Achieving an ion-homogenizing and corrosion-resisting interface through nitro-coordination chemistry for stable zinc metal anodes

Suppression of uncontrollable dendrite growth and water-induced side reactions of Zn metal anodes is crucial for achieving long-lasting cycling stability and facilitating the practical implementations of aqueous Zn-metal batteries.To address these challenges,we report in this study a functional nitro-cellulose interfacial layer(NCIL)on the surface of Zn anodes enlightened by a nitro-coordination chemistry strategy.The NCIL exhibits strong zincophilicity and superior coordination capability with Zn^(2+)due to the highly electronegative and highly nucleophilic nature of the nitro functional group.This characteristic facilitates a rapid Zn-ion desolvation process and homogeneous Zn plating,effectively preventing H_(2) evolution and dendrite formation.Additionally,the negatively charged surface of NCIL acts as a shield,repelling SO_(4)^(2-)anions and inhibiting corrosive reactions on the Zn surface.Remarkably,reversible and stable Zn plating/stripping is achieved for over 5100 h at a current density of 1 mA cm^(-2),which is nearly 30 times longer than that of bare Zn anodes.Furthermore,the Zn/V_(2)O_(5) full cells with the functional interface layer deliver a high-capacity retention of 80.3%for over 10,000 cycles at 5 A g^(-1).This research offers valuable insights for the rational development of advanced protective interface layers in order to achieve ultra-long-lifeZnmetal batteries.

Self-assembly of perovskite nanocrystals:From driving forces to applications

Self-assembly of metal halide perovskite nanocrystals(NCs)into superlattices can exhibit unique collective properties,which have significant application values in the display,detector,and solar cell field.This review discusses the driving forces behind the self-assembly process of perovskite NCs,and the commonly used self-assembly methods and different self-assembly structures are detailed.Subsequently,we summarize the collective optoelectronic properties and application areas of perovskite superlattice structures.Finally,we conclude with an outlook on the potential issues and future challenges in developing perovskite NCs.

Simultaneous regulation on coordination environment and interfacial chemistry via taurine for stabilized Zn metal anode

Aqueous Zn-ion batteries(AZIBs)are the potential options for the next-generation energy storage scenarios due to the cost effectiveness and intrinsic safety.Nevertheless,the industrial application of AZIBs is still impeded by a series of parasitic reactions and dendrites at zinc anodes.In this study,taurine(TAU)is used in electrolyte to simultaneously optimize the coordination condition of the ZnSO4electrolyte and interfacial chemistry at the anode.TAU can preferentially adsorb with the zinc metal and induce an in situ stable and protective interface on the anode,which would avoid the connection between H_(2)O and the zinc metal and promote the even deposition of Zn^(2+).The resulting Zn//Zn batteries achieve more than 3000 hours long cyclic lifespan under 1 mA cm^(-2)and an impressive cumulative capacity at 5 mA cm^(-2).Moreover,Zn//Cu batteries can realize a reversible plating/stripping process over 2,400cycles,with a desirable coulombic efficiency of 99.75%(1 mA cm^(-2)).Additionally,the additive endows Zn//NH_(4)V_(4)O_(10)batteries with more stable cyclic performance and ultrafast rate capability.These capabilities can promote the industrial application of AZIBs.

CATHODIC REDUCTION OF METAL-CHLORIDE COORDINATION IONS

ＣＡＴＨＯＤＩＣＲＥＤＵＣＴＩＯＮＯＦＭＥＴＡＬ－ＣＨＬＯＲＩＤＥＣＯＯＲＤＩＮＡＴＩＯＮＩＯＮＳＺｅｎ，Ｚｈｅｎｏｕ（ＤｅｐａｒｔｍｅｎｔｏｆＡｐｐｌｉｅｄＣｈｅｍｉｓｔｒｙＣｈｅｍｉｓｔｒｙ，ＳｏｕｔｈＣｈｉｎａＵｎｉｖｅｒｓｉｔｙｏｆＴｅｃｈｎ...

An Exploratory Study of Tridentate Amine Extractants: Solvent Extraction and Coordination Chemistry of Base Metals with <i>Bis</i>((1<i>R</i>-benzimidazol-2-yl)methyl)amine

Solvent extraction of base metals using bis((1-decylbenzimidazol-2-yl)methyl)amine (BDNNN) showed a lack of pH-metric separation of the metals. The extraction system was described quantitatively using the equilibria involved to derive the mathematical explanation for the two linear log D vs pHe plots for each metal ion extraction curve, and coordination numbers could also be extracted from the two slopes. The lack of separation was attributed to the absence of stereochemical “tailor making” since the complexes isolated from the reaction of the ligand, bis((1H-benzimidazol- 2-yl)methyl)amine (NNN), with base metals suggested the formation of similar octahedral complex species from spectral and crystal structure evidence. The bis tridentate coordination observed was in agreement with information extracted from the extraction data. This investigation opens up an opportunity and an approach for the evaluation of amines as extractants but cautions against tridentate ligands.

Two Isostructural 2-D Metal(Ⅱ)-organic Coordination Polymers from 4,4'-Bipyridyl and (E)-2,6-Dimethyl-4-styrylpyridine-3,5-dicarboxylic Acid

（E）-2,6-Dimethyl-4-styrylpyridine-3,5-dicarboxylic acid （H2mspda） is firstly employed in coordination chemistry.Two isostructural two-dimensional （2-D） 4-connected metal-organic coordination polymers with a general formula of {M2[（mspda）2（bpy）（H2O）2]}n （M=Zn（1） and Co（2）） are assembled from H2mspda,4,4＇-bipyridyl （bpy）,zinc and cobalt ions under hydrothermal conditions,and characterized by single-crystal X-ray diffraction analyses.Complex 1 crystallizes in monoclinic,space group P21/n with a=14.551（4）,b=10.941（3）,c=14.945（4）,β=98.817（4）o,V=2351.3（1）3,Dc=1.511 g/cm3,μ（MoKα）=1.090 mm-1,F（000）=1104,Z=4,the final R=0.0335 and wR=0.0485 for 3296 observed reflections （I 〉 2σ（I））.In compound 1,mspda2-spacers are only arrayed in a head-to-tail fashion which corresponds to a 2-D coordination polymer.Solid-state H2mspda and complex 1 have expected photoluminescence （λem=475～496 nm） at room temperature.

Metal-directed Assembly of Two Distinct Coordination Polymers with 2,5-Furandicarboxylic Acid and 4,4'-Bipyridine

By using solvothermal method, two new metal coordination polymers based on 2,5-furandicarboxylic acid（H2FDA） ligand and 4,4＇-bipyridine（bipy）, [Cu（FDA）（4,4＇-bipy）（DMF）]n·solvent（1） and {[Zn（4,4＇-bipy）（FDA）（DMF）]·DMF}n（2）, were produced and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR and powder X-ray diffraction. Compound 1 crystallizes in monoclinic space group P21/c with a = 11.104（2）, b = 10.396（2）, c = 18.772（4） , β = 96.20（3）o, V = 2154.2（7） 3, Dc = 1.378 g/cm^3, C19H17 Cu N3O6, Mr = 446.90, F（000） = 916, μ（Mo Kα） = 1.05 mm^-1, Z = 4, R = 0.0691 and wR = 0.1341 for 3537 observed reflections（I 2σ（I））, and R = 0.1062 and w R = 0.1482 for all data. Compound 2 crystallizes in monoclinic space group C2/c with a = 29.779（6）, b = 9.6417（19）, c = 17.292（3）, β = 105.69（3）°, V = 4779.9（16） 3, Dc = 1.445 g/cm^3, C22H22N4O7 Zn, Mr = 519.81, F（000） = 2144, μ（Mo Kα）= 1.08 mm^-1, Z = 8, R = 0.0641 and w R = 0.1007 for 2985 observed reflections（I 2σ（I））, and R = 0.1028 and w R = 0.1112 for all data. Different coordination geometry of metal ions, square pyramid of Cu2＋ and trigonal bipyramid of Zn2＋, bring about different orientations of FDA2- ligands as well as 4,4＇-bipyridine ligands, and furthermore distinct assembly structures for 1 and 2. The thermal stabilities of 1 and 2 are also investigated.

Three-dimensional 3d-4d Heterometallic Coordination Polymer——Synthesis,Structure,Magnetic and Luminescent Properties

A new three-dimensional 3d-4d heterometallic coordination polymer,[Cd2Mn（H2O）4（BTC）2]·2H2O（BTC=1,3,5-benzenetricarboxylate） was prepared under hydrothermal conditions and characterized by single crystal X-ray diffraction.This compound crystallized in the monoclinic space group C2/c,with cell parameters a=1.9452（4） nm,b=0.7094（2） nm,c=1.8064（4） nm,β=118.02（3）°,V=2.2004（8） nm3 and Z=4.Its structure contains trinuclear mixed metal clusters,which are further connected by BTC to form a three-dimensional framework.The compound exhibits intense photoluminescence at room temperature.Magnetic studies of the compound show a dominant antiferromagnetic exchange between the Mn（Ⅱ） ions.

COORDINATION POLYMERIZATION OF BENZOTRIAZOLE ON THE SURFACE OF METALLIC COPPER

The coordination polymerization of benzotriazole with metallic copper has been investigated by infrared and X-ray photoelectron spectroscopies. We found that benzotriazole could react with copper (0) under mild conditions to form bis (benzotriazolato) copper (Ⅱ) and benzotriazolato copper (Ⅰ)which covered the surface of copper metal in the shape of polymeric materials. Since benzotriazole is of great interest as a ligand in that its presence in many biological system with metal ions, and is considered as a corrosion inhibitor, this work will be in favour of the study of protective corrosion.

Rare π_5~6…Pb Interactions in a Two-dimensional Metal-organic Coordination Polymer with Two Distinct Kinds of Axially Chiral Units

A new metal-organic coordination polymer [Pb（mfpdc）（CH3OH）]n （1, mfpdc = 2,6-dimethyl-4-（2-furanyl） pyridine-3,5-dicarboxylate） was synthesized and characterized by single-crystal X-ray analyses. The crystal is orthorhombic, space group Pbca, a = 15.6297（18）, b = 9.4803（11）, c = 18.598（2） A, V= 2755.8（6） A3, Z = 8, Mr= 498.44, Dc= 2.403 Mg/m3, F（000） = 1872, the final R = 0.0275 and wR = 0.0726 （1 〉 2σ（I））. There are interesting polynuclear zigzag （PbOs）n chains in the structure of 1, and there have interesting axially chiral S- and R-unit Pb4L units constructed from prochiral organic ligands through C-H...O bonding. The （R/S）-Pb4L units by sharing Pb centers generate a 2-D coordination network, in which there exist rare n65Pb （3.2610 A） interactions. The solid-state photoluminescent emission of compound 1 appears at 487 nm.

Anisotropic Thermally-Accessible Lattice Distortion of a Cu（ll）-Cr（VI） Complex Bimetallic Oxide by Adsorbing a Chiral One-Dimensional Cu（ll）-Cr（VI） Coordination Polymer

The authors have prepared and characterized a chiral one-dimensional Cu（II）-Cr（VI） coordination polymer, [CuL2][Cr207] （L = （IR, 2R）-diaminocyclohexane）, which exhibited intense d-d bands as well as charge transfer bands in the solid state electronic and CD spectra. Thermally-accessible lattice distortion was observed along the crystallographic a axis, which corresponded to Jahn-Teller distortion of Cu（II） chromophores. After firing [CuL2][Cr207], they could obtain a Cu（II）-Cr（VI） complex bimetallic oxide showing ferromagnetism and isotropic thermally-accessible lattice distortion. Preparation of composite materials of the coordination polymers and a complex bimetallic oxide could be confirmed by IR spectra and magnetic properties. It should be noted that the complex bimetallic oxide as the composite exhibited anisotropic thermally-accessible lattice distortion by adsorption of the chiral one-dimensional coordination polymer.

A New Thionine Modified Electrode by Anchorage to Bi-(2-aminoethyl)-aminodithiocarboxyl Acid Self-assembled Monolayers through Coordination with Cu^(2+#)

A new method for preparing chemically modified gold electrode by anchoring thionine to self-assembled bi - (2 -aminoethyl) -aminodithiocarboxyl acid(BANTC) monolayers through coordination with Cu2+ is described. This thionine modified electrode exhibits two-new redox couples.Two protons were involved in the electrochemical process undergone by the couple I in the pH range of 5.0-10.0. The apparent surface electron transfer rate constant is about 0.050s-1.

THE SYNTHESIS AND CHARACTERISTICS OF THE COORDINATION COMPOUNDS OF 2-MERCAPTOPYRIDINE-1-OXIDE WITH THE FIPST TRANSITION SERIES METALS

The stability of the coordination compounds of the first transition series metal ions(Mn(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ)and Zn(Ⅱ))with 2-mercaptopyridine-1- oxide is reported.A coordination compound CoL_2 is synthesized and characterized for the first time.

Coordination environment of active sites and their effect on catalytic performance of heterogeneous catalysts

The structural complexity of supported metal catalysts,playing significant role in a wide range of chemical technologies,have prevented us from deeply understanding their catalytic mechanisms at atomic level.A fundamental understanding of the nature of active sites and structure–performance relationship of supported metal catalysts from a comprehensive view will open up numerous new opportunities for the development of advanced catalysts to address the global challenges in energy conversion and environmental protection.This review surveys the effects of multiple factors,including the metal size,shape,support,alloy and ligand modifier,on the coordinated environment of active center and further their influence on the catalytic reactions,aiming to provide guidance for the design of industrialized heterogeneous catalysts with extraordinary performance.Subsequently,the key structure characterization techniques in determining the coordination structure of active metal sites,especially the dynamic coordination structure change under the reaction condition,are well summarized.A brief summary is finally provided together with personal perspectives on the further development in the field of heterogeneous metal catalysts.

Syntheses,Crystal Structures and Thermal Stabilities of Two New Mixed Ligated Coordination Polymers with Rigid Dicarboxylate and Flexile N-donor Ligands

Two new coordination polymers,[Co（BIPA）（bpp）]（1） and [Zn（BIPA）（bpp）（H2O）]（2）（H2BIPA = 5-bromoisophthalic acid,bpp = 1,3-di（4-pyridyl）propane） have been synthesized via hydrothermal reactions.The two compounds were characterized by elemental analysis,IR spectra,TG analysis and single-crystal X-ray determination.Compound 1 crystallizes in triclinic,space group P1 with a = 9.0316（13）,b = 10.1179（14）,c = 11.8884（17） ,α = 68.022（2）,β = 84.749（2）,γ = 77.791（2）°,V = 984.5（2） 3,Z = 2,C21H17BrN2O4Co,Mr = 500.21,Dc = 1.687 g.cm-3,μ = 2.932 mm-1,S = 0.981,F（000） = 502,R = 0.0440 and wR = 0.1357 for 3773 observed reflections with I 2σ（I）.Compound 2 crystallizes in the monoclinic system,space group P21/c with a = 7.8466（10）,b = 27.483（4）,c = 9.6583（13） ,β = 96.663（3）°,V = 2068.8（5） 3,Z = 4,C21H19BrN2O5Zn,Mr = 524.66,Dc = 1.685 g.cm-3,μ = 3.155 mm-1,S = 0.969,F（000） = 1056,R = 0.0441 and wR = 0.0517 for 4058 observed reflections with I 2σ（I）.The two compounds are constructed from the BIPA2-and bpp ligands but they exhibit different kinds of one-dimensional chain structures.In 1,the chains are composed of the Co（Ⅱ） ions and BIPA2-ligands,and the chains are further extended into a 2D framework structure by π...π interactions of the benzene rings from the BIPA2-ligands between the adjacent chains.In 2,the chains are made up of Zn（Ⅱ） ions and BIPA2-ligands through another fashion,and the chains are further linked via hydrogen bonding interactions to yield a two-dimensional supramolecular layer structure.Furthermore,the bpp ligand features two kinds of different coordination modes in the two compounds.

Synthesis and Structure of a Novel 3-Fold Interpenetrating Three-dimensional Coordination Polymer:[Ni(Hbyip^(2-))(bix)_(0.5)(H_2O)]_n

A three-dimensional coordination polymer,[Ni（Hbyip2-）（bix）0.5（H2O）]n,has been hydrothermally synthesized.Each Ni2＋ ion is five-coordinated by three carboxylate O atoms from three different 5-（benzoic acid-4-yldiazenyl）isophthalate（Hbyip2-） anions,one N atom from one 1,4-bis（imidazol-1-ylmethyl）benzene（bix） ligand and one O atom from an aqua ligand displaying a distorted square-pyramid.Each Ni atom is defined by three Hbyip2-anions and each Hbyip2-anion adopts a tris（mono-dentate） ligand coordinating to three Ni2＋ ions affording a 36-membered inorganic ring.These rings are further arranged into an undulated two-dimensional layer parallel to the（101） plane.Adjacent two-dimensional networks are linked by bix ligands into a three-dimensional {63,83}{63} framework with a large channel（ca.26.3 × 13.6） along the [100] direction.Each individual {63,83}{63} network interpenetrates with two others in a parallel fashion to generate a 3-fold interpenetrating network.

High-temperature treatment to engineer the single-atom Pt coordination environment towards highly efficient hydrogen evolution

Development of high-performance and cost-effective catalysts for electrocatalytic hydrogen evolution reaction(HER)play crucial role in the growing hydrogen economy.Recently,the atomically dispersed metal catalysts have attracted increasing attention due to their ultimate atom utilization and great potential for highly cost-effective and high-efficiency HER electrocatalyst.Herein,we propose a hightemperature treatment strategy to furtherly improve the HER performance of atomically dispersed Ptbased catalyst.Interestingly,after appropriate high-temperature treatment on the atomically dispersed Pt0.8@CN,the Pt species on the designed N-doped porous carbon substrate with rich defect sites can be re-dispersed to single atom state with new coordination environment.The obtained Pt0.8@CN-1000 shows superior HER performance with overpotential of 13 m V at 10 m A cm^(-2)and mass activity of 11,284 m A/mgPtat-0.1 V,much higher than that of the pristine Pt0.8@CN and commercial Pt/C catalyst.The experimental and theoretical investigations indicate that the high-temperature treatment induces the restructuring of coordination environment and then the optimized Pt electronic state leads to the enhanced HER performances.This work affords new strategy and insights to develop the atomically dispersed high-efficiency catalysts.

Nano/Micro HKUST-1 Fabricated by Coordination Modulation Method at Room Temperature

A simple and fast route for the synthesis of metal-organic framework（MOF） particles was presented.Cu 3（BTC） 2（HKUST-1,BTC=1,3,5-benzenetricarboxylate）,one of the most well-known MOFs,was synthesized at room temperature via coordination modulation method.By adding different modulators（monocarboxylic acids） into the reaction system,the morphologies of HKUST-1 crystals were tuned from nano spheres to micro octahedrons at room temperature without any complex equipment.X-Ray diffractions and gas sorption measurements revealed highly crystalline particles with large Brunauer-Emmett-Teller（BET） surface areas（1116―1273 m^ 2 /g） and total pore volumes（0.62―0.73 cm^ 3 /g）.The significantly small particle sizes and high capacity of gas sorption are considered advantageous for envisaged application in practical industrial process.