Some basic characteristics of lanthanide-oxygen bonds in various trivalent lanthanide metal-organic complexes are quantitatively studied by the bond valence model. Some important relationships among the electronegativ...Some basic characteristics of lanthanide-oxygen bonds in various trivalent lanthanide metal-organic complexes are quantitatively studied by the bond valence model. Some important relationships among the electronegativity, bond valence parameter, bond length and lanthanide coordination number in these complexes are generally found , which show that for each trivalent lanthanide cation all calculated parameters may well be correlated with its coordination number in their coordination complexes. Specifically,32 new data for the bond valence parameter are first calculated in this work.An approximate linear relationship between the Ln-O bond valence parameter and the coordination number of Ln^(3+) is obtained.The Ln-O bond length increases with the increase in the lanthanide coordination number.The difference of electronegative values decreases with the increase in the lanthanide coordination number.展开更多
General guidelines for the design of ligands for the enrichment of rare-earth elements by solid-liquid adsorption are described using coordination chemistry.Relevant properties of ligands include selectivity of metal ...General guidelines for the design of ligands for the enrichment of rare-earth elements by solid-liquid adsorption are described using coordination chemistry.Relevant properties of ligands include selectivity of metal ions based on adjustment of donor atom polarizability,denticity,and the pKarange of the binding sites.The selectivity of solid-phase materials for the enrichment of rare-earth ions by the ligand design guidelines is outlined,with special consideration of additional variable factors including steric hindrance,saturated binding sites,variability in speciation caused by the identity of counterions and ionic strength,and size-exclusivity in ligands stemming from differences in bite angle,preo rganization of ligands,or intraligand interactions.This review analyzes some principles of selectivity of rare-earth elements with ligands organized by donor type from examples collected from reports published between 2009 and 2021.展开更多
Uranium and molybdenum are important strategic elements. The production of ^(99)Mo and the hydrometallurgical process of uranium ore face difficult problems of separation of uranium and molybdenum.In this study, the f...Uranium and molybdenum are important strategic elements. The production of ^(99)Mo and the hydrometallurgical process of uranium ore face difficult problems of separation of uranium and molybdenum.In this study, the four phenanthroline diamide ligands were synthesized, and extraction and stripping experiments were performed under different conditions to evaluate the potential application of these ligands for separation of U(Ⅵ) over Mo(Ⅵ). With the growth of alkyl chain, the solubility of ligands could be greatly improved, and the separation effect of U(Ⅵ) over Mo(Ⅵ) gradually increased. The SF_(U/Mo) were around 10,000 at 4 mol/L HNO3. Three stripping agents were tested with the stripping efficiency of Na_(2)CO_(3)(5%) > H_(2)O > HNO_(3)(0.01 mol/L). The stripping percentages of the three stripping agents were all close to unity, indicating that the ligands had the potential to be recycled. The chemical stoichiometry of U(Ⅵ) complexes with ligands was evaluated as 1:1 using electrospray ionization mass spectrometry,ultraviolet visible spectroscopy and single-crystal X-ray diffraction. The consistency between theoretical calculation and experimental results further explains the coordination mechanism.展开更多
The pursuit of high energy density while achieving long cycle life remains a challenge in developing transition metal(TM)oxide cathode materials for sodium-ion batteries(SIBs).Here,we present a concept of precisely ma...The pursuit of high energy density while achieving long cycle life remains a challenge in developing transition metal(TM)oxide cathode materials for sodium-ion batteries(SIBs).Here,we present a concept of precisely manipulating structural evolution via local coordination chemistry regulation to design high-performance composite cathode materials.The controllable structural evolution process is realized by tuning magnesium content in Na0.6Mn1-xMgxO2,which is elucidated by a combination of experimental analysis and theoretical calculations.The substitution of Mg into Mn sites not only induces a unique structural evolu-tion from layered–tunnel structure to layered structure but also mitigates the Jahn–Teller distortion of Mn3+.Meanwhile,benefiting from the strong ionic inter-action between Mg2+and O2-,local environments around O2-coordinated with electrochemically inactive Mg2+are anchored in the TM layer,providing a pinning effect to stabilize crystal structure and smooth electrochemical profile.The layered–tunnel Na0.6Mn0.95Mg0.05O2 cathode material delivers 188.9 mAh g-1 of specific capacity,equivalent to 508.0 Wh kg-1 of energy density at 0.5C,and exhibits 71.3%of capacity retention after 1000 cycles at 5C as well as excellent compatibility with hard carbon anode.This work may provide new insights of manipulating structural evolution in composite cathode materials via local coordi-nation chemistry regulation and inspire more novel design of high-performance SIB cathode materials.展开更多
Sulfurized polyacrylonitrile(SPAN)represents a unique class of cathode material for lithium sulfur(Li-S)batteries as it eradicates the polysulfides shuttling issue in carbonate-based electrolyte.However,due to the ess...Sulfurized polyacrylonitrile(SPAN)represents a unique class of cathode material for lithium sulfur(Li-S)batteries as it eradicates the polysulfides shuttling issue in carbonate-based electrolyte.However,due to the essential chemical S-linking and organic nature of SPAN,the active mass percentage and rate capability are two bottleneck issues preventing its ultimate deployment outside of laboratories.In the current work,aiming to endow both the charge conductivity and catalytic activity to SPAN for maximizing the redox kinetics of S conversion,a freestanding nanofibrous SPAN cathode embedding conductive CNTs and atomically dispersed Co centers is fabricated via multivariate electrospinning.While the CNTs enable dramatically enhancing the fiber conductivity and generating mesoscopic porosity for facilitating charge and mass transportation,the cross-linking of SPAN by Co-N_(4) S motifs creates extra charge conduction pathways and further serves as the catalytic active sites for expediting redox S conversion.As a result,an extraordinary Li-SPAN performance is achieved with a high specific capacity up to 1856 mAh g^(-1)@0.2 C,a superb rate capability up to 10 C,and an ultra-long battery life up to 1500 cycles@1 C.Consequently,our study here provides insights into the adoption of coordination chemistry to maximize the sulfur utilization by ensuring a more complete redox conversion from SPAN to Li2 S,and vice versa.展开更多
Sodium-ion batteries(SIBs)have attracted considerable interest as an alternative to lithium-ion batteries owing to their similar electrochemical performance and superior long-term cycle stability.Organic materials are...Sodium-ion batteries(SIBs)have attracted considerable interest as an alternative to lithium-ion batteries owing to their similar electrochemical performance and superior long-term cycle stability.Organic materials are regarded as promising anode materials for constructing SIBs with high capacity and good retention.However,utilization of organic materials is rather limited by their low energy density and poor stability at high current densities.To overcome these limitations,we utilized a novel polymeric disodium phthalocyanines(pNaPc)as SIB anodes to provide stable coordination sites for Na ions as well as to enhance the stability at high current density.By varying the linker type during a one-pot cyclization and polymerization process,two pNaPc anodes with O-(O-pNaPc)and S-linkers(S-pNaPc)were prepared,and their structural and electrochemical properties were investigated.The O-pNaPc binds Na ions with a lower binding energy compared with S-pNaPc,which leads to more facile Na-ion coordination/dissociation when engaged as SIB anode.The use of O-pNaPc significantly improves the redox kinetics and cycle stability and allows the fabrication of a full cell against Na_(3)V_(2)(PO_(4))_(2)F_(3)/C cathode,which demonstrates its practical application with high energy density(288 Wh kg^(-1))and high power density(149 W kg^(-1)).展开更多
The complexation of high-spin lanthanides to porphyrinoids is a powerful strategy for the development of advanced molecular magnets.In this context,the use of expanded porphyrinoids remains elusive since their coordin...The complexation of high-spin lanthanides to porphyrinoids is a powerful strategy for the development of advanced molecular magnets.In this context,the use of expanded porphyrinoids remains elusive since their coordination chemistry is challenging to control.Herein,taking inspiration from on-surface chemistry,we explored the coordination of Dy^(3+)to a six-membered porphyrinoid,namely,the hemihexaphyrazine H3Hhp.Remarkably,we observed the selective formation of a mono-nuclear off-centered,out-of-plane H_(2)Hhp-Dy^(3+)complex when performing the complexation under reductive conditions.During this reaction,the oxidation state of the macrocycle did not change.Employing X-ray diffraction analysis,we found that the coordination number of Dy in this complex was 8.The macrocycle cocrystallized with decamethylcobaltocene(Cp_(2)^(*)Co)molecules,giving rise to a wellordered solid-state packing,governed byπ-πinteractions.As a result of this organization,a small magnetic coupling between the neighboring molecules was observed.All in all,this work provides key insights into the coordination of magnetically active metals with expanded porphyrinoids,thus motivating the development of advanced spintronic devices.展开更多
Reaction of 3-(pyridin-2-yl)-imidazo[1,5-a]pyridine (HPIP), CuCi2·2H20 and picolinaldehyde in the mixture of CHaCOOH and EtOH under solvothermal conditions gave complexes [LCuCI][CuECI3] (1) and [HLCuC1]E[C...Reaction of 3-(pyridin-2-yl)-imidazo[1,5-a]pyridine (HPIP), CuCi2·2H20 and picolinaldehyde in the mixture of CHaCOOH and EtOH under solvothermal conditions gave complexes [LCuCI][CuECI3] (1) and [HLCuC1]E[CuCI2]2[CuCI3].2H20 (2) (L = 1,1'-(pyridin-2- ylmethylene)bis[3-(pyridin-2-yl)imidazo[1,5-a]pyridine]) simultaneously. The ligand L was generated via in situ metal-ligand reaction between HPIP and picolinaldehyde. When CuCI2·2H20 was replaced by CuC1, the 2:1:1(HPIP:picolinaldehyde:CuCI) reaction afforded complex [CuaL2CI2][CuCI2]·2H20 (3) and the analogous 2:1:3 reaction generated compound [CuaL2][CuCI2]3 (4). Complexes 1 and 2 are Cun/CuI mixed-valence compounds. Complexes 1-4 display four various structures. It is found that the formation of the L ligand is controlled by CH3COOH. This work reveals that the structures of complexes 1-4 could be rationally tuned via the inclusion of CH3COOH in the reaction systems, the proper selection of different starting materials and the dexterous adjustment of the ratio of the starting materials.展开更多
Metal and amino acid(AA),as two kinds of entities,have been widely involved in biomaterials and nanomedicines.Recently,the marriage of them has developed new nanoformulations,amino acid-metal coordinated nanomaterials...Metal and amino acid(AA),as two kinds of entities,have been widely involved in biomaterials and nanomedicines.Recently,the marriage of them has developed new nanoformulations,amino acid-metal coordinated nanomaterials(AMCNs),which show great biomedical application potential in cancer therapy,antibacterial applications,biomedical imaging,etc.With the respective characteristics of metal and AA with rich biological and chemical properties,AMCNs can not only act as drug carriers with specific tumor targeting ability,but also realize synergistic therapy and imaging-guided therapy.Although the design and synthesis of amino acid-metal coordinated nanomaterials have been in-depth investigated,there are few systematic reviews on their biomedical application.In this review,we give a comprehensive summary of recent progresses in the design,fabrication,and biomedical applications of AMCNs.We also propose the future outlooks and challenges in aforementioned field.We expect that this review would contribute some inspiration for future research and development for amino acid metal coordinated nanomaterials.展开更多
In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff...In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety,and their complexes,were revised,and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized.Porphyrin and phthalocyanine ligands are not included in this review,which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen.The synthetic methods,structural characterization,based on single X-ray crystal data,and properties of the lanthanoid complexes,with special attention to magneto-structural correlations,are presented herein.展开更多
Main observation and conclusion Two new uranium(VI)phosphonate compounds,namely K_(8)[N(C_(2)H_(5))_(4)]_(2)(UO_(2))_(17)(H_(2)O)_(4)[CH_(2)(PO_(3))_(2)]_(8)[CH_(2)(PO_(3))(PO_(3)H)]_(4)·16(H_(2)O)(1)and[N(C_(2)H...Main observation and conclusion Two new uranium(VI)phosphonate compounds,namely K_(8)[N(C_(2)H_(5))_(4)]_(2)(UO_(2))_(17)(H_(2)O)_(4)[CH_(2)(PO_(3))_(2)]_(8)[CH_(2)(PO_(3))(PO_(3)H)]_(4)·16(H_(2)O)(1)and[N(C_(2)H_(5))_(4)]_(4)(H_(3)O)_(2)(UO_(2))_(10)[CH_(2)(PO_(3))_(2)]_(5)[CH_(2)(PO_(3))(PO_(3)H)]_(2)·10H_(2)O(2),have been synthesized under mild hydro/solvothermal condition.The structural analysis of the two compounds reveals that they both contain all three typical coordination geometries of the U(VI)ions,including UO;tetragonal,UO,pentagonal,and UOg hexagonal bipyramids.Moreover,compound 1 displays a tempera-ture-induced single crystal to single crystal phase transformation as confirmed by the Single-crystal X-ray diffraction data collected at different temperatures.Temperature-dependent fluorescence spectra presented herein illustrate the perturbation of the electronic structure of uranyl centers.展开更多
Due to their dynamic nature and strength tunability,metallo-supramolecular polymers have been introduced into various materials.The mechanical strength of the metallo-supramolecular polymers in the system directly inf...Due to their dynamic nature and strength tunability,metallo-supramolecular polymers have been introduced into various materials.The mechanical strength of the metallo-supramolecular polymers in the system directly influences the mechanical properties(e.g.,the toughness)of the materials.Therefore,it is necessary to explore the mechanical behavior of the metallo-supramolecular polymers.Herein,we present a single-molecule method to systematically explore the chain structure and mechanical properties of metallo-supramolecular polymer by using a loop protected architecture.Notably,we found that the mechanical stability of the individual chain,which is determined by the strength of terpyridine-Fe^(2+) -terpyridine(tpy-Fe^(2+)-tpy)bonds,was about 0.6–1.0 nN,depending on the pulling speed.This value is around three times higher than those measured using old methods.In addition,the unique loop protected structure further reduces the interference of non-specific polymer-AFM tip(or polymer-substrate)interactions on the quantification of the actual strength and kinetic parameter of noncovalent interactions in supramolecular polymers.Furthermore,the single chain flexibility of the metallo-supramolecular polymer was investigated and found to be comparable to the corresponding covalent analogues.Our findings provide a new way to explore the force response of supramolecular polymers composed of metal-ligand interactions and will be useful for the design of metallo-supramolecular polymer-based functional materials with tailored mechanical properties.展开更多
The second example of tetravalent plutonium carboxyl-based organic framework,^(242)Pu(OH)[PO[(C_(6)H_(4))COO]_(3)]·H_(2)O,termed as PuTPO(TPO=tris(4-carboxylphenyl)-phosphineoxide),was reported in this work.A ser...The second example of tetravalent plutonium carboxyl-based organic framework,^(242)Pu(OH)[PO[(C_(6)H_(4))COO]_(3)]·H_(2)O,termed as PuTPO(TPO=tris(4-carboxylphenyl)-phosphineoxide),was reported in this work.A series of characterizations of PuTPO,such as X-ray crystallography and solid-state UV-Vis-NIR spectroscopy,were carried out to expatiate its structure and physicochemical properties.PuTPO is constructed by dimers of the plutonium-oxygen subunit of[Pu_(2)O_(16)].Characteristic peaks located at approximately 1100 nm can be considered to be the fingerprint peaks of tetravalent plutonium.While PuTPO can maintain high crystallinity within several months after synthesis,it exhibits a radiation-induced swelling effect probed by the expansion of cell parameter of b axis after self-irradiation fromα-decay of ^(242)Pu.This result enriches the inventory of tetravalent plutonium compounds and provides an insight into the irradiation resistance of metal-organic frameworks.展开更多
A method for the non-destructive purification of single-walled carbon nanotubes(SWNTs)using classical coordination chemistry to remove the metal catalyst has been developed.In preliminary tests,the conductivity of fil...A method for the non-destructive purification of single-walled carbon nanotubes(SWNTs)using classical coordination chemistry to remove the metal catalyst has been developed.In preliminary tests,the conductivity of films based on the resulting SWNTs was markedly better than that of films prepared from SWNTs purified by treatment with oxidizing acid solutions.The transparent and conducting SWNT films have potential applications in optoelectronic devices.展开更多
In the past decades,metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)basically enjoy the coordination chemistry and covalent chemistry,respectively,and such uniqueness has become the major obstacle h...In the past decades,metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)basically enjoy the coordination chemistry and covalent chemistry,respectively,and such uniqueness has become the major obstacle hampering their further scope diversity and application multi-functionalization.Inspired from the principle of organic retrosynthesis,combining coordination bond and covalent bond together offers additional opportunities for constructing novel MOFs,COFs and MOF@COF hybrids as well as confer on them superior performances in versatile application fields.In this review,we firstly classify and summarize the recently reported synthesis strategies based on the integration of metal-ligand coordination and dynamic covalent bonds.Then,the application performances of as-constructed MOFs,COFs as well as MOF@COF hybrids are discussed and highlighted in the fields of adsorption,separation,catalysis,biosensing,energy storage and so on.Last,our personal insights of the remaining challenges and further prospects are also provided,in order to trigger much more inspirations and endeavors for this hot research field.展开更多
Attaching DNA/RNA to nanomaterials is the basis for nucleic acid-based assembly and drug delivery.Herein,we report that small interfering RNA(siRNA)effectively coordinates with ligand-free lanthanide nanoparticles(NaG...Attaching DNA/RNA to nanomaterials is the basis for nucleic acid-based assembly and drug delivery.Herein,we report that small interfering RNA(siRNA)effectively coordinates with ligand-free lanthanide nanoparticles(NaGdF4 NPs),and forms siRNA/NaGdF4 spherical nucleic acids(SNA).The coordination is primarily attributed to the interaction between Gd and phosphate backbone of the siRNA.Surprisingly,an efficient encapsulation and rapid endosomal escape of siRNA from the endosome/lysosome were achieved,due to its flexible ability to bound to phospholipid head of endosomal membrane,thereby disrupting the membrane structure.Resorting to the dual properties of NaGdF4 NPs,siRNA loading,and endosomal escape,siRNA targeting programmed cell death-ligand 1(siPD-L1)/NaGdF4 SNA triggers significant gene silencing in vitro and in vivo,and effectively represses the tumor growth in both CT26 tumor model and 4T1 orthotopic murine model.展开更多
Metal-organic polyhedra(MOPs)possess a microporous framework and impose hierarchical constraints on their surface ligands,leading to the long-ignored,logarithmic ligand exchange dynamics.Herein,polymer networks with M...Metal-organic polyhedra(MOPs)possess a microporous framework and impose hierarchical constraints on their surface ligands,leading to the long-ignored,logarithmic ligand exchange dynamics.Herein,polymer networks with MOP as nanoscale cross-linkers(MOP-CNs)can integrate unique ligand exchange dynamics and microporosity,affording vitrimer-like gas separation membranes with promising mechanical performance and(re)processability.All the ligands on the MOP surfaces are confined and correlated via a 3D coordination framework and their neighboring spaces,giving rise to a high energy barrier for ligand exchange.Therefore,MOP-CNs demonstrate high mechanical strengths at room temperature due to their negligible ligand dynamics.The thermo-activated ligand exchange process with integrated network topology enables facile(re)processing and high solvo-resistance at high temperatures.This facilitates Arrhenius type temperature dependence of flowability and stress relaxation,giving rise to the simultaneous achievement of promising mechanical strengths and(re)processability.Finally,the cage topologies of MOPs endow the materials with a bonus microporous feature and spur their applications as gas separation membranes.展开更多
Safe confinement of fission iodine isotopes for long-term radioactive waste disposal remains a formidable challenge,as conventional sorbents provide inherently weak iodine-host interactions.We report here a novel halo...Safe confinement of fission iodine isotopes for long-term radioactive waste disposal remains a formidable challenge,as conventional sorbents provide inherently weak iodine-host interactions.We report here a novel halogen bond(X-bond)directed strategy to sequester volatile iodine in hydrogen-bonded(H-bonded)frameworks with unprecedented stability.Charge-assisted Hbonded frameworks bearing open halide sites are developed,showing distinctive iodine encapsulation behaviors without compromising the crystallinity.Direct crystallographic evidence indicates the formation of X-bonds,i.e.,I–I···Cl−and I–I···Br^(−),within the confined pore channels.Unusual polyhalogen anions,i.e.,[I_(2)Cl_(2)]^(2−)and[I_(2)Br_(2)]^(2−),sustained in H-bonded frameworks are identified for the first time.The X-bond reinforced host-guest interaction affords robust iodine trapping without leaking out even at elevated temperatures up to 180°C.By integrating the halogen-bond chemistry with H-bonded frameworks,this study offers fresh concepts for developing effective host reservoirs to secure fission iodine isotopes from spent fuel reprocessing off-gases.展开更多
文摘Some basic characteristics of lanthanide-oxygen bonds in various trivalent lanthanide metal-organic complexes are quantitatively studied by the bond valence model. Some important relationships among the electronegativity, bond valence parameter, bond length and lanthanide coordination number in these complexes are generally found , which show that for each trivalent lanthanide cation all calculated parameters may well be correlated with its coordination number in their coordination complexes. Specifically,32 new data for the bond valence parameter are first calculated in this work.An approximate linear relationship between the Ln-O bond valence parameter and the coordination number of Ln^(3+) is obtained.The Ln-O bond length increases with the increase in the lanthanide coordination number.The difference of electronegative values decreases with the increase in the lanthanide coordination number.
基金Project supported by the U.S.Army Engineer Research and Development Center (W912HZ-21-2-0048)。
文摘General guidelines for the design of ligands for the enrichment of rare-earth elements by solid-liquid adsorption are described using coordination chemistry.Relevant properties of ligands include selectivity of metal ions based on adjustment of donor atom polarizability,denticity,and the pKarange of the binding sites.The selectivity of solid-phase materials for the enrichment of rare-earth ions by the ligand design guidelines is outlined,with special consideration of additional variable factors including steric hindrance,saturated binding sites,variability in speciation caused by the identity of counterions and ionic strength,and size-exclusivity in ligands stemming from differences in bite angle,preo rganization of ligands,or intraligand interactions.This review analyzes some principles of selectivity of rare-earth elements with ligands organized by donor type from examples collected from reports published between 2009 and 2021.
基金supported by the National Natural Science Foundation of China(Nos.U1967216,22076188,U20B2019,21876174)the National Science Fund for Distinguished Young Scholars(No.21925603).
文摘Uranium and molybdenum are important strategic elements. The production of ^(99)Mo and the hydrometallurgical process of uranium ore face difficult problems of separation of uranium and molybdenum.In this study, the four phenanthroline diamide ligands were synthesized, and extraction and stripping experiments were performed under different conditions to evaluate the potential application of these ligands for separation of U(Ⅵ) over Mo(Ⅵ). With the growth of alkyl chain, the solubility of ligands could be greatly improved, and the separation effect of U(Ⅵ) over Mo(Ⅵ) gradually increased. The SF_(U/Mo) were around 10,000 at 4 mol/L HNO3. Three stripping agents were tested with the stripping efficiency of Na_(2)CO_(3)(5%) > H_(2)O > HNO_(3)(0.01 mol/L). The stripping percentages of the three stripping agents were all close to unity, indicating that the ligands had the potential to be recycled. The chemical stoichiometry of U(Ⅵ) complexes with ligands was evaluated as 1:1 using electrospray ionization mass spectrometry,ultraviolet visible spectroscopy and single-crystal X-ray diffraction. The consistency between theoretical calculation and experimental results further explains the coordination mechanism.
基金National Natural Science Foundation of China,Grant/Award Numbers:51772093,51971124,52171217,52202284National Key Research and Devel opment Programs,Grant/Award Number:2021YFB2400400+4 种基金Zhejiang Natural Science Foundation,Grant/Award Number:LQ23E020002WenZhou Natural Science Foundation,Grant/Award Numbers:G20220019,G20220021State Key Laboratory of Electrical Insulation and Power Equipment,Xi'an Jiaotong University,Grant/Award Number.EIPE22208Cooperation between Industry and Education Project of Ministry of Education,Grant/Award Number:220601318235513Doctoral Innovation Foundation of Wenzhou University,Grant/Award Number.3162023001001。
文摘The pursuit of high energy density while achieving long cycle life remains a challenge in developing transition metal(TM)oxide cathode materials for sodium-ion batteries(SIBs).Here,we present a concept of precisely manipulating structural evolution via local coordination chemistry regulation to design high-performance composite cathode materials.The controllable structural evolution process is realized by tuning magnesium content in Na0.6Mn1-xMgxO2,which is elucidated by a combination of experimental analysis and theoretical calculations.The substitution of Mg into Mn sites not only induces a unique structural evolu-tion from layered–tunnel structure to layered structure but also mitigates the Jahn–Teller distortion of Mn3+.Meanwhile,benefiting from the strong ionic inter-action between Mg2+and O2-,local environments around O2-coordinated with electrochemically inactive Mg2+are anchored in the TM layer,providing a pinning effect to stabilize crystal structure and smooth electrochemical profile.The layered–tunnel Na0.6Mn0.95Mg0.05O2 cathode material delivers 188.9 mAh g-1 of specific capacity,equivalent to 508.0 Wh kg-1 of energy density at 0.5C,and exhibits 71.3%of capacity retention after 1000 cycles at 5C as well as excellent compatibility with hard carbon anode.This work may provide new insights of manipulating structural evolution in composite cathode materials via local coordi-nation chemistry regulation and inspire more novel design of high-performance SIB cathode materials.
基金supported by the National Natural Science Foundation of China(No.21805201)the NSFC-NRF China-Korea International Joint Research Project(No.51911540473)+1 种基金the Postdoctoral Research Foundation of China(No.2018T110544 and No.2017 M611899)the support by Suzhou Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies。
文摘Sulfurized polyacrylonitrile(SPAN)represents a unique class of cathode material for lithium sulfur(Li-S)batteries as it eradicates the polysulfides shuttling issue in carbonate-based electrolyte.However,due to the essential chemical S-linking and organic nature of SPAN,the active mass percentage and rate capability are two bottleneck issues preventing its ultimate deployment outside of laboratories.In the current work,aiming to endow both the charge conductivity and catalytic activity to SPAN for maximizing the redox kinetics of S conversion,a freestanding nanofibrous SPAN cathode embedding conductive CNTs and atomically dispersed Co centers is fabricated via multivariate electrospinning.While the CNTs enable dramatically enhancing the fiber conductivity and generating mesoscopic porosity for facilitating charge and mass transportation,the cross-linking of SPAN by Co-N_(4) S motifs creates extra charge conduction pathways and further serves as the catalytic active sites for expediting redox S conversion.As a result,an extraordinary Li-SPAN performance is achieved with a high specific capacity up to 1856 mAh g^(-1)@0.2 C,a superb rate capability up to 10 C,and an ultra-long battery life up to 1500 cycles@1 C.Consequently,our study here provides insights into the adoption of coordination chemistry to maximize the sulfur utilization by ensuring a more complete redox conversion from SPAN to Li2 S,and vice versa.
基金financial supports from the Research Grants Council of the Hong Kong Special Administrative Region(Poly U15217521)the Hong Kong Polytechnic University(Q-CDA3)Initiative for fostering University of Research and Innovation Program of the National Research Foundation(NRF)funded by the Korean government(MSIT)(No.2020M3H1A1077095)
文摘Sodium-ion batteries(SIBs)have attracted considerable interest as an alternative to lithium-ion batteries owing to their similar electrochemical performance and superior long-term cycle stability.Organic materials are regarded as promising anode materials for constructing SIBs with high capacity and good retention.However,utilization of organic materials is rather limited by their low energy density and poor stability at high current densities.To overcome these limitations,we utilized a novel polymeric disodium phthalocyanines(pNaPc)as SIB anodes to provide stable coordination sites for Na ions as well as to enhance the stability at high current density.By varying the linker type during a one-pot cyclization and polymerization process,two pNaPc anodes with O-(O-pNaPc)and S-linkers(S-pNaPc)were prepared,and their structural and electrochemical properties were investigated.The O-pNaPc binds Na ions with a lower binding energy compared with S-pNaPc,which leads to more facile Na-ion coordination/dissociation when engaged as SIB anode.The use of O-pNaPc significantly improves the redox kinetics and cycle stability and allows the fabrication of a full cell against Na_(3)V_(2)(PO_(4))_(2)F_(3)/C cathode,which demonstrates its practical application with high energy density(288 Wh kg^(-1))and high power density(149 W kg^(-1)).
基金financial support from the Russian Science Foundation (project N 21-13-00221)for the synthesis and studies of optical and magnetic properties of 1supported by the Ministry of Science and Higher Education of the Russian Federation (Registration number 124013100858-3)+2 种基金E.N.I.and M.K.I.acknowledge Grant from the Ministry of Science and Higher Education of the Russian Federation (no.075-15-2021-579)for synthesis of H3Hhp and preliminary DFT calculationssupport from the Spanish MCIN/AEI/10.13039/501100011033 (PID2020-116490GB-I00,TED2021-131255B-C43)the Comunidad de Madrid,and the Spanish State through the Recovery,Transformation and Resilience Plan[“Materiales Disruptivos Bidimensionales (2D)” (MAD2D-CM) (UAM1)-MRR Materiales Avanzados],and the European Union through the Next Generation EU funds.Instituto madrileno de estudios avanzados Nanociencia acknowledges support from the“Severo Ochoa”Programme for Centres of Excellence in R&D (Ministerio de asuntos economicos y transformacion digital,Grant SEV2016-0686).
文摘The complexation of high-spin lanthanides to porphyrinoids is a powerful strategy for the development of advanced molecular magnets.In this context,the use of expanded porphyrinoids remains elusive since their coordination chemistry is challenging to control.Herein,taking inspiration from on-surface chemistry,we explored the coordination of Dy^(3+)to a six-membered porphyrinoid,namely,the hemihexaphyrazine H3Hhp.Remarkably,we observed the selective formation of a mono-nuclear off-centered,out-of-plane H_(2)Hhp-Dy^(3+)complex when performing the complexation under reductive conditions.During this reaction,the oxidation state of the macrocycle did not change.Employing X-ray diffraction analysis,we found that the coordination number of Dy in this complex was 8.The macrocycle cocrystallized with decamethylcobaltocene(Cp_(2)^(*)Co)molecules,giving rise to a wellordered solid-state packing,governed byπ-πinteractions.As a result of this organization,a small magnetic coupling between the neighboring molecules was observed.All in all,this work provides key insights into the coordination of magnetically active metals with expanded porphyrinoids,thus motivating the development of advanced spintronic devices.
基金Supported by NNSFC(21272167)the Priority Academic Program Development of Jiangsu Higher Education Institution,and KLSLRC(KLSLRC-KF-13-HX-1)
文摘Reaction of 3-(pyridin-2-yl)-imidazo[1,5-a]pyridine (HPIP), CuCi2·2H20 and picolinaldehyde in the mixture of CHaCOOH and EtOH under solvothermal conditions gave complexes [LCuCI][CuECI3] (1) and [HLCuC1]E[CuCI2]2[CuCI3].2H20 (2) (L = 1,1'-(pyridin-2- ylmethylene)bis[3-(pyridin-2-yl)imidazo[1,5-a]pyridine]) simultaneously. The ligand L was generated via in situ metal-ligand reaction between HPIP and picolinaldehyde. When CuCI2·2H20 was replaced by CuC1, the 2:1:1(HPIP:picolinaldehyde:CuCI) reaction afforded complex [CuaL2CI2][CuCI2]·2H20 (3) and the analogous 2:1:3 reaction generated compound [CuaL2][CuCI2]3 (4). Complexes 1 and 2 are Cun/CuI mixed-valence compounds. Complexes 1-4 display four various structures. It is found that the formation of the L ligand is controlled by CH3COOH. This work reveals that the structures of complexes 1-4 could be rationally tuned via the inclusion of CH3COOH in the reaction systems, the proper selection of different starting materials and the dexterous adjustment of the ratio of the starting materials.
基金supported by the National Natural Science Foundation of China(82072065,81471784)the National Key Research and Development Program of the Minister of Science and Technology,China(2016YFA0202703)the National Youth Talent Support Program。
文摘Metal and amino acid(AA),as two kinds of entities,have been widely involved in biomaterials and nanomedicines.Recently,the marriage of them has developed new nanoformulations,amino acid-metal coordinated nanomaterials(AMCNs),which show great biomedical application potential in cancer therapy,antibacterial applications,biomedical imaging,etc.With the respective characteristics of metal and AA with rich biological and chemical properties,AMCNs can not only act as drug carriers with specific tumor targeting ability,but also realize synergistic therapy and imaging-guided therapy.Although the design and synthesis of amino acid-metal coordinated nanomaterials have been in-depth investigated,there are few systematic reviews on their biomedical application.In this review,we give a comprehensive summary of recent progresses in the design,fabrication,and biomedical applications of AMCNs.We also propose the future outlooks and challenges in aforementioned field.We expect that this review would contribute some inspiration for future research and development for amino acid metal coordinated nanomaterials.
基金Xunta de Galicia for his postdoctoral fellowship(ED481B-2022-068)the Fundación Segundo Gil Dávila for her PhD fellowship。
文摘In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety,and their complexes,were revised,and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized.Porphyrin and phthalocyanine ligands are not included in this review,which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen.The synthetic methods,structural characterization,based on single X-ray crystal data,and properties of the lanthanoid complexes,with special attention to magneto-structural correlations,are presented herein.
基金the National Natural Science Foundation of China(21906113,21561018,21790374,and 22066014)the Priority Academic Pro-gram Development of Jiangsu Higher Education Institutions(PAPD)the Applied Basic Research Foundation of Yunnan Province(2017FH001-023).
文摘Main observation and conclusion Two new uranium(VI)phosphonate compounds,namely K_(8)[N(C_(2)H_(5))_(4)]_(2)(UO_(2))_(17)(H_(2)O)_(4)[CH_(2)(PO_(3))_(2)]_(8)[CH_(2)(PO_(3))(PO_(3)H)]_(4)·16(H_(2)O)(1)and[N(C_(2)H_(5))_(4)]_(4)(H_(3)O)_(2)(UO_(2))_(10)[CH_(2)(PO_(3))_(2)]_(5)[CH_(2)(PO_(3))(PO_(3)H)]_(2)·10H_(2)O(2),have been synthesized under mild hydro/solvothermal condition.The structural analysis of the two compounds reveals that they both contain all three typical coordination geometries of the U(VI)ions,including UO;tetragonal,UO,pentagonal,and UOg hexagonal bipyramids.Moreover,compound 1 displays a tempera-ture-induced single crystal to single crystal phase transformation as confirmed by the Single-crystal X-ray diffraction data collected at different temperatures.Temperature-dependent fluorescence spectra presented herein illustrate the perturbation of the electronic structure of uranyl centers.
基金financially supported by the National Natural Science Foundation of China (Nos.21827805 and 21525418 for W.Z.) and (No.22071079 for M.W)。
文摘Due to their dynamic nature and strength tunability,metallo-supramolecular polymers have been introduced into various materials.The mechanical strength of the metallo-supramolecular polymers in the system directly influences the mechanical properties(e.g.,the toughness)of the materials.Therefore,it is necessary to explore the mechanical behavior of the metallo-supramolecular polymers.Herein,we present a single-molecule method to systematically explore the chain structure and mechanical properties of metallo-supramolecular polymer by using a loop protected architecture.Notably,we found that the mechanical stability of the individual chain,which is determined by the strength of terpyridine-Fe^(2+) -terpyridine(tpy-Fe^(2+)-tpy)bonds,was about 0.6–1.0 nN,depending on the pulling speed.This value is around three times higher than those measured using old methods.In addition,the unique loop protected structure further reduces the interference of non-specific polymer-AFM tip(or polymer-substrate)interactions on the quantification of the actual strength and kinetic parameter of noncovalent interactions in supramolecular polymers.Furthermore,the single chain flexibility of the metallo-supramolecular polymer was investigated and found to be comparable to the corresponding covalent analogues.Our findings provide a new way to explore the force response of supramolecular polymers composed of metal-ligand interactions and will be useful for the design of metallo-supramolecular polymer-based functional materials with tailored mechanical properties.
基金supported by grants from the National Natural Science Foundation of China(21825601,21790374,21906113,21727801)a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘The second example of tetravalent plutonium carboxyl-based organic framework,^(242)Pu(OH)[PO[(C_(6)H_(4))COO]_(3)]·H_(2)O,termed as PuTPO(TPO=tris(4-carboxylphenyl)-phosphineoxide),was reported in this work.A series of characterizations of PuTPO,such as X-ray crystallography and solid-state UV-Vis-NIR spectroscopy,were carried out to expatiate its structure and physicochemical properties.PuTPO is constructed by dimers of the plutonium-oxygen subunit of[Pu_(2)O_(16)].Characteristic peaks located at approximately 1100 nm can be considered to be the fingerprint peaks of tetravalent plutonium.While PuTPO can maintain high crystallinity within several months after synthesis,it exhibits a radiation-induced swelling effect probed by the expansion of cell parameter of b axis after self-irradiation fromα-decay of ^(242)Pu.This result enriches the inventory of tetravalent plutonium compounds and provides an insight into the irradiation resistance of metal-organic frameworks.
基金We are grateful for the financial support from the National Natural Science Foundation of China(Nos.60736004,50673093,and 20721061)the Major State Basic Research Development Program(2006CB806200 and 2006CB932103)+1 种基金the National High-Tech Research Development Program of China(2008AA03Z101)the Chinese Academy of Sciences and SONY Corporation,Japan.
文摘A method for the non-destructive purification of single-walled carbon nanotubes(SWNTs)using classical coordination chemistry to remove the metal catalyst has been developed.In preliminary tests,the conductivity of films based on the resulting SWNTs was markedly better than that of films prepared from SWNTs purified by treatment with oxidizing acid solutions.The transparent and conducting SWNT films have potential applications in optoelectronic devices.
基金This work was supported by the National Natural Science Foundation of China(Nos.21905195 and 22103055)the Natural Science Foundation of Tianjin City(No.20JCYBJC00800)PEIYANG Young Scholars Program of Tianjin University(No.2020XRX-0023).
文摘In the past decades,metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)basically enjoy the coordination chemistry and covalent chemistry,respectively,and such uniqueness has become the major obstacle hampering their further scope diversity and application multi-functionalization.Inspired from the principle of organic retrosynthesis,combining coordination bond and covalent bond together offers additional opportunities for constructing novel MOFs,COFs and MOF@COF hybrids as well as confer on them superior performances in versatile application fields.In this review,we firstly classify and summarize the recently reported synthesis strategies based on the integration of metal-ligand coordination and dynamic covalent bonds.Then,the application performances of as-constructed MOFs,COFs as well as MOF@COF hybrids are discussed and highlighted in the fields of adsorption,separation,catalysis,biosensing,energy storage and so on.Last,our personal insights of the remaining challenges and further prospects are also provided,in order to trigger much more inspirations and endeavors for this hot research field.
基金supported by the Beijing Nova Program from Beijing Municipal Science&Technology Commission(No.Z201100006820005)the Beijing-Tianjin-Hebei Basic Research Cooperation Project(No.19JCZDJC64100)+2 种基金the National Key Research&Development Program of China(Nos.2018YFE0117800,2021YFA1201000,and 2021YFE0106900)the National Natural Science Foundation of China(Nos.32030060 and 31871003)the Natural Science Foundation of China international collaboration key project(No.51861135103).
文摘Attaching DNA/RNA to nanomaterials is the basis for nucleic acid-based assembly and drug delivery.Herein,we report that small interfering RNA(siRNA)effectively coordinates with ligand-free lanthanide nanoparticles(NaGdF4 NPs),and forms siRNA/NaGdF4 spherical nucleic acids(SNA).The coordination is primarily attributed to the interaction between Gd and phosphate backbone of the siRNA.Surprisingly,an efficient encapsulation and rapid endosomal escape of siRNA from the endosome/lysosome were achieved,due to its flexible ability to bound to phospholipid head of endosomal membrane,thereby disrupting the membrane structure.Resorting to the dual properties of NaGdF4 NPs,siRNA loading,and endosomal escape,siRNA targeting programmed cell death-ligand 1(siPD-L1)/NaGdF4 SNA triggers significant gene silencing in vitro and in vivo,and effectively represses the tumor growth in both CT26 tumor model and 4T1 orthotopic murine model.
基金The work is supported by the National Natural Science Foundation of China(grant nos.51873067 and 21961142018)the Natural Science Foundation of Guangdong Province(grant no.2021A1515012024).
文摘Metal-organic polyhedra(MOPs)possess a microporous framework and impose hierarchical constraints on their surface ligands,leading to the long-ignored,logarithmic ligand exchange dynamics.Herein,polymer networks with MOP as nanoscale cross-linkers(MOP-CNs)can integrate unique ligand exchange dynamics and microporosity,affording vitrimer-like gas separation membranes with promising mechanical performance and(re)processability.All the ligands on the MOP surfaces are confined and correlated via a 3D coordination framework and their neighboring spaces,giving rise to a high energy barrier for ligand exchange.Therefore,MOP-CNs demonstrate high mechanical strengths at room temperature due to their negligible ligand dynamics.The thermo-activated ligand exchange process with integrated network topology enables facile(re)processing and high solvo-resistance at high temperatures.This facilitates Arrhenius type temperature dependence of flowability and stress relaxation,giving rise to the simultaneous achievement of promising mechanical strengths and(re)processability.Finally,the cage topologies of MOPs endow the materials with a bonus microporous feature and spur their applications as gas separation membranes.
基金supported by the National Natural Science Foundation of China(No.22376117)the Tsinghua University Initiative Scientific Research Program.
文摘Safe confinement of fission iodine isotopes for long-term radioactive waste disposal remains a formidable challenge,as conventional sorbents provide inherently weak iodine-host interactions.We report here a novel halogen bond(X-bond)directed strategy to sequester volatile iodine in hydrogen-bonded(H-bonded)frameworks with unprecedented stability.Charge-assisted Hbonded frameworks bearing open halide sites are developed,showing distinctive iodine encapsulation behaviors without compromising the crystallinity.Direct crystallographic evidence indicates the formation of X-bonds,i.e.,I–I···Cl−and I–I···Br^(−),within the confined pore channels.Unusual polyhalogen anions,i.e.,[I_(2)Cl_(2)]^(2−)and[I_(2)Br_(2)]^(2−),sustained in H-bonded frameworks are identified for the first time.The X-bond reinforced host-guest interaction affords robust iodine trapping without leaking out even at elevated temperatures up to 180°C.By integrating the halogen-bond chemistry with H-bonded frameworks,this study offers fresh concepts for developing effective host reservoirs to secure fission iodine isotopes from spent fuel reprocessing off-gases.