Extraction Of Lanthanides Research Articles

Recovery of rare earth elements from ion-adsorption deposits using electro kinetic technology: A comparative study on leaching agents

Ion-adsorption rare earth deposits are crucial sources of heavy rare earth elements. Conventional ammonium-salt leaching techniques have resulted in severe environmental impacts. Electrokinetic mining technology has emerged as a potential solution that can enhance recovery efficiency. However, persistent issues associated with ammonium salts and the influence of electric fields on rare earth elements extraction from ion-adsorption rare earth deposits with alternative leaching agents remain unexplored. In addition, the electrokinetic behavior and mechanisms of rare earth ions and various ions in weathering crusts in an electric field have not been studied. Thus, we report a comparative study of rare earth elements recovery using electrokinetic mining technology with three leaching agents. The results demonstrate that the electrokinetic mining efficiency is enhanced by using magnesium sulfate and ammonium sulfate; however, hindered by sodium sulfate. These differences arise from the diversities in adsorption amounts, and transport characteristics of the leaching cations in soil. Surprisingly, electrokinetic mining technology exhibits superior mining efficiency in high-density soils, contrasting with conventional leaching techniques. Our findings indicate that electromigration, electroosmosis, and electrolysis mechanisms collectively influence the mining process. Remarkably, electrokinetic mining technology achieves a significant rare earth element recovery efficiency of 90 % using magnesium sulfate synergically promoted by the voltage and leaching agent concentration. The findings of this study are expected to provide valuable insights into rare earth elements transport and exchange behavior in an electric field with various leaching agents, thereby contributing to the advancement of sustainable rare earth elements mining practices.

Coal ash resources and potential for rare earth element production in the United States

The renewable energy industry is heavily reliant on rare earth elements, underscoring the need to develop resources and production. The objective of this work was to estimate coal ash resources and potential for extraction of rare earth elements using data for the US. Data on spatiotemporal variability in coal ash resources and disposition were compiled from various federal databases and rare earth elements levels in ash were compiled from the literature. Results show that ~ 52 gigatons (Gt) of coal were produced in the US (1950–2021). Power plants account for most of the coal use, particularly since 1980. Coal ash (5.3 Gt) represents a mean of 10% of coal by weight, ranging from 6% for subbituminous to 14% for lignite. About 70% of coal ash is potentially accessible for rare earth element extraction (1985–2021) and was disposed in landfills and ponds with the remaining coal ash used onsite or sold. Median values of total rare earth elements are much higher in ashes derived from the Appalachian Basin (median 431 mg/kg) than in the Illinois (282 mg/kg) or Powder River basins (264 mg/kg). Considering the market value of rare earth oxides, potentially accessible ash volumes, and percent rare earth element extraction (30% Appalachian and Illinois Basins; 70% Powder River Basin) results in an estimated $8.4 billion value. This study provides fundamental information on accessible coal ash resources in the US, linkages to coal sources, and preliminary estimates of rare earth element levels for future development within the US.

Using Diglycolamide Extractants in an Imidazolium-Based Ionic Liquid for Rare Earth Element Extraction and Recovery.

Growing demands for rare earth elements (REEs) have prompted sustainability concerns worldwide. Given the need for sustainable extraction methods amidst REEs, ionic liquids (ILs) have been investigated as tunable extraction substitutes for conventional organic solvents, offering negligible volatility and diverse physical and chemical properties. Recent reports have shown that the introduction of extractants, like N,N,N',N'-tetraoctyldiglycolamide (TODGA) or N,N-dioctyldiglycolamic acid (DODGAA), into ILs can provide high selectivity and affinity for REE capture. Precipitate formation has been observed in IL-extractant systems across several studies; however, the molecular interactions that drive this phenomenon have yet to be explored. This study investigates the coordination environment in the precipitate formed between [Yb3+], DODGAA, and the 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM+][PF6 -]) IL. The composition of the precipitate was confirmed using several spectroscopic techniques and revealed an underlying hydrogen bonding interaction between the fluorine atom of [PF6 -] anion and -OH of the Yb-DODGAA complex. Computational studies were also conducted to examine the coordination environment of the Yb-TODGA and Yb-DODGAA complexes. The binding affinity of the extractants toward [Yb3+] is analyzed by calculating the associated binding energy values. The results clearly show a stronger binding affinity of the extractants toward [Yb3+], supporting the observed high extraction efficiencies of DODGAA and TODGA.

Development of a Hydrometallurgical Process for the Extraction of Cobalt, Manganese, and Nickel from Acid Mine Drainage Treatment By-Product

Critical minerals (CMs) are pivotal in modern industries, such as telecommunications, defense, medicine, and aerospace, contributing significantly to regional and global economic growth. However, the reliance on external sources for 26 out of 50 identified CMs raises concerns about supply chain vulnerabilities. To address this, the research focused on developing a hydrometallurgical process for extracting cobalt, manganese, and nickel from acid mine drainage (AMD) treatment by-products, emphasizing the need to diversify CM supply chains within the United States (US). A solution composed of an REE solvent extraction raffinate loaded with cobalt, manganese, nickel, and various impurity metals was utilized as a feedstock in this study. The developed hydrometallurgical process involved initial sodium hydroxide precipitation to remove impurities like aluminum and iron from an SX raffinate solution generated during the extraction of rare earth elements (REEs). Precipitation stages were performed in a pH region ranging from 2 to 12 to identify the optimum pH values, achieving a tradeoff between recovery and impurity removal. A subsequent precipitation process at pH 5–10 yielded a product rich in CMs, such as manganese, cobalt, and nickel. Further separation steps involved nitric acid washing, resulting in a Mn product with a purity of 47.9% by weight and a solution with extractable concentrations of cobalt and nickel. Stagewise precipitation with sodium sulfide subsequently produced three solid products: cobalt and nickel product at pH 1–5, manganese product at pH 5–10, and magnesium at pH 10–12. The study also explored other separation approaches, including solvent extraction, to enhance the separation of nickel from cobalt. Overall, the developed hydrometallurgical process generated the following products with varying degrees of purities: cobalt (9.92 wt.%), nickel (14 wt.%), manganese (47.9 wt.%), and magnesium (27.49 wt.%). This research aimed to contribute to the sustainable extraction of CMs from secondary sources, reducing the US’ reliance on imports and promoting a more resilient supply chain for these crucial elements.

Decomposition Model of Bastnaesite and Its Fluorine Oxygen Coupling Escape Mechanism.

Nearly 90% of rare earths worldwide currently originate from bastnaesite (REFCO3). Oxidative roasting, an effective method for the treatment of bastnaesite, has been extensively employed in industrial production practice. However, the roasting decomposition mechanism of bastnaesite at the molecular level remains controversial. In this study, two roasting atmospheres (i.e., Ar and O2) were adopted for the treatment of the mixed rare earth concentrate in Bayan Obo. Ar-Roasting ore was skillfully treated as an intermediate and then underwent oxidation roasting. The results achieved using research methods (e.g., XRD, FT-IR, TEM, and XPS) first revealed that the oxidation roasting of bastnaesite was performed in several stages. The first stage was the thermal decomposition of bastnaesite and the oxidation of cerium (REFCO3 → REOF + CO2). The second stage was the escape pathway of fluorine (REOF + O2 → RE x O y + O x F and O x F → O2 + F2), describing the migration rules of F and O elements and the oxidation behavior of Ce. The results of this study can provide more theoretical support and guidance for the clean extraction of bastnaesite and mixed rare earth in Bayan Obo.

Enhanced rare earth element recovery with cross-linked glutaraldehyde-lanthanide binding peptides in foam-based separations

HypothesisLanthanide Binding Tag (LBT) peptides that coordinate selectively with lanthanide ions can be used to replace the energy intensive processes used for the separation of rare earth elements (REEs). These surface-active biomolecules, once selectively complexed with the trivalent REE cations, can adsorb to air/aqueous interfaces of bubbles for foam-based REEs recovery. Glutaraldehyde, an organic compound that is a homobifunctional crosslinker for proteins and peptides, can be used to enhance the adsorption and interfacial stabilization of lanthanide-bound peptides films. ExperimentsThe stability of the interfacial cross-linked films was tested by measuring their dilational and shear surface rheological properties. Surface activity of the adsorbed species was analyzed using pendant drop tensiometry, while surface density and molecular arrangement were determined using x-ray reflectivity and x-ray fluorescence near total reflection. FindingsGlutaraldehyde cross-linked REE-peptide complexes enhance the adsorption of lanthanides to air-water interfaces, resulting in thicker interfacial structures. Subsequently, these thicker layers enhance the dilational and shear interfacial rheological properties. The interfacial film stabilization and REEs extraction promoted by the cross-linker presented in this work provides an approach to integrate glutaraldehyde as a substitute of common foam stabilizers such as polymers, surfactants, and particles to optimize the recovery of REEs when using biomolecules as extractants.

Sulfuric Acid Leaching of Carbonatite ore with High Calcite Content in Lugiin Gol under Ambient Condition

AbstractCarbonatite bearing rare earth elements are rich sources of rare earth elements and play a critical role in the global supply chain. While carbonatite deposits are less accessible compared to ion adsorption clays, their mineral composition makes them essential for rare earth element extraction. Extraction of rare earth elements from carbonatite ore involves acid leaching, a process that we aim to explore in this study using the carbonatite ore from Lugiin gol. Characterization of the raw material and solid residue post‐leaching was conducted using X‐ray diffractometry, inductively coupled plasma optical emission spectroscopy, and a zeta potential analyzer. These analytical techniques were utilized for kinetic modeling, assessing the influencing factors of leaching, and determining metal recovery in the pregnant solution. The results of the study highlight the significant role of surface charge formation on target particles during milling in the acidic leaching process. This finding shed light on the importance of understanding the surface properties of the particles in the extraction of rare earth elements from carbonatite ores. The surface of particles in the supernatant of rare earth elements’ ore was negatively charged, with the median zeta potential of the 0.025 mm fraction being at its minimum of −60.6 mV.

Extraction and purification of thorium and rare earth elements from bastnaesite mineral: a comprehensive leaching and precipitation study

Extraction and purification of thorium and rare earth elements from bastnaesite mineral: a comprehensive leaching and precipitation study

Membrane transport of rare earth metal ions N, N’-bisdioctylphosphorylmethyl-1,4-diaminobutane by the active transport mechanism

The method of membrane extraction for rare earth elements (REE) using the carrier N, N’-bisdioctylphosphorylmethyl-1,4-diaminobutane (DPDA-8) ions, leveraging an active transport mechanism, has been optimized. The distribution of DPDA-8 within the membrane pores was confirmed using scanning electron microscopy (SEM). Both light and heavy REE extractions from a simulated solution using DPDA-8 and trioctylphosphine oxide (TOPO) in 1,2-dichlorobenzene were explored. The influence of feed solution pH, carrier and anion concentration, supported liquid membrane (SLM) type and stability, and cell temperature, among other parameters, were meticulously examined. The results indicate a decrease in permeability with a decrease in feed solution pH attributed to competitive acid transport through the membrane. Additionally, the formation of H-complexes between carriers and perchloric or phosphoric acids was investigated using Fourier Transform Infrared (FTIR) spectroscopy and X-ray diffraction (XRD) techniques. Changes in the stretching bands of amino and phosphine oxide groups in DPDA-8 were monitored and characterized. XRD analysis of the crystal structures of salts DPDA-6·ClO4 and DPDA-12·H2PO4 revealed a two-dimensional layered supramolecular organization with varying anion positions relative to hydrophobic fragments. The DPDA-8 carrier demonstrated significantly higher permeability values compared to TOPO, with differences in permeability exceeding twofold for certain metals. FTIR spectroscopy identified the main coordination centers of DPDA-8 during the liquid–liquid extraction of specific REEs.

Novel nitrogen-rich hydrogel adsorbent for selective extraction of rare earth elements from wastewater

Efficient recovery of rare earth elements (REEs) from wastewater is crucial for advancing resource utilization and environmental protection. Herein, a novel nitrogen-rich hydrogel adsorbent (PEI-ALG@KLN) was synthesized by modifying coated kaolinite-alginate composite hydrogels with polyethylenimine through polyelectrolyte interactions and Schiff’s base reaction. Various characterizations revealed that the high selective adsorption capacity of Ho (155 mg/g) and Nd (125 mg/g) on PEI-ALG@KLN is due to a combination of REEs (Lewis acids) via coordination interactions with nitrogen-containing functional groups (Lewis bases) and electrostatic interactions; its adsorption capacity remains more than 85 % after five adsorption-desorption cycles. In waste NdFeB magnet hydrometallurgical wastewater, the recovery rate of PEI-ALG@KLN for Nd and Dy can reach more than 93 %, whereas that of Fe is only 5.04 %. Machine learning prediction was used to evaluate adsorbent properties via different predictive models, with the random forest (RF) model showing superior predictive accuracy. The order of significance for adsorption capacity was pH > time > initial concentration > electronegativity > ion radius, as indicated by the RF model feature importance analysis and SHapley Additive exPlanations values. These results confirm that PEI-ALG@KLN has considerable potential in the selective extraction of REEs from wastewater.

Efficient extraction of rare earth elements from coal-series kaolin by combining alkali fusion and sulfamic acid leaching

As a solid waste produced by coal mining, the comprehensive utilization of coal-series kaolin is the focus of attention. In this paper, the extraction of rare earth elements (REEs) from coal-series kaolin was carried out by alkali fusion and sulfamic acid leaching. The occurrence modes of REEs in coal-series kaolin was analyzed by means of inductively coupled plasma-mass spectrometry analyse and sequential chemical extraction. The influence of alkali fusion conditions on the leaching of REEs was investigated, and the activation mechanism of alkali fusion was revealed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and field emission scanning electron microscope (FESEM) analysis. In addition, the effect of key operating parameters on the leaching efficiency of REEs from coal-series kaolin was further investigated. The results show that REEs mainly existed in silicate & aluminosilicate state of coal-series kaolin. The mineral structure was destroyed by alkali fusion, and the leaching efficiency of REEs was increased by 59.08 %. At the sulfamic acid concentration of 0.5 mol/L, H2O2 concentration of 0.2 mol/L, solid to liquid ratio of 1/50, the leaching efficiencies of total rare earth elements, light rare earth elements and heavy rare earth elements were 84.91 %, 88.43 % and 71.03 %, respectively.

A cationic three-dimensional covalent organic framework membrane for nanofiltration of molecules and rare Earth ions

Permanently microporous materials have evolved as focal point of research for tackling issues in separation science and membrane technology. Covalent organic frameworks (COFs) stand out for their distinctive synergy of crystalline nature, uniform channels, and structural diversities. Three-dimensional (3D) COFs, distinguished by angstrom-sized and interconnected channels, hold special promise for separating small targets; however, this potential remains underexplored. Here, we report feasible growth of cationic 3D COF membranes on a flexible polymer substrate for versatile nanofiltration toward both molecules and ions. Through comprehensive performance evaluations, we reveal that the resultant membrane exhibits durable and prominent molecular selectivity to separate fine species with molecular weights above 300 g mol−1 at fast methanol permeation. Lanthanide ions of industrial value also can be harvested by the membrane with rejection rates of up to 91.4%. Together with its nonselectivity to competing ions, our membrane implements efficient extraction of rare earth elements from ion mixtures. These findings illuminate the potential of 3D COFs for liquid separation and offer a solution to building versatile membranes.

New Insights on Y, La, Nd, and Sm Extraction with Bifunctional Ionic Liquid Cyphos IL 104 Incorporated in a Polymer Inclusion Membrane.

In this study, an ionic liquid-based polymer inclusion membrane (IL-PIM) made of (50% polymer-50% CyphosIL104) was used to extract and separate the rare earth elements (REEs) Y, La, Nd, and Sm in chloride solutions. The effect of extraction time and pH was studied to optimize the extraction and separation conditions. The four REEs were effectively extracted at pH 4-5 from both single and mixed metals solutions. However, at pH 2, only Y was extracted. The recovery of the extracted REEs from the loaded PIM was achieved using HNO3 and H2SO4. In the case of La, it was quantitatively back-extracted with H2SO4 after a contact time of 1 h, while up to 4 h was necessary to recover 70% of the extracted Y, Sm, and Nd. Extraction isotherms were studied, and the Freundlich isotherm model was the most adequate to describe the interaction between the PIM and the REEs. Finally, the developed PIM was investigated for the extraction of REEs from mixtures containing other metals, which showed great selectivity for the REEs.

Iron(III) and neodymium co-extraction mechanism with TODGA from chloride medium

In the context of NdFeB magnets recycling, solvent extraction of lanthanides using diglycolamides is promising but their separation from iron(III) remains a challenge. Here, the extraction mechanisms of iron(III) and neodymium by TODGA (N,N,N′,N′-tetraoctyldiglycolamide) were examined in chloride medium. The choice of chloride media was driven by the efficiency of HCl in dissolving NdFeB magnets. Neodymium was chosen as a representative lanthanide to examine the co-extraction mechanism. For the extraction of iron(III), UV–visible and FT-IR spectra provide evidence for the extraction of FeCl4- with the participation of TODGA carbonyl groups. For the extraction with both elements, the solvent extraction study points out that there is co-extraction of neodymium and iron(III). Neodymium(III) extraction percentage increases from 6 to more than 97 % by adding iron(III). From spectroscopic studies (UV–visible, FT-IR) and thermodynamic modelling of extraction data, it is shown that three molecules of TODGA extract neodymium, as for neodymium-only extraction. They also reveal the presence of Fe(III) as FeCl4- anion in the outer sphere of [Nd(TODGA)3]3+. This brings to the conclusion that [Nd(TODGA)3](FeCl4)3 complex is formed in the organic phase. DFT (Density Functional Theory) calculations confirm that FeCl4- can replace Cl- in the outer sphere of [Nd(TODGA)3]3+, in a two-step reaction, with the initial formation of [Nd(TODGA)3]Cl3 followed by the binding of FeCl3 to the outer-sphere chloride ion. These results pave the way to the design of new diglycolamides that are selective towards iron(III) from chloride medium. The complete dissolution solution of NdFeB is represented by a highly acidic medium (a solution of 3 M HCl), whereas the leaching solution (partial dissolution of NdFeB) is represented by a weakly acidic medium (NaCl).

Acute and chronic toxicity of rare earth elements-enriched sediments from a prospective mining area: Effects on life history traits, behavioural and physiological responses of Gammarus fossarum (Crustacea Amphipoda)

Rare earth elements (REE) have an essential role and growing importance in the world's economy. They are attracting interest from society, policymakers, and scientists. The rapidly growing global demand for REE in several strategic industrial and agricultural sectors led many countries to consider the (re)-opening of mining activities for REE extraction. Hence, their increasing use led to the disruption of their biogeochemical cycles with anthropic abnormalities already observed in aquatic ecosystems. Nonetheless, REE remain less studied, and their mechanisms of toxicity actions are not fully understood. As amphipods, Gammarus fossarum represent an important part of the aquatic macroinvertebrate assemblage and are generally used in ecotoxicological studies for their high ecological relevance. However, their use for the study of REE effects has been rather limited so far. The current study aims to assess the potential effects of two naturally REE-enriched sediments (N2 and B4) on G. fossarum. Effects on life history traits, behavioural and physiological responses have been evaluated. Exposing G. fossarum males for 72h to sediments N2 and B4 led to a decrease in haemolymph osmolality and locomotion while an increase in ventilatory activity was observed. Exposing G. fossarum pre-copula pairs with females at the same reproductive stage to the naturally REE-enriched sediments, for one moult cycle duration (∼30 days) showed that sediment B4 led to i) a significant uptake of REE, ii) a significant decrease in the proportion of females with oocytes and iii) a significant reduction in the total number of juveniles. The physicochemical analyses of sediments showed that B4 contains the highest amount of REE with a higher proportion of light REE. The present study gives the first insights into the potential toxicity of REE on G. fossarum as they may have deleterious effects on G. fossarum population's dynamics, which may alter the functioning of aquatic ecosystems.

Critical minerals and rare earth elements in a planetary just transition: An interdisciplinary perspective

While vital for the development of ‘clean’ energy technologies, the extraction and processing of critical minerals and rare earth elements entail a range of overlapping social and environmental harms in local communities across the world. The transition to low-carbon economies invokes a host of multiscalar dilemmas, injustices and trade-offs, notably between the global imperative to reduce greenhouse gas emissions and the local consequences of mineral mining. There are profound barriers to delivering a just energy transition at a planetary scale given the reliance of green technologies upon socio-environmentally harmful extractive practices across critical mineral supply chains. Adopting an interdisciplinary lens and drawing from a set of international case studies, we critically examine the intersection of critical minerals with just transition governance and explore possibilities for more plural, holistic and integrated just energy transition pathways. In this introduction article, we detail the ways in which the production of low-carbon technologies is bound up with global inequalities and ongoing coloniality. We then demonstrate the importance of adopting a global, inclusive outlook on just energy transitions. Drawing from the concept of planetary just transition, we provide an overview of the key debates around the role of critical minerals in a just energy transition.

Maximized Lanthanide Extraction Using Supercritical CO2 and Fluorinated Organophosphate Extractants

Maximized Lanthanide Extraction Using Supercritical CO₂ and Fluorinated Organophosphate Extractants

Intra-lanthanide separation performance of DOTP: Solid-phase extraction and selective precipitation studies

The applicability of 1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetra(methylene phosphonic acid) (DOTP) for intra-lanthanide (Ln) separation was investigated through two approaches: the synthesis of inorganic–organic hybrid sorbents and selective precipitation in an aqueous solution. Hybrid sorbents combining zirconium oxide and DOTP were fabricated through post-synthetic grafting and hydrothermal synthesis. The successful syntheses were verified by FTIR and 31P magic-angle spinning (MAS) NMR spectroscopies. All the hybrid sorbents showed a lanthanide uptake of approximately 10–20 μmol/g at pH 3 and displayed only moderate selectivity, with the highest separation factor (SF) of about 10 for Lu3+ over La3+. In contrast, the selective precipitation of lanthanides by DOTP in an aqueous solution was successful in the presence of Cu2+. When a Cu-DOTP complex was introduced into a La/Lu equimolar solution, lanthanide ions were selectively precipitated with an SF of approximately 30–190. When the initial stoichiometry was set to Ln:Cu-DOTP = 8:1, roughly 95 % of the lanthanides in the precipitate were Lu3+, regardless of the pH ranging from 3 to 5. This precipitation process demonstrated selectivity even for adjacent lanthanide pairs. The selectivity is assumed to be a result of structural variations in the precipitates of Ln-Cu-DOTP, which is supported by the characterization results obtained from X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and UV–Vis spectroscopy. The findings presented in this study indicate that DOTP has the potential for use in the selective extraction of lanthanides, which may offer promising advancements in intra-lanthanide separation.

Selective extraction and recovery of rare earth elements from coal fly ash by carboxylated mesoporous carbon

The separation of Rare Earth Elements (REEs) from non-conventional sources is very critical to maintain the supply-chain balance of REEs in the Western world. Despite Coal Fly Ash (CFA) being designated as a prominent non-conventional source of REEs and several studies have reported on the extraction of REEs from CFA, the selectivity of REEs with respect to non-REEs in the CFA has never been reported. In this work, for the time, we have reported the selectivity of REEs over non-REEs using carboxylated mesoporous carbon (CMC) as the sorbent. The CMC was produced by carboxylating the soft-templated mesoporous carbon and then it was characterized successfully for porosity, FTIR, and SEM-EDX. The leachate produced from REEs contains 16 REEs and 20 non-REEs from groups 1 through 3 and 6 through 15 of the modern periodic table. The REEs were extracted within 80–90% in the 3 cycles along with the elements from groups of 1,3, 5, 8, and 11. Although a few other elements were also extracted, the values of the distribution coefficient confirmed that the CMC has a much higher affinity towards REEs except the non-REEs from groups 1 and 3. In the recovery mode, the REEs were recovered in the range of 20–100%, and heavier REEs demonstrated a better recovery. The recovery percent of non-REEs was also much lower compared to that of REEs, except for the elements from groups 3, 8, and 11. The non-REEs from group 3 demonstrated the highest competition, which can be attributed to the fact the REEs also belong to the same group of the periodic table. The ratio of extracted and recovered REEs over non-REEs was always greater than unity, suggesting that the CMC was selective towards REEs over non-REEs in extraction and recovery. The overall results suggest that CMC can potentially be used for selective extraction and recovery of REEs from coal fly ash.

Effect of Ionic Liquid on the Extraction of Lanthanides(III) from Nitric Acid Solutions with Phosphoryl-Containing Podands

Effect of Ionic Liquid on the Extraction of Lanthanides(III) from Nitric Acid Solutions with Phosphoryl-Containing Podands