Boehmite nanorod‐reinforced‐polyethylenes and ethylene/1‐octene thermoplastic elastomer nanocomposites prepared by in situ olefin polymerization and melt compounding

Nanocomposites of polyethylene (HDPE) and poly(ethylene‐co‐1‐octene) thermoplastic elastomers, both containing boehmites with variable sizes, shapes, and aspect ratios (1–20), were prepared by means of in situ olefin polymerization and melt compounding. The in situ olefin polymerization in the presence of boehmite nanorods afforded nanocomposites containing 4–8 wt % of boehmite. In an alternative process, the in situ olefin polymerization was used to produce polyolefins with high boehmite content of 50 wt % as masterbatches for polyolefin melt compounding with ethylene homo‐ and copolymers. The addition of the boehmite nanofillers improved the stiffness without sacrificing high elongation at break. The stiffness, as expressed by Young's modulus, increased with increasing boehmite aspect ratio. In case of thermoplastic elastomer nanocomposites the increase of stiffness was accompanied by a simultaneous increase of elongation at break. According to transmission electron microscopy (TEM), fine dispersion of the polar boehmite nanorods and nanoplatelets within the nonpolar hydrocarbon polymer matrix was obtained without requiring the addition of special dispersing agents or functionalized polyolefin compatibilizers. The comparison of melt compounding of polyethylene with boehmites or polyethylene/boehmite masterbatches revealed that compounding of masterbatches prepared by in situ polymerization filling afforded much finer and more uniform nanoboehmite dispersions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2755–2765, 2008     

Synthesis and surface characterization of yttrium doped boehmite nanofibers

Yttrium doped boehmite nanofibers with varying yttrium content have been synthesized at low temperatures using a soft-chemistry route in the presence of polyglycol ether surfactant. The effect of yttrium content, hydrothermal temperature on the growth of boehmite nanostructures was systematically studied. Nanofibers were formed in all samples with varying doped Y% treated at 100 °C; large Y(OH)₃ crystals were also formed at high yttrium doping. Treated at an elevated temperatures resulted in a remarkable changes in size and morphology for samples with the same doped Y content. The resultant nanofibers were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy-dispersive X-ray analysis (EDX), N₂ adsorption and thermogravimetric analysis. The detailed characterization and discussion on the Y doped nanostructures are presented.     

XRD,TEM and thermal analysis of yttrium doped boehmite nanofibres and nanosheets

Yttrium doped boehmite nanofibres with varying yttrium content have been prepared at low temperatures using a hydrothermal treatment in the presence of poly(ethylene oxide) surfactant (PEO). The resultant nanofibres were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). TEM images showed the resulting nanostructures are predominantly nanofibres when Y-doping is less than 5%; in contrast Y-rich phases were formed when doping was around 10%. The doped boehmite and the subsequent nanofibres/nanotubes were analyzed by thermogravimetric and controlled rate thermal analysis methods. The boehmite nanofibres produced in this research thermally transform at higher temperatures than boehmite crystals and boehmite platelets. Boehmite nanofibres decompose at higher temperatures than non-hydrothermally treated boehmite.     

XRD,TEM and thermal analysis of Fe doped boehmite nanofibres and nanosheets

Iron doped boehmite nanofibres with varying iron content have been prepared at low temperatures using a hydrothermal treatment in the presence of poly(ethylene oxide) surfactant. The resultant nanofibres were characterized by X-ray diffraction (XRD), and transmission electron microscopy (TEM). TEM images showed the resulting nanostructures are predominantly nanofibres when Fe doping is no more than 5%; in contrast nanosheets were formed if Fe doping was above 5%. For the 10% Fe doped boehmite, a mixed morphology of nanofibres and nanosheets were obtained. Nanotubes instead of nanofibres were observed in samples with 20% added iron. The Fe doped boehmite and the subsequent nanofibres/nanotubes were analysed by thermogravimetric and differential thermogravimetric methods. Boehmite nanofibres decompose at higher temperatures than non-hydrothermally treated boehmite and nano-sheets decompose at lower temperatures than the nanofibres.     

Preparation,Antibacterial Activity,and Catalytic Application of Magnetic Graphene Oxide-Fucoidan in the Synthesis of 1,4-Dihydropyridines and Polyhydroquinolines

Polymer-coated magnetic nanoparticles are emerging as a useful tool for a variety of applications, including catalysis. In the present study, fucoidan-coated magnetic graphene oxide was synthesized using a natural sulfated polysaccharide. The prepared BaFe₁₂O₁₉@GO@Fu (Fu=fucoidan, GO=graphene oxide) was characterized using Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) analysis, vibrating sample magnetometry (VSM), thermogravimetric analysis (TGA), Raman spectroscopy, and X-ray diffraction (XRD). The catalytic proficiency of BaFe₁₂O₁₉@GO@Fu was investigated in the synthesis of 1,4-dihydropyridine and polyhydroquinoline derivatives. Excellent turnover numbers (TON) and turnover frequencies (TOF) (6330 and 25320 h⁻¹) testify to the high efficiency of the catalyst. Moreover, the antimicrobial activity of BaFe₁₂O₁₉@GO@Fu was evaluated against Escherichia coli (E. coli), and Staphylococcus aureus (S. aureus) through the Agar well diffusion method, indicating that BaFe₁₂O₁₉@GO@Fu has antibacterial activity against S. aureus.     

Zinc(II) complex immobilized on amine functionalized silica gel: a novel,highly efficient and recyclable catalyst for multicomponent click synthesis of 1,4-disubstituted 1,2,3-triazoles

We report a highly efficient and recyclable heterogeneous zinc catalytic system via covalent immobilization of 2-hydroxyacetophenone (2-HAP) onto an amine functionalized silica gel followed by metallation with zinc chloride and its catalytic application in three component click synthesis of 1,4-disubstituted 1,2,3-triazoles. The structure of the synthesized organic–inorganic hybrid material (SiO₂@APTES@2HAP-Zn) has been confirmed by various physicochemical characterization techniques, such as solid-state ¹³C CPMAS NMR spectroscopy, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction analysis (XRD), Brunauer–Emmett–Teller (BET) surface area analysis, scanning electron microscopy (SEM), atomic absorption spectroscopy (AAS), energy-dispersive X-ray fluorescence spectroscopy (ED-XRF), and elemental analysis. The newly designed catalyst works under mild reaction conditions and also exhibits excellent performance in terms of good product yield and high turnover number (TON). One of the most important attributes of the present methodology is that the catalyst can be recycled several times without appreciable loss in its activity as proved by FTIR spectroscopy and SEM analysis. Besides, the heterogeneity test also confirms that no leaching of active catalytic species occurs from the silica supported zinc catalyst which confirms its remarkable structural stability under the reaction conditions.     

Thermal and combustion behavior of polyethersulfone-boehmite nanocomposites

In this paper, we report a thorough study on the thermal stability and fire behavior of polyethersulfone (PES) filled with 2 wt% nano-sized aluminum oxide hydroxide particles (boehmite). The nanocomposite was prepared through melt compounding technique in a co-rotating twin screw extruder. The obtained morphology of the composite was studied by scanning electron microscopy (SEM) coupled with elemental analysis, proving that an even distribution of sub-micron boehmite particles was obtained. PES shear modulus, measured by DMA, is increased by 30% in the boehmite nanocomposite. Thermal stability of the produced materials was studied through thermal gravimetric analysis (TGA), whereas the combustion behavior through cone calorimeter and vertical burning (UL-94) tests. Cone calorimeter results show that a significant overall flame retardant effect was observed due to the presence of boehmite nanoparticles, which could not be detected by UL-94 fire scenario where neat PES is already top ranked V0.     

Biogenic synthesis of palladium nanoparticles using Boswellia sarrata and their applications in cross-coupling reactions

A facile and green route for biogenic synthesis of palladium nanoparticles (PdNPs) using aqueous extract of nontoxic and renewable Boswellia sarrata leaves is reported. The as-synthesized PdNPs were systematically characterized by using ultraviolet (UV)–visible spectroscopy, X-ray diffraction analysis, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The PdNPs were crystalline and cubic in nature with average particle size of ~6 nm and successfully employed as heterogeneous catalyst in the Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions. The PdNPs could be recycled up to five times with modest change in the catalytic activity.     

Efficient synthesis of β-aminoketones catalyzed by Fe3O4@ quillaja sapogenin/Ni (II) as a novel magnetic nano-catalyst

A new nano-magnetic core–shell Fe₃O₄@quillaja sapogenin/Ni (II) was synthesized and characterized thoroughly using various tests including energy-dispersive X-ray spectroscopy (EDS), Brunauer–Emmett–Teller (BET), thermo-gravimetric analysis (TGA), high-resolution transmission electron microscopy (HR-TEM), vibrating sample magnetometer (VSM), Fourier transform infrared (FT-IR) spectroscopy, inductively coupled plasma (ICP), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The achievements demonstrated that the proposed agents were beneficial to synthesis the derivatives of β-aminoketone. Moreover, it was possible to recover the catalyst by means of simple magnetic decantation quickly. Besides, no reduction in the activity of the catalyst occurred, even though it was utilized in various reactions.     

Thermal, rheological, and barrier properties of waterborne acrylic nanocomposite coatings based on boehmite or organo-modified montmorillonite

An organo-modified montmorillonite (Cloisite^®30B) or an unmodified boehmite (Disperal^®40) have been added to two acrylic latex dispersions (one of them UV-curable) for obtaining nanocomposite coatings. X-ray diffraction and transmission electron microscopy show a high degree of exfoliation in the nanocoatings based on montmorillonite, together with the deagglomeration of the micrometer-sized boehmite powder and the presence of single boehmite crystallites within the polymer matrix. Such morphologies are found to enhance the thermal and thermo-oxidative stability of the latexes and to significantly decrease their oxygen permeability, as well.     

Synthesis, characterization, and surface properties of iron-doped boehmite nanofibers

Iron-doped boehmite nanofibers with varying iron contents have been prepared at low temperatures using hydrothermal treatment in the presence of poly(ethylene oxide) surfactant. The resulting nanofibers were characterized by transmission electron microscopy (TEM), X-ray diffraction, energy-dispersive X-ray analysis, and N2 adsorption. TEM images showed that the resulting nanostructures are predominantly nanofibers when the doped iron content is less than 5% (mol/mol); in contrast, nanosheets were formed when iron doping was above 4%. Nanotubes instead of nanofibers and iron-rich particles were observed in samples with 20% added iron. A detailed characterization and discussion on the iron-doped nanofibers is presented.     

Rapid synthesis of novel flowerlike K0.46Mn2O4(H2O)1.4 hierarchical architectures and their catalytic degradation of formaldehyde in aqueous solution

Novel flower-like birnessite type manganese oxide hierarchical architectures were hydrothermally synthesized from KMnO₄ solution using sodium fluorite as a reductant in sulfuric acid medium at low temperature. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and X-ray photoelectron (XPS) spectroscopes confirm that the composition of the as-fabricated product. Field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), selected area electron diffraction (SA-ED), high resolution transmission electron microscopy (HR-TEM) and N₂ adsorption–desorption isotherm reveal that the as-synthesized sample exhibits a microsized flower-like crystal with dense nanoleaves standing on their surfaces, polycrystalline, monoclinic phase structure and high BET surface area. On the basis of time-dependent experimental results, a possible mechanism for the formation of flowerlike structures is speculated. Their capability of catalytic degradation of formaldehyde solution with oxygen air bubbles were studied by using an acetylacetone calorimetric spectra, total organic carbon (TOC) method and turnover number (TON). In addition, the birnessite nanoflower is stable during the reaction and can be used repeatedly.     

Linear low‐density polyethylene nanocomposites by in situ polymerization using a zirconium‐nickel tandem catalyst system

A series of linear low‐density polyethylene (LLDPE) nanocomposites containing different types of nanofiller (TiO₂, MWCNT, expanded graphite, and boehmite) were prepared by in situ polymerization using a tandem catalyst system composed of {Tp^Ms}NiCl ( 1 ) and Cp₂ZrCl₂ ( 2 ), and analyzed by differential scanning calorimetry, dynamic mechanical analysis (DMA), and transmission electron microscopy (TEM). Based on these analyses, the filler content varied from 1.30 to 1.80 wt %. The melting temperatures and degree of crystallinity of the LLDPE nanocomposites were comparable to those of neat LLDPE. The presence of MWCNT as well as boehmite nucleated the LLDPE crystallization, as indicated by the increased crystallization temperature. The DMA results showed that the presence of TiO₂, EG, and CAM 9080 in the LLDPE matrix yielded nanocomposites with relatively inferior mechanical properties compared to neat LLDPE, suggesting heterogeneous distribution of these nanofillers into the polymer matrix and/or the formation of nanoparticle aggregates, which was confirmed by TEM. However, substantial improvement in the storage modulus was achieved by increasing the sonication time. The highest storage modulus was obtained using MWCNT (1.30 wt %). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3506–3512     

Solution-based chemical synthesis of boehmite nanofibers and alumina nanorods

This article reports an easy chemical method of synthesizing boehmite nanofibers by a modified sol-gel process involving aluminum isopropoxide precursor. Nanorods of gamma-alumina have been successfully prepared after dehydration of the viscous sol at 600 degrees C for 4 h in air. The boehmite nanofibers and gamma-alumina nanorods were characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy for surface chemistry and functional groups, scanning electron microscopy, high-resolution transmission electron microscopy with selected area electron diffraction, and energy-dispersed spectroscopy for morphology and structure identification. The length of the boehmite nanofibers was found to be more than 10 mum with a crystalline lattice structure. The mechanism of formation of the boehmite nanofibers included the preferential growth along the longitudinal axis due to interaction between the solvent molecules and the surface OH- groups of hydrogen bonds. It is also suggested that the boehmite nanofibers may have formed due to the inherent instability of the planar structure of the boehmite lattice. The diameter of the gamma-alumina nanorods was found to be less than 10 nm with a varying length in the range of 50-200 nm. Boehmite to gamma-Al2O3 transformation was attributed to the loss of water molecules by internal condensation of protons and hydroxyl ions.     

由单层薄水铝石制备的活性氧化铝处理水中氟离子

The preparation of high-efficiency and low-cost adsorbents for the defluoridation of drinking water remains a huge challenge. In this study, single-layer and multi-layer boehmite were first synthesized via an organic-free method, and active alumina used for fluoride removal from water was obtained from the boehmite. The advantage of a single layer is that more aluminum is exposed to the surface, which can provide more adsorption sites for fluoride. The active alumina adsorbent derived from single-layer boehmite exhibits a high specific surface area and excellent adsorption capacity. The high surface area ensures a high adsorption capacity, and the organic-free synthesis method lowers the preparation cost. The as-prepared adsorbent was characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Fourier-transform infrared spectroscopy (FTIR) and nitrogen adsorption-desorption analysis. The single-layer structure of boehmite was determined from the simulated XRD diffraction pattern of single-layer boehmite. The disappearance of the (020) diffraction peak of boehmite illustrates that the dimensions in the b direction are extremely small, and according to the XRD simulation results, the single-layer structure of boehmite could be determined. Single-layer boehmite with a surface area of 789.4 m²·g^-1 was formed first. The active alumina obtained from the boehmite had a surface area of 678.4 m²·g^-1, and the pore volume was 3.20 cm³·g^-1. The fluoride adsorption of the active alumina was systematically studied as a function of the adsorbent dosage, contact time, concentration, co-existing anions, and pH. The fluoride adsorption capacity of the active alumina obtained from the single-layer boehmite reached up to 67.6 mg·g^-1, which is higher than those of most alumina adsorbents reported in the literature. The adsorption capacities of the active alumina are related to the specific surface area and the number of hydroxyl groups on the surface. Dosages of 0.6, 1.0, and 2.6 g·L^-1 of active alumina were able to lower the 10, 20, and 50 mg·L^-1 fluoride solutions, respectively, below the maximum permissible limit of fluoride in drinking water in China (1.0 mg·L^-1), suggesting that the active alumina synthesized in this work is a promising adsorbent for defluoridation of drinking water. In addition, the fluoride adsorption is applicable in a wide pH range from 4 to 9 and is mainly interfered by SO₄^2- and PO₄^3-. Further investigation suggested that the fluoride adsorption of the active alumina follows the pseudo second-order model and Langmuir isotherm model     

Catalytic activity and electrochemical properties of Cu(II)-Schiff base complex encapsulated in the nanocavities of zeolite-Y for oxidation of olefins and sulfides

Copper(II) complex of a Schiff base ligand (H₂L) was synthesized, characterized, and encapsulated in the cavities of zeolite-Y by a fixed ligand method. The zeolite encapsulated metal complex (CuL-Y) was characterized using FT-IR, UV–Vis and atomic absorption spectroscopy, thermogravimetric analysis (TGA), X-ray powder diffraction (XRD), scanning electron microscopy images (SEM), energy-dispersive X-ray spectroscopy (EDX), and Brunauer-Emmett-Teller (BET). The catalytic activity and electrochemical behavior of the encapsulated complex has been studied in the oxidation of a wide range of sulfides and olefins using H₂O₂ in ethanol. This heterogeneous catalytic system shows a dramatic increase in total turnover number (46,500) for oxidation of styrene. It could be readily reused for at least eight successive times without discernible activity and selectivity deterioration, which displays potential for practical applications.     

Spirooxindole-fused pyrazolo pyridine derivatives: NiO–SiO2 catalyzed one-pot synthesis and antimicrobial activities

We describe here a one-pot synthesis of 13 spirooxindole-fused pyrazolo pyridine derivatives using NiO–SiO₂ catalyst via three-component reaction of isatin, 5-amino-3-methylpyrazole, and malononitrile. This multicomponent one-pot protocol also features shorter reaction time, good yield, and simple work-up using a recoverable and reusable solid acid heterogeneous catalyst. The NiO–SiO₂ catalyst was characterized using different instrumental techniques such as X-ray diffraction study, surface area analysis, transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, UV-DRS (diffuse reflectance spectroscopy), and energy dispersive X-ray analysis (EDX). The new compounds were tested for in-vitro anti-microbial activity.     

Investigation of tannery liming waste water using green synthesised iron oxide nano particles

ABSTRACT

The present study aimed that non-toxic, less expensive, easily available, safer to environment and previously unreported Eclipta prostrata leaf extract is used for the green synthesis of iron oxide nano particles. The iron oxide nanoparticles (NPs) were characterised by UV–visible, Fourier Transform Infrared Spectroscopy (FTIR), scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM). Tannery effluents treated by photodegradation process and the removal efficiency of chemical oxygen demand (COD), biological oxygen demand (BOD) and sulphide were analysed. The maximum removal efficiency correlated with operating parameters was explained using response surface methodology with Boxmen Beckmen design.     

Effect of Phosphorus Amount on the Particle Size and Catalytic Performance of Heterogeneous Nickel(II) Schiff-Base Complex in Aldol Condensation Reaction

Abstract

The organic–inorganic hybrid of citric acid, tetraethoxysilane (TEOS), and triethylphosphate (TEP) doped by a nickel Schiff-base complex was prepared by sol–gel method. The prepared composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmittance electron microscopy (TEM), scanning tunnelling microscopy (STM), and infrared spectroscopy (IR). In order to determine the phosphorus amount effect on the catalytic activity of the prepared composites, the aldol condensation was used as a model reaction. The results revealed that the composite with 10% phosphorus is a better catalyst in comparison with other composites.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the following free supplemental files: Additional figures file.]     

Mo对非晶态合金Ni-B/薄水铝石催化剂上噻吩加氢脱硫性能的影响

采用浸渍-化学还原法制备了一系列不同Mo含量的Ni-Mo-B/薄水铝石非晶态合金催化剂样品.以噻吩加氢脱硫为探针反应,考察了样品的催化性能,并采用X射线衍射、差示扫描量热法、电感耦合等离子体发射光谱、程序升温还原、程序升温脱附、X射线光电子能谱和透射电镜等技术对样品进行了表征.结果表明,Mo的添加促进了Ni活性物种的分散,提高了催化剂的热稳定性,降低了催化剂的还原温度;同时,催化剂的吸氢强度减弱,酸性增强,从而显著提高了催化剂活性.当催化剂中Mo/Ni质量比为12%时活性最高,于220oC反应时,噻吩转化率达到73.9%.