New Inorganic-organic Hybrid Compound Containing One Dimensional Keggin Polyoxometalate [SiW_(11)O_(39)Co]^(6-) Chains: Preparation, Characterization and Application in Chemically Bulk-modified Electrode

A new inorganic-organic hybrid compound based on polyoxometalate and organic ligand formulated as （H2bpp）3[SiWlIO39Co]-2H20（1）[bpp=l,3-bis（4-pyridyl）propane] was hydrothermally synthesized and structurally characterized by elemental analysis, single-crystal X-ray diffraction, IR, TG, and cyclic voltammetry. Single-crystal X-ray diffraction analysis reveals that compound 1 consists of interesting cobalt-monosubstituted POMs one dimensional chain together with protonated bpp ligands. Additionally, the polyoxoanions combined with the discrete organic substrates by hydrogen bond interactions to afford a supramolecular 3D network structure. The hybrid compound 1 was used as a bulk modifier to fabricate a three-dimensional chemically modified carbon paste electrode（1-CPE） by direct mixing. The electrochemical behavior and electrocatalysis of 1-CPE were studied in detail. The results indicate that 1-CPE has good electrocatalytic activities toward the reduction of nitrite or bromate in 1 mol/L 1-12SO4 aqueous solution. 1-CPE shows remarkable stability that can be ascribed to the insolubility of compound 1 and the supramolecular interactions existed between 1D POM anion chains and organic ligand bpp, which is very important for practical applications in electrode modification.

Synthesis and Characterization of Two New Photochromic Inorganic-organic Hybrid Materials Based on Keggin-type Polyoxometalates

Two new photochromic inorganic-organic hybrid materials formed from Keggin-type polyoxometalates（POMs） and metronidazole （C6H9N3O3, MNZ）, formulated as H3PMo12OaO-3MNZ·3H2O （1） and H3PW12O40.3MNZ·3H2O（2）, were synthesized and characterized by elemental analysis, IR spectra, electronic spectra, electron spin resonance （ESR） spectra and thermogravi-metry-differential thermal analysis （TG-DTA）. Reflectance spectra show the presence of weak intermolecular charge transfer between the organic and inorganic moieties in the solid state. The photochromic properties were studied by solid diffuse reflectance spectra and ESR spectra, and the photochromic reactions were found to exhibit first-order kinetics. TG-DTA showed that two hybrid materials have similar thermal behavior.

Recent progress of hybrid cathode interface layer for organic solar cells

Organic solar cells(OSCs)have gained conspicuous progress during the past few decades due to the development of materials and upgrading of the device structure.The power conversion efficiency(PCE)of the single-junction device had surpassed 19%.The cathode interface layer(CIL),by optimizing the connection between the active layer and the cathode electrode,has become a momentous part to strengthen the performances of the OSCs.Simultaneously,CIL is also indispensable to illustrating the working mechanism of OSCs and enhancing the stability of the OSCs.In this essay,hybrid CILs in OSCs have been summarized.Firstly,the advancement and operating mechanism of OSCs,and the effects and relevant design rules of CIL are briefly concluded;secondly,the significant influence of CIL on enhancing the stability and PCE of OSCs is presented;thirdly,the characteristics of organic hybrid CIL and organic-inorganic hybrid CIL are introduced.Finally,the conclusion and outlook of CIL are summarized.

Construction of all-organic low dielectric polyimide hybrids via synergistic effect between covalent organic framework and cross-linking structure

Polyimide(PI)is a promising electronic packaging material,but it remains challenging to obtain an all-organic PI hybrid film with decreased dielectric constant and loss without modifying the monomer.Herein,a series of allorganic PI hybrid films were successfully prepared by introducing the covalent organic framework(COF),which could induce the formation of the cross-linking structure in the PI matrix.Due to the synergistic effects of the COF fillers and the cross-linking structure,the PI/COF hybrid film containing 2 wt%COF exhibited the lowest dielectric constant of 2.72 and the lowest dielectric loss(tanδ)of 0.0077 at 1 MHz.It is attributed to the intrinsic low dielectric constant of COF and a large number of mesopores within the PI.Besides,the cross-linking network of PI prevents the molecular chains from stacking and improves the fraction of free volume(FFV).The molecular dynamics simulation results are well consistent with the dielectric properties data.Furthermore,the PI/COF hybrid film with 5 wt%COF showed a significant enhancement in breakdown strength,which increased to 412.8 kV/mm as compared with pure PI.In addition,the PI/COF hybrid film achieve to reduce the dielectric constant and thermal expansion coefficient(CTE).It also exhibited excellent thermal,hydrophobicity,and mechanical performance.The all-organic PI/COF hybrid films have great commercial potential as next-generation electronic packaging materials.

A NOVEL SECOND-ORDER TRANSITION IN ORGANIC HYBRIDS CONSISTING OF POLYMERS AND SMALL MOLECULES

A novel transition appeared above thc glass transition temperature of chlorinated polyethylene (CPE) for binaryblends of CPE and additives such as organic small molecules or oligomers. This transition was assigned to the dissociation ofintermolecular hydrogen bonds between the polymer ard additive within the edditive rich phase. Of particular interest is thata novel pyramid crystal was observed in the annealed CPE/hindered phenol blends. Another intriguing observation is thatthese polymer/small molecule blends organized by intermolecular hydrogen bonding have several potential properties, suchas shape-memorization, self-restoration, self-adhesiveness and super damping.

A new strategy for the fabrication of covalent organic framework‐metal‐organic framework hybrids via in‐situ functionalization of ligands for improved hydrogen evolution reaction activity

The development of novel porous materials have attracted significant attention owing to its possible application in several fields.In this study,we designed a novel covalent organic framework‐metal‐organic framework(COF‐MOF)material through an in‐situ ligand self‐assembly method.The in‐situ modified ligands not only act as nucleation sites to form Ti‐MOF,but also as a channel to rapidly transfer photogenerated electrons without introducing additional chemical bonds.The photocatalytic hydrogen production rate achieved over B‐CTF‐Ti‐MOF(1:1)was 1975μmol·g^(–1)·h^(–1) with an apparent quantum efficiency of 4.76%,which is 11.8 times higher than that of the pure CTF‐1.In addition,compared with the sample prepared by separating the ligands(CTF‐1/Ti‐MOF),B‐CTF‐Ti‐MOF shows excellent activity and stability.Finally,a reasonable photocatalytic mechanism was proposed using the results of electrochemical tests and spectral analyses.This study provides a universal method for the construction of highly efficient and stable COF/MOF materials with excellent properties.

Syntheses and Characterizations of Two New Organic-inorganic Hybrids Based on Heteropolymolybdates and Piperidine Molecules

Two new organic-inorganic compounds [（CH2）5NH2]3[PMo12O40]·3[（CH2）NH] 1 and [（CH2）5NH2]6[P2Mo18O62]·5H2O 2 have been synthesized using conventional and hydrothermal methods, respectively, and characterized by elemental analyses, IR, TG and single-crystal X-ray diffraction. X-ray analyses show that in these compounds heteropolymolybdates [PMo12O40]^3- and [P2Mo18O62]^6- are reserved their Keggin or Dawson structures and linked to piperidine through electrostatic and hydrogen-bonding interactions.

Organic-inorganic Hybrids Towards the Preparation of Nanoporous Composite Thin Films for Microelectronic Application

Silicon containing materials have traditionally been used in microelectronic fabrication. Semiconductor devices often have one or more arrays of patterned interconnect levels that serve to electrically couple the individual circuit elements forming an integrated circuit. These interconnect levels are typically separated by an insulating or dielectric film. Previously, a silicon oxide film was the most commonly used material for such dielectric films having dielectric constants( k ) near 4 0. However, as the feature size is continuously scaling down, the relatively high k of such silicon oxide films became inadequate to provide efficient electrical insulation. As such, there has been an increasing market demand for materials with even lower dielectric constant for Interlayer Dielectric(ILD) applications, yet retaining thermal and mechanical integrity. We wish to report here our investigations on the preparation of ultra low k ILD materials using a sacrificial approach whereby organic groups are burnt out to generate low k porous ORMOSIL films. We have been able to prepare a variety of organically modified silicone resins leading to highly microporous thin films, exhibiting ultra low k from 1 80 to 2 87, and good to high modulus, 1 5 to 5 5 GPa. Structure property influences on porosity, dielectric constant and modulus will be discussed.

Preparation of polythiophene/WO_3 organic-inorganic hybrids and their gas sensing properties for NO_2 detection at low temperature

Polythiophene/WO3（PTP/WO3）organic-inorganic hybrids were synthesized by an in situ chemical oxidative polymerization method,and char- acterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM）and thermo-gravimetric analysis（TGA）.The Polythiophene/ WO3 hybrids have higher thermal stability than pure polythiophene,which is beneficial to potential application as chemical sensors.Gas sensing measurements demonstrate that the gas sensor based on the Polythiophene/WO3 hybrids has high response and good selectivity for de- tecting NO2 of ppm level at low temperature.Both the operating temperature and PTP contents have an influence on the response of PTP/WO3 hybrids to NO2.The 10 wt%PTP/WO3 hybrid showed the highest response at low operating temperature of 70-C.It is expected that the PTP/WO3 hybrids can be potentially used as gas sensor material for detecting the low concentration of NO2 at low temperature.

Synthesis and Characterization of Layered Perovskite-type Organic-inorganic Hybrids(CnH2n+1NH3)2(CH3NH3)m-1PbmI3m+1(n=5-10,m=1,2)

Layered organic-inorganic hybrids（CnH2n＋1NH3）2（CH3NH3）m-1PbmI3m＋1 containing monolayer（m=1） and bilayer（m=2） perovsikte were synthesized by reactions in solution.The influences of the reactant ratio,solvent,reaction temperature,and reaction time on the structures of the products were investigated.The structures and the properties of the hybrids were characterized using X-ray diffraction（XRD）,scanning electron microscopy（SEM）,and ultraviolet and visible（UV） absorption spectroscopy.The XRD patterns and the SEM images demonstrate that the pure bilayer perovskite hybrids are obtained.The UV-vis spectra indicate that the number of the inorganic perovskite layer（m） has greater impact on the band gap than the number of the carbon atoms（n）.The band gap of bilayer hybrids（around 1.9 eV） is significantly less than that of monolayer hybrids（around 2.2 eV）.

Synthesis and Characterization of Layered Perovskite-type Organic-inorganic Hybrids (R-NH_3)_2(CH_3NH_3)Pb_2I_7

Layered organic-inorganic hybrids containing bilayer perovsikte （R-NH3）2（CH3NH3）Pb2I7 （where R=C12H25,C6H5C2H4） were synthesized by reactions in solution. The influences of the solvents and the reactant ratio on the structures of the products were investigated. The structures and the properties of the hybrids were characterized using X-ray diffraction （XRD） and ultraviolet and visible （UV） adsorption spectra. For comparing with the bilayer perovskite hybrids in structure and band gap magnitude, the hybrids containing monolayer perovskite （R-NH3）2PbI4 were also synthesized and characterized. The results demonstrate that the thickness of inorganic layer has obvious effect on the tunneling magnitude of the band gap but the organic part can be micro actuator of band gap.

Hybridization of metal–organic framework and monodisperse spherical silica for chromatographic separation of xylene isomers

Metal–organic frameworks(MOFs) packed in the column have been a promising candidate as the stationary phase for high performance liquid chromatography(HPLC). However, the direct packing of irregular MOF powder could raise some problems like high back pressure and low column efficiency in the HPLC separation. In this work, UiO-66 capable of separating xylenes was supported effectively on the surface of the monodisperse spherical silica microspheres by one-pot method. The hybridization of Ui O-66 and silica microspheres(termed UiO-66@SiO2 shell–core composite) was prepared by stirring the suspension of the precursors of Ui O-66 and\\COOH terminated silica in the N,N-dimethylformamide with heating. The shell–core composite material UiO66@SiO2 was characterized by SEM, TEM, PXRD and FTIR. Then, it was used as a packing material for the chromatographic separation of xylene isomers. Xylene isomers including o-xylene, m-xylene and p-xylene were efficiently separated on the column with high resolution and good reproducibility. Moreover, the Ui O-66@SiO2 shell–core composites packed column still remained reverse shape selectivity as Ui O-66 possessed, and the retention of xylenes was probably ascribed to the hydrophobic effect between analytes and the aromatic rings of the Ui O-66 shell. The Ui O-66@SiO2 shell–core composites obtained in this study have some potential for the separation of structural isomers in HPLC.

Ultrathin 2D Metal–Organic Framework Nanosheets In situ Interpenetrated by Functional CNTs for Hybrid Energy Storage Device

The controllable construction of two-dimensional(2D)metal–organic framework(MOF)nanosheets with favorable electrochemical performances is greatly challenging for energy storage.Here,we design an in situ induced growth strategy to construct the ultrathin carboxylated carbon nanotubes(C-CNTs)interpenetrated nickel MOF(Ni-MOF/C-CNTs)nanosheets.The deliberate thickness and specific surface area of novel 2D hybrid nanosheets can be effectively tuned via finely controlling C-CNTs involvement.Due to the unique microstructure,the integrated 2D hybrid nanosheets are endowed with plentiful electroactive sites to promote the electrochemical performances greatly.The prepared Ni-MOF/C-CNTs nanosheets exhibit superior specific capacity of 680 C g^−1 at 1 A g^−1 and good capacity retention.The assembled hybrid device demonstrated the maximum energy density of 44.4 Wh kg^−1 at a power density of 440 W kg^−1.Our novel strategy to construct ultrathin 2D MOF with unique properties can be extended to synthesize various MOF-based functional materials for diverse applications.

An Explosive Organic/Inorganic Hybrid: Synthesis and Thermal Property of Octa(2,4-dinitrophenyl)silsesquioxane

Octaphenylsilsesquioxane(OPhS) was prepared by a modifying method and a new core-shell nanocomposite, octa(2,4-dinitrophenyl)silsesquioxane, [(R_2PhSiO_ 1.5)_8, R=—NO_2, ODNPhS], was synthesized by nitration of OPhS in a mixed acid solution of nitric and sulfuric acids at about 60 ℃. Their molecular structures were determined by DRIFTS, 1H NMR, 13C NMR spectra analysis. The thermal analysis shows that ODNPhS is an explosive that detonates at about 420 ℃.

Very-High Color Rendering Index Hybrid White Organic Light-Emitting Diodes with Double Emitting Nanolayers

A very-high color rendering index white organic light-emitting diode(WOLED) based on a simple structure was successfully fabricated. The optimized device exhibits a maximum total efficiency of 13.1 and 5.4 lm/W at 1,000 cd/m2. A peak color rendering index of 90 and a relatively stable color during a wide range of luminance were obtained. In addition, it was demonstrated that the 4,40,400-tri(9-carbazoyl) triphenylamine host influenced strongly the performance of this WOLED.These results may be beneficial to the design of both material and device architecture for high-performance WOLED.

Preparation and Conducting Behavior of Amphibious Organic/Inorganic Hybrid Proton Exchange Membranes Based on Benzyltetrazole

A series of novel amphibious organic/inorganic hybrid proton exchange membranes with H3PO4 doped which could be used under both wet and dry conditions was prepared through a sol-gel process based on acrylated triethoxysilane（A-TES） and benzyltetrazole-modified triethoxysilane（BT-TES）.The dual-curing approach including UV-curing and thermal curing was used to obtain the crosslinked membranes.Polyethylene glycol（400） diacrylate（PEGDA） was used as an oligomer to form the polymeric matrix.The molecular structures of precursors were characterized by 1 H,13 C and 29 Si NMR spectra.The thermogravimetric analysis（TGA） results show that the membranes exhibit acceptable thermal stability for their application at above 200 oC.The differential scanning calorimeter（DSC） determination indicates that the crosslinked membranes with the mass ratios of below 1.6 of BT-TES to A-TES and the same mass of H3PO4 doped as that of A-TES possess the-T g s,and the lowest T g（-28.9 ℃） exists for the membrane with double mass of H3PO4 doped as well.The high proton conductivity in a range of 9.4―17.3 mS/cm with the corresponding water uptake of 19.1%―32.8% of the membranes was detected at 90 oC under wet conditions.Meanwhile,the proton conductivity in a dry environment for the membrane with a mass ratio of 2.4 of BT-TES to A-TES and double H3PO4 loading increases from 4.89×10-2 mS/cm at 30 ℃ to 25.7 mS/cm at 140 ℃.The excellent proton transport ability under both hydrous and anhydrous conditions demonstrates a potential application in the polymer electrolyte membrane fuel cells.

An ionic 2D inorganic-organic hybrid of tris[((1H-tetrazol-5-yl)methyl)morpholine] dodecatungstophosphate(Ⅴ) pentahydrate:Synthesis X-ray crystal structure and spectroscopic characterizations

A unique ionic hybrid material[C_6H_(12)N_5O]_3[(PO_4)W__(12)O_(36)]·5H_2O has been synthesized from the reaction of((1H-tetrazole-5- yl)methyl)morpholine andα-H_3[(PO_4)W_(12)O_(36)]·21H_2O.It has successfully been characterized by elemental analysis,IR and ~1H NMR spectroscopies,TGA and single-crystal X-ray diffraction method.The title compound is constructed from the three [C_6H_(12)N_5O]^+ cations andα-Keggin[(PO_4)W_(12)O_(36)]^(3-) polyoxoanion.The most remarkable structural feature of this hybrid can...

Pyridinic nitrogen enriched porous carbon derived from bimetal organic frameworks for high capacity zinc ion hybrid capacitors with remarkable rate capability

Aqueous zinc ion hybrid capacitors(ZIHCs)hold great potential for large-scale energy storage applications owing to their high safety and low cost,but suffer from low capacity and energy density.Herein,pyridinic nitrogen enriched porous carbon(nPC)was successfully synthesized via the growth,subsequent annealing and acid etching of bimetal organic frameworks for high capacity and safe ZIHCs with exceptional rate capability.Benefiting from the mesopores for easy ion diffusion,high electrical conductivity enabled by in-situ grown carbon nanotubes matrix and residual metal Co nanoparticles for fast electron transfer,sufficient micropores and high N content(8.9 at%)with dominated pyridinic N(54%)for enhanced zinc ion storage,the resulting nPC cathodes for ZIHCs achieved high capacities of 302 and137 m Ah g^(-1) at 1 and 18 A g^(-1),outperforming most reported carbon based cathodes.Theoretical results further disclosed that pyridinic N possessed larger binding energy of-4.99 eV to chemically coordinate with Zn2+than other N species.Moreover,quasi-solid-state ZIHCs with gelatin based gel electrolytes exhibited high energy density of 157.6 Wh kg^(-1) at 0.69 kW kg^(-1),high safety and mechanical flexibility to withstand mechanical deformation and drilling.This strategy of developing pyridinic nitrogen enriched porous carbon will pave a new avenue to construct safe ZIHCs with high energy densities.

Hybrid Self-Assembled Multilayer Films Formed by Alternating Layers of Keggin Polyoxometalates and 1,10DAD

Hybrid self-assembled multilayer films were prepared by alternate adsorption of 1,10-diaminodecane (1,10-DAD) and Keggin polyoxometalates of SiW12O404-, SiW11VO405-, and PMo12O403-, respectively. The films were reproducibly grown at each adsorption cycle as monitored by UV spectroscopy.

Supramolecular Structural Inorganic-organic Hybrid[(4-Bromoanilimiun)([18]crown-6)]3[PMo(12)O(40)]·CH3CN

A novel supramolecular structural inorganic-organic hybrid [（4-bromoanilimiun）（[18]crown-6）]3[PMo（12）O40]·CH3 CN has been synthesized through standard solvent evaporated method. The structure of the title compound was determined through single-crystal X-ray diffraction analysis. It crystallizes in monoclinic system with P21/n space group. The crystal data are a = 18.9529（4）, b = 26.4444（5）, c = 19.0985（4） A, β = 90.132（6）o, V = 9572.1（3） A^3, Z = 4, Dc= 2.203 g·cm^（–1）, μ = 14.956 mm^（–1）, F（000） = 6192, S = 1.098, the final R = 0.0859 and w R（I 〉 2σ（I）） = 0.2100. Supramolecular cations are constructed through strong N–H…O hydrogen bonding interaction between the six oxygen atoms of [18]crown-6 molecule and nitrogen atom of（4-bromoanilimiun） cation. Three kinds of different arranged supramolecular cations exist in the title compound, which are filled into the large space formed by [PMo（12）O40] polyoxoanions. Thermogravimentic differential thermal analysis revealed that hydrogen bonding interaction and intermolecular interaction play an important role in maintaining the stability of the title compound.