In Situ Formed Tribofilms as Efficient Organic/Inorganic Hybrid Interlayers for Stabilizing Lithium Metal Anodes

The practical application of Li metal anodes(LMAs)is limited by uncontrolled dendrite growth and side reactions.Herein,we propose a new friction-induced strategy to produce high-performance thin Li anode(Li@CFO).By virtue of the in situ friction reaction between fluoropolymer grease and Li strips during rolling,a robust organic/inorganic hybrid interlayer(lithiophilic LiF/LiC_(6)framework hybridized-CF_(2)-O-CF_(2)-chains)was formed atop Li metal.The derived interface contributes to reversible Li plating/stripping behaviors by mitigating side reactions and decreasing the solvation degree at the interface.The Li@CFO||Li@CFO symmetrical cell exhibits a remarkable lifespan for 5,600 h(1.0 mA cm^(-2)and 1.0 mAh cm^(-2))and 1,350 cycles even at a harsh condition(18.0 mA cm^(-2)and 3.0 mAh cm^(-2)).When paired with high-loading LiFePO4 cathodes,the full cell lasts over 450 cycles at 1C with a high-capacity retention of 99.9%.This work provides a new friction-induced strategy for producing high-performance thin LMAs.

Effect of Bio-Based Organic‒Inorganic Hybrid Hydrogels on Fire Prevention of Spontaneous Combustion of Coals

To solve the fire accidents caused by coal combustion,this work prepared four hybrid hydrogel materials using bio-based polymers,flame retardants,and inorganic materials.Compared to pure water and 3.5 wt%MgCl_(2)solution,the as-prepared hydrogel presents good fire prevention performance.In addition,it is found that CO and CO_(2)are not produced by coal when the pyrolysis temperature is lower than 200℃.During low-temperature pyrolysis,CO is more likely to be produced than CO_(2),indicating inadequate pyrolysis behavior.At the same time,the addition of fire-preventing hydrogel can not only decrease the maximum CO_(2)concentration before the critical temperature but also prolong the corresponding time.In addition,based on the cone calorimeter test,the inhibition effects of pure water,magnesium chloride solution,and four hybrid hydrogels on heat release behavior are evaluated.It is demonstrated that different dosages of different hydrogels affected the fire prevention effect.Phosphorous-modified cellulose/silica and carrageenan/DMMP/vermiculite composite hydrogels have the weakest fire prevention effect at 20 g,which is weaker than that of water.However,the fire prevention effect of carrageenan/DMMP/vermiculite composite hydrogels exceeded that of water at 40 and 60 g.Additionally,the fire prevention effect of the sodium alginate/sepiolite/ammonium polyphosphate composite hydrogel is most significant in common tests,attributed to the intumescent flame retardant system.

A New Bismuth(Ⅲ) Iodide Inorganic/organic Hybrid Solid Containing Large Heterocyclic Conjugated Organic Ligand: Synthesis, Properties and Calculations

A new bismuth（III） iodide inorganic/organic hybrid containing larger heterocyclic conjugated organic ligand, [（dppz）2Bi2I6]·2DMF （1） （dppz = dipyrido[3,2-a：2＇,3＇-c]phenazine）, has been synthesized by solution process and structurally determined by X-ray diffraction method. 1 crystallizes in triclinic, space group Pī with Mr= 1844.08, α = 9.215（5）, b = 11.488（6）, c = 12.424（9） ？, α = 106.66（2）, β = 90.84（2）, γ = 92.34（2）°, V = 1258.5（13） ？3, Z = 1, Dc = 2.433 g/cm3, F（000） = 830, μ（MoKα） = 10.702 mm–1, the final R = 0.0834 and wR = 0.1947 for 2749 observed reflections with I 〉 2σ（I）. 1 consists of a dimeric structure [（dppz）2Bi2I6], in which two [（dppz）BiI3] fragments are bridged by a pair of iodine atoms. Hydrogen bonds and π···π stacking interactions contribute to the structural extension and stabilization. Experimental band gap of about 2.13 eV indicates its semiconductor nature. The optical absorption spectrum and electronic structure were also discussed.

A New Method to Study the Sol-gel Transition Process of Organic/Inorganic Hybrid Materials

The sol-gel transition process of PMMA/SiO2 hybrid materials was first studied by means of the dynamic torsional vibration method. The different stages of the transition can be described by the change of torque. The temperature-dependent measurement of the gel time（ tg ） gives the possibility to determine the apparent activation energy.（ Ea ） of this transition according to Flory＇s gelation theory. The non-equilibrium thermodynamic fluctuation theory was used to predict the transition behavior. The isothermal transition experiments on hybrid sols with different TEOS（tetraethyl orthosilicate） contents were carried out. The results show that the Ea of a hybrid sol is higher than that of a non- hybrid sol of a TEOS-water-ethanol system. The increasing of TEOS content in a hybrid sol has no obvious effect on the Ea value, but it can enhance the sol-gel .reaction rate.

SYNTHESIS AND CHARACTERIZATION OF NOVEL SOL-GEL DOPED ORGANIC/INORGANIC HYBRID NONLINEAR OPTICAL MATERIALS

hydroxy-4-nitro azobenzene (NHA) and 4-amino-4-nitro azobenzene (DO3) were prepared respectively from p-nitrophenylamine as a precursor compound. Two kinds of doped organic/inorganic hybrid nonlinear optical (NLO) materials containing NHA and DO3 were synthesized by Sol-Gel process. The preparation and properties of two NLO materials were studied and characterized by FTIR, 1H-NMR, UV-VIS, SEM, DSC and SHG measurements. The results show that the maximum doping amounts of NHA and DO3 in two doped hybrid NLO materials are 7.2(wt)% and 11.3(wt)% respectively, and the corresponding second-order NLO coefficients (d33 values) are 2.91×10 8esu and 6.14×10 8esu. Two doped NLO materials have relatively good RT stability, after 90 days at RT the d33 values can maintain about 85% of their initial values, but after 10h at 100℃ can only maintain about 50% of their initial values. In this report, the reasons for high-temperature instability of doped materials were discussed, and the possible improvements were also suggested.

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 ℃.

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.

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.

SYNTHESIS AND BIOTECHNOLOGICAL APPLICATIONS OF VINYL POLYMERINORGANIC HYBRID AND MESOPOROUS MATERIALS

We describe the sol-gel synthesis of a new family of organic-inorganic hybrid materials, in which various vinyl polymers are covalently bonded to and uniformly distributed in inorganic oxide matrices. The materials can be tailored to have both good toughness and hardness while maintaining excellent optical transparency. Doping the sol-gel metal oxides with optically active compounds such as D-glucose results in new optical rotatory composite materials. Removal of the dopant compounds from the composites affords mesoporous oxide materials; which represents a new, nonsurfactant-templated route to mesoporous molecular sieves. We have successfully immobilized a series of enzymes and other bioactive agents in mesoporous materials. Catalytical activities of the enzyme encapsulated in mesoporous materials were found to be much higher than those encapsulated in microporous materials.

A Novel Inorganic-organic Hybrid Borate with Unique One-dimensional Infinite Aluminium-oxygen Chains

A novel inorganic-organic hybrid borate,[Al2（fum）（H3BO3）（OH） 4]n·n（H3BO3） （1,H2fum = fumaric acid） ,has been synthesized and characterized by single-crystal X-ray diffraction,FTIR and elemental analysis. Crystal data for compound 1： orthorhombic,space group Pnma,a = 14.108（3） ,b = 6.9412（14） ,c = 14.995（3）A,V = 1468.3（5）A^3,Z = 4,Mr = 359.72,Dc = 1.627 g/cm^3,μ = 0.254 mm^-1,F（000） = 736,the final R = 0.0492 and wR = 0.1650 with I 〉 2σ（I） . In compound 1,each Al^Ⅲ ion is coordinated by six oxygen atoms to adopt a distorted octahedral geometry. Both fumarate anion and the coordinated boric acid act as bidentate bridging ligands to link two neighboring Al^Ⅲ centers simultaneously. Each Al^Ⅲ ion is bridged by two μ2-hydroxyl ligands to construct an infinite wave-like [Al2（fum）（H3BO3）（OH） 4]n chain. These one-dimensional chains form hydrogen bonds with free boric acid molecules giving rise to a three-dimensional supramolecular network.

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.

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...

Synthesis and characterization of luminescent organic-inorganic hybrid nanocomposite from polyhedral oligomeric silsesquioxane

A novel polyhedral oligomeric silsesquioxane(POSS)-based organic-inorganic hybrid nanocomposite(EF-POSS) was prepared by Pt-catalyzed hydrosilylation reaction of octahydridosilsesquioxane(T_8H_8,POSS) with a luminescent substituted acetylene(2- ethynyl-7-(4-(4-methylstyryl)styryl)-9,9-dioctyl-9H-fluorene(EF)) in high yield.The hybrid nanocomposite was soluble in common solvents such as CH_2Cl_2,CHCl_3,THF and 1,4-dioxane.Its structure and property were characterized by FTIR, NMR,TGA,UV and PL,respectively.The results show that the hybrid nanocomposite with high thermal stability emits stable blue light as a result of photo excitation and possesses high photoluminescence quantum efficiency(φ_(FL)).

An Organic-inorganic Hybrid Assembly Based on Novel Arsenatomolybdate and Cu~Ⅰ-Organic Units

A novel organic-inorganic hybrid arsenatomolybdate based on infrequent[AsMoO(OH)]unit,[Cu ~I(phen)][AsMoO(OH)]·3HO(1,phen=1,10-phenanthroline),has been hydrothermally synthe-sized.This structure was determined by single-crystal X-ray diffraction analysis,and further characterized by elemental analysis,and IR and UV spectra.To the best of our knowledge,it is the first report of a novel arsenatomolybdate subunit[AsMoO(OH)].Photoluminescence of 1 is ascribed to???*emission of the aromatic rings derived from the phen ligand.

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.

Hydrothermal Synthesis and Crystal Structure of Inorganic-organic Hybrid Compound [H_3NC_2H_4NH_2]VOPO_4

An inorganic-organic hybrid compound, [H_3NC_2H_4NH_2]VOPO_4 was synthesized by means of the hydrothermal method. It was crystallized in a monoclinic system, a space group P2_1/c, with the crystal cell parameters: a=0.92285(11) nm, b=0.72994(9) nm, c=0.98495(11) nm, β=101.280(3)°, V=0.65067(13) nm^3, M_r=223.02 g/mol, D_c=2.277 g/cm^3, Z=4, R=0.0315, ωR=0.0865, GOF=1.085. The VO_5N octahedra chains are corner-linked by PO_4 tetrahedra; the VO_5N octahedra are all trans-linked with V—O bonds being alternately short and long. The monoprotonated ethylenediamine was intercalated between the layers with one end coordinating to V and the other end as an H-bond donor interacting with a terminal O atom of PO_4 from a neighboring sheet. The elementary analysis, infrared spectrum characters and thermal stability were also given.

A New Inorganic-organic Hybrid Based on Biisoquinoline and Hexachloridostannate:Structure, Photoluminescence, Electrochemical Behavior and Theoretical Study

A new inorganic-organic hybrid constructed from biisoquinoline dication and tin halide, [（BIQBT）（Sn Cl6）]n（1, BIQBT = 1,4-bis（isoquinoline） butane）, has been synthesized and structurally determined by X-ray diffraction method. 1 crystallizes in the monoclinic system, space group Cc with Mr = 644.82, a = 16.589（3）, b = 18.388（4）, c = 8.5532（17）A, β = 108.75（3）°, V = 2470.6（9） A3, Z = 4, Dc = 1.736 g/cm^3, F（000） = 1281, μ（Mo Kα） = 1.697 mm^–1, the final R = 0.0197 and wR = 0.0493 for 4614 observed reflections with I 〉 2（I）. 1 consists of BIQBT^2＋dications and mononuclear hexachloridostannate Sn Cl62- anion, and hydrogen bonds among them contribute to the formation of a 1-D chain. Strong fluorescence can be detected in 1, which was explained by theoretical calculation. Its electrochemical behavior was investigated, and the theoretical calculations reveal that the π···π stacking interaction is dominated for their structural stabilization.

Recent advances in atomic imaging of organic-inorganic hybrid perovskites

Three-dimensional organic-inorganic hybrid perovskites(OHPs)hold a great prospect for photovoltaic applications due to their outstanding electronic and optical properties.These fascinating properties of OHPs in combination with their scalable and low-cost production make OHPs promising candidates for next-generation optoelectronic devices.The ability to obtain atomistic insights into physicochemical properties of this class of materials is crucial for the future development of this field.Recent advances in various scanning probe microscopy techniques have demonstrated their extraordinary capability in real-space imaging and spectroscopic measurements of the structural and electronic properties of OHPs with atomic-precision.Moreover,these techniques can be combined with light illumination to probe the structural and optoelectronic properties of OHPs close to the real device operation conditions.The primary focus of this review is to summarize the recent progress in atomic-scale studies of OHPs towards a deep understanding of the phenomena discovered in OHPs and OHP-based optoelectronic devices.

Characterization of structural transitions and lattice dynamics of hybrid organic–inorganic perovskite CH3NH3PbI3

By combining temperature-dependent x-ray diffraction(XRD) with temperature-dependent Raman scattering, we have characterized the structural transitions and lattice dynamics of the hybrid organic–inorganic perovskite CH3NH3PbI3.The XRD measurements cover distinct phases between 15 K and 370 K and demonstrate a general positive thermal expansion.Clear anomalies are found around the transition temperatures.The temperature evolution of the lattice constants reveals that the transition at 160 K/330 K is of the first-/second-order type.Raman measurements uncover three strong lowfrequency modes, which can be ascribed to the vibration of the Pb/I atoms.The temperature evolution of the modes clearly catches these transitions at 160 K and 330 K, and confirms the transition types, which are exactly consistent with the XRD results.The present study may set an experimental basis to understand the high conversion efficiency in methylammonium lead iodide.

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.