetry, electron microscopy, including determination of the elemental composition of the studied objects, and X-ray diffraction analysis were applied for the present study. The reduction degree of rare-earth metal (REM) oxides was determined using both the bromine method and reduction melting of the samples in the graphite crucible. The formation of the metallic phase composed of the rare-earth elements (REEs) was not observed even at the cathode potentials, corresponding to the formation of the liquid alkali metal phase, and lithium extraction, which, in the quantitative ratio, exceeds greatly the values needed for the reduction reaction. CeO2 was found to reduce to Ce2O3.

Modeling and equilibrium studies on the recovery of praseodymium (III), dysprosium (III) and yttrium (III) using acidic cation exchange resin.

In this research, the possibility of using hydrogenated Dowex 50WX8 resin for the recovery and separation of Pr(III), Dy(III) and Y(III) from aqueous nitrate solutions were carried out. Dowex 50WX8 adsorbent was characterized before and after sorption of metal ions using Fourier-transform infrared spectroscopy (FT-IR), Scanning Electron Microscope (SEM) and Energy Dispersive X-Ray Analysis (EDX) techniques. Sorption parameters were studied which included contact time, initial metal ion concentration, nitric acid concentration and adsorbent dose. The equilibrium time has been set at about 15.0 min. The experimental results showed that the sorption efficiency of metal ions under the investigated conditions decreased with increasing nitric acid concentration from 0.50 to 3.0 M. The maximum sorption capacity was found to be 30.0, 50.0 and 60.0 mg/g for Pr(III), DY(III) and Y(III), respectively. The desorption of Pr(III) from the loaded resin was achieved with 1.0 M citric acid at pH = 3 and found to be 58.0%. On the other hand, the maximum desorption of Dy(III) and Y(III) were achieved with 1.0 M nitric acid and 1.0 M ammonium carbonate, respectively. The sorption isotherm results indicated that Pr(III) and Y(II) fitted with nonlinear Langmuir isotherm model with regression factors 0.995 and 0.978, respectively; while, Dy(III) fitted with nonlinear Toth isotherm model with R2 = 0.966. A Flow sheet which summarizes the sorption and desorption processes of Pr(III), DY(III) and Y(III) using Dowex 50WX8 from nitric acid solution under the optimum conditions is also given.