The ion coordination affinities of the commonly found metal ions were evaluated using DFT calculations.The results indicate that the lowest unoccupied molecular orbital(LUMO)energy of metal ions correlates positively ...The ion coordination affinities of the commonly found metal ions were evaluated using DFT calculations.The results indicate that the lowest unoccupied molecular orbital(LUMO)energy of metal ions correlates positively with their binding energies with O(S)ligands,and some metal ions with various valence states also present different affinities.Besides,due to the steric hindrance effects,the mono-and hexa-coordinated metal ions may exhibit different affinities,and the majority of the studied hexa-coordinated metal ions exhibit oxophilicity.These affinity differences perfectly illustrate the activation flotation practice in which the oxyphilic ions are applied to activating oxide minerals,while thiophilic ions are applied to activating sulfide minerals.展开更多
A facile method for the preparation of sodium alginate（SA）/carboxyl-functionalized graphene（G-COOH）composite hydrogel was developed. Based on the coordination ability of lanthanide ions to the carboxyl groups, a s...A facile method for the preparation of sodium alginate（SA）/carboxyl-functionalized graphene（G-COOH）composite hydrogel was developed. Based on the coordination ability of lanthanide ions to the carboxyl groups, a series of hydrogel derived from different ratios of SA and G-COOH was fabricated by neodymium（Nd3＋） ions coordination. A relatively uniform layered structure was recorded by SEM at the interior of SA/G-COOH hydrogel. Several parameters such as water content, swelling ratio（SR）, tensile test and solvent resistance were also investigated. The SA/G-COOH composite hydrogel showed excellent mechanical strength, and the tensile strength of SA/G-COOH composite hydrogel reaches 53.72 MPa at high water content. Due to the coordination ability of Nd3＋ ions, the hydrogel also exhibited an excellent solvent resistance and stability.展开更多
A new two-step synthetic method was successfully developed to simplify the recrystallization process of lithium difluoro(oxalate)borate(LiODFB).Meanwhile,the purity of LiODFB as-prepared was determined by NMR,ICP-AES ...A new two-step synthetic method was successfully developed to simplify the recrystallization process of lithium difluoro(oxalate)borate(LiODFB).Meanwhile,the purity of LiODFB as-prepared was determined by NMR,ICP-AES and Karl Fisher measurements,respectively.The as-prepared LiODFB presents a high purity up to 99.95%.Its metal ions and water contents are under good control as well.Besides,its structure information and thermal properties were confirmed by FTIR,Raman and DSC-TGA analyses,respectively.LiODFB exerts fine thermostability and hypo-water-sensitivity and its structure information agrees well with previous literature.Furthermore,a combination of phase diagram and Raman spectroscopy were utilized to study the thermal phase behavior and ions coordination of LiODFB-DMC binary system to optimize the synthesis and recrystallization process.Although there are three types of molecular interaction forms(CIPs,AGG-IIa,AGG-IIIb)in LiODFB-DMC binary system,LiODFB can only be isolated as large single crystal solvate as LiODFB·(DMC)3/2 by slowly cooling subjected to the nucleation kinetics.Therefore,the fundamental information of our work is helpful in accelerating the application of LiODFB in Li-ion secondary batteries.展开更多
Metal-organic frameworks(MOFs),assembled periodically by coordinating inorganic metal ions and organic motifs,have arisen widespread curiosity and intensive investigation owing to their tailorable electronic propertie...Metal-organic frameworks(MOFs),assembled periodically by coordinating inorganic metal ions and organic motifs,have arisen widespread curiosity and intensive investigation owing to their tailorable electronic properties and well-defined topological structure.However,the majority of MOFs are intrinsically dielectric or insulative[1]and typically form as 3D bulk or powder crystals,making them incompatible with complementary metal-oxide semiconductor(CMOS)techniques.In recent years,layer-stacked two-dimensional conjugated MOFs(2D c-MOFs),composed of planar conjugated ligands and linkages[2],have demonstrated high in-plane π conjugation and weak out-of-plane van der Waals interactions,due to their long-range electron delocalization over metal ions and ligands[3].As a result,highly tunable band gaps from semiconductor to conductor,modulable porosity from micropore to macropore and versatile processability into conductive 2D thin films with controllable lateral thickness and domain size are presented,rendering charming potential for applications in(opto-)electronics compared with classic 2D metal oxide,chalcogenide and crystalline polymer materials.To improve interfacial charge-transport and precisely tune the charge extraction and band alignment of 2D c-MOFs in(opto-)electronic devices[4],developing highly efficient synthetic methods of 2D c-MOFs is of utmost importance.展开更多
It is the first time in experiment that we have found that the ionic strength effects on E(%)-pH curves of the systems with clay minerals as solid particles and those systems with hydrous oxides as solid particles, ar...It is the first time in experiment that we have found that the ionic strength effects on E(%)-pH curves of the systems with clay minerals as solid particles and those systems with hydrous oxides as solid particles, are 'right-left shift phenomenon' and 'left monodirectional shift phenomenon', respectively.The corresponding ionic strength effects on isotherms are 'downward-upward shift phenomenon' and 'upward monodirectional shift phenomenon', respectively.All the four phenomena are consistent with each other.In order to explain the above phenomena, the composite model of interracial ion/coordination particle exchange-electrostatic exchange is put forward to make a unified explanation and quantitative treatment.From the structures of the two kinds of materials——clay minerals and hydrous oxides, we know that the former has two kinds of exchange actions, i.e. when one increases,the other decreases, which makes the position of curves shift didirectionally,while the latter only has interfacial stepwise ion/coordin ation particle exchange,the curves of which shift therefore monodirectionally.The calculated results of the model accord with the experimental.展开更多
Ionic skin(I-skin)is an emerging skin-inspired sensor that has received increasing interest for the next-generation wearable electronics.However,profound challenges for I-skin remain in achieving multiple signal respo...Ionic skin(I-skin)is an emerging skin-inspired sensor that has received increasing interest for the next-generation wearable electronics.However,profound challenges for I-skin remain in achieving multiple signal responses(e.g.,strain,pressure,and humidity)and self-healability to fully mimic human skin.Herein,a Fe;ion-coordinated poly(acrylic acid)ionogel(PAIFe)with high stretchability,extreme temperature tolerance,and self-healing capability is prepared by a dynamic ionic cross-linking strategy.The ionic coordination in the PAIFe contributes to the formation of a highly dynamic network,achieving its high-efficient and reliable self-healing performance even at a low temperature of-20℃.Using of 1-butyl-3-methylimidazolium tetrafluoroborate([BMIm][BF^(3+)])as the solvent achieves a widetemperature tolerance of the PAIFe under low and high temperatures.More interestingly,a humidity sensing function is realized in the PAIFe by skillfully utilizing the hygroscopic properties of[BMIm][BF_(4)].The resultant PAIFe is proof-ofconcept demonstrated as a deformation-tolerant ionic conductor in a skin-inspired ionic sensor,showing a variety of sensory capabilities towards compression,strain and humidity.展开更多
Two one-dimensional coordination polymers were synthesized:[M(hfac)_(2)(9-PhentNIT)]_(n),where M=Mn(1)or Co(2),hfac^(-)is hexafluoroacetylacetonato and 9-PhentNIT is a new stable nitronyl nitroxide organic radical,2-(...Two one-dimensional coordination polymers were synthesized:[M(hfac)_(2)(9-PhentNIT)]_(n),where M=Mn(1)or Co(2),hfac^(-)is hexafluoroacetylacetonato and 9-PhentNIT is a new stable nitronyl nitroxide organic radical,2-(9-phenanthrenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide.These two complexes are isomorphous and crystallized with metal ions coordinated by two aminoxyl groups,arising from two bridging 9-PhentNIT radicals and two hfac^(-)chelating ligands.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.52074356,U20A20269)the Key Technology Research and Development Program,China(No.2022YFC2904503)+4 种基金the Special Fund for the Construction of Hunan Province,China(No.2023SK2061)the Science and Technology Innovation Program of Hunan Province,China(No.2022RC1183)the Changsha Science and Technology Project(Changsha Outstanding Innovative Youth Training Program),ChinaInnovation-driven Project of Central South University,China(No.2023CXQD002)Higher Education Discipline Innovation Project,China(No.B14034)。
文摘The ion coordination affinities of the commonly found metal ions were evaluated using DFT calculations.The results indicate that the lowest unoccupied molecular orbital(LUMO)energy of metal ions correlates positively with their binding energies with O(S)ligands,and some metal ions with various valence states also present different affinities.Besides,due to the steric hindrance effects,the mono-and hexa-coordinated metal ions may exhibit different affinities,and the majority of the studied hexa-coordinated metal ions exhibit oxophilicity.These affinity differences perfectly illustrate the activation flotation practice in which the oxyphilic ions are applied to activating oxide minerals,while thiophilic ions are applied to activating sulfide minerals.
基金supported by the National Natural Science Foundation of China under Grant Nos.21274020 and 21304019
文摘A facile method for the preparation of sodium alginate（SA）/carboxyl-functionalized graphene（G-COOH）composite hydrogel was developed. Based on the coordination ability of lanthanide ions to the carboxyl groups, a series of hydrogel derived from different ratios of SA and G-COOH was fabricated by neodymium（Nd3＋） ions coordination. A relatively uniform layered structure was recorded by SEM at the interior of SA/G-COOH hydrogel. Several parameters such as water content, swelling ratio（SR）, tensile test and solvent resistance were also investigated. The SA/G-COOH composite hydrogel showed excellent mechanical strength, and the tensile strength of SA/G-COOH composite hydrogel reaches 53.72 MPa at high water content. Due to the coordination ability of Nd3＋ ions, the hydrogel also exhibited an excellent solvent resistance and stability.
基金Project(51371198)supported by the National Natural Science Foundation of ChinaProject(K1202039-11)supported by the Science and Technology Project of Changsha,China
文摘A new two-step synthetic method was successfully developed to simplify the recrystallization process of lithium difluoro(oxalate)borate(LiODFB).Meanwhile,the purity of LiODFB as-prepared was determined by NMR,ICP-AES and Karl Fisher measurements,respectively.The as-prepared LiODFB presents a high purity up to 99.95%.Its metal ions and water contents are under good control as well.Besides,its structure information and thermal properties were confirmed by FTIR,Raman and DSC-TGA analyses,respectively.LiODFB exerts fine thermostability and hypo-water-sensitivity and its structure information agrees well with previous literature.Furthermore,a combination of phase diagram and Raman spectroscopy were utilized to study the thermal phase behavior and ions coordination of LiODFB-DMC binary system to optimize the synthesis and recrystallization process.Although there are three types of molecular interaction forms(CIPs,AGG-IIa,AGG-IIIb)in LiODFB-DMC binary system,LiODFB can only be isolated as large single crystal solvate as LiODFB·(DMC)3/2 by slowly cooling subjected to the nucleation kinetics.Therefore,the fundamental information of our work is helpful in accelerating the application of LiODFB in Li-ion secondary batteries.
基金supported by the National Natural Science Foundation of China(Nos.22201086,22471084,92261204,21925104,and 22431005).
文摘Metal-organic frameworks(MOFs),assembled periodically by coordinating inorganic metal ions and organic motifs,have arisen widespread curiosity and intensive investigation owing to their tailorable electronic properties and well-defined topological structure.However,the majority of MOFs are intrinsically dielectric or insulative[1]and typically form as 3D bulk or powder crystals,making them incompatible with complementary metal-oxide semiconductor(CMOS)techniques.In recent years,layer-stacked two-dimensional conjugated MOFs(2D c-MOFs),composed of planar conjugated ligands and linkages[2],have demonstrated high in-plane π conjugation and weak out-of-plane van der Waals interactions,due to their long-range electron delocalization over metal ions and ligands[3].As a result,highly tunable band gaps from semiconductor to conductor,modulable porosity from micropore to macropore and versatile processability into conductive 2D thin films with controllable lateral thickness and domain size are presented,rendering charming potential for applications in(opto-)electronics compared with classic 2D metal oxide,chalcogenide and crystalline polymer materials.To improve interfacial charge-transport and precisely tune the charge extraction and band alignment of 2D c-MOFs in(opto-)electronic devices[4],developing highly efficient synthetic methods of 2D c-MOFs is of utmost importance.
基金Project supported by the National Natural Science Foundation of China.
文摘It is the first time in experiment that we have found that the ionic strength effects on E(%)-pH curves of the systems with clay minerals as solid particles and those systems with hydrous oxides as solid particles, are 'right-left shift phenomenon' and 'left monodirectional shift phenomenon', respectively.The corresponding ionic strength effects on isotherms are 'downward-upward shift phenomenon' and 'upward monodirectional shift phenomenon', respectively.All the four phenomena are consistent with each other.In order to explain the above phenomena, the composite model of interracial ion/coordination particle exchange-electrostatic exchange is put forward to make a unified explanation and quantitative treatment.From the structures of the two kinds of materials——clay minerals and hydrous oxides, we know that the former has two kinds of exchange actions, i.e. when one increases,the other decreases, which makes the position of curves shift didirectionally,while the latter only has interfacial stepwise ion/coordin ation particle exchange,the curves of which shift therefore monodirectionally.The calculated results of the model accord with the experimental.
基金financially supported by the National Natural Science Foundation of China(21875033 and 52122303)。
文摘Ionic skin(I-skin)is an emerging skin-inspired sensor that has received increasing interest for the next-generation wearable electronics.However,profound challenges for I-skin remain in achieving multiple signal responses(e.g.,strain,pressure,and humidity)and self-healability to fully mimic human skin.Herein,a Fe;ion-coordinated poly(acrylic acid)ionogel(PAIFe)with high stretchability,extreme temperature tolerance,and self-healing capability is prepared by a dynamic ionic cross-linking strategy.The ionic coordination in the PAIFe contributes to the formation of a highly dynamic network,achieving its high-efficient and reliable self-healing performance even at a low temperature of-20℃.Using of 1-butyl-3-methylimidazolium tetrafluoroborate([BMIm][BF^(3+)])as the solvent achieves a widetemperature tolerance of the PAIFe under low and high temperatures.More interestingly,a humidity sensing function is realized in the PAIFe by skillfully utilizing the hygroscopic properties of[BMIm][BF_(4)].The resultant PAIFe is proof-ofconcept demonstrated as a deformation-tolerant ionic conductor in a skin-inspired ionic sensor,showing a variety of sensory capabilities towards compression,strain and humidity.
基金CAPES-PrInt-Universidade Federal Fluminense-988887.310269/2018-00.T.A.C.thanks CAPES for the fellowshipThe authors thank FAPERJ and CNPq(Brazil),ICUB(University of Bucharest)and UEFISCDI(Romania)for financial support.This research used facilities of the Brazilian Synchrotron Light Laboratory(LNLS)The MANACÁbeamline(projects 20231062 and 20233038)as well as staff member Dr Andrey F.Z.Nascimento are acknowledged.
文摘Two one-dimensional coordination polymers were synthesized:[M(hfac)_(2)(9-PhentNIT)]_(n),where M=Mn(1)or Co(2),hfac^(-)is hexafluoroacetylacetonato and 9-PhentNIT is a new stable nitronyl nitroxide organic radical,2-(9-phenanthrenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide.These two complexes are isomorphous and crystallized with metal ions coordinated by two aminoxyl groups,arising from two bridging 9-PhentNIT radicals and two hfac^(-)chelating ligands.
