The efficient extraction of sodium(Na^(+))and lithium(Li^(+))from seawater and salt lakes is increasingly demanding due to their great application value in chemical industries.However,coexisting cations such as divale...The efficient extraction of sodium(Na^(+))and lithium(Li^(+))from seawater and salt lakes is increasingly demanding due to their great application value in chemical industries.However,coexisting cations such as divalent calcium(Ca^(2+))and magnesium(Mg^(2+))ions are at the subnanometer scale in diameter,similar to target monovalent ions,making ion separation a great challenge.Here,we propose a simple and fast secondary growth method for the preparation of MIL-53(Al)-NH_(2)membranes on the surface of anodic aluminum oxide.Such membranes contain angstrom-scale(~7Å)channels for the entrance of small monovalent ions and water molecules,endowing the selectivities for monovalent cations over divalent cations and water over salt molecules.The resulting high-connectivity MIL-53(Al)-NH_(2)membranes exhibit excellent ion separation performance(a selectivity of 121.42 for Na^(+)/Ca^(2+)and 93.81 for Li^(+)/Mg^(2+))and desalination performance(a water/salt selectivity of up to 5196).This work highlights metal–organic framework membranes as potential candidates for realizing ion separation and desalination in liquid treatment.展开更多
Nano-assisted inclusion separation of alkali metals from basic solutions was reported by inclu sion-facilitated emulsion liquid membrane process. The novelty of this study is application of nano-baskets of calixcrown ...Nano-assisted inclusion separation of alkali metals from basic solutions was reported by inclu sion-facilitated emulsion liquid membrane process. The novelty of this study is application of nano-baskets of calixcrown in the selective and efficient separation of alkali metals as both the carrier and the surfactant. For this aim, four derivatives of diacid calix[4]-1,3-crowns-4,5 were synthesized, and their inclusion-extraction parameters were optimized including the calixcrown scaffold (4.4%, by mass) as the carrier/demulsifier, the commercial kero sene as diluent in membrane, sulphonic acid (0.2 mol.L-1) and ammonium carbonate (0.4 mol.L-1) as the strip and the feed phases, the phase and the treat ratios of 0.8 and 0.3, mixing speed (300 r.min-1), and initial solute concentration (100 mg.L-1). The selectivity of membrane over more than ten interfering cations was examined and the re sults reveled that under the optimized operating condition, the degree of inclusion-extraction of alkali metals was as high as 98%-99%.展开更多
Toxic Zn(II) ion imprinted interpenetrating polymer networks were synthesized for the selective sorption of Zn(ll) from aqueous solutions using a biopolymer alginic acid. The polymeric biosorbant was prepared usin...Toxic Zn(II) ion imprinted interpenetrating polymer networks were synthesized for the selective sorption of Zn(ll) from aqueous solutions using a biopolymer alginic acid. The polymeric biosorbant was prepared using Zn(II) ion as template, acrylamide as functional monomer, cross linker NNMBA (N,N' Methylene-bis-acrylamide) and potassium persulphate as an initiator. The non-imprinted polymer networks were also prepared without use of the Zn(II) ion. The synthesized interpenetrating networks were characterized by various spectral techniques. Metal ion binding studies were carried out and the factors affecting binding were also optimized. Competitive sorption studies were investigated to determine the selectivity of Zn(II) ion imprinted interpenetrating polymer network. Zinc ion imprinted polymer networks showed good selectivity for the target ion.展开更多
The transport of metal ions of indium, gallium and thallium from source solution to receiving phase through the chromatographic fiber supported solid membrane in the acetylacetone (HAA) containing mixed solvent syst...The transport of metal ions of indium, gallium and thallium from source solution to receiving phase through the chromatographic fiber supported solid membrane in the acetylacetone (HAA) containing mixed solvent system has been explored. The fibers supported solid membranes were prepared with chemical synthesis from cellulose fibers and citric acid with the carboxylic acid ion exchange groups introduced. The experimental variables, such as concentration of metal ions (10^-2 to 10^-4 mol.L^-1) in the source solution, mixed solvent composition [for exampl, e, acetylacetone, (2,4-pentanedione), (HAA) 20% (by volume), 1,4-dioxane 10% to 60% and HC1 0.25 to 2 mol.L^-1] in the receiving phase and stirring speed (50-130 r.min ) of the bulk source and receiving phase, were explored. The efficiency of mixed solvents for the transport of metal ions from the source to receiving phase through the fiber supported solid membrane was evaluated. The combined ion exchange solvent extraction (CIESE) was observed effective for the selective transport of thallium, indium and gallium metal ions through fiber supported solid membrane in mixed solvents. The oxonium salt formation in the receiving phase enhances thallium, indium and gallium metal ion transport through solid membrane phase. The selective transport of thallium metal ions from source phase was observed from indium and gallium metal ions in the presence of hydrochloric acid in organic solvents in receiving phase. The separation of thallium metal ions from the binary mixtures of Be(II), Ti(IV), AI(III) Ca(II), Mg(II), K (I), La(III) and Y(III) was carried out in the mixed solvent system using cellulose fiber supported solid membrane.展开更多
A series of crescent aromatic oligothioamides(4, 6, 8, 15, and 18) bearing different number of sulfur atoms were designed and synthesized via thionation of their corresponding aromatic oligoamides(3, 5, and 7) using L...A series of crescent aromatic oligothioamides(4, 6, 8, 15, and 18) bearing different number of sulfur atoms were designed and synthesized via thionation of their corresponding aromatic oligoamides(3, 5, and 7) using Lawesson's reagent. The X-ray structure of a trimeric analogue(13) revealed the presence of intramolecular three-center hydrogen bonds that are responsible for the rigidification of the molecular backbone. The extraction by these novel receptors toward some representative heavy metal cations(Zn2+, Cd2+, Co2+, Ni2+, Pb2+, and Cu2+) and alkali and alkaline earth metal cations(Li+, Na+, K+, Rb+, Cs+, Ca2+, and Sr2+) demonstrated high efficiency(83.5%–96.4%) and superior selectivity for Cu2+ over other selected metal cations. Particularly, the extractability was correlated to both the number of sulfur atoms and orientation of thiocarbonyl groups as revealed in the order: 6 > 4 > 18 > 15. This is in stark contrast to the oligoamides that only gave much lower extractability(5.9%–16.4%), suggestive of the importance of replacement of carbonyl oxygen atoms with sulfur atoms in the extraction of Cu2+. The complexation behavior of 4, 6, and 8 with Cu2+ was also examined by UV-Vis and NMR techniques.展开更多
This review discusses chiral-at-metal complexes and introduces enantiomorphs from assembly structure.Owing to the diverse coordination number and activity of metal ions as chiral centers, abundant structures for chira...This review discusses chiral-at-metal complexes and introduces enantiomorphs from assembly structure.Owing to the diverse coordination number and activity of metal ions as chiral centers, abundant structures for chiral selectivity, catalysis, and polarized light-response are the notable advantages of the chiral-at-metal complexes. The rational design and preparation of linear multi-dentate ligands is a good choice to improve the stability of chiral complexes, such as multi-bonding structure for high stability as a self-limiting system. The bio-significance and potential application of chiral-at-metal complexes are discussed, such as the synergistic effect of catalysis and chiral selectivity of the metal center in enzymes.Enzyme could be remolded to replace the original central metal ions with highly active rare earth or precious metal ions to form artificial metalloenzyme or to remove the ‘‘redundant" part around the metal center to improve the accessibility of substrate. The polarized light-response mechanism of chiral opsin is introduced in relation to its role in animal migration. Metal-organic frameworks(MOFs) are crystalline and porous materials built from metal nodes or clusters and organic linkers and provide the possibility to prepare artificial enantiomorphs. The preparations, applications, and characterization methods of MOF enatiomorphs are therefore introduced. We hope this review inspires researchers at all levels of their career to consider the title topic in their own research in terms of its application and potential value.展开更多
基金supported by the Fundamental Research Funds for the Central Universities(WK2060000030)USTC Research Funds of the Double First Class Initiative(YD2060002022)Major Science and Technology Innovation Projects in Shandong Province(2022CXGC020415).
文摘The efficient extraction of sodium(Na^(+))and lithium(Li^(+))from seawater and salt lakes is increasingly demanding due to their great application value in chemical industries.However,coexisting cations such as divalent calcium(Ca^(2+))and magnesium(Mg^(2+))ions are at the subnanometer scale in diameter,similar to target monovalent ions,making ion separation a great challenge.Here,we propose a simple and fast secondary growth method for the preparation of MIL-53(Al)-NH_(2)membranes on the surface of anodic aluminum oxide.Such membranes contain angstrom-scale(~7Å)channels for the entrance of small monovalent ions and water molecules,endowing the selectivities for monovalent cations over divalent cations and water over salt molecules.The resulting high-connectivity MIL-53(Al)-NH_(2)membranes exhibit excellent ion separation performance(a selectivity of 121.42 for Na^(+)/Ca^(2+)and 93.81 for Li^(+)/Mg^(2+))and desalination performance(a water/salt selectivity of up to 5196).This work highlights metal–organic framework membranes as potential candidates for realizing ion separation and desalination in liquid treatment.
基金supported by Islamic Azad University (Shahreza Branch)Iran Nanotechnology Initiative Council
文摘Nano-assisted inclusion separation of alkali metals from basic solutions was reported by inclu sion-facilitated emulsion liquid membrane process. The novelty of this study is application of nano-baskets of calixcrown in the selective and efficient separation of alkali metals as both the carrier and the surfactant. For this aim, four derivatives of diacid calix[4]-1,3-crowns-4,5 were synthesized, and their inclusion-extraction parameters were optimized including the calixcrown scaffold (4.4%, by mass) as the carrier/demulsifier, the commercial kero sene as diluent in membrane, sulphonic acid (0.2 mol.L-1) and ammonium carbonate (0.4 mol.L-1) as the strip and the feed phases, the phase and the treat ratios of 0.8 and 0.3, mixing speed (300 r.min-1), and initial solute concentration (100 mg.L-1). The selectivity of membrane over more than ten interfering cations was examined and the re sults reveled that under the optimized operating condition, the degree of inclusion-extraction of alkali metals was as high as 98%-99%.
文摘Toxic Zn(II) ion imprinted interpenetrating polymer networks were synthesized for the selective sorption of Zn(ll) from aqueous solutions using a biopolymer alginic acid. The polymeric biosorbant was prepared using Zn(II) ion as template, acrylamide as functional monomer, cross linker NNMBA (N,N' Methylene-bis-acrylamide) and potassium persulphate as an initiator. The non-imprinted polymer networks were also prepared without use of the Zn(II) ion. The synthesized interpenetrating networks were characterized by various spectral techniques. Metal ion binding studies were carried out and the factors affecting binding were also optimized. Competitive sorption studies were investigated to determine the selectivity of Zn(II) ion imprinted interpenetrating polymer network. Zinc ion imprinted polymer networks showed good selectivity for the target ion.
文摘The transport of metal ions of indium, gallium and thallium from source solution to receiving phase through the chromatographic fiber supported solid membrane in the acetylacetone (HAA) containing mixed solvent system has been explored. The fibers supported solid membranes were prepared with chemical synthesis from cellulose fibers and citric acid with the carboxylic acid ion exchange groups introduced. The experimental variables, such as concentration of metal ions (10^-2 to 10^-4 mol.L^-1) in the source solution, mixed solvent composition [for exampl, e, acetylacetone, (2,4-pentanedione), (HAA) 20% (by volume), 1,4-dioxane 10% to 60% and HC1 0.25 to 2 mol.L^-1] in the receiving phase and stirring speed (50-130 r.min ) of the bulk source and receiving phase, were explored. The efficiency of mixed solvents for the transport of metal ions from the source to receiving phase through the fiber supported solid membrane was evaluated. The combined ion exchange solvent extraction (CIESE) was observed effective for the selective transport of thallium, indium and gallium metal ions through fiber supported solid membrane in mixed solvents. The oxonium salt formation in the receiving phase enhances thallium, indium and gallium metal ion transport through solid membrane phase. The selective transport of thallium metal ions from source phase was observed from indium and gallium metal ions in the presence of hydrochloric acid in organic solvents in receiving phase. The separation of thallium metal ions from the binary mixtures of Be(II), Ti(IV), AI(III) Ca(II), Mg(II), K (I), La(III) and Y(III) was carried out in the mixed solvent system using cellulose fiber supported solid membrane.
基金supported by the National Natural Science Foundation of China(21172158)the Joint Fund of National Natural Science Foundation of China and the China Academy of Engineering Physics(11076018)+3 种基金the Doctoral Program of the Ministry of Education of China(20130181110023)the National Science Foundation for Fostering Talents in Basic Research of the National Natural Science Foundation of China(J1210004,J1103315)Open Project of State Key Laboratory of Supramolecular Structure and Materials(SKLSSM201408)Open Project of State Key Laboratory of Structural Chemistry(20140013)
文摘A series of crescent aromatic oligothioamides(4, 6, 8, 15, and 18) bearing different number of sulfur atoms were designed and synthesized via thionation of their corresponding aromatic oligoamides(3, 5, and 7) using Lawesson's reagent. The X-ray structure of a trimeric analogue(13) revealed the presence of intramolecular three-center hydrogen bonds that are responsible for the rigidification of the molecular backbone. The extraction by these novel receptors toward some representative heavy metal cations(Zn2+, Cd2+, Co2+, Ni2+, Pb2+, and Cu2+) and alkali and alkaline earth metal cations(Li+, Na+, K+, Rb+, Cs+, Ca2+, and Sr2+) demonstrated high efficiency(83.5%–96.4%) and superior selectivity for Cu2+ over other selected metal cations. Particularly, the extractability was correlated to both the number of sulfur atoms and orientation of thiocarbonyl groups as revealed in the order: 6 > 4 > 18 > 15. This is in stark contrast to the oligoamides that only gave much lower extractability(5.9%–16.4%), suggestive of the importance of replacement of carbonyl oxygen atoms with sulfur atoms in the extraction of Cu2+. The complexation behavior of 4, 6, and 8 with Cu2+ was also examined by UV-Vis and NMR techniques.
基金supported by the National Natural Science Foundation of China (21675090, 21435001, and 21375064)
文摘This review discusses chiral-at-metal complexes and introduces enantiomorphs from assembly structure.Owing to the diverse coordination number and activity of metal ions as chiral centers, abundant structures for chiral selectivity, catalysis, and polarized light-response are the notable advantages of the chiral-at-metal complexes. The rational design and preparation of linear multi-dentate ligands is a good choice to improve the stability of chiral complexes, such as multi-bonding structure for high stability as a self-limiting system. The bio-significance and potential application of chiral-at-metal complexes are discussed, such as the synergistic effect of catalysis and chiral selectivity of the metal center in enzymes.Enzyme could be remolded to replace the original central metal ions with highly active rare earth or precious metal ions to form artificial metalloenzyme or to remove the ‘‘redundant" part around the metal center to improve the accessibility of substrate. The polarized light-response mechanism of chiral opsin is introduced in relation to its role in animal migration. Metal-organic frameworks(MOFs) are crystalline and porous materials built from metal nodes or clusters and organic linkers and provide the possibility to prepare artificial enantiomorphs. The preparations, applications, and characterization methods of MOF enatiomorphs are therefore introduced. We hope this review inspires researchers at all levels of their career to consider the title topic in their own research in terms of its application and potential value.