Adsorption Of Rare Earth Elements Research Articles

Rare Earth Element Adsorption from Water Using Alkali-Activated Waste Fly Ash

As new technologies are developed, the demand for rare earth elements (REEs) has increased, despite limited awareness of their significant impact on people and the environment. In this study, waste fly ash was used as a precursor to synthesize inorganic aluminosilicate polymers by adding an activator to the alumina and silica compounds of the ash. Due to their structure and adsorption potential, their application for the removal of selected REEs (Gd3+, Y3+, and Sc3+) from water has been investigated. A decrease in the intensity of the quartz peak at 2θ of 26.6° in the XRD spectrum and the disappearance of the albite and mullite peaks due to dissolution during alkaline activation in both modified samples were observed. The appearance of a peaks at 2θ of 29.3° and 39.3° corresponding to calcite in the modified sample indicates the presence of wood ash. A shifting of the band in the DRIFT spectrum to 1030 cm−1 on the spectra of modified samples corresponds to the vibrations of Al-O and Si-O bonds and the formation of a polymeric network structure (Si-O-Si or Si-O-Al). According to pHPZC values, thermodynamic and kinetic parameters, and chemical composition, the presumed mechanism of REE adsorption is chemisorption and ion exchange. The highest adsorption efficiencies (up to 95%) for all examined REEs in both single and mixed REE solutions were obtained from an alkali-activated mixture of fly ash and wood ash. The results of this research are significant for expanding knowledge about the removal of REEs from the environment, the reduction of waste ash by their modification, and their potential subsequent use in construction as additives.

Advancements in functional adsorbents for sustainable recovery of rare earth elements from wastewater: A comprehensive review of performance, mechanisms, and applications.

Rare earth elements (REEs) are crucial metallic resources that play an essential role in national economies and industrial production. The reclaimation of REEs from wastewater stands as a significant supplementary strategy to bolster the REEs supply. Adsorption techniques are widely recognized as environmentally friendly and sustainable methods for the separation of REEs from wastewater. Despite the growing interest in adsorption-based REEs separation, comprehensive reviews of both traditional and novel adsorbents toward REEs recovery remain limited. This review aims to provide a thorough analysis of various adsorbents for the recovery of REEs. The types of adsorbents examined include activated carbons, functionalized silica nanoparticles, and microbial synthetic adsorbents, with a detailed evaluation of their adsorption capacities, selectivity, and regeneration potential. This study focuses on the mechanisms of REEs adsorption, including electrostatic interactions, ion exchange, surface complexation, and surface precipitation, highlighting how surface modifications can enhance REEs recovery efficiency. Future efforts in designing high-performance adsorbents should prioritize the optimization of the density of functional groups to enhance both selectivity and adsorption capacity, while also maintaining a balance between overall capacity, cost, and reusability. The incorporation of covalently bonded functional groups onto mechanically robust adsorbents can significantly strengthen chemical interactions with REEs and improve the structural stability of the adsorbents during reuse. Additionally, the development of materials with high specific surface areas and well-defined porous structures is benifitial to facilitating mass transfer of REEs and maximizing adsorption efficiency. Ultimately, the advancement of the design of efficient, highly selective and recyclable adsorbents is critical for addressing the growing demand for REEs across diverse industrial applications.

Rare Earth Selectivity and Electric Potentials at Mica Interfaces.

Controlling materials' composition and structure to selectively adsorb rare earth elements (REE) is critical for better separations. Understanding how local electric potentials affect REE adsorption and how they can be modified via chemical substitution is of fundamental importance. We present calculated mean inner potentials for muscovite and phlogopite micas in excellent agreement with measured values of +10.6 V. Natural substituents for aluminum significantly influence the electric potentials at the basal surface, altering the REE adsorption energies (Ead). Nd3+ adsorption is generally favored over that of Yb3+ on both micas. Substituents with lower charge than aluminum increase the Lewis basicity of adjacent oxygen atom lone electron pairs, enhancing Ead by 20 to 30 kcal/mol. These substitutions modify the electric potential's magnitude and spatial extent, highlighting the role of high-resolution electron holography/tomography and the importance of understanding atomic-scale variations in electric potentials for improving REE cation adsorption and selectivity on micas. In summary, the adsorption energies of REE cations are correlated with the substituent charge and local electrostatic potential variations because these factors dictate the electrostatic interactions between the cations and the interface.

Recovery of Nd3+ and Dy3+ from E-Waste Using Adsorbents from Spent Tyre Rubbers: Batch and Column Dynamic Assays.

This paper investigates the use of spent tyre rubber as a precursor for synthesising adsorbents to recover rare earth elements. Through pyrolysis and CO2 activation, tyre rubber is converted into porous carbonaceous materials with surface properties suited for rare earth element adsorption. The study also examines the efficiency of leaching rare earth elements from NdFeB magnets using optimised acid leaching methods, providing insights into recovery processes. The adsorption capacity of the materials was assessed through batch adsorption assays targeting neodymium (Nd3⁺) and dysprosium (Dy3⁺) ions. Results highlight the superior performance of activated carbon derived from tyre rubber following CO2 activation, with the best-performing adsorbent achieving maximum uptake capacities of 24.7 mg·g⁻1 for Nd3⁺ and 34.4 mg·g⁻1 for Dy3⁺. Column studies revealed efficient adsorption of Nd3⁺ and Dy3⁺ from synthetic and real magnet leachates with a maximum uptake capacity of 1.36 mg·g⁻1 for Nd3⁺ in real leachates and breakthrough times of 25 min. Bi-component assays showed no adverse effects when both ions were present, supporting their potential for simultaneous recovery. Furthermore, the adsorbents effectively recovered rare earth elements from e-waste magnet leachates, demonstrating practical applicability. This research underscores the potential of tyre rubber-derived adsorbents to enhance sustainability in critical raw material supply chains. By repurposing waste tyre rubber, these materials offer a sustainable solution for rare earth recovery, addressing resource scarcity while aligning with circular economy principles by diverting waste from landfills and creating value-added products.

Characterization of ion-adsorption clay rare earth elements (REEs) in weathered granite rock in North-Western area of Pahang state, Malaysia

Abstract This study characterised the weathered granite profiles in a selected area in northwestern Pahang State and determined the content of ion-adsorption clay rare earth elements (REEs). The geochemical study analyzed the REE elements and major elements in the samples, while the XRD analysis identified the clay mineral known to adsorb REEs. Quantification of REE concentration by ICP-MS analysis revealed significant differences between samples, with sample C1 from upper horizon C and sample B2 from lower horizon B (ΣREE+Y: 915.98 and 454.52 ppm respectively) from moderately weathered granite. Lower REE content was observed in sample C2 (lower horizon C and sample B1 (upper horizon B). Kaolinite and halloysite in XRD analysis, provide a higher ionic adsorption of REEs. These results emphasize the potential of REEs deposit in this area and call for a follow-up study to explore the ion-adsorption clay REEs in the whole weathered granitic profiles of Pahang State.

Rare earth elements accumulation and patterns in abiotic and biotic compartments of a large river system influenced by natural and anthropogenic sources in Eastern Canada.

The mobilization of rare earth elements (REEs) in aquatic ecosystems is expected to rise significantly due to intensified exploitation, erosion, and climate change. As a result, more attention has been brought to study their environmental fate. However, our ability to assess contamination risks in freshwater organisms remains limited due to scarce data on the composition and accumulation of REEs. Understanding how organisms bioaccumulate REEs requires knowledge of their environmental conditions, exposure pathways, and ecological characteristics-areas few studies have explored. In this study, we examined the fate of REEs across abiotic (water, suspended sediments, and sediments) and biotic (invertebrates and fishes) compartments in the St. Lawrence River (Canada), identifying the main drivers of their accumulation and relative composition. The results were consistent with REE biodilution along the food chain, with concentrations greater in suspended (REEs = 76.1 - 241.4 μg·g-1) and bulk sediments (REEs = 4.2 - 204.2 μg·g-1). Higher concentrations were found in fine-grained sediments, with a relative enrichment in middle REEs, likely due to REE adsorption onto Fe- or Mn-bearing minerals. Nonpredatory invertebrates ingesting suspended sediments, such as Ephemeroptera and Diptera larvae, exhibited higher concentrations of REEs than both filter-feeding species (i.e., mussels, polychaetes) and fish. Additionally, some amphipods displayed anomalous concentrations of gadolinium (Gd/Gd*=5.7, 2.6, and 2.0), possibly originating from anthropogenic activities near Montreal Island. While fish bioaccumulated only light REEs in their liver, multiple regression models revealed how their length and the concentration of REEs in surrounding water-in dissolved form or as free ions-influenced their concentrations. Finally, benthivorous species like Moxostoma spp. and Ictalurus punctatus accumulated more REEs compared to piscivorous Sander spp., reflecting differences in feeding behavior and trophic level. Overall, these findings provide insights into how REE concentrations and compositions varied among organisms, likely due to differences in environmental conditions and ecological characteristics.

One-step pyrolysis of ZIF-8 after recovering rare earth elements from mining wastewater as a functional fenton-like catalyst

The management of rare earth elements (REEs) from mining wastewater has consistently a key issue. Our previous research has demonstrated the selective adsorption of REEs in mining wastewater by ZIF-8. Herein, one-step pyrolysis of ZIF-8 after recovering REEs from mining wastewater as a high-value product was further proposed. The resulting REEs-based magnetic nanoporous carbon materials (REEs-MPC) was utilized for the activation of peroxymonosulfate (PMS) in the removal of bisphenol A (BPA). Experimental results indicate substantial BPA removal efficiencies of 74.62 %, 83.57 %, and 70.06 % with REEs-MPC synthesized at different pyrolysis temperatures (700 °C, 800 °C, and 900 °C). The detailed characterizations reveal the REEs-MPC at 800 °C was obtained (REEs-MPC/800) exhibit prominent graphitic and defective characteristics. In addition, electrochemical analysis revealed that the REEs-MPC/800 demonstrate elevated conductivity and superior capacitive current, with Tafel slopes as high as 294 mV/dec. Functional theory (DFT) calculations demonstrate that the presence of graphitic-N and REEs-N species significantly enhance PMS activation. Finally, a neural network model constructed through machine learning techniques provided a comprehensive overview of the structure–property relationship. Overall, the proposal to synthesize a high-value product using mining wastewater has been put forward. This initiative is expected to contribute to the advancement of the green economy within the rare earth mining industry.

Facet-Dependent Adsorption of Rare Earth Elements (REEs) and Actinides onto Goethite: REE Pattern Variability and Cerium Anomaly.

Assessing the fate of contaminants in the environment requires a deep understanding of intrinsic adsorption mechanisms on natural minerals such as Fe-oxyhydroxides. In this study, we proposed an innovative approach to probe site heterogeneities on the goethite surface by comparing the adsorption behavior of rare earth elements (REEs, including Sc, Y, and all lanthanides; Ln) except Pm, as well as Th and U. A surface loading-dependent adsorption of Ln and Y was observed, with a shift from (i) preferential middle to heavy REE adsorption and (ii) limited to substantial fractionation between Y and Ho as the loading increased. These observations are likely attributable to the formation of strong and weak complexes onto the (021) and (110)/(100) goethite faces at low and high loadings, respectively. Additionally, Ce-anomaly, characteristic of Ce(III) partial oxidation to Ce(IV), was observed only at high loading. By drawing an analogy with Th(IV) and Sc(III), Ce(IV) is expected to outcompete Ln(III) and Y adsorptions and stabilize primarily at the strong sites on the (021) face, even under conditions of high loading. The outcome of this study, supported by charge distribution-multisite complexation (CD-MUSIC) calculation, provides new insights into the impact of facet-dependent adsorption and redox processes on Fe-oxyhydroxides.

Micro-Topographic Controls on Rare Earth Element Accumulation and Fractionation in Weathering Profiles: Case Study of Ion-Adsorption Rare Earth Element Deposit in Hedi, Zhejiang Province, China

Ion-adsorption rare earth element (REE) deposits are a major source of REEs and are found mainly in China. The formation of such deposits is affected by a combination of endogenic and exogenic factors. This study investigated the effect of micro-topography on the REE distribution in four weathering profiles at different topographic sites on a knoll in Hedi, Zhejiang Province, China. The weathering profile and REE accumulation are both most developed at mid-slope positions of the knoll. The intensity of chemical weathering decreases in the order of mid-slope > base > summit. As weathering progressed, REE enrichment initially increased but later decreased, with a progressive increase in light/heavy REE fractionation. REE fractionation is more pronounced on the north-facing slope than on the south-facing slope. Weathering degrees and clay mineral characteristics are key factors influencing the varying REE distributions on the knoll. Water leaching and the evolution of clay minerals towards higher maturity reduce REE adsorption capacity. Clay minerals also play a significant role in REE fractionation; the abundance of these minerals and the presence of illite enable the retention of more HREEs with minimal desorption. Taking into account water content, it is inferred that hydrological conditions, modulated by the micro-topography, strongly affect the depth and extent of REE accumulation, as well as fractionation.

Estimating in situ prepared alkaline soluble flavan as an advanced adsorbent for rare earth elements

The design and synthesis of organic adsorbents for rare earth element (REEs) separation remain significant scientific aspect and industrial endeavor. In a single-pot reaction, acetone and resorcinol in acidic media over a two-day period facilitated the formation of the 2, 4, 4-trimethyl-7, 2′, 4′ trihydroxy flavan (flavan adsorbent). Under acidic conditions, flavan effectively adsorbs REEs (adsorbate), while under alkaline conditions, flavan rapidly dissolves completely. A series of adsorption experiments was conducted to determine the optimal adsorption conditions, including pH variations (1–5), REEs solution concentrations (250–1000 mg/L), adsorption time (5–60 min), and flavan mass (10–100 mg). The maximum adsorption capacity for flavan under optimal conditions was 258 mg g−1. Various analytical instruments were employed for flavan characterization, including Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS), which were essential for analyzing the surface morphology and structural properties of the flavan. Adsorption isotherms suggested that the adsorption of REEs onto the flavan surface followed the Langmuir model, which in turn exhibited a theoretical adsorption capacity of 263.2 mg g−1 better off the Freundlich model. Kinetically, the adsorption of REEs on the flavan is best run in a pseudo-second-order model trajectory, which in turn exhibited an adsorption capacity value of 283 mg g−1. Interference studies revealed that flavan is a selective adsorbent; however, aluminum ions may exert a minor interference effect of 4% (in term of REEs uptake). Other competing elements, including Na, K, Mg, Ba, Mn, Cu, Fe, and Sn, exhibited a minimal decline in flavan uptake for REEs.

Selective separation and recovery of rare-earth elements (REEs) from acidic solutions and coal fly ash leachate by novel TODGA-Impregnated organosilica media

Rare-earth elements (REEs) are essential in a wide range of applications including magnets and satellite technology, with demand driven by geopolitical factors. While multiple techniques exist for REE recovery including solvent extraction and selective precipitation, solid–liquid extraction offers key advantages in selectivity, scalability, and recyclability. N,N,N′,N′-tetraoctyl diglycolamide (TODGA) is a tridentate ligand widely used in solvent extraction, but the incorporation in a solid support to separate individual lanthanides from acid solutions remains largely unexplored. A novel TODGA-organosilica sorbent material was developed and tested to evaluate recovery of 17 elements (REEs and thorium) in terms of selectivity, kinetics, and equilibrium isotherms in 0.01 to 15.9 M nitric acid. Characterization of the new sorbent was performed before and after sorption using FTIR, XPS, and SSA techniques to help elucidate sorption mechanisms and limiting variables. REE adsorption increased from 1.26 mg g−1 to 10 mg g−1 with nitric acid concentrations of 0.01 M and 15.9 M, respectively. TODGA-organosilica exhibits high selectivity towards heavy REEs (Dy to Lu), with minimal sorption of lighter REEs (Ce to Gd). Batch adsorption experiments confirm pseudo-second-order kinetics and a Langmuir adsorption isotherm with TODGA binding to REEs in a 3:1 complex. A packed bed column study confirmed the high selectivity of TODGA-impregnated organosilica towards heavy REEs and a proof-of concept experiment with coal fly ash leachate shows high selectivity for REEs over Al, Fe, and Ca present in several orders of magnitude higher concentrations. Fractionation was observed where loading cycle effluent contained 84% light REEs while strip cycle effluent contained 80% heavy REEs. More than 90% of loaded REEs were successfully stripped with water as the stripping agent.

Opportunities and Constraints of the Adsorption of Rare Earth Elements onto Pyrolytic Carbon-Based Materials: A Mini-Review

Rare earth elements (REEs), comprising seventeen metallic elements, including lanthanides, scandium, and yttrium, are indispensable for modern technological industries due to their unique properties. However, their supply is critically risky for the European Union, with 95% of global production concentrated in China, Brazil, Vietnam, Russia, India, and Australia. This mini-review examines the adsorption of REEs onto pyrolytic carbon-based materials as a sustainable recovery method from secondary raw materials. The review covers different types of carbon-based adsorbents used in several research works, such as activated carbon, chars, and biochar, and discusses their adsorption mechanisms and influencing factors. Comparative analyses of adsorption capacities highlight the significance of surface area and functionalization in enhancing adsorption efficiency. Despite promising results, the variability in adsorption performance due to experimental conditions and the scarcity of real-world application studies are noticed. This review underscores the need for further research using real e-waste leachates to validate the practical applicability of pyrolytic carbon-based adsorbents for REEs’ recovery, aiming for an economically and environmentally sustainable solution.

Construction of Ion-Imprinted Graphene Oxide Mixed-Matrix Membranes for Selective Adsorption and Separation of Tm3.

Efficient adsorption and separation of rare earth from other similar rare earth wastewater has become an urgent demand for resource utilization of ion-type rare earth minerals in China. Herein, thulium (Tm) ion-imprinted graphene oxide (GO)-doped polyether sulfone (PES) membranes (GO-TII/PES-2 membranes) were prepared, in which ion-imprinted graphene oxide was applied as an efficient Tm3+ ionic ligand in the imprinted layer and polyether sulfone was applied as a carrier in the membrane matrix to achieve the selective adsorption and separation of Tm3+ and neighboring rare earth ions. Combined with an ion rectifier, the separation and purification performances of Tm3+ were explored. The separation factors β(Tm3+/Tb3+), β(Tm3+/Sm3+), β(Tm3+/Nd3+), and β(Tm3+/Ce3+) in the dynamic adsorption process increased significantly from 1.22, 1.04, 1.04, and 1.02 for nonimprinting to 3.07, 3.91, 3.91, and 3.33 for imprinted membranes. The GO-TII/PES-2 membrane adsorbed about three times more Tm3+ than the nonionic-imprinted (GO-NII/PES) membrane by adding a color developer and quantifying Tm3+ based on a fast and easy UV-photometric method. After eight dynamic permeations, the adsorption of Tm3+ by the GO-TII/PES-2 membrane decreased by only 13%, indicating that the membrane has good reuse performance. Additionally, the investigation examined the influence of Tm3+ on wheat seed germination, underscoring its potential application in agriculture and the importance of adsorbing and separating rare earth ions.

Interpretation of vertical migration and enrichment processes of rare earth elements (REEs) in ion-adsorption-type mineralization in Japan based on REE speciation analyses

Typical vertical profiles of ion-adsorption-type rare earth element (REE) deposits discovered in southwest Japan were studied by conducting speciation analyses, including X-ray absorption fine structure and laser-induced fluorescence spectroscopy combined with transmission electron microscopy and adsorption/desorption experiments. The results revealed that REE speciation, migration, and enrichment in weathered granite is largely controlled by soil pH, which in turn controls the variable charges of kaolinite, the REE host phase. Both the distribution coefficient Kd and the soil pH increase with depth. As a result, (i) REE dissolution and migration occur in the near-surface acidic environment of the upper layers, where hydroxyls of kaolinite basal surfaces and edges are deprotonated to a lesser degree, and (ii) REEs accumulate in the relatively high-pH environment below the surface, where hydroxyls of kaolinite basal surfaces and edges are deprotonated to a larger degree, producing REE adsorption sites with variable charges. An increase of soil pH to greater than 6 in deeper layers promotes inner-sphere complexation of REEs. Although inner-sphere complexation inhibits the ion-exchange extraction of REEs, the inner-sphere complexes can be still extracted by lowering the pH of the extraction solution. This fact, which indicates that the adsorption of both inner- and outer-sphere complexes is reversible, is important in terms of both (i) understanding vertical REE profiles in which the pH varies and (ii) the efficient recovery of REEs from REE-enriched layers at all depths in weathered granite.

Elucidating the selective adsorption of heavy rare earth by phosphate modified silica: The cooperation of pore confinement and surface structure regulating

Rare earths are considered strategic metals, with heavy rare earth elements of greater importance due to their supply and utilization field. However, efficient separation of heavy rare earth elements is a great challenge as the similar physicochemical properties between light and heavy rare earths. In this study, the highly efficient adsorbents with confinement effect are synthesized by the modification of MCM-41 materials with dimethyl clodronate (NP2) and methylene dichlorophosphate (NDP2). The adsorbents were characterized by XRD, TEM, SEM-EDS, N2 adsorption–desorption, FTIR, TG, 13C NMR, and XPS. It was discovered that the pore size of MCM-41 affected markedly the adsorption selectivity, and the cooperation of the organic adsorption center and pore confinement of MCM-41 support enabled the selective adsorption of heavy rare earth ion. The adsorbent modified by NP2 exhibited high adsorption selectivity toward heavy rare earth ions (Lu3+) with the increase in pore size of MCM-41. In contrast, the expanded pore of MCM-41 enhanced the selectivity of light rare earth ions for the NDP2 modified adsorbents. The distribution coefficient of Lu3+ adsorption over NP2-MCM-41(III) adsorbent reached 20,132 mL g−1 and the separation factor of Lu to La reached 82.17. DFT calculations revealed that a vital driving force for the selective adsorption of Lu was the gap of binding energy between Lu and La complexes with the surface NP2/NDP2 groups. The synergy of pore confinement and organic functional groups in adsorbents in this paper offers a valuable strategy for designing efficient materials in the separation of rare earth elements.

Impact of particle size and associated minerals on rare earth desorption and incorporation mechanisms in a South American ion-adsorption clay

This research delves into the intricate nexus of particle size, mineralogical composition, surface attributes, elemental mapping, and rare earth element (REE) adsorption mechanisms within an ion-adsorption clay sample from South America. The investigation entails the fractionation of the ion-adsorption clay into three size categories: S1 (< 0.25 mm), S2 (0.25–0.5 mm), and S3 (0.5–2 mm). Each fraction undergoes meticulous characterization to unveil its elemental composition, mineralogical composition, surface area, morphological characteristics, elemental mapping, and the mechanisms governing REE incorporation. The results indicate that S1 has 31% physiosorbed, 8% chemisorbed, and 61% mineralized REEs, while S2 has 40% physiosorbed, 5% chemisorbed, and 55% mineralized REEs, and S3 has 24% physiosorbed, 5% chemisorbed, and 71% mineralized REEs. The physisorbed REEs are attributed to the presence of kaolinite, conducive to mostly physisorption. In terms of grain size and REE content/type relationship, the results show that REE content decreases with increasing grain size; however, there is not a clear trend in terms of REE occurrence modes with grain size. Heavy rare earth elements (HREEs) are discernibly favored in adsorption over light rare earth elements (LREEs). This preference is underpinned by the weathering processes that led to the formation of ion-adsorption clay, which facilitated the transport and accumulation of HREEs. Notably, the ion-adsorption clay encompasses a substantial content of mineralized REEs, necessitating more demanding extraction methodologies, such as acid baking followed by water leaching if complete extraction of all REEs is desired. Among the desorbable REEs, physisorption dominates, encompassing over 80% of the total. Chemisorbed REEs exhibit versatility in association with various minerals, encompassing kaolinite, quartz, and goethite. In essence, this study unveils the intricate interplay between particle dimensions, mineralogical constitution, surface attributes, and REE adsorption modes within this ion-adsorption clay sample. The ion-adsorption clay in this study contains a significant portion of mineralized REEs that cannot be extracted using the mild conditions typically employed for the desorption process. Additionally, the REE concentration in this ion-adsorption clay is notably higher than the average found in clay deposits worldwide, reaching levels comparable to those of regolith deposits in China, which are a major global source of REEs. This remarkable concentration of REEs, along with the unique modes of their occurrence in this deposit, presents a significant interest to the scientific community.

Efficient Capture and Release of the Rare-Earth Element Neodymium in Aqueous Solution by Recyclable Covalent Organic Frameworks.

Rare-earth elements (REEs) are present in a broad range of critical materials. The development of solid adsorbents for REE capture could enable the cost-effective recycling of REE-containing magnets and electronics. In this context, covalent organic frameworks (COFs) are promising candidates for REE adsorption due to their exceptionally high surface area. Despite having attractive physical properties, COFs are heavily underutilized for REE capture applications due to their limited lifecycle in aqueous acidic environments, as well as synthetic challenges associated with the incorporation of ligands suitable for REE capture. Here, we show how the Ugi multicomponent reaction can be leveraged to postsynthetically modify imine-based COFs for the introduction of a diglycolic acid (DGA) moiety, an efficient scaffold for REE capture. The adsorption capacity of the DGA-functionalized COF was found to be more than 40 times higher than that of the pristine imine COF precursor and more than four times higher than that of the next-best reported DGA-functionalized solid support. This rationally designed COF has appealing characteristics of high adsorption capacity, fast and efficient capture and release of the REE ions, and reliable recyclability, making it one of the most promising adsorbents for solid-liquid REE ion extractions reported to date.

Interface Modulation of 2D Superlattice Heterostructures with Oxygen-enriched Sites and Dissolution Restraint for Effective Rare-earth Elements Extraction

Effective recovery of rare earth elements from wastewater is crucial for the modern industry, as well as for protecting the human health and ecosystem. Nevertheless, it is still challenging to realize efficient and selective low-concentration rare earth extraction in systems containing high levels competing metal ions. Here, we report on the fabrication of two-dimensional superlattice heterostructures (VOGO-x) through the alternating restacking of VOPO4 nanosheets and GO-PDDA nanosheets via electrostatic self-assembly. The meticulously organized molecular scale of superlattice heterostructures enable the full exposure of accessible adsorption sites and facilitate the transport of rare earth ions, meanwhile the abundant oxygen-containing phosphate groups within the interlayer can realize selective rare earth ions extraction. Furthermore, the tunable interlayer interaction can promote structure stability to prevent dissolution. Consequently, VOGO-11 possesses excellent rare earth adsorption performance, with a saturated adsorption capacity (Nd(III) 631.52 mg/g, Dy(III) 689.48 mg/g, Lu(III) 716.06 mg/g), high utilization rate of adsorption sites and short adsorption equilibrium time of simply 10 min in the REE aqueous solution. Furthermore, VOGO-11 exhibits outstanding selective rare earth adsorption ability over a wide range of metal ions in the low-concentration simulated wastewater and actual leaching tailings. These results demonstrate the material’s promising potential in capturing rare earth ions and pave the way to the development of two-dimensional superlattice heterostructures through interface modulation for effective rare earth extraction.

Indigenous microbial influence on REE enrichment and fractionation in South China weathering crusts: Insights from experimental simulations

The activity of microorganism plays an important role on the enrichment, migration and fractionation of rare earth elements (REEs) in the supergene environment. To investigate the characteristics of indigenous microorganisms on the enrichment and fractionation of REEs, we studied the adsorption efficiencies of REEs by 30 indigenous microbial strains that were isolated and cultured from the weathering profile of a regolith-hosted REE deposit in South China. Most microbial strains exhibited high adsorption efficiencies for REEs, ranging from 2.3 to 42.9 mg g−1. Notably, the taxonomic classification of microorganisms significantly influenced the adsorption selectivity. Gram-positive bacteria exhibited a pronounced enrichment of the heavy REEs, while gram-negative bacteria showed no obvious adsorption preference. The tetrad effects were observed in REE adsorption patterns of gram-negative bacteria and fungi; however, fungi demonstrated a much higher affinity for light and medium REEs. Chemically modified microbial cells were employed to investigate the adsorption mechanism, revealing that distinct functional groups of microbial cells corresponded to the adsorption preference of microorganisms towards REE. Carboxyl and phosphate groups contributed to a relatively high adsorption capacity for light REEs and heavy REEs, respectively. The findings of our study suggest that the distinct composition of microbial groups may exert a significant influence on the biogeochemical cycle of REE in weathering profiles.

Grain size control on organo-clay complexation and REE fractionation in the Paleozoic strata of the Permian Basin (West Texas, U.S.A.)

As a major component of mudstone, clay minerals are known to conserve organic matter (OM) as well as a range of trace elements through the mechanisms of adsorption, encapsulation, and/or intercalation. The associations of the clay minerals on one hand and trace elements and OM on the other hand impact the diagenetic evolution of such rocks and is of substantial importance for their characterization and assessment. Subsurface core samples collected from Late Paleozoic mudstone within the Permian Basin of Texas were separated into four grain size fractions (&amp;gt;2 µm, 2 to 1 µm, 1 to 0.6 µm, and &amp;lt;0.6 µm) to determine the clay mineralogy, OM abundances, and rock geochemistry using a suite of diffraction, spectroscopic, and chemical analysis. All separates were largely consisted of illite-smectite (I-S), illite-tobelite-smectite (I-T-S), mica/illite and chlorite coupled with some minor quartz and feldspar. The smectite component of I-S was shown to increase with decreasing grain size fractions. Additionally, t he rise in the content of smectite interlayers correlated with an increase in the total organic carbon (TOC) content towards the finest grain size separates in all samples. This suggested that a significant portion of the TOC content resided in the fraction below 2 µm and that smectite interlayers promoted the preservation of OM. Rare earth elements (REE) concentrations were found to be the highest in the finest grain size separates and align with an increased content of smectite interlayers, denoting a plausible interaction between the two. Further on, REE and TOC concentrations display a significant positive correlation in all size fractions and increase with respect to smectite interlayer content. This three-component relation suggests the REE adsorption to illite-smectite was likely promoted by OM. Understanding the close relation between the clay minerals, OM, and trace element content is indicative of polyvalent cationic bridging, ligand exchange, and organo-metallic complexation, which eventually l eads to the enrichment of OM and fractionation of REE in mudstone.