Precambrian Geochronology, Chronotectonic Framework and Model of Chronocrustal Structure of the Zhongtiao Mountains

The Zhongtiao Mountains, a typical exposure area of Precambrian rocks, are a concentration area of vari-ous types of copper deposit. The rocks were dated using several dating methods. Based on the age data ob-tained by means of three methods, several aspects are dealt with: (1) the dating results obtained by differentmethods and their geological implications have been compared; (2) a chronotectonic framework has been con-structed by means of these reliable ages, which indicates that the ages of the rocks of the Proterozoic mobilebelt fall in a time span of 2400 to 2000 Ma during which global magmatic records are lacking and reflects theages of important events in the mobile belt; (3) according to the ages of inherited zircons, neodymium modelage of the depleted mantle sources (T_(DM)) and geochemical and geological data, a model of Precambrianchronocrustal structure has been constructed, representing a typical for the North China craton.

A Zinc(Ⅱ) Coordination Framework Based on Terpyridine and 5-Nitroisophthalic Acid Mixed Ligands: Synthesis, Crystal Structure and Fluorescence Property

A new coordination framework, {[Zn（L1）（5-nipc）]·H2O}n（1, L1 = 4ˊ-（4-pyridyl）-4,2ˊ：6ˊ,4ˊˊ-terpyridine, 5-nipc = 5-nitroisophthalic acid）, has been prepared under hydrothermal conditions, and determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR and powder X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a = 29.983（9）, b = 13.709（3）, c = 14.391（3）A, β = 114.93（4）°, V = 5364（2） A3, Dc = 1.493 g/cm^3, C28H19N5O7 Zn, Mr = 602.85, F（000） = 2464, μ（Mo Kα） = 0.972 mm^-1, Z = 8, R = 0.0935 and w R = 0.1509 for 4724 observed reflections（I 〉 2σ（I））. The structure of 1 exhibits a three-dimensional（3D） network with a layer-pillar structure. The fluorescence property of 1 is also investigated.

Synthesis, Crystal Structure and Gas Adsorption of a Two-fold Interpenetrated Three-dimensional Framework {[Cd(2-NO_2-BDC)(4,4？-DPA)]·(DMF)}_n

The reaction of Cd（NO_3）_2·4H_2O with 4,4？-dipyridylacetylene（4,4？-DPA） and 2-nitroterephthalic acid（2-NO_2-H_2BDC） in DMF/H_2O mixed solvent has afforded a compound {[Cd（2-NO_2-BDC）（4,4？-DPA）]·（DMF）}_n（1）. Compound 1 has been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry analysis, and IR spectrum. Compound 1 crystallizes in the monoclinic system, space group P21/n, with a = 12.1488（3）, b = 14.6689（3）, c = 13.1615（3） ？, β = 111.809（3）o, V = 2177.63（9） ？~3, Z = 4, C_（23）H_（18）N_4O_7 Cd, M_r = 574.81, D_c = 1.753 g/cm^3, μ = 8.523 mm^（-1）, F（000） = 1152, the final R = 0.0411 and wR = 0.1064 for 3589 observed reflections with I 〉 2s（I）. In compound 1, the Cd（Ⅱ） ions are linked by the carboxylate groups of 2-NO_2-BDC ligands to give a two-dimensional layered structure based on the centrosymmetric dinuclear Cd_2（COO）_2 units, which are further connected by the 4,4？-DPA ligands to produce a three-dimensional framework with pcu topology. Careful examination revealed that compound 1 is a 2-fold interpenetrating framework. Furthermore, the gas adsorption properties of 1 for N_2 and CO_2 have also been investigated.

A New 3-Fold Interpenetrating 3D Zn(Ⅱ) Metal-organic Framework: Synthesis,Structure and Luminescent Property

A new Zn（Ⅱ） coordination polymer,namely {[Zn_（1.5）（1,3,5-btc^（3-））（dtb）（H_2O）]（H_2O）_2}_n（1）（1,3,5-H_3btc = 1,3,5-benzenetricarboxylic acid,dtb = 1,3-di-（1,2,4-triazole-4-yl）benzene）,has been hydrothermally synthesized and structurally characterized. X-ray single-crystal diffraction determination reveals that 1 crystallizes in the monoclinic C2/c space group with a = 33.811（12）,b = 8.406（2）,c = 17.296（4） ？,β = 120.593（2）°,V = 4232（2） ？~3,Z = 4,Mr = 1142.88,Dc = 1.794 Mg/m^3,μ = 1.783 mm^（-1）,F（000） = 2320,the final R = 0.0338 and wR = 0.0827 for 3043 observed reflections with I 〉 2σ（I）. Compound 1 exhibits 1D Zn（Ⅱ）-carboxylate chains,which are connected into a 3D porous framework with large channels by dtb,and then three identical 3D networks are interpenetrated with each other. In addition,the luminescence property of the complex has also been investigated.

Steric Effect Modulating the Structures of Trinuclear Zinc Carboxylate Frameworks

By the reaction of different aromatic dicarboxylic acid with zinc nitrate, three metal-carboxylate frameworks, [Zn3（BDC）3（EtOH）2]（1）, [Zn3（BDC）3（py）2]·2DMF（2）, and [Zn3（NH2-BDC）3（H2O）2]·5DMF（3） which are constructed on the same linear trinuclear Zn3（RCOO）6 secondary building units, have been synthesized and characterized by X-ray diffraction analyses. Structural analyses showed that there are terephthalic acids as ligand linkers to form the hxl topological layer structures for 1 and 2. The introduction of the rigid aromatic ring pyridine in 2 as the terminal co-ligand of Zn3-SBU to instead of the flexible ethanol in 1, will form the layer-pillared supramolecular systems with 2-D crisscross channels, through its π-π stacking interactions. Owing to the steric hindrance of amino groups, 3 was assembled into a three-dimensional porous structure with pcu topology derived from the 2-amino-terephthalic acid as linkers to connect the Zn3-SBUs through a head-to-tail type.

Metal-ion Interactions with Sugars:Crystal Structure of Bis(4-dehydro-L-arabinose) Calcium Methanol Bishydrate

The crystal structure of the metal-organic frame Ca（C5H9O5）2·CH3OH·2H2O（1） has been synthesized and characterized.Complex 1 belongs to a tetragonal P43212 space group.In complex 1,the sugar moiety shows a beta-L configuration of pyranose form.The calcium（Ⅱ） is eight-coordinated,binding to four such sugar moieties,via O（1）,O（2） of two molecules and O（3）,O（4） of the other two,with the 4-hydroxy group being deprotonated.The water and methanol molecules are not coordinated to the calcium ion.

Synthesis, Structure, and Luminescent Property of a 3-D Strontium Complex [Sr_3(pda)_2(Hpda)_2(H2O)_2]_n·2nH_2O

The title complex [Sr3（pda）2（Hpda）2（H2O）2]n·2nH2O（H2pda = pyridine-2,6-dicar- boxylic acid） has been prepared under solvothermal conditions. It has been characterized by X-ray single-crystal diffraction, IR and elemental analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 10.3795（8）, b = 9.2225（7）, c = 18.5726（14） , β = 104.377（2）o, V = 1722.2（2） 3, C28H22N4O20Sr3, Mr = 997.36, Z = 2, Dc = 1.923 g/cm3, μ = 4.722 mm-1, F（000） = 984, the final R = 0.0269 and wR = 0.0538. This complex possesses a 3-D structure which is constructed from 1-D chain motifs linked by carboxylate groups. The luminescent property of the title complex has been investigated.

Synthesis and Characterization of a Water-stable Metal-organic Framework Based on Mixed Ligands

A new water-stable metal-organic framework,[Cu_2（bdc）_2（tpt）_3]·2H_2O（1,H_2 bdc = terephthalic acid,tpt = 2,4,6-tri（4-pyridinyl）-1,3,5-triazine）,has been synthesized and characterized by elemental analysis,infrared（IR） spectrum,thermogravimetric analysis（TGA）,powder X-ray diffraction（PXRD） and single-crystal X-ray diffraction. Compund 1 crystalizes in monoclinic,space group C2/c with a = 30.147（5）,b = 11.0548（17）,c = 20.867（4） ？,β = 115.035（2）o,C_（70）H_（48）Cu_2N_（18）O_（10）,Mr = 1428.34,V = 6301.0（18） ？~3,Z = 8,D_c = 1.506 g/cm^3,μ = 0.754 mm^（–1）,F（000） = 2928,GOOF = 1.058,λ（MoK α） = 0.71073 ？,the final R = 0.0387 and wR = 0.1091 for 6230 observed reflections with I 〉 2σ（I）. In compound 1,the half metallacycles [Cu_2（tpt）_3] are linked by the bdc2-ligands to form a 1D bent ladder-like chain featured with a nano-sized channel,and these chains link each other via intermolecular hydrogen bonds and π-π stacking interactions to form a 3D supramolecular architecture with the voids filled with free water molecules. In addition,the water stability of 1 was investigated by PXRD patterns,which indicate that compound 1 keeps its structural integrity in boiling water for at least three days.

Synthesis, Crystal Structure and Luminescence of a Trinuclear Magnesium Coordination Polymer Based on a Triangle Flexible Carboxylic Ligand

A novel two-dimensional metal organic coordination compound based on flexible 1,3,5-tri（4-carboxyphenoxy）benzene （HaTCPB）, {[Mgl.5（TCPB）（DMF）（H20）]＇（DMF）}n （1）, has been prepared and structurally characterized by single-crystal X-ray diffraction, TGA, and PXRD measurements. Complex 1 crystalizes in triclinic, space group Pi with a = 10.2521（6）, b = 11.0974（7）, c = 16.1113（9） A, C33H31Mg1.5N2012, Mr = 684.06, V= 1669.46（17） A3, Z = 2, Dc = 1.361 g·cm^-3, p = 0.129 mm^-1, F（000） = 714, 3.06≤0≤25°, λ（MoKa） = 0.71073 A, T= 273（2） K, the final R = 0.0386, wR = 0.0892 and S = 1.031. X-ray diffraction analysis reveals that complex 1 possesses a two-dimensional framework constructed by trinuclear Mg SBUs and three-connected TCPB3- linker. In addition, the solid state luminescent property of complex 1 was also investigated at room temperature.

Room-temperature synthesis of layered open framework cathode for sodium-ion batteries

The synthesis of active electrode materials at room temperature is one of the effective strategies to reduce the fabrication cost of sodium ion batteries(SIBs).Herein,a layered material(Na_(2)[(VO)_(2)(HPO_(4))_(2)C_(2)O_(4)]·2H_(2)O,abbreviated as NVPC followingly)with open-framework structures has been successfully prepared at room temperature under ambient conditions and is evaluated as a cathode for SIBs.It is revealed that NVPC cathode can deliver a maximum reversible capacity of ca.70 mAh/g at 10 mA/g,and exhibit superior rate capability and cycling performance:at 50 mA/g,maximum reversible capacity ca.50 m Ah/g with capacity retention of 88.4%over 250 cycles corresponds to only 0.046%capacity decay per cycle;at 100 mA/g,a maximum reversible capacity of 35 mAh/g with capacity retention of60.9%over 500 cycles.This study demonstrates a practical example of a low-cost synthesis of the cathode materials for SIBs.At the same time,the systematic electrochemical research results also show promising prospects for long lifespan low-cost SIBs.

A new breakthrough in selective catalysis: metal-organic framework nanocomposites with sandwich structure

Selective hydrogenation of C=O group that is conjugated with a C=C group in a,b-unsaturated aldehydes(R–CH=CH–CHO)is one of important reactions in industry due to the resulting product unsaturated alcohols(R–CH=CH–CH2OH)with broad applications in synthesis of fine chemicals such as flavour,fragrance,pharmaceuticals[1].However,despite the increasing reported catalysts on the selectivity[2,3],developing an effective

Metal-organic framework-derived porous shuttle-like vanadium oxides for sodium-ion battery application

Vanadium oxides with a layered structure are promising candidates for both lithium-ion batteries and sodium-ion batteries （SIBs）. The self-template approach, which involves a transformation from metal-organic frameworks （MOFs） into porous metal oxides, is a novel and effective way to achieve desirable electrochemical performance. In this stud~ porous shuttle-like vanadium oxides （i.e., V205, V203/C） were successfully prepared by using MIL-88B （V） as precursors with a specific calcination process. As a proof-of-concept application, the as- prepared porous shuttle-like VaOdC was used as an anode material for SIBs. The porous shuttle-like V203/C, which had an inherent layered structure with metallic behavior, exhibited excellent electrochemical properties. Remarkable rate capacities of 417, 247, 202, 176, 164, and 149 mAh.g-1 were achieved at current densities of 50, 100, 200, 500, 1,000, and 2,000 mA.g-1, respectively. Under cycling at 2 A.g-1, the specific discharge capacity reached 181 mAh.g-1, with a low capacity fading rate of 0.032% per cycle after 1,000 cycles. Density functional theory calculation results indicated that Na ions preferred to occupy the interlamination rather than the inside of each layer in the V203. Interestingly, the special layered structure with a skeleton of dumbbell-like V-V bonds and metallic behavior was maintained after the insertion of Na ions, which was beneficial for the cycle performance. We consider that the MOF precursor of MIL-88B （V） can be used to synthesize other porous V-based materials for various applications.

A two-dimensional microporous metal–organic framework for highly selective adsorption of carbon dioxide and acetylene

Solvothermal reaction of 3-aminoisonicotinic acid（Haina） and Cu（NO_3）_2·2.5H_2O gave a novel twodimensional（2D） microporous metal–organic framework, [Cu（aina）_2（DMF）]·DMF（1, DMF = N,N-dimethylformamide）. Single-crystal X-ray crystallographic study of compound 1 revealed that Cu（II）ions are linked by ainaàligands forming square grid-like layers, which stack together via multiple hydrogen bonding interactions. The solvent-free framework of 1a displayed considerable porosity（void = 46.5%） with one-dimensional（1D） open channels（4.7 ？ ？ 4.8 ？） functionalized by amino groups.Gas sorption measurements of 1 revealed selective carbon dioxide（CO_2） and acetylene（C_2H_2） adsorption over methane（CH_4） and nitrogen（N_2） at ambient temperature.

Prussian-blue materials:Revealing new opportunities for rechargeable batteries

The demand to increase energy density of rechargeable batteries for portable electronic devices and electric vehicles and to reduce the cost for grid-scale energy storage necessitates the exploration of new chemistries of electrode materials for rechargeable batteries.The open framework-structure of Prussian-blue materials has recently been demonstrated as a promising cathode host for a variety of monovalent and multivalent cations with the tunable working voltage and discharge capacities.Recent progress toward the application of Prussian-blue cathode materials for rechargeable batteries is reviewed,with special emphasis on charge-storage mechanisms of different insertion species,factors influencing electrochemical performances,and possible approaches to overcome their intrinsic limitations.

Rechargeable solid-state Li-air batteries： a status report

The theoretical specific energy of lithium-air battery is as high as 3436 Wh.kg^-1, and the possible achieved value may reach 600-700 Wh.kg^-l, which enables this energy storage system as an important propulsion power sources for electric vehicles with the driving range of 500-800 km. Currently, Li-air batteries are facing main challenges at stability, efficiency, applicability and safety. In particular, from a practical view of point, the Li-air batteries should be operated directly in ambient air. Solid-state battery system is the best avenue to eventually solve these main issues. At the heart of the solid state, Li-air technology is the solid-state Li^＋-conducting ceramic material. Developing solid-state lithium-air batteries （SSLAB） can solve the problem of applicability fundamentally and circumvent the safety issues completely, and it is also an important avenue to improve the stability of the battery system. In this paper, we provide a systematical review of the progress in the cell construction, the regulation of the electrode/electrolyte interface, the cell assembly, the electrochemical performance and the mechanism for the SSLAB. In every section, the contributions of the recent research progress in the main challenges and the remained questions will be commented. Based on these reviews, we attempt to propose some alternative approaches for the next stage and suggest a development prospective for the SSLAB.