A gel polymer electrolyte with IL@UiO-66-NH_(2) as fillers for high-performance all-solid-state lithium metal batteries

All solid-state electrolytes have the advantages of good mechanical and thermal properties for safer energy storage,but their energy density has been limited by low ionic conductivity and large interfacial resistance caused by the poor Li~+transport kinetics due to the solid-solid contacts between the electrodes and the solid-state electrolytes.Herein,a novel gel polymer electrolyte(UPP-5)composed of ionic liquid incorporated metal-organic frameworks nanoparticles(IL@MOFs)is designed,it exhibits satisfying electrochemical performances,consisting of an excellent electrochemical stability window(5.5 V)and an improved Li^(+)transference number of 0.52.Moreover,the Li/UPP-5/LiFePO_(4) full cells present an ultra-stable cycling performance at 0.2C for over 100 cycles almost without any decay in capacities.This study might provide new insight to create an effective Li^(+)conductive network for the development of all-solid-state lithium-ion batteries.

Activating coordinative conjugated polymer via interfacial electron transfer for efficient CO_(2) electroreduction

With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative to the well-known M-N-C electrocatalysts.Herein,the coordination reaction between Cu^(2+)and 1,2,4,5-tetraaminobenzene(TAB) was conducted on the surface of metallic Cu nanowires,forming a thin layer of CuN4-based CCP(Cu-TAB) on the Cu nanowire.More importantly,interfacial transfer of electrons from Cu core to the CuN4-based CCP nanoshell was observed within the resulting CuTAB@Cu,which was found to enrich the local electronic density of the CuN4sites.As such,the CuTAB@Cu demonstrates much improved affinity to the*COOH intermediate formed from the rate determining step;the energy barrier for C-C coupling,which is critical to convert CO_(2)into C2products,is also decreased.Accordingly,it delivers a current density of-9.1 mA cm^(-2)at a potential as high as 0.558 V(vs.RHE) in H-type cell and a Faraday efficiency of 46.4% for ethanol.This work emphasizes the profound role of interfacial interaction in tuning the local electronic structure and activating the CuN4-based CCPs for efficient electroreduction of CO_(2).

Hydrothermal Synthesis,Structure and Properties of a 3D Pillar-layered Metal-organic Framework Based on Amino-arenedisulfonate Ligand

One novel metal-organic framework(MOF), [Ba(L)(HO)](1, HL =aniline-2,5-disulfonic acid), has been synthesized by hydrothermal method. Each barium atom is eleven-coordinated into a distorted monocapped pentagonal antiprismatic arrangement. Compound 1 shows an interesting 3 D pillar-layered structure constructed from 2 D inorganic layers[Ba(SO)(HO)]and organic pillars of phenyl moieties of L2-linkages. The inorganic layers are supported by the organic pillars, generating a novel 3 D open framework structure with {3, 4~6, 5~5, 6~5,7~4}2{3}{5} topology. The result of fluorescence measurement can reveal that the decayed emission band centered at 492 nm may be caused by the interactions of the ligands and the metal ions.Compound 1 exhibits selective toward the adsorption of COover Nat 273 K.

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.

Synthesis and Characterization of a Novel 3D Coordination Polymer Based on Cu(II) Cations and Mellitic Acid

A new mellitate complex [Cu3（μ2-mellitate）（μ2-H2O）（H2O）2·H2O]n 1 has been synthesized by the reaction of mellitic acid and Cu（CH3COO）2·H2O in the presence of base. Crystallographic data for 1： C12H8O16Cu3, Mr = 598.80, orthorhombic, Pbcn, a = 8.4378（6）, b = 10.0396（7）, c = 17.6799（12）A, V = 1497.70（18）A^3, Z = 4, De = 2.656 g/cm^3, μ = 4.327 mm^-1, F（000） = 1180, R = 0.0431 and wR = 0.0964 for 1075 observed reflections （I 〉 2σ（I））. X-ray crystal structural analysis revealed that the mellitate anions behave as the bridging ligands and link eight copper atoms repeatedly to form a novel three-dimensional metal-organic coordination polymer with two different rhombic tunnels in the solid-state structure.

Anisotropic self-diffusion of fluorinated poly(methacrylate) in metal-organic frameworks assessed with molecular dynamics simulation

Utilizing the periodically structured metal-organic framework （MOF） as the reaction vessel is a promising technique to achieve the aligned polymer molecular chains, where the diffusion procedure of the polymer monomer inside MOF is one of the key mechanisms. To investigate the diffusion mechanism of fluorinated polymer monomers in MOFs, in this paper the molecular dynamics simulations combined with the density functional theory and the Monte Carlo method are used and the all-atom models of TFMA （trifluoroethyl methacrylate） monomer and two types of MOFs,[Zn2（BDC）2（TED）]n and[Zn2（BPDC）2（TED）]n, are established. The diffusion behaviors of TFMA monomer in these two MOFs are simulated and the main influencing factors are analyzed. The obtained results are as follows. First, the electrostatic interactions between TFMA monomers and MOFs cause the monomers to concentrate in the MOF channel, which slows down the monomer diffusion. Second, the anisotropic shape of the one-dimensional MOF channel leads to different diffusion speeds of monomers in different directions. Third, MOF with a larger pore diameter due to a longer organic ligand,[Zn2（BPDC）2（TED）]n in this paper, facilitates the diffusion of monomers in the MOF channel. Finally, as the number of monomers increases, the self-diffusion coefficient is reduced by the steric effect.

Synthesis and Characterization of a Metal-Organic Framework Bridged by Long Flexible Ligand

3D supramolecular network with considerable volume pores was created via hydrogen bond & C-H--π. By tightening of The metal-organic frameworks (MOF) namely [Ni(μ-pmb)2(H2O)2]n (pmb = 3,5-bis(4-pyridylmethylenoxyl) benzoate, that have been synthesized by hydrothermal method. Complex 1 crystallizes in triclinic P-1 space group and consists of 1D semi zigzag chain.

Coordination Polymer of Cobalt (ΙΙ) Nitrate with Imidazole: Synthesis, Properties and Crystal Structure

Layered metal-organic polymer [Co(L)6](NO3)2 was obtained (where, L = C3H4N2) and structurally characterized by X-Ray diffraction (XRD) analysis. Crystals have trigonal structure: a = b = 12.3555(10) Ǻ, c = 14.4833(3) Ǻ;α = β = 90˚;γ = 120˚;V = 1914.78(5) Ǻ;R3, Z = 3. The structure of the complex consists of discrete [Co(L)6]2+ cations and anions. The Co2+ ion has a centrosymmetric octahedron configuration with a coordination site—CoN6. The ligand is coordinated monodentate through the pyridine nitrogen atom (N3) to the Co2+ ion with an average Co-N bond distance of 2.1590 Ǻ. Molecules in the coordination polymer are additionally linked by intermolecular hydrogen bonds through the pyrrole nitrogen atom (-N-H) and oxygen of the nitrate group with the formation of a polymer chain of the type: N-H…O. The chains are linked in layers along the (001) plane.

ZIF-8-functionalized polymer electrolyte with enhanced performance for high-temperature solid-state lithium metal batteries

Solid polymer electrolytes(SPEs)with high ionic conductivity are desirable for solid-state lithium metal batteries(SSLMBs)to achieve enhanced safety and energy density.Incorporating nanofillers into a polymeric matrix to develop nanocomposite solid electrolytes(NCSEs)has become a promising method for improving the ionic conductivity of the SPEs.Here,a novel ZIF-8-functionalized NCSE was prepared for high-temperature S SLMB s using an in situ radical polymerization method.It is found that the ZIF-8 nanoparticles could reduce the crystallinity of polymer segments and offer a Lewis acid surface that promotes the dissociation of lithium bis(trifluoromethanesulfonyl)imide(LiTFSI)and stabilizes the TFSI^(-) anion movement.Thus,the as-prepared NCSE exhibits an outstanding ionic conductivity of 1.63×10^(-3)S·cm^(-1),an electrochem ical stability window of 5.0 V at 80℃,and excellent interface compatibility with lithium metal anode with a stable polarization over 2000 h.Furthermore,the assembled SSLMBs with LiFePO_(4)cathode show dendrite-free Li-metal surface,good rate capability,and stable cycling stability with a capacity retention of 70%over 1000 cycles at a high temperature of 80℃.This work provides valuable insights into promoting the ionic conductivity of SPEs.

Two-Dimensional Conductive Metal-Organic Framework Reinforced Spinterface in Organic Spin Valves

Interface engineering in device fabrication is a significant but complicated issue.Although great successes have been achieved by conventional physical in situ or ex situ methods,it still suffers from complicated procedures.In this work,we present a facile method for fabricating phthalocyanine(Pc)-based two-dimensional conductive metal–organic framework(MOF)films.Based on PcM-Cu(M=Ni,Cu,H_(2))MOF films,spin valves with a vertical configuration of La_(0.67)Sr_(0.33)MnO_(3)/PcM-Cu MOFs/Co were constructed successfully,and exhibited notably high negative magnetoresistance(MR)up to -22% at 50 K.The penetrated Co atoms coordinated with the dehydrogenated hydroxy groups in the MOFs resulting in an antiferromagnetic layer of the PcM-Cu-Co hybrid structure.Interestingly,a significant exchange bias effect was demonstrated at the PcM-Cu MOF/Co interface,beneficial for the MR behavior.Thus,our present study provides new insights into developing high-performance organic spin valves via de novo molecular design.

Hierarchical porous metal-organic frameworks/polymer microparticles for enhanced catalytic degradation of organic contaminants

This work reports on a simple microfluidic strategy to controllably fabricate uniform polymeric microparticles containing hierarchical porous structures integrated with highly accessible catalytic metal organic frameworks for efficient degradation of organic contaminants.Monodisperse(W1/O)/W2 emulsion droplets generated from microfluidics are used as templates for the microparticle synthesis.The emulsion droplets contain tiny water microdroplets from homogenization and water nanodroplets from diffusion-induced swollen micelles as the dual pore-forming templates,and Fe-based metal-organic framework nanorods as the nanocatalysts.The obtained microparticles possess interconnected hierarchical porous structures decorated with highly accessible Fe-based metal-organic framework nanorods for enhanced degradation of organic contaminants via a heterogeneous Fenton-like reaction.Such a degradation performance is highlighted by using these microparticles for efficient degradation of rhodamine B in hydrogen peroxide solution.This work provides a simple and general strategy to flexibly combine hierarchical porous structures and catalytic metal-organic frameworks to engineer advanced microparticles for water decontamination.

A fiber-reinforced solid polymer electrolyte by in situ polymerization for stable lithium metal batteries

Solid polymer electrolytes(SPEs)by in situ polymerization are attractive due to their good interfacial contact with electrodes.Previously reported in situ polymerized SPEs,however,suffer from the low polymerization degree that causes poor mechanical strength,Li dendrite penetration,and performance decay in Li-metal batteries.Although highly polymerized SPEs are more stable than lowly polymerized ones,they are restricted by their sluggish long-chain mobility and poor ionic conductivity.In this work,a three-dimensional fibrous membrane with ion selectivity was prepared and used as a functional filler for the in situ formed SPE.The obtained SPE has high stability due to its high polymerization degree after the long-term heating process.The fibrous membrane plays a vital role in improving the SPE’s properties.The rich anion-adsorption sites on the fibrous membrane can alleviate the polarization effect and benefit a uniform current distribution at the interface.The fibrous nanostructure can efficiently interact with the polymeric matrix,providing rich hopping sites for fast Li+migration.Consequently,the obtained SPE enables a uniform Li deposition and long-term cycling performance in Li-metal batteries.This work reported an in situ formed SPE with both high polymerization degree and ionic conductivity,paving the way for designing high-performance SPEs with good comprehensive properties.

Porous coordination polymers based on three planar rigid ligands

During the last two decades,porous coordination polymers(PCPs),usually called as metal-organic frameworks(MOFs),have been developed rapidly due to their versatile structural diversities and potential physical and chemical functions.This article provides a short review of recent advances in the design and constructions of porous coordination polymers based on three planar rigid ligands,including imidazole-4,5-dicarboxlate(H3IDC),1H-tetrazole(HTz),as well as 1H-tetrazole-5-carboxylate(H2Tzc).Their preparations,crystal structures,and desirable properties have been reviewed.

Organic ammonium ion-occluded flexible coordination polymers:Thermal activation,structure transformation and proton transfer

Solvothermal reactions of 1,3,5-benzenetricarboxylic acid (H3btc) with cadmium acetate or zinc acetate yielded two compounds formulated as (Me2NH2)[Cd(btc)]·DMA (1) (btc = 1,3,5-benzenetricarboxylate, DMA = N,N-dimethylacetamide) and (Me2NH2)[Zn(btc)]·DMF (2) (DMF = N,N-dimethylformamide). Both are 3-D frameworks with the rutile topology, which are constructed from six-connected dimeric metal cores and three-connected btc linkers. The solvent molecules and counter cations are located in the 1-D channels of the frameworks. A slight difference between the two compounds is the different connectivity modes of the metal atoms with the carboxylate groups of the ligands. However, this slight difference results in distinct flexibilities of the two frameworks. Variable-temperature powder X-ray diffraction studies revealed that the framework of 1 collapses when heated at 180 °C with loss of the guest species, but compound 2 undergoes two structural transformations below 380 °C. Thermogravimetry-infrared spectroscopy analysis for 2 showed that the two structural transformations are induced by separate losses of solvent molecules and counter cations, and that the dimethylammonium cations are eliminated as neutral dimethylamine molecules. IR spectroscopy demonstrated that the protons are transferred from the counter cations onto the uncoordinated carboxylate oxygen atoms on the channel walls. Sorption and proton conduction studies have also been performed for the compounds.

MOF-Conductive Polymer Composite Film as Electrocatalyst for Oxygen Reduction in Acidic Media

A metal-organic framework(MOF)-conductive polymer composite film was constructed from PCN-222(Fe)nanoparticles and PEDOT:PSS solution by simple drop-casting approach.The composite film was tested as an electrocatalytic device for oxygen reduction reaction(ORR).The combination of PCN-222(Fe)MOF particles and conductive PEDOT matrix facilitates electron transfer in the composite material and improves the ORR performance of PCN-222(Fe).Levich plot and H_(2)O_(2)quantification experiment show that PCN-222(Fe)/PEDOT:PSS film mainly catalyzes two-electron oxygen reduction and produces H_(2)O_(2).

Three alkaline earth metal-organic frameworks based on fluorene-containing carboxylates:syntheses,structures and properties

Three metal-organic frameworks,{[Mg_2(MFDA)_2(DMF)_3]·0.5H_2O}_n(1),{[Ca(MFDA)(DMF)(H_2O)]·0.5DMF}_n(2)and[Ca(MFDA)(DMF)_2]_n(3)(DMF=N,N-dimethylformamide)have been synthesized by the solvothermal reactions between the ligand 9,9-dimethylfluorene-2,7-dicarboxylic acid(H_2MFDA)and the corresponding metal salts,respectively.The single crystal X-ray structural analyses reveal that compounds 1-3 display three-dimensional structures based on the M(Ⅱ)-O-C chains.It is interesting that the MFDA ligands in 1-3 have different dihedral angles between the two carboxylate groups ranging from 9.9(1)°to 41.8(2)°.All of compounds exhibit strong ligand-centered blue emissions under UV lights.Their thermal properties have also been studied.

Dynamic Pendulum Effect of an Exceptionally Flexible Pillared-Layer Metal-Organic Framework

Main observation and conclusion Magnifying the controllable directional motions of molecular machines to the macroscopic levels is a significant topic for chemists.Flexible metal–organic frameworks with long-range order and responsive structural transformation under external stimuli may be an appropriate platform for achieving the target.By taking advantage of the single-crystal to single-crystal manner of soft porous crystals,we utilize single-crystal X-ray diffraction to directly observe the dynamic structural inversion of a new three-fold interpenetrated pillared-layer metal-organic framework[Co(edba)(bpy)](MCF-83,H2edba=4,4’-(ethyne-1,2-diyl)dibenzoic acid,bpy=4,4’-bipyridine).More interestingly,the dynamic inversions of the pillars and layers are selectively guest-controllable and independent,allowing precise control of the directional shape changes,which is the key of constructing intelligent materials to accomplish a complex task.The mechanism is further studied by combining the X-ray diffraction analyses,sorption measurements and molecular simulations.

Two-Dimensional Metal-Organic Frameworks and Covalent Organic Frameworks

Two-dimensional(2D)metal/covalent organic framework(MOF/COF)materials have ultra-thin thickness and large surface area.These advantages bestow them the characteristics of low resistance and high flux in the process of material transportation.Meanwhile,more active sites promote their application in the fields of catalysis and sensing.Recently,2D MOF/COF materials usher in a new wave of research.It is necessary to summarize the latest developments in this field in a timely and systematic manner and clarify future trends.In this review,we firstly introduce the advantages of 2D MOF/COF materials in hetero-porous structure and functional modification.Then,we discuss advanced strategies for preparing 2D MOF/COF materi-als,such as in-situ growth,interface synthesis,exfoliation method,electrochemical method,surfactant-assisted synthesis,and laminated assembly of MOF/COF nanosheets.Finally,we summarize the applications of 2D MOF/COF materials in membrane separation,sensors,and energy storage.In ad-dition,we discuss some unresolved scientific and technological challenges related to the future prospects of this field.

Sub-5 nm porous polymer decoration toward superhydrophobic MOFs with enhanced stability and processability

Metal-organic frameworks(MOFs) show great potential for various applications, but many of them suffer from the drawbacks of hydrolysis propensity and poor processability. Herein, we employ polymers of intrinsic microporosity(PIMs) with hydrophobic pores to decorate MOFs toward substantially improved water stability and shapeability. Through simple PIM-1 decoration, the sub-5 nm polymer layers can be uniformly deposited on MOF surfaces with almost no deterioration in porosity. Owing to the existence of superhydrophobic coating and the obstruction of water entrance into MOFs, the PIM-1 coated Cu BTC exhibits impressive water resistance and excellent pore preservation ability after exposure in water, even in acidic and alkaline solutions. Moreover, polymer decoration improves the processability of MOFs, while various MOF/PIM-1 bulk wafers and oil-water separators can be obtained straightforwardly.

Regulating the dimensionality of diphosphaperylenediimide-based polymers by coordinating the out-of-plane anisotropic π-framework toward Ag^(+)

The development of hetero-π-conjugated molecules is of significance for constructing diverse assembling superstructures based on heteroatom-related bonded or nonbonded interactions.Herein,we developed one-pot P-heteroannulation via palladiumcatalyzed dual P-C bonds formation and subsequent sulfidation to construct two isomeric diphosphaperylenediimides(cis-5 and trans-5).The unique out-of-plane anisotropic π-framework induced a cumulative anisotropy with a dipole moment of up to 8.82 D for cis-5,leading to distinct supramolecular packing arrangements.Optical and electrochemical characterizations demonstrated that they showed the largest redshifts extending to 574 nm and rather low-lying LUMO levels of −4.41 eV.Furthermore,the introduced P=S moieties endowed these diphosphaperylenediimides with prominent coordination ability towards Ag^(+),and thus the first example of perylene diimide(PDI)core-involved metal-organic coordination polymers(MOCPs)with tunable dimensionality varying from 1D,2D,to 3D was tactfully achieved.In view of easy accessibility and 2D layered porous structure,thus 2D(trans-5)·(AgOTf)based MOCP showed high crystallinity and good CO_(2) adsorption capacity with surface area of 112 m^(2)/g.The result opens a span-new avenue for exploring rylene imide-based MOCPs and related properties by integrating P functionality.