Selective oxidation of alkenes using [bmim]5[PW11ZnO39]·3H2O hybrid catalyst

The catalytic activity of [bmim]₅[PW₁₁ZnO₃₉]·3H₂O as a hybrid catalyst was studied in the oxidation of various alkenes in acetonitrile, using hydrogen peroxide as oxygen source. The effect of reaction parameters such as type of solvent and oxidant, amount of catalyst and oxidant, and temperature was also investigated. From our results, [bmim]₅[PW₁₁ZnO₃₉]·3H₂O hybrid catalyst gave higher yields and selectivity in the oxidation of alkenes and was reused four times without loss of its catalytic activity.     

Hydrothermal synthesis of 2D ordered macroporous ZnO films

The ZnO films with two-dimensional ordered macroporous structure were successfully fabricated through hydrothermal crystal growth of ZnO on the ZnO substrate covered with a monolayer of polystyrene (PS) spheres as template. The precursor solution of hydrothermal crystal growth of ZnO were prepared by equimolar solution of Zn(NO₃)₂·6H₂O and hexamethylenetramine (HMT). The confinement effect of the PS spheres template on the growth of ZnO nanorods and the influence of sodium citrate on the crystal growth of ZnO had been studied. The film surface morphology and the preferential growth of ZnO crystal were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. Also, the photoluminescence spectrum of ZnO films had been measured, and the corresponding mechanism was discussed. __________ Translated from Chemistry, 2007, 70 (8): 587–592 [译自: 化学通报]     

Fabrication of Porous Metal Oxide Semiconductor Films by a Self-Template Method Using Layered Hydroxide Metal Acetates

Porous metal oxide (Co₃O₄, NiO, or ZnO) films were fabricated by a self-template method using layered hydroxide metal acetates (LHMA; metal = Co, Ni, or Zn) as templates. LHMAs were initially grown on glass substrates through a chemical bath deposition in methanolic-aqueous solutions of metal acetates at 60°C. The template films had a unique, nest-like morphology consisting of interlaced flake-like particles as a result of two-dimensional crystal growth of LHMAs in supersaturated solutions. The templates were successfully converted into porous Co₃O₄, NiO, or ZnO films by heating at 500°C for 10 min in air without microstructural deformation.     

微波水热两步法合成高可见光响应Ag2S/ZnO及其光催化性能、机理

在不同的制备条件下,通过微波水热两步法获得了一系列Ag₂S/ZnO光催化剂,采用X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见漫反射吸收光谱(UV-Vis/DRS)、扫描电子显微镜(SEM)和N₂吸附-脱附等测试手段对产物结构和形貌进行了表征。结果表明,产物以六方纤锌矿ZnO为主,其晶型结构并未随着反应温度和Ag₂S物质的量的增加而改变。Ag₂S的引入显著增强了光催化剂在可见光区的吸收,使吸收边带发生红移,同时抑制了ZnO(001)晶面的生长。另外,所得产物的形貌随着Ag₂S物质的量的增加从爆米花状转变为少量的柱体颗粒,且BET比表面积经过复合后明显减小。以罗丹明B为目标降解物,研究并比较了一系列Ag₂S/ZnO光催化剂对罗丹明B的光降解性能。结果表明,n_Ag2S/n_ZnO为1:10时,光催化剂在紫外光、可见光和模拟日光的照射下具有最好的光催化效果,优于目前应用最广泛的市售P25。另外,所制备的光催化材料Ag₂S/ZnO经4次循环使用后,其降解效率没有明显下降,表明该催化材料具有一定的光催化稳定性。经捕获实验研究发现,在Ag₂S/ZnO的光催化反应中空穴起主要作用,并根据绝对电负性估算了复合材料Ag₂S/ZnO的能带位置,据此提出了可能的光催化反应机理。     

微波水热两步法合成高可见光响应Ag2S/ZnO及其光催化性能、机理

在不同的制备条件下,通过微波水热两步法获得了一系列Ag₂S/ZnO光催化剂,采用X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见漫反射吸收光谱(UV-Vis/DRS)、扫描电子显微镜(SEM)和N₂吸附-脱附等测试手段对产物结构和形貌进行了表征。结果表明,产物以六方纤锌矿ZnO为主,其晶型结构并未随着反应温度和Ag₂S物质的量的增加而改变。Ag₂S的引入显著增强了光催化剂在可见光区的吸收,使吸收边带发生红移,同时抑制了ZnO(001)晶面的生长。另外,所得产物的形貌随着Ag₂S物质的量的增加从爆米花状转变为少量的柱体颗粒,且BET比表面积经过复合后明显减小。以罗丹明B为目标降解物,研究并比较了一系列Ag₂S/ZnO光催化剂对罗丹明B的光降解性能。结果表明,n_Ag2S/n_ZnO=1:10时,光催化剂在紫外光、可见光和模拟日光的照射下具有最好的光催化效果,优于目前应用最广泛的市售P25。另外,所制备的光催化材料Ag₂S/ZnO经4次循环使用后,其降解效率没有明显下降,表明该催化材料具有一定的光催化稳定性。经捕获实验研究发现,在Ag₂S/ZnO的光催化反应中空穴起主要作用,并根据绝对电负性估算了复合材料Ag₂S/ZnO的能带位置,据此提出了可能的光催化反应机理。     

Crystal growth of calcium carbonate on the cellulose acetate/pyrrolidon blend films in the presence of L-aspartic acid

The morphogenesis and growth process of calcium carbonate on the cellulose acetate/polyvinyl pyrrolidone (CA/PVP) blend films in the presence of L-aspartic acid was carefully investigated. The results showed that the concentration of L-aspartic acid, the initial pH value of reaction solution and temperature turned out to be important factors for the control of morphologies and polymorphs of calcium carbonate. Complex morphologies of CaCO₃ particles, such as cubes, rose-like spheres, twinborn-spheres, cone-like, bouquet-like, etc. could be obtained under the different experimental conditions. The dynamic process of formation of rose-like sphere crystals was analyzed by monitoring the continuous morphological and structural evolution and components of crystals in different crystal stages. This research may provide a promising method to prepare other inorganic materials with complex morphologies.     

Poly(zinc dimethacrylate) as a precursor in the low-temperature formation of ZnO nanoparticles

We present a simple, low-temperature synthesis of pure ZnO nanoparticles and polymer-ZnO hybrid materials formed by the NaOH-mediated conversion of poly(zinc dimethacrylate) in 1-butanol. The polymer poly(zinc dimethacrylate) was used as a precursor to prepare neat ZnO particles. It has a double role in the ZnO formation process, acting as a template and simultaneously controlling the crystal growth. The obtained single-crystalline ZnO nanorods show a low tendency to aggregate. The reaction mechanism of ZnO formation was proposed on the basis of a model system of the base-mediated conversion of a monomer zinc dimethacrylate Zn(MA)(2).     

Inorganic‐organic Microporous Solid of Wells‐Dawson Type Polyoxometalate: Synthesis,Characterization, and Electrochemical Properties

An inorganic‐organic hybrid solid (H_6/5bppy)₅[P₂W₁₈O₆₂]·4.5H₂O ( 1 ) (bppy = 4‐(5‐(4‐bromophenyl)pyridin‐2‐yl)pyridine) was hydrothermally synthesized by using pre‐constructed Wells‐Dawson type salt α‐K₆P₂W₁₈O₆₂·15H₂O as inorganic moiety. The crystal structure keeps integrated and steady under the interactions together of aryl packing, hydrogen bonding and halogen bonding. X‐ray single crystal structure analysis reveals that compound 1 contains cavities with the sizes of about 6 × 8Å, in which H₂O molecules are captured. The hybrid was used as a solid bulk modifier to fabricate a three‐dimensional bulk‐modified carbon paste electrode ( 1 ‐CPE) by direct mixing. The electrochemical and electrocatalytic behavior of the 1 ‐CPE has been studied in detail. The results exhibit that the redox ability of the Wells‐Dawson polyanions can be maintained in the hybrid solid, which has a good electrocatalytic activity toward the reduction of bromate and hydrogen peroxide. A hydrodynamic voltammetric experiment was performed to characterize the electrode as an amperometric sensor for the determination of hydrogen peroxide. The 1 ‐CPE showed long‐term stability and excellent reproducibility of surface renewal.     

Evaluation of novel ZnO–Ag cathode for CO2 electroreduction in solid oxide electrolyser

CO₂ and steam/CO₂ electroreduction to CO and methane in solid oxide electrolytic cells (SOEC) has gained major attention in the past few years. This work evaluates, for the very first time, the performance of two different ZnO–Ag cathodes: one where ZnO nanopowder was mixed with Ag powder for preparing the cathode ink (ZnO_mix–Ag cathode) and the other one where Ag cathode was infiltrated with a zinc nitrate solution (ZnO_inf –Ag cathode). ZnO_mix–Ag cathode had a better distribution of ZnO particles throughout the cathode, resulting in almost double CO generation while electrolysing both dry CO₂ and H₂/CO₂ (4:1 v/v). A maximum overall CO₂ conversion of 48% (in H₂/CO₂) at 1.7 V and 700 °C clearly indicated that as low as 5 wt% zinc loading is capable of CO₂ electroreduction. It was further revealed that for ZnO_inf –Ag cathode, most of CO generation took place through RWGS reaction, but for ZnO_mix–Ag cathode, it was the synergistic effect of both RWGS reaction and CO₂ electrolysis. Although ZnO_inf –Ag cathode produced trace amount of methane at higher voltages, with ZnO_mix–Ag cathode, there was absolutely no methane. This seems to be due to strong electronic interaction between Zn and Ag that might have suppressed the catalytic activity of the cathode towards methanation.

     

A thiocyanate-based hybrid molecular salt as a new fluorescent chemosensor for fluoride

An organic–inorganic hybrid solid [(dpaH)⁺(NCS)^?] (1) (dpa?=?2,2′-dipyridylamine) based on an anionic template NCS^? has been synthesized. Single crystal X-ray structural analysis reveals that NCS^? templates assemble dpaH⁺ units into a 3-D layer structure along the b axis through strong hydrogen bonding. Molecular salt 1 works as an anion-binder efficiently and selectively for recognition and sensing purposes in aprotic solvents. This receptor shows changes both in its UV-Vis absorption and fluorescence emission spectra upon the addition of F^?, resulting in high selectivity for fluoride detection in CH₃CN. It is promising to use these systems in various sensing applications.     

Ein neues Oxozincat: Li6[ZnO4] [1]

A New Oxozincate: Li₆[ZnO₄] Colourless single crystals of Li₆[ZnO₄] are formed by reaction of Li₂O and ZnO [(Li₂O:ZnO = 3.3:1, 700°C 50 d), Space group P4₂/nmc, Z = 2, a = 652.76 pm, c = 465.09 pm R = 2.6%, Rw = 2.1%, 173 symmetry independend I₀(hkl), MoK]. The crystal structure has been determined.     

Breakage of λ-DNA by inorganic tin and organotin compounds as environmental pollutants

In proportion to the environmental pollution problems caused by organotin compounds, the genotoxicities of tin compounds in the environments have become of interest so as to estimate their safety in recent years. In this work, isolated λ-DNA (double-strand DNA) was incubated with inorganic tin(II) and tin(IV) and five organotin compounds [n-butyltin trichloride, di(n-butyltin) dichloride, methyltin trichloride, dimethyltin dichloride and trimethyltin chloride] in reaction systems both with and without hydrogen peroxide (H₂O₂) content. The tin compounds tested in this study did not induce DNA breakage in the absence of hydrogen peroxide. Divalent inorganic tin (SnCl₂) and tetravalent inorganic tin (SnCl₄) caused DNA breakage in the presence of hydrogen peroxide (10 mM), and the DNA damage activity of inorganic tin was much more potent in divalent inorganic tin (SnCl₂) than in tetravalent inorganic tin (SnCl₄). Divalent inorganic tin (SnCl₂) induced DNA breakage in a concentration-dependent fashion at concentrations greater than 0.1 mM of SnCl₂ in the presence of hydrogen peroxide (10 mM). DNA breakage was not caused by n-butyltin compounds and methyltin compounds either in the presence or in the absence of hydrogen peroxide.     

Preparation of nitrogen doped zinc oxide nanoparticles and thin films by colloidal route and low temperature nitridation process

Nitrogen doped zinc oxide (ZnO) nanoparticles have been synthesized using a colloidal route and low temperature nitridation process. Based on these results, 200 nm thick transparent ZnO thin films have been prepared by dip-coating on SiO₂ substrate from a ZnO colloidal solution. Zinc peroxide (ZnO₂) thin film was then obtained after the chemical conversion of a ZnO colloidal thin film by H₂O₂ solution. Finally, a nitrogen doped ZnO nanocrystalline thin film (ZnO:N) was obtained by ammonolysis at 250 °C. All the films have been characterized by scanning electron microscopy, X-ray diffraction, X-Ray photoelectron spectroscopy and UV–Visible transmittance spectroscopy.     

Coordination bonding assembly and photophysical properties of Europium organic/inorganic/polymeric hybrid materials

Ternary organic/inorganic/polymeric hybrid material PVP-Eu-(DBM-Si)₃ (DBM = dibenzoylmethane; PVP = poly(4-vinylpyridine)) have been synthesized through the coordination bonds. The precursor DBM-Si is obtained by the modification of DBM molecule with a cross-linking reagent TEPIC (3-(triethoxysilyl)-propyl isocyanate), which is used to form the inorganic Si–O–Si networks with TEOS (tetraethoxysilane) after a hydrolysis and polycondensation process. PVP, which is obtained through the polymerization reaction using 4-vinylpyridine as the monomer in the presence of BPO (benzoyl peroxide), is used to form the organic polymeric C–C chains. For comparison, the binary organic/inorganic hybrid material Eu-(DBM-Si)₃ was also synthesized simultaneously. FT-IR (Fourier-transform infrared spectra), UV (ultraviolet absorption spectra), UV-DR (ultraviolet–visible diffuse reflection absorption spectra), SEM (scanning electron micrograph), PL (photoluminescence spectroscopy) and LDT (luminescence decay time) measurements are used to investigate the physical properties of the obtained hybrid materials. The results reveal that the ternary hybrids presents more regular morphology, higher red/orange ratio, stronger luminescent intensity, higher ⁵D₀ luminescence quantum efficiency and longer lifetime than the binary one, suggesting the property of the overall hybrid system is improved with the introduction of the organic polymer PVP.     

Crystallographic report: A two‐dimensional zinc phosphate framework: [H3N(CH2)3NH3]0.5[Zn2(PO4)(HPO4)]

The two‐dimensional zinc phosphate [H₃N(CH₂)₃NH₃]_0.5[Zn₂(PO₄)(HPO₄)], has been synthesized hydrothermally using 1,3‐diaminopropane as the template. Its structure contains an inorganic framework with three‐, four‐, or six‐membered rings, built from PO₄, PO₃(OH) and ZnO₄ tetrahedral moieties sharing vertexes. The protonated 1,3‐diaminopropane molecules interact with the framework through hydrogen bonds. Copyright © 2004 John Wiley & Sons, Ltd.     

Scaled‐up,selective and green synthesis of sulfoxides under mild conditions using (CeIII‐MoVI)Ox/aniline hybrid rods as an efficient catalyst

A novel hybrid material, (Ce^III‐Mo^VI)O_x/aniline, with rod‐like morphology is synthesized through a wet chemical method using Mo₃O₁₀(C₆H₅NH₃)₂.2H₂O nanowires as precursor. The synthesized materials are characterized by XRD, XPS, SEM, TEM, FTIR, Raman, UV–Vis, TGA, and elemental analysis. Also, their catalytic activities as a hybrid catalyst are tested in the selective oxidation of sulfides using hydrogen peroxide as a green oxidant. The proposed novel hybrid catalyst shows an excellent performance under green conditions at mild temperature. Furthermore, the scalability of the oxidation reaction is shown by making multi‐gram quantities at optimized conditions.     

Application of ZnO‐Al2O3 Nanocomposite as Nanocatalyst for Photodegradation of Acid Violet 5B

ZnO‐Al₂O₃ nanocomposite (ZANC) is used as nanocatalyst for photodegradation of acid violet 5B (AV5B) as an industrial dye. The experimental data shows that the degradation of AV5B is accelerated by ZANC and UV light. The effects of various parameters such as pH, hydrogen peroxide and ethanol are investigated on the photodegradation efficiency. Photocatalytic degradation rate of AV5B is increased by ethanol and hydrogen peroxide. Based on the kinetic studies, the rate constant of the photodegradation reaction is estimated 2.829 × 10^‐1 min^‐1.     

Novel Green Route of Synthesis of ZnO Nanoparticles by Using Natural Biodegradable Polymer and Its Application as a Catalyst for Oxidation of Aldehydes

ZnO nanoparticles have been synthesized by using biodegradable natural biopolymer viz. Gum Tragacanth. This single step approach is very cost effective and reproducible. The reaction time and concentration of precursor zinc acetate play a major role in the nature and growth of ZnO nanoparticles. ZnO nanoparticles were characterized by X-ray diffraction, SEM, FTIR, EDAX, UV-visible spectroscopy and TEM. ZnO nanoparticles with 20-30 nm in diameter and hexagonal morphology were found; dispersed uniformly. Raman spectrum shows the mode E₂ high at 437 cm^?1 that is related to the vibration of wurtzite Zn-O bond in crystal structure of ZnO. The space between adjacent lattice fringes is ～ sharp 2.42 Å. UV-visible absorption spectrum shows the sharp absorption band at 308 nm assigned to the intrinsic transition from valance band to conduction band. The ZnO nanoparticles display superior catalytic activity of conversion of aldehyde to acid as compared to bulk-ZnO material, because of high surface area of ZnO nanoparticles. A trace amount of ZnO nanoparticles catalyst required for organic conversion. The ZnO nanoparticles as catalyst are highly stable, recyclable and efficient in its activity.     

LiFe5O8 prepared by sol–gel synthesis: microstructural and morphological effects by organic and inorganic templates

Lithium ferrite was prepared using a sol–gel growth process using different fuels and inorganic templates. The aim of this study is to evaluate the influence of inorganic template agent like KCl, KBr and KI as well as the effect of different fuels like urea, glycine and citric acid on the morphology change of lithium ferrite. The structure, morphology and magnetic properties of the ferrite were investigated using powder X-ray diffraction (XRD), Infrared red spectroscopy and vibrating sample magnetometer. Thermal decomposition studies reveal the formation of lithium ferrite at a low temperature ~440 °C. Powder XRD pattern has shown the formation of a single α-phase lithium ferrite except the sample with inorganic template KBr, in which the presence of hematite as a secondary phase was observed. Scanning electron microscopy studies show that the structural morphology is highly sensitive to the inorganic template as well as on the fuel. The rod shaped nanoparticles are observed with the inorganic template KCl and KBr. The decrease in grain size is observed for LiFe₅O₈/glycine as compared to LiFe₅O₈/citric acid and flake shaped dense particles are observed for LiFe₅O₈/urea. The magnetic properties of the ferrite have also been investigated.