Fluorine-Rich Supramolecular Nano-Container Crosslinked Hydrogel for Lithium Extraction with Super-High Capacity and Extreme Selectivity

Extraction and recovery of lithium from reserves play a critical role in the sustainable development of energy due to the explosive growth of the lithium-battery market. However, the low efficiency of extraction and recovery seriously threatens the sustainability of lithium supply. In this contribution, we fabricate a novel mechanically robust fluorine-rich hydrogel, showing highly efficient Li⁺ extraction from Li-containing solutions. The hydrogel was facilely fabricated by simple one-pot polymerization of supramolecular nanosheets of fluorinated monomers, acrylic acid and a small amount of chemical crosslinkers. The hydrogel exhibits a remarkable lithium adsorption capacity (Q_m Li⁺=122.3 mg g⁻¹) and can be reused. Moreover, it can exclusively extract lithium ions from multiple co-existing metal ions. Notably, the separation of Li⁺/Na⁺ in actual wastewater is achieved with a surprising separation factor of 153.72. The detailed characterizations as well as calculation showed that the specific coordination of Li−F plays a central role for both of the striking recovery capability and selectivity for Li⁺. Furthermore, an artificial device was constructed, displaying high efficiency of extracting lithium in various complex actual lithium-containing wastewater. This work provides a new and promising avenue for the efficient extraction and recovery of lithium resource from complex lithium-containing solutions.     

Selective Separation of Lithium,Magnesium and Calcium using 4-Phosphoryl Pyrazolones as pH-Regulated Receptors

Ensuring continuous and sustainable lithium supply requires the development of highly efficient separation processes such as LLE (liquid-liquid extraction) for both primary sources and certain waste streams. In this work, 4-phosphoryl pyrazolones are used in an efficient pH-controlled stepwise separation of Li⁺ from Ca²⁺, Mg²⁺, Na⁺ and K⁺. The factors affecting LLE process, such as the substitution pattern of the extractant, diluent/water distribution, co-ligand, pH, and speciation of the metal complexes involved, were systematically investigated. The maximum extraction efficiency of Li⁺ at pH 6.0 was 94 % when Mg²⁺ and Ca²⁺ were previously separated at pH<5.0, proving that the separation of these ions is possible by simply modulating the pH of the aqueous phase. Our study points a way to separation of lithium from acid brine or from spent lithium ion battery leaching solutions, which supports the future supply of lithium in a more environmentally friendly and sustainable manner.     

三辛基氧化膦(TOPO)萃取铟的研究

本文研究了三辛基氧化膦(TOPO)自盐酸溶液中萃取铟的性能,其萃取率是随酸度的增加而增加。与P_(350)和TBP相比较,萃取能力大小顺序为:TOPO>P_(350)>TBP经斜率法和化学分析法研究确定,TOPO白盐酸溶液中萃取铟的反应为:In_((a))~(3+)+H_((a))~++4Cl_((a))~-+2TOPO_((o))F(?)HInCl_4·2TOPO_((o))IR和NMR研究证明:铟是以H[InCl_4]形式被萃入TOPO有机相中的。     

Synergistic extraction of uranium(VI) and thorium(IV) with mixtures of Cyanex272 and other organophosphorus ligands

The extraction of thorium(IV) and uranium(VI) from nitric acid solutions has been studied using mixtures of bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex272 or HA), and synergistic extractants (S) such as tri-butylphosphate (TBP), tri-octylphosphine oxide (TOPO) or bis(2,4,4-trimethylpentyl)thiophosphinic acid (Cyanex301). The results showed that these metallic ions are extracted into kerosene as Th(OH)₂(NO₃)A·HA and UO₂(NO₃)A·HA with Cyanex272 alone. In the presence of neutral organophosphorus ligands TBP and TOPO, they are found to be extracted as Th(OH)₂(NO₃)A·HA·S and UO₂(NO₃)A·HA·S. On the other hand, Th(IV), U(VI) are extracted as Th(OH)₂(NO₃)A·HA·2S and UO₂(NO₃)A·HA·S in the presence of Cyanex301. The addition of neutral extractants such as TOPO and TBP to the extraction system enhanced the extraction efficiency of both elements while Cyanex301 as an acidic extractant has improved the selectivity between uranium and thorium. The effect of TOPO on the extraction was higher than other extractants. The equilibrium constants of above species have been estimated by non-linear regression method. The extraction amounts were determined and the results were compared with those of TBP. Also, it was found that the binding to the neutral ligands by the thorium–Cyanex272 complexes follows the neutral ligand basicity sequence.     

Effect of 1,10-phenanthroline on the extraction and separation of lithium(I), sodium(I) and potassium(I) with thenoyltrifluoroacetone

The extraction of Li⁺ with thenoyltrifluoroacetone (Htta) in the presence of 1,10-phenanthroline (phen) has been studied in various organic solvents. The remarkable enhancement of the extraction of Li⁺, that is a synergistic effect, was observed by the addition of phen, and the high extractability of Li⁺ was attained in toluene, benzene, chlorobenzene and o-dichlorobenzene. The extraction equilibrium of Li⁺, Na⁺ and K⁺ (denoted as M⁺) in the presence or absence of phen in chlorobenzene and the adduct formation reaction in the organic phase were studied in detail. The adduct of Li⁺ was Li(tta)(phen) in the wide concentration range of phen in the organic phase, while in Na⁺ and K⁺ M(tta)(phen)₂ also exists in the high concentration region. The maximum value of the separation factor between Li⁺ and Na⁺ was observed in the present system and was larger than that in the Htta-trioctylphosphine oxide (TOPO)-benzene system reported previously.     

Mixed-phase WO3 Cocatalysts on Hierarchical Si-based Photocathode for Efficient Photoelectrochemical Li Extraction

Photoelectrochemical lithium (Li) extraction can be expected to provide a useful recycle of Li⁺ from waste Li-containing battery, but the process is limited by the photocathodes with poor Li⁺ absorption and low yield rate. Here, we have designed a hierarchical silicon (Si)-based photocathode with mixed-phase tungsten oxide (WO₃) cocatalysts for photoelectrochemical Li extraction under 1 sun illumination, achieving a high Li yield rate of ≈223.0 μg cm⁻² h⁻¹ and an excellent faradaic efficiency of 91.9 % at 0.0817 V versus Li^0/+ redox couple. The WO₃ cocatalysts with the mixture of amorphous and crystalline phase accelerates the Li⁺ insertion and precipitation and enriches the concentration of Li⁺ at the photocathode surface. This robust photoelectrochemical Li extraction system provides a new insight on designing green and efficient route for cyclic utilization of Li resources in the sustainable energy field.     

Iron,copper and their proteins in substantia nigra of human brain during aging

Liquid-liquid extraction of zirconium(IV) was investigated from dilute hydrochloric acid medium by salicyaldoxime (HA) in dichloromethane. The metal was spiked with ⁹⁵Zr and analyzed by its radioactivity. The effects of different donors, like trioctyl phosphine oxide (TOPO), triphenyl phosphine oxide (TPPO), tributyl phosphine oxide (TBPO), tributyl phosphate (TBP), trioctyl amine (TOA) and Amberlite LA-2 were studied. The adduct formation constants for both binary species (metal-ligand) and ternary species (metal-ligand-donor) were also calculated form the distribution data.One of the authors (S.B.) thanks The University of Burdwan for providing senior research fellowship to her. She also wishes to thank Dr. D. Mukherjee and Dr. S. Bhattacharya, B.U. for their valuable suggestions.     

Synergistic effect of neutral donors on the extraction of zirconium(IV) by salicylaldoxime in dichloromethane

Liquid-liquid extraction of zirconium(IV) was investigated from dilute hydrochloric acid medium by salicyaldoxime (HA) in dichloromethane. The metal was spiked with ⁹⁵Zr and analyzed by its radioactivity. The effects of different donors, like trioctyl phosphine oxide (TOPO), triphenyl phosphine oxide (TPPO), tributyl phosphine oxide (TBPO), tributyl phosphate (TBP), trioctyl amine (TOA) and Amberlite LA-2 were studied. The adduct formation constants for both binary species (metal-ligand) and ternary species (metal-ligand-donor) were also calculated form the distribution data.One of the authors (S.B.) thanks The University of Burdwan for providing senior research fellowship to her. She also wishes to thank Dr. D. Mukherjee and Dr. S. Bhattacharya, B.U. for their valuable suggestions.     

Influence of hydrophobic solids upon the extraction capability of extractants

The influence of solid phase media such as multilayer porous polymer films (nuclear filters) upon extraction of U(VI), Fe(III) and Sc by using main classes of extractants: tributyl phosphate (TBP), tributylphosphine oxide (TBPO), di-(2-ethylhexyl)phosphoric acid (HDEHPA), trioctylammonium nitrate (TOA) have been studied. The increase of distribution coefficients (D) up to 10–100 times in the presence of nuclear filters as compared to common liquid-liquid extraction has been established.     

介电法研究萃取过程中分子间的络合作用

用介电法测定若干重要萃取剂的摩尔极化度和偶极矩，研究协萃体系中萃取剂之间的络合作用和协同萃了现象，求得缔合物、萃合物的摩尔极化度、偶极矩及缔合常数。     

Synergistic extraction of radium using 2-thenoyltrifluoroacetone and tributyl phosphate or trioctylphosphine oxide

The extraction of radium into a mixture of 2-thenoyltrifluoroacetone (HTTA) and tributyl phosphate (TBP) or trioctylphosphine oxide (TOPO) in n-hexane or cyclohexane has been investigated with regard to the dependence on pH, and TBP and TOPO concentrations. It has been found that the formation of mixed complexes of the type Ra(TTA)₂ (TBP)₂ and Ra(TTA)₂(TOPO)₂ occurs and the overall extraction constants of both complexes were calculated. With the systems described, very high distribution ratios of radium have been attained; these may advantageously be used for the separation and concentration of traces of radium.     

盐湖卤水萃取提锂及其机理研究

本文以磷酸三丁酯(TBP)为萃取剂,煤油为稀释剂,在FeCl₃存在的条件下,选择性萃取盐湖卤水中的锂。系统研究了相比、萃取剂组成、铁锂比等对锂萃取率的影响,及洗涤、反萃取工艺条件。得到最佳工艺条件为：萃取相比V_O/V_A为1.5,TBP质量分数为75%,c_Fe³⁺/c_Li⁺=2,c_H⁺=0.02 mol·L^-1,萃取时间为20 min;洗涤相比V_O/V_A为15;反萃取相比V_O/V_A为20。并运用红外与核磁方法分析研究,表明是TBP上的P=O双键与LiFeCl₄金属配合物的配位水分子产生氢键作用而使金属配合物与TBP结合。     

Lithium ions in the van der Waals gap of Bi2Se3 single crystals

Insertion/extraction of lithium ions into/from Bi₂Se₃ crystals was investigated by means of cyclic voltammetry. The process of insertion is reflected in the appearance of two bands on voltammograms at ∼1.7 and ∼1.5 V, corresponding to the insertion of Li⁺ ions into octahedral and tetrahedral sites of the van der Waals gap of these layered crystals. The process of extraction of Li⁺ ions from the gap results in the appearance of four bands on the voltammograms. The bands 1 and 2 at ∼2.1 and ∼2.3 V correspond to the extraction of a part of Li⁺ guest ions from the octahedral and tetrahedrals sites and this extraction has a character of a reversible intercalation/deintercalation process. A part of Li⁺ ions is bound firmly in the crystal due to the formation of negatively charged clusters of the (LiBiSe₂.Bi₃Se₄⁻) type. A further extraction of Li⁺ ions from the van der Waals gap is associated with the presence of bands 3 and 4 placed at ∼2.5 and ∼2.7 V on the voltammograms as their extraction needs higher voltage due to the influence of negative charges localized on these clusters.     

协同萃取液膜体系从Li+、Na+、K+混合溶液中提取Li+

从卤水、海水中提取Li是目前较为活跃的研究课题。用液膜法从Li~+、Na~+、K~+混合溶液中分离Li~+的报道很少。协同效应在乳状液型液膜中的应用还未见报道。本文采用噻吩甲酰三氟丙酮(HTTA)和磷酸三丁酯(TBP)作为混合载体的液膜体系,快速、高效地从Li~+、Na~+、K~+的混合溶液中分离、浓缩Li~+,为从卤水、海水中提取Li~+提供了重要的依据。     

Supramolecular Polymer Ion Conductor with Weakened Li Ion Solvation Enables Room Temperature All-Solid-State Lithium Metal Batteries

Improved durability, enhanced interfacial stability, and room temperature applicability are desirable properties for all-solid-state lithium metal batteries (ASSLMBs), yet these desired properties are rarely achieved simultaneously. Here, in this work, it is noticed that the huge resistance at Li metal/electrolyte interface dominantly impeded the normal cycling of ASSLMBs especially at around room temperature (<30 °C). Accordingly, a supramolecular polymer ion conductor (SPC) with “weak solvation” of Li⁺ was prepared. Benefiting from the halogen-bonding interaction between the electron-deficient iodine atom (on 1,4-diiodotetrafluorobenzene) and electron-rich oxygen atoms (on ethylene oxide), the O-Li⁺ coordination was significantly weakened. Therefore, the SPC achieves rapid Li⁺ transport with high Li⁺ transference number, and importantly, derives a unique Li₂O-rich SEI with low interfacial resistance on lithium metal surface, therefore enabling stable cycling of ASSLMBs even down to 10 °C. This work is a new exploration of halogen-bonding chemistry in solid polymer electrolyte and highlights the importance of “weak solvation” of Li⁺ in the solid-state electrolyte for room temperature ASSLMBs.     

Polystyrene Sulfonate Threaded through a Metal–Organic Framework Membrane for Fast and Selective Lithium‐Ion Separation

Extraction of lithium ions from salt‐lake brines is very important to produce lithium compounds. Herein, we report a new approach to construct polystyrene sulfonate (PSS) threaded HKUST‐1 metal–organic framework (MOF) membranes through an in situ confinement conversion process. The resulting membrane PSS@HKUST‐1‐6.7, with unique anchored three‐dimensional sulfonate networks, shows a very high Li⁺ conductivity of 5.53×10^?4 S cm^?1 at 25 °C, 1.89×10^?3 S cm^?1 at 70 °C, and Li⁺ flux of 6.75 mol m^?2 h^?1, which are five orders higher than that of the pristine HKUST‐1 membrane. Attributed to the different size sieving effects and the affinity differences of the Li⁺, Na⁺, K⁺, and Mg²⁺ ions to the sulfonate groups, the PSS@HKUST‐1‐6.7 membrane exhibits ideal selectivities of 78, 99, and 10296 for Li⁺/Na⁺, Li⁺/K⁺, Li⁺/Mg²⁺ and real binary ion selectivities of 35, 67, and 1815, respectively, the highest ever reported among ionic conductors and Li⁺ extraction membranes.     

Synergistic extraction of uranium(VI) with 1-phenyl-3-methyl-4-acylpyrazolone-5 and neutral extractants

The synergistic extraction of uranium(VI) from hydrochloric acid solution with five chelating agents: 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (PMBP), 1-phenyl-3-methyl-4-acetylpyrazolone-5 (PMAP), 1-phenyl-3-methyl-4-(2-chlorobenzoyl)pyrazolone-5 (PMCBP), 1-phenyl-3-methyl-4-(p-nitrobenzoyl)pyrazolone-5 (PMNBP) and 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5 (PMTFP) plus the neutral extractants tributylphosphate (TBP), dioctyl sulfoxide (DOSO) and trioctylphosphine oxide (TOPO) in chloroform has been investigated. The extraction coefficients have been found to be greater for such mixtures than the individual component. The formulas of the extracted species have been determined to be UO₂A₂B (where HA = chelating agent, B = neutral extractant). Extraction power of these chelating agents increases as follows: PMCBP>PMNBP>PMTFP=PMBP>PMAP. Synergistic extraction power of the neutral extractants increases as follows: TOPO>DOSO>TBP. The extraction equilibrium constants have been calculated. The mechanism of the synergistic extraction and possible structure of the extracted species are discussed.     

Highly Selective Lithium Transport through Crown Ether Pillared Angstrom Channels

Biological ion channels use the synergistic effects of various strategies to realize highly selective ion sieving. For example, potassium channels use functional groups and angstrom-sized pores to discriminate rival ions and enrich target ions. Inspired by this, we constructed a layered crystal pillared by crown ether that incorporates these strategies to realize high Li⁺ selectivity. The pillared channels and crown ether have an angstrom-scale size. The crown ether specifically allows the low-barrier transport of Li⁺. The channels attract and enrich Li⁺ ions by up to orders of magnitude. As a result, our material sieves Li⁺ out of various common ions such as Na⁺, K⁺, Ca²⁺, Mg²⁺ and Al³⁺. Moreover, by spontaneously enriching Li⁺ ions, it realizes an effective Li⁺/Na⁺ selectivity of 1422 in artificial seawater where the Li⁺ concentration is merely 25 μM. We expect this work to spark technologies for the extraction of lithium and other dilute metal ions.     

Determination of plutonium by solvent extraction—Liquid scintillation method

A combined solvent extraction—liquid scintillation method is suggested for the determination of plutonium. The quenching by twenty four extracting reagents was examined systematically, and the organo phosphorus extractants such as tributylphosphate (TBP), bis-(2-ethyhexyl) phosphoric acid (HDEHP), and tri-n-octylphosphineoxide (TOPO) were shown to be least quenching compared with amines and beta-diketones. Using TOPO, plutonium from 1 ng to 2 μg was determined within 5% of standard deviation, and the detection limit was 3·10⁻¹⁰ g of²³⁹Pu. The quenching by the different ions and the effects of the radioactive elements were also shown.     

Synergistic effect of tri-<Emphasis Type="Italic">n</Emphasis>-butyl phosphate (TBP) or tri-<Emphasis Type="Italic">n</Emphasis>-octyl phosphine oxide (TOPO) with didodecylphosphoric acid (HDDPA) on extraction of uranium(VI) and thorium(IV) ions

Importance of removal of radioactive elements from wastewater was the motivation behind this work. Synergistic solvent extraction of U(VI) and Th(IV) ions from perchlorate solution using didodecylphosphoric acid (HDDPA) incorporated with tri-n-butyl phosphate (TBP) or tri-n-octylphosphine oxide (TOPO) as a synergists have been studied for the first time. The effects of HDDPA concentration, synergist’s concentration, pH values and temperature on the extraction process have been studied. The thermodynamic parameters of the extraction process for these ions were calculated. It was found that the synergistic contribution of TOPO is higher than TBP in the extraction of Th(IV) and U(VI).