Rare Earth Research Articles

Construction of CeO2/Co/CNT electrocatalyst with adsorption-catalytic synergistic effect for the suppression of the shuttle effect in lithium sulfur batteries

Lithium‑sulfur batteries are recognized as a strong candidate for the next generation of high capacity density batteries. However, the shuttle effect of soluble polysulfide intermediates during the charging and discharging process of lithium‑sulfur batteries leads to a rapid decrease in their electrochemical performance, thus limiting their practical applicability. In this study, the rare earth element cerium (Ce) was introduced into a bimetallic electrocatalyst to modify the separator in order to inhibit the shuttle effect for soluble polysulfide intermediates in lithium‑sulfur batteries. The CeO2/Co bimetallic electrocatalyst composite with in situ-grown carbon nanotubes (CeO2/Co/CNT) was obtained by a simple single-step high-temperature carbonization process. The strong polarity of CeO2 in CeO2/Co/CNT could trap soluble polysulfide intermediates onto the composite surface, synergizing with Co to further enhance the catalytic efficiency of soluble polysulfide intermediates into insoluble Li2S. Simultaneously, CNTs in CeO2/Co/CNT provided fast Li+ and electron transfer channels for the efficient catalytic conversion of soluble polysulfide intermediate. The initial discharge specific capacity of lithium‑sulfur batteries assembly by using CeO2/Co/CNT modified separator presented an initial discharge specific capacity of 1377.05 mAh g−1 at 0.1 C, and 676.8 mAh g−1 after 200 cycles at 1 C, demonstrating a significant performance improvement compared to blank control battery.

Advances in Functional Ceramics for Water Splitting: A Comprehensive Review

The global demand for sustainable energy sources has led to extensive research regarding (green) hydrogen production technologies, with water splitting emerging as a promising avenue. In the near future the calculated hydrogen demand is expected to be 2.3 Gt per year. For green hydrogen production, 1.5 ppm of Earth’s freshwater, or 30 ppb of saltwater, is required each year, which is less than that currently consumed by fossil fuel-based energy. Functional ceramics, known for their stability and tunable properties, have garnered attention in the field of water splitting. This review provides an in-depth analysis of recent advancements in functional ceramics for water splitting, addressing key mechanisms, challenges, and prospects. Theoretical aspects, including electronic structure and crystallography, are explored to understand the catalytic behavior of these materials. Hematite photoanodes, vital for solar-driven water splitting, are discussed alongside strategies to enhance their performance, such as heterojunction structures and cocatalyst integration. Compositionally complex perovskite oxides and high-entropy alloys/ceramics are investigated for their potential for use in solar thermochemical water splitting, highlighting innovative approaches and challenges. Further exploration encompasses inorganic materials like metal oxides, molybdates, and rare earth compounds, revealing their catalytic activity and potential for water-splitting applications. Despite progress, challenges persist, indicating the need for continued research in the fields of material design and synthesis to advance sustainable hydrogen production.

The Geometric and Electronic Effects of Ceria on Promoting PdZn catalyst for Enhanced Acetylene Semi‐Hydrogenation

AbstractPdZn intermetallic compounds (IMCs) have been extensively reported for acetylene semi‐hydrogenation due to unique geometric and electronic structure of isolated Pd sites. However, to achieve high ethylene selectivity at high conversion remains challenging. Here we show the promotional role of ceria in modifying the geometric and electronic structure of PdZn IMCs towards enhanced catalytic performance for acetylene semi‐hydrogenation. The Ce (0.1 wt%) promoted Pd−Zn‐Al catalyst shows by far the best catalytic performance among other Pd based catalysts in literature, maintaining high selectivity (>95 %) and excellent stability (~130 h) at high acetylene conversion (~90 %). Using in situ spectroscopic techniques, the geometric and electronic effects of CeOx promotor were clearly elucidated. At low Ce content, the presence of highly dispersed Ce3+ species in the periphery of PdZn alloys enhanced electronic metal‐oxide interaction, resulting in electron‐rich Pd sites that promote hydrogen dissociation and ethylene desorption, and account for the outstanding catalytic performance. At high Ce content, the formation of bulk‐phase CeO2 suppressed the PdHx formation during PdZn alloying and led to phase separation yielding highly dispersed Pd ensembles, consequently lowering ethylene selectivity. Our results provide a new route for the design of PdZn catalyst by applying rare earth promoters towards high‐performance acetylene semi‐hydrogenation.

Negative magnetization and magnetic ordering of rare earth and transition metal sublattices in NdFe0.5Cr0.5O3

We investigate the effect of alloying at the 3d transition metal site of a rare-earth-transition metal oxide, by considering NdFe0.5Cr0.5O3 mixed perovskite with two equal and random distribution of 3d ions, Cr and Fe, interacting with an early 4f rare earth ion, Nd. Employing temperature- and field- dependent magnetization measurements, temperature-dependent x-ray diffraction, neutron powder diffraction, and Raman spectroscopy, we characterize its structural and magnetic properties. Our study reveals bipolar magnetic switching (arising from negative magnetization) and magnetocaloric effect which underline the potential of the studied mixed perovskite in device application. The neutron diffraction study shows the absence of spin reorientation transition over the entire temperature range of 1.5–320 K, although both parent compounds exhibit spin orientation transition. We discuss the microscopic origin of this curious behavior. The neutron diffraction results also reveal the ordering of Nd spins at an unusually high temperature of about 40 K, which is corroborated by Raman measurements.

Energy transfer of Er3+-Nd3+ co-doped in tellurite glass via energy level match

Er3+/Nd3+ co-doped tellurate glass was prepared by melt quenching method. The relationship between the energy levels of two rare earth ions was studied by absorption spectra and excitation spectra. At 379/407/488 nm excitation, visible light, near-infrared (NIR) emission spectra, and fluorescence attenuation curves were measured. The NIR emission spectrum and fluorescence lifetime show that Er3+ can transfer energy to Nd3+, thus enhancing the NIR emission of Nd3+ in tellurate glass. In the co-doped sample, under excitation of 379/407/488 nm, the NIR emission of Nd3+ has a concentration quenching point related to Er3+, and the optimal co-doped concentration is 1mol% ErF3. At 365/451 nm excitation, NIR emission was not enhanced and no energy transfer occurred. In contrast to the energy transfer between conventional Er3+-Nd3+ co-doped glasses, this paper investigates the effect of matching the higher Er3+ energy levels with adjacent Nd3+ levels on the energy transfer. The energy transfer process of Er3+-Nd3+ co-doped glasses is studied in the energy level diagram.

Dynamic modeling of a synchronous reluctance machine for transient simulation of vibrations under variable rotor magnetization

This work introduces a new approach for the dynamic simulation of a permanent magnet-assisted synchronous reluctance machine with the ability to consider dynamic changes in the rotor magnetization. The aim is to comprehensively analyze the dynamics of a machine through transient simulations of the occurring magnetic and mechanical forces that influence the noise and vibration characteristics. A simplified magnetic model considering the effects of magnetic reluctances, leakage flux, and magnetic saturation is utilized to efficiently calculate the dynamically changing magnetic forces in the air gap. Unlike conventional designs employing rare earth magnets in the rotor, the design at hand utilizes non-rare earth magnets that enable adjustments of the magnets’ flux output. The novelty of the presented approach lies in its ability to consider these dynamic changes when calculating the air gap flux. The magnetic forces are then applied to an elastic multibody model of the motor, which includes the rotor, stator, bearings, and the housing, for the computation of the bearing forces and housing deformations. The presented multi-physical model allows for transient simulations of the forces acting on the bearings and the housing, capturing the dynamic response of the motor under varying rotor magnetization, air gaps, and loads. With the proposed approach, this study offers predictions regarding critical vibration characteristics that occur during dynamic operation, providing valuable insights for noise reduction efforts.

Effects of Sn on Corrosion Resistance of Rare-Earth-Free Mg-2Zn Alloy

Alloys of Magnesium metal have attracted the attention of the automobile industries in the past two decades due to their greater specific strength as well as stiffness. However, increasing the corrosion performance of alloys of magnesium has remained a prime concern in order to attain better performance without using expensive rare-earth elements. In this study, the result of Sn addition (0%, 2%, 4%) to hot rolled binary Mg-2Zn alloy was examined in terms of their corrosion and microstructural properties. To understand microstructural features, optical micrography, and SEM-EDX study were conducted. SEM and EDX analysis confirmed the presence of Sn phase after 2% and 4% addition of Sn. The number of particles increased with the gradual increase in the addition of Sn. However, Sn lowered the melting point of Zn precipitates. Thus, the presence of Zn particles was reduced with the addition of Sn. Electrochemical analyses were conducted in order to study the corrosion performance of the selected alloys by submerging it in NaCl (3.5 wt.%) solution, supported by the SEM micrographs of the corroded surface. It was found that adding tin up to 2% increases corrosion resistance. The addition of 4% Sn, on the other hand, introduced large-size particles of Mg2Sn, leading to local corrosion initiation sites, micro galvanic in nature, and hence, reducing corrosion resistance.

Selective adsorption of actinides and rare earth elements from leach liquor using metal oxide-polymer nanocomposites

Selective adsorption of actinides and rare earth elements from leach liquor using metal oxide-polymer nanocomposites

A comprehensive solid-state NMR and theoretical modeling study to reveal the structural evolution of layered yttrium hydroxide upon calcination

Layered rare earth hydroxides (LREHs) are a new family of ion-exchangeable layered metal hydroxides, which have extensive applications in various fields due to the unique properties of rare earth cations in the layered structure and the anion exchange capacity. The transformation of layered metal hydroxides to new layered phases that can be restored through the memory effect is critical for their chemistry and applications. However, the structure details of these new phases such as the coordination environments of rare earth cations/counterions and their evolution as a function of calcination temperature remain unclear to date. Herein, a comprehensive 89Y/35Cl solid-state NMR (ssNMR) and theoretical modeling approach was used to reveal the structural evolution of a representative LREH, namely LYH-Cl, upon calcination. We first identified partial decomposition products of Y3O(OH)5Cl2 and Y(OH)3 during the dehydration stage, then uncovered the preferential removal of hydroxide ions on yttrium sites coordinated with chlorine during the dehydroxylation stage, and finally determined the preferential removal of chlorine exposed to the surface of layers during the dechlorination stage. The coordination environments of Y3+ and Cl− undergo significant changes upon calcination, revealed by ssNMR experiments. These findings thus help us to overcome the obstacles impeding the rational design and synthesis of LREH-based functional materials via memory effect, underscoring the vast potential of ssNMR in deepening the understanding of layered metal hydroxides and related materials.

Large magnetocaloric effect and giant magnetoresistance in rare earth based intermetallic compound ErAl3: construction of magnetic phase diagram

This study explores the magnetic and magnetotransport behavior of polycrystalline ErAl3 compound. The polycrystalline compound adopts HoAl3-type structures with the R-3m space group, No. 166-2 and hR60 configurations. Multiple magnetic orderings and two field-induced metamagnetic transitions are observed. ErAl3 exhibits a significant magnetocaloric effect (MCE), −ΔSM = 15.25 J kg−1 K−1 and high relative cooling power of 383 J kg−1 with applied magnetic field change (ΔH) of 70 kOe near the paramagnetic to ferromagnetic transition, showcasing its potential for magnetic refrigeration technology. The compound also demonstrates metallic behavior, with a notable magnetoresistance of 48.5 % at 2 K due to the suppression of antiferromagnetism. The magnetic phase diagram reveals four distinct phases influenced by temperature and magnetic field, identified through the study of the MCE.

Unleashing the Power of Closed-Loop Supply Chains: A Stackelberg Game Analysis of Rare Earth Resources Recycling

Unleashing the Power of Closed-Loop Supply Chains: A Stackelberg Game Analysis of Rare Earth Resources Recycling

Drivers and Pathways for the Recovery of Critical Metals from Waste-Printed Circuit Boards.

The ever-increasing importance of critical metals (CMs) in modern society underscores their resource security and circularity. Waste-printed circuit boards (WPCBs) are particularly attractive reservoirs of CMs due to their gamut CM embedding and ubiquitous presence. However, the recovery of most CMs is out of reach from current metal-centric recycling industries, resulting in a flood loss of refined CMs. Here, 41 types of such spent CMs are identified. To deliver a higher level of CM sustainability, this work provides an insightful overview of paradigm-shifting pathways for CM recovery from WPCBs that have been developed in recent years. As a crucial starting entropy-decreasing step, various strategies of metal enrichment are compared, and the deployment of artificial intelligence (AI) and hyperspectral sensing is highlighted. Then, tailored metal recycling schemes are presented for the platinum group, rare earth, and refractory metals, with emphasis on greener metallurgical methods contributing to transforming CMs into marketable products. In addition, due to the vital nexus of CMs between the environment and energy sectors, the upcycling of CMs into electro-/photo-chemical catalysts for green fuel synthesis is proposed to extend the recycling chain. Finally, the challenges and outlook on this all-round upgrading of WPCB recycling are outlined.

Ceria-Optimized Oxygen-Species Exchange in Hierarchical Bimetallic Hydroxide for Electrocatalytic Water Oxidation.

The utilization of rare earth elements to regulate the interaction between catalysts and oxygen-containing species holds promising prospects in the field of oxygen electrocatalysis. Through structural engineering and adsorption regulation, it is possible to achieve high-performance catalytic sites with a broken activity-stability tradeoff. Herein, we fabricate a hierarchical CeO2/NiCo hydroxide for electrocatalytic oxygen evolution reaction (OER). This material exhibits superior overpotentials and enhanced stability. Multiple potential-dependent experiments reveal that CeO2 promotes oxygen-species exchange, especially OH- ions, between catalyst and environment, thereby optimizing the redox transformation of hydroxide and the adsorption of oxygen-containing intermediates during OER. This is attributed to the reduction in the adsorption energy barrier of Ni to *OH facilitated by CeO2, particularly the near-interfacial Ni sites. The less-damaging adsorbate evolution mechanism and the CeO2 hierarchical shell significantly enhance the structural robustness, leading to exceptional stability. Additionally, the observed "self-healing" phenomenon provides further substantiation for the accelerated oxygen exchange. This work provides a neat strategy for the synthesis of ceria-based complex hollow electrocatalysts, as well as an in-depth insight into the co-catalytic role of CeO2 in terms of oxygen transfer. This article is protected by copyright. All rights reserved.

The effect of extracellular polymeric substances on MICP solidifying rare earth slags and stabilizing Th and U.

Microbially induced carbonate precipitation (MICP) has been used to cure rare earth slags (RES) containing radionuclides (e.g. Th and U) and heavy metals with favorable results. However, the role of microbial extracellular polymeric substances (EPS) in MICP curing RES remains unclear. In this study, the EPS of Lysinibacillus sphaericus K-1 was extracted for the experiments of adsorption, inducing calcium carbonate (CaCO3) precipitation and curing of RES. The role of EPS in in MICP curing RES and stabilizing radionuclides and heavy metals was analyzed by evaluating the concentration and morphological distribution of radionuclides and heavy metals, and the compressive strength of the cured body. The results indicate that the adsorption efficiencies of EPS for Th (IV), U (VI), Cu2+, Pb2+, Zn2+, and Cd2+ were 44.83%, 45.83%, 53.7%, 61.3%, 42.1%, and 77.85%, respectively. The addition of EPS solution resulted in the formation of nanoscale spherical particles on the microorganism surface, which could act as an accumulating skeleton to facilitate the formation of CaCO3. After adding 20 mL of EPS solution during the curing process (Treat group), the maximum unconfined compressive strength (UCS) of the cured body reached 1.922 MPa, which was 12.13% higher than the CK group. The contents of exchangeable Th (IV) and U (VI) in the cured bodies of the Treat group decreased by 3.35% and 4.93%, respectively, compared with the CK group. Therefore, EPS enhances the effect of MICP curing RES and reduces the potential environmental problems that may be caused by radionuclides and heavy metals during the long-term sequestration of RES.

Rapid quantitative analysis of multiple rare earth elements in NdFeB alloys based on laser-induced breakdown spectroscopy (LIBS) and random forest (RF)

NdFeB material has excellent comprehensive magnetic properties, which plays a crucial role in the field of rare earth magnetic materials, and is one of the important basic materials to support modern high-tech industries. In the production of NdFeB alloys, the control of rare earth elements (REEs) is directly related to the quality and resource utilization efficiency of NdFeB materials. Therefore, the prediction of REEs content in NdFeB alloys is of great research significance and application value for the quality control of products, the enhancement of production efficiency and reduction of energy consumption by the rare earth material industry. In this study, a combination of laser-induced breakdown spectroscopy (LIBS) and random forest (RF) was used to investigate the quantitative analysis of four REEs (Nd, Pr, Tb and Dy) in NdFeB alloys. Firstly, the original LIBS spectra were screened by principal component analysis-mahalanobis distance (PCA-MD). Then, the effects of different data processing methods on the screened LIBS spectra were explored, and next, the feature variables were extracted from the preprocessed spectral data by the variable importance measurement (VIM). In order to further verify the prediction performance of the model, the prediction results of the RF models based on the different methods were compared. Finally, a PCA-VIM-RF calibration model was established on the basis of the optimized spectra, selected feature variables and parameters. Leave-one-out cross validation (LOOCV) was used to optimize the parameters of PCA-MD method, spectral preprocessing method and variable importance thresholds during the construction of the calibration model. The results show that the PCA-VIM-RF model has better prediction performance than the RF calibration model based on the raw spectra. For the PCA-VIM-RF calibration method of Nd, Pr, Tb and Dy elements, the values of R2CV are 0.9991, 0.9998, 0.9986, and 0.9984, respectively, the values of RMSECV are 0.06296%, 0.02788%, 0.04647% and 0.05252%, respectively. The values of R2P are 0.9508, 0.9975, 0.9691 and 0.9457, respectively, and the values of RMSEP are 0.6082%, 0.09205%, 0.5776% and 0.2631%, respectively.The above results indicate that LIBS combined with PCA-VIM-RF algorithm is a promising method for rapid quantitative analysis of REEs in NdFeB alloys without complicated sample preparation, which can provide some new ideas or strategies for the future research, development and quality control of rare earth materials.

Utilization of Eggshell Waste Calcite as a Sorbent for Rare Earth Element Recovery.

The green energy transition requires rare earth elements (REE) for the permanent magnets used in electric cars and wind turbines. REE extraction and beneficiation are chemically intensive and highly damaging to the environment. We investigated the use of eggshell waste as a sustainable alternative sorbent for the capture and separation of REE from aqueous solutions. Hen eggshell calcite was placed in multi-REE (La, Nd, Dy) solutions at 25 to 205 °C for up to 3 months. A pervasive diffusion of the REE inside the eggshell calcite was observed along pathways formed by the intracrystalline organic matrix and calcite crystal boundaries. At 90 °C, kozoite (REECO3OH, orthorhombic) spherulites precipitate on the surface of the dissolving calcite. At 165 and 205 °C, an interface-coupled dissolution-precipitation mechanism is observed, resulting in the complete dissolution of the calcite shell and its pseudomorphic replacement by polycrystalline kozoite. At 205 °C, kozoite is slowly replaced by hydroxylbastnäsite (REECO3OH, hexagonal), the stable form of the rare earth hydroxycarbonate polymorphs. Our results demonstrate two potential applications of eggshell waste for the uptake of rare earth elements in solution: at low temperatures, as a mixed organic-inorganic adsorbent and absorbent, given sufficient sorption time; and at higher temperatures, as an efficient sacrificial template for the precipitation of rare earth hydroxycarbonates.

Purifying 7CrSiMnMoV Steel from Scrap Modified with Rare Earth Cerium Alloying

Purifying 7CrSiMnMoV Steel from Scrap Modified with Rare Earth Cerium Alloying

Constructing Two-Dimensional (2D) Heterostructure Channels with Engineered Biomembrane and Graphene for Precise Scandium Sieving.

The special properties of rare earth elements (REE) have effectively broadened their application fields. How to accurately recognize and efficiently separate target rare earth ions with similar radii and chemical properties remains a formidable challenge. Here, precise two-dimensional (2D) heterogeneous channels are constructed using engineered E. coli membranes between graphene oxide (GO) layers. The difference in binding ability and corresponding conformational change between Lanmodulin (LanM) and rare earth ions in the heterogeneous channel allows for precisely recognizing and sieving of scandium ions (Sc3+). The engineered E. coli membranes not only can protect the integrity of structure and functionality of LanM, the rich lipids and sugars, but also help the Escherichia coli (E. coli) membranes closely tile on the GO nanosheets through interaction, preventing swelling and controlling interlayer spacing accurately down to the sub-nanometer. Apparently, the 2D heterogeneous channels showcase excellent selectivity for trivalent ions (SFFe /Sc≈3), especially for Sc3+ ions in REE with high selectivity (SFCe/Sc≈167, SFLa/Sc≈103). The long-term stability and tensile strain tests verify the membrane's outstanding stability. Thus, this simple, efficient, and cost-effective work provides a suggestion for constructing 2D interlayer heterogeneous channels for precise sieving, and this valuable strategy is proposed for the efficient extraction of Sc.

A Rare Earth Chalcogenide Nonlinear Optical Crystal KLaGeS4: Achieving Good Balance among Band Gap, Second Harmonic Generation Effect, and Birefringence.

Midinfrared nonlinear optical (NLO) rare earth chalcogenides have attracted extensive research interest in recent several decades. Employing charge-transfer engineering strategy in the early stage, rigid tetrahedral [GeS4] was introduced into rare-earth sulfides to synthesize KYGeS4, which had an enlarged band gap while maintaining a strong second harmonic generation (SHG) effect. Based on KYGeS4, La was equivalently substituted to successfully synthesize KLaGeS4 with a stronger SHG effect (dij = 1.2 × AgGaS2) and lower cost. Meanwhile, a larger band gap (Eg = 3.34 eV) was retained and realized phase matching (Δn = 0.098 @ 1064 nm). KLaGeS4 enabled an effective balance among band gap, SHG effect, and birefringence, making it a promising candidate for infrared NLO optical materials among various rare-earth sulfides.

Recovery of europium from E-waste using redox active tetrathiotungstate ligands

Rare-earth elements (REEs) are critical to our modern economy, yet their mining from natural ores bears a profound environmental impact. Traditional separation techniques are chemical and energy-intensive because their chemical similarities make REEs very challenging to purify, requiring multiple extraction steps to achieve high purity products. This emphasizes the need for sustainable and straightforward separation methods. Here we introduce a strategy for the direct separation of europium (Eu) from complex mixtures under ambient conditions, leveraging on the redox non innocence of purely inorganic tungsten tetrathiolate (WS42−) ligands. The recovery of Eu is achieved upon reduction of Eu(III) to a Eu(II) coordination polymer, driven by an induced internal electron transfer from the tetrathiotungstate ligand. Applying this strategy to unconventional feedstock such as spent energy-saving lamps allows selective europium recovery with separation factors over 1000 and recovery efficiency as high as 99% without pre-treatment of the waste.