Preparation, phase transition and thermal expansion studies on low-cristobalite type Al1−xGaxPO4 (x=0.0, 0.20, 0.50, 0.80 and 1.00)

The orthorhombic (α) low-cristobalite type AlPO₄ and GaPO₄ and their solid solutions are prepared by co-precipitation followed by high temperature annealing of the precipitate. The single phasic nature of the products is ascertained by powder XRD at room temperature. The high temperature behavior of these samples is studied by HT-XRD over the temperature range of 25-1000°C. All these compositions undergo an orthorhombic to cubic (β, high-cristobalite) phase transition at elevated temperature. The unit cell parameters at different temperatures are determined by refining the observed powder diffraction profiles. The phase transition is accompanied by a significant increase in the unit cell volume, leading to the formation of a low dense structure. The variation of unit cell volume with temperature for each composition shows that the orthorhombic phase has a significantly larger thermal expansion than the cubic (high temperature) phase. The high temperature behavior of all the compositions except the GaPO₄ is similar. GaPO₄ undergoes a phase separation to a more stable quartz type phase above 800°C. However, the quartz type phase again transforms to the high cristobalite (β) phase at 1000°C. Thermal expansions of all these phases are explained in term of the variation of M-O-P angle as a function of temperature.     

On α-β phase transition in cristobalite-type Al1−xGaxPO4 (0.00?x?1.00)

The results of variable temperature powder X-ray diffraction and differential thermal analysis (DTA) studies on the orthorhombic (α) low-cristobalite to cubic (β) high-cristobalite phase transition for Al_1−xGa_xPO₄, (0.00?x?1.00) are presented. These studies reveal that all these compositions undergo reversible phase transitions from orthorhombic to cubic form at higher temperature. The high-temperature behavior of GaPO₄ is observed to have a different behavior compared to all other compositions in this series. Orthorhombic low-cristobalite-type GaPO₄ transforms to cubic high-cristobalite form at ∼605 °C. Above ∼700 °C, the cubic high-cristobalite-type GaPO₄ slowly transforms to trigonal quartz type structure. At about 960 °C, the quartz type GaPO₄ transforms back to the cubic high-cristobalite form. During cooling cycles the cubic phase of GaPO₄ reverts to trigonal quartz type phase. However, annealing of GaPO₄ at higher temperatures for longer duration can stabilize the orthorhombic low cristobalite phase. The phase transition temperatures and associated enthalpies are related to the change in unit cell volume and the orthorhombicity of the respective low cristobalite lattice.     

Water‐Soluble Gold Nanoparticles: From Catalytic Selective Nitroarene Reduction in Water to Refractive Index Sensing

Water‐soluble gold nanoparticles (Au NPs) stabilized by a nitrogen‐rich poly(ethylene glycol) (PEG)‐tagged substrate have been prepared by reduction of HAuCl₄ with NaBH₄ in water at room temperature. The morphology and size of the nanoparticles can be controlled by simply varying the gold/stabilizer ratio. The nanoparticles have been fully characterized by TEM, high‐resolution (HR) TEM, electron diffraction (ED), energy‐dispersive X‐ray spectroscopy (EDS), UV/Vis, powder XRD, and elemental analysis. The material is efficient as a recyclable catalyst for the selective reduction of nitroarenes with NaBH₄ to yield the corresponding anilines in water at room temperature. Furthermore, the potential ability of the Au NPs as a refractive index sensor owing to their localized surface plasmon resonance (LSPR) effect has also been assessed.     

Synthesis of the Dy: SrMoO4 with High Photocatalytic Activity under Visible Light Irradiation

Dysprosium (Dy)‐doping SrMoO₄ (with different molar ratio of Dy/Sr = 0/100, 10/100, 15/100 and 20/100) have been synthesized by high temperature thermal decomposition of metal–organic salt in organic solvent with a high boiling point. Their structures, morphology, and optical properties were characterized by X‐ray diffraction (XRD), high‐resolution tuning electron microscopy ((HR)TEM), X‐ray photo‐electron spectroscopy (XPS), and UV–vis diffuse reflectance spectroscopy (UV–vis DRS). Using this method, the pure phase, nano‐size, and low band gap of SrMoO₄ sample are obtained. The results shows that the size of as‐synthesized SrMoO₄ nanoparticles was about 200 nm. The band gap of Dy‐doped SrMoO₄ ranges from 3.76–3.90 eV, and decreases with increasing Dy concentration. The photocatalytic performance of as‐syntheszied products were determined from the degradation of methylene blue (MB) by UV–vis light irradiation. The 15 mol%Dy‐doped SrMoO₄ sample shows the best performance for photocatalytic degradation of methyl blue of nearly 100% in 120 min under visible irradiation, which is higher than most of those reported before. The present work is meaningful for revealing the underlying mechanism in photocatalyst and improving the photocatalytic performance.     

GaPO4 high temperature crystal microbalance demonstration up to 720°C

Quartz-homeotypic gallium (ortho-) phosphate, GaPO₄, is of special interest for resonator applications asking for temperature compensated cuts with higher electro-mechanical coupling than quartz and operational temperatures up to 970°C. The crystal microbalance technique, well known for quartz (QCM) which can be used only at moderate temperatures, can now be extended to much higher temperatures using GaPO₄ crystals, benefiting from all three advantages mentioned above. Two different experiments were done to demonstrate the advantages of a crystal microbalance based on GaPO₄. First, the GaPO₄ resonator was used for film thickness determination and compared with a commercial QCM. This experiment demonstrated that the measuring range can be extended by using GaPO₄ resonators instead of quartz. The second experiment demonstrates the possibility for thermogravimetric analysis up to 720°C by using a new concept for resonator mounting.This revised version was published online in November 2005 with corrections to the Cover Date.     

单分散Fe3O4纳米颗粒的控制合成和表征

以十八烯为溶剂、乙酰丙酮铁为铁源,并在油酸、油胺的辅助作用下,通过热分解法成功合成了单分散Fe3O4纳米颗粒。讨论了实验参数如反应温度、表面活性剂的量和种类、溶剂、油酸、油胺对单分散Fe3O4纳米颗粒的尺寸及形貌的影响。利用X射线衍射（XRD）、透射电子显微镜（TEM）、选区电子衍射（SAED）和高分辨透射电子显微镜（HRTEM）对所得产物的物相、结构、尺寸和形貌进行了表征分析。通过振动样品磁强计（VSM）表征产物磁性能,表明在室温下,Fe3O4纳米颗粒的饱和磁化强度（Ms）和矫顽力（Hc）分别为74.0 emu/g,72.6 Oe。     

Low Temperature Solvent Evaporation-induced Crystallization Synthesis of Nanocrystalline TiO2 Photocatalyst

A novel and efficient methodology for obtaining highly active photocatalyst of bi-phase TiO2 with small particle size and high specific surface area was developed by solvent evaporation-in-duced crystallization (SEIC) method at low temperature. The prepared TiO2 powder was characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM) and BET surface areas. The photocatalyfic activity was evaluated by the photocatalyflc oxidation of acetone in air. The results showed that the photocatalytic activity of the TiO2 powder preDared by this method approached that of Degnssa P25. This may be atotributed to the fact that the predated TiO2 powder had larzer specific surface areas (265 m2. g- 1 ) and smaller crystallite size (about 5 nm), but relatively low crystallinity, as compared with Degussa P25.     

Synthesis,Stabilization, Functionalization and,DFT Calculations of Gold Nanoparticles in Fluorous Phases (PTFE and Ionic Liquids)

Gold nanoparticles (Au‐NPs) were reproducibly obtained by thermal, photolytic, or microwave‐assisted decomposition/reduction under argon from Au(CO)Cl or KAuCl₄ in the presence of n‐butylimidazol dispersed in the ionic liquids (ILs) BMIm⁺BF₄^?, BMIm⁺OTf^?, or BtMA⁺NTf₂^? (BMIm⁺=n‐butylmethylimidazolium, BtMA⁺=n‐butyltrimethylammonium, OTf^?=^?O₃SCF₃, NTf₂^?=^?N(O₂SCF₃)₂). The ultra small and uniform nanoparticles of about 1–2 nm diameter were produced in BMIm⁺BF₄^? and increased in size with the molecular volume of the ionic liquid anion used in BMIm⁺OTf^? and BtMA⁺NTf₂^?. Under argon the Au‐NP/IL dispersion is stable without any additional stabilizers or capping molecules. From the ionic liquids, the gold nanoparticles can be functionalized with organic thiol ligands, transferred, and stabilized in different polar and nonpolar organic solvents. Au‐NPs can also be brought onto and stabilized by interaction with a polytetrafluoroethylene (PTFE, Teflon) surface. Density functional theory (DFT) calculations favor interactions between IL anions instead of IL cations. This suggests a Au???F interaction and anionic Au_n stabilization in fluorine‐containing ILs. The ¹⁹F NMR signal in BMIm⁺BF₄^? shows a small Au‐NP concentration‐dependent shift. Characterization of the dispersed and deposited gold nanoparticles was done by transmission electron microscopy (TEM/HRTEM), transmission electron diffraction (TED), dynamic light scattering (DLS), UV/Vis absorbance spectroscopy, scanning electron microscopy (SEM), electron spin resonance (ESR), and electron probe micro analyses (EPM, SEM/EDX).     

Hydrothermal Synthesis of Na0.28V2O5 Nanobelts and their Electrochemical Behavior in Lithium Batteries

A simple low temperature hydrothermal method was found to yield Na_0.28V₂O₅ nanobelts after two days at 130 °C in acidic medium (H₂SO₄) without using any surfactant. The obtained products were characterized by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR), and Raman spectroscopy. Their morphology was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Additionally, their electrochemical behavior in a lithium battery was investigated. The XRD pattern shows that the product is composed of monoclinic Na_0.28V₂O₅ nanobelts. From the FTIR spectrum, the band centered at 961 cm^–1 is assigned to V=O stretching vibration, which is sensitive to intercalation and suggests that Na⁺ ions are inserted between the vanadium oxide layers. SEM/TEM analyses reveal that the products consist of a large quantity of nanobelts which have a thickness of 60–150 nm and a length of several tens of micrometers. The electrochemical results show that the nanobelts exhibit an initial discharge specific capacity of 390 mAh · g^–1, and its stabilized capacity still remained around 200 mAh · g^–1 after the 18th cycle.     

Structural and thermal properties of chemically synthesized Bi2Te3 nanoparticles

Bi₂Te₃ nanoparticles (NPs) have been synthesized at 50?°C by a low-cost wet chemical route. The structural properties of product sample were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy. Thermal properties of product sample were investigated by differential scanning calorimetry (DSC), thermogravimetric (TG), and transient plane source techniques. The XRD and selected area electron diffraction of Bi₂Te₃ NPs result showed the polycrystalline nature with a rhombohedral (R3m) structure of the nanocrystallites. The average grain size of Bi₂Te₃ NPs was found to be about 30?nm by XRD and TEM measurements. DSC result shows one endothermic peak and one exothermic peak. TG result shows that only 48?% mass loss has occurred in Bi₂Te₃ sample. The obtained lower thermal conductivity of Bi₂Te₃ NPs is about 0.3?W m^?1 K^?1 at room temperature, which is caused by considering the crystalline nature of this material.     

Spontaneous Hierarchical Assembly of Crown Ether‐like Macrocycles into Nanofibers and Microfibers Induced by Alkali‐Metal and Ammonium Salts

Schiff base macrocycle 1 , which has a crown ether like central pore, was combined with different alkali‐metal and ammonium salts in chloroform, resulting in one‐dimensional supramolecular aggregates. The ion‐induced self‐assembly was studied with solid‐state NMR spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). It was found that the lengths and widths of the superstructures depend on the cation and counteranion of the salts. Among the salts being used, Na⁺ and NH₄⁺ ions with BF₄^? ions showed the most impressive fibrous structures that can grow up to 1 μm in diameter and hundreds of microns in length. In addition, the size of the fibers can be controlled by the evaporation rate of the solvent. A new macrocycle with bulky triptycenyl substituents that prevent supramolecular assembly was prepared and did not display any nanofibers with alkali‐metal ions in chloroform when studied with TEM.     

Synthesis and Characterization of Ordered Mesoporous Aluminosilicate Molecular Sieves with High Stability in High-Temperature Steam

The ordered mesoporous aluminosilicate molecular sieve （MASMS-1） stable in the high-temperature steam has been successfully synthesized from the assembly of diluted ZSM-5-type precursor with mesoporous MCM-41. The material was characterized by XRD, N2 adsorption-desorption, FE-SEM, TEM, FT-IR spectroscopy and 27A1 MAS NMR techniques. This mesoporous material shows high stability in the high-temperature steam [H2O （φ=20%） in N2 at 800 ℃ for 4 h], which might be ascribed to the synergistic effect of both thick walls containing zeolite-like five-membered ring subunits and highly condensed surface silanol groups.     

Promotion of Mn Doped Co/CNTs Catalysts for CO Hydrogenation to Light Olefins

With various contents, Mn was introduced into carbon nanotubes (CNTs) supported cobalt catalysts and the obtained Mn‐Co/CNTs catalysts were investigated for CO hydrogenation to light alkenes and characterized by N₂ adsorption, X‐ray diffraction (XRD), X‐ray photoelectron spectra (XPS), H₂ temperature programmed reduction (TPR), CO temperature programmed desorption (TPD) and transmission electron microscope (TEM). The results indicate that the addition of a small amount of Mn (0.3 wt%) to CNTs‐supported Co catalyst significantly increased the selectivity of C₂–C₄ olefins and decreased the selectivity of CH₄. However, with further addition of Mn to the cobalt catalysts, the CH₄ selectivity decreased obviously along with the increase of the C₅₊ selectivity. Compared with the unpromoted catalysts, the Mn‐promoted cobalt catalysts increased the C₂^?–C₄^?/C₂⁰–C₄⁰ molar ratio.     

Thermosensitive water‐soluble poly(ethylene glycol)‐based polythiophene graft copolymers

Diethyleneglycol methylethermethacrylate(MeO₂MA) and oligoethylene glycol methylethermethacrylate(OEGMA) are polymerized on polythiophene(PT) backbone to produce water‐soluble PT‐g‐PMeO₂MA(PTD) and PT‐g‐P(MeO₂MA‐co‐OEGMA)(PTDO) using atom transfer radical polymerization. They are characterized by ¹H NMR and GPC techniques. TEM micrographs indicate that PT‐chains self‐organize as nanospheres, and atomic force micrographs suggest that aggregated PT‐chains are present at the centre surrounded by dispersed PMeO₂MA fibers producing miceller‐type aggregates. Dynamic light scattering study indicates an initial decrease followed by sharp increase of Z‐average particle size of PTD with temperature for attaining lower critical solution temperature (LCST) at 20 °C. The LCST increases with OEGMA concentration in PTDO. The temperature dependent PL emission of PTD shows a minimum at 19 °C, followed by a sharp increase till 21 °C, and in the cooling cycle, it shows a complete reversibility. In the PTDO copolymers, the PL intensity shows the hike at progressively higher temperatures due to the increase of LCST with increasing OEGMA concentration. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

LGS and GaPO4 piezoelectric crystals: New results

Theoretical and experimental results of two interesting piezoelectric crystals for vibrating sensors, the La₅Ga₃SiO₁₄ (also written LGS) and the GaPO₄, are presented. First a comparison of different piezoelectric crystals in terms of quality factor and temperature stability is given and shows the theoretical interest of the GaPO₄ and the LGS isomorphs (LGX). Then an experimental validation has been undertaken: a dedicated decoupling structure allowing high insulation of two flexural modes is described, as well as its micromachining by ultrasonic machining (USM). The experimental measurements of the LGS resonator gave disappointing results with very low measured quality factors of about 10,000 (under vacuum) for a beam working at 10 kHz. On the other hand, the GaPO₄ resonator behaves very well: a quality factor higher than 700,000 (beam frequency 9 kHz) at room temperature and under vacuum has been obtained, as well as a low temperature frequency dependence of ?12 ppm/K, in accordance with the theoretical predictions. The impact of the Au excitation/detection electrodes on the quality factor has also been studied in detail and it clearly explains why the measured quality factors are lower than the thermoelastic limit.     

Multiresponsive Viscoelastic Vesicle Gels of Nonionic C12EO4 and Anionic AzoNa

Viscoelastic vesicle gels were prepared by mixing a nonionic surfactant, tetraethylene glycol monododecyl ether (C₁₂EO₄), and an anionic dye, sodium 4‐phenylazobenzoic acid (AzoNa). The gels, which were composed of multilamellar vesicles, were analyzed by cryogenic transmission electron microscopy (cryo‐TEM), freeze–fracture transmission electron microscopy (FF‐TEM), ²H NMR spectroscopy, and small‐angle X‐ray scattering (SAXS). The mechanism of vesicle‐gel formation is explained by the influence of anionic molecules on the bilayer bending modulus. Interestingly, the vesicle gels were observed to be sensitive to temperature, pH, and light. The viscoelastic vesicle gels respond to heat; they thin at lower temperatures and become thicker at higher temperatures. The vesicle gels are only stable from pH 7 to 11, and the gels become thinner outside of this range. UV light can also trigger a structural phase transition from micelles to multilamellar vesicle gels.     

Room Temperature Synthesis of Gold Nanokites in Polyvinyl Alcohol‐Sodium Dodecyl Sulfate Aggregations Aqueous Solution

Controlled synthesis of asymmetrical gold nanokites was realized by reducing HAuCl₄ with polyvinyl alcohol (PVA) in PVA‐sodium dodecyl sulfate (SDS) aggregations aqueous solution at room temperature without any additional reducing agents. The crystal structures, optical property and growth process of the gold nanokites were investigated by X‐ray diffraction (XRD), Vis‐NIR spectrum and transmission electron microscope (TEM). HAuCl₄ concentration dramatically influenced the morphologies of the products. When HAuCl₄ concentration was increased from 0.5 mmol·L⁻¹ to 2.2 mmol·L⁻¹, the products changed from network‐like nanostructures to nanokites, nanoleaves and microplates. SDS was indispensable for the formation of gold nanokites and without SDS super‐branched structures became the dominant products.     

Magnetic NiFe2O4 nanoparticles: efficient,heterogeneous and reusable catalyst for synthesis of acetylferrocene chalcones and their anti‐tumour activity

A robust synthesis of magnetic NiFe₂O₄ nanoparticles via a hydrothermal technique was investigated. The prepared magnetic NiFe₂O₄ nanoparticles were characterized using powder X‐ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy (TEM), high‐resolution TEM, energy‐dispersive X‐ray spectroscopy, thermogravimetric analysis, infrared spectroscopy and vibrating sample magnetometry. XRD and TEM analyses confirmed the formation of single‐phase ultrafine nickel ferrite nanoparticles with highly homogeneous cubic shape and elemental composition. Moreover, the prepared magnetic NiFe₂O₄ nanoparticles were used as an efficient, cheap and eco‐friendly catalyst for the Claisen–Schmidt condensation reaction between acetylferrocene and various aldehydes (aromatic and/or heterocyclic) yielding acetylferrocene chalcones in excellent yields, with easy work‐up and reduced reaction time. The products were purified via crystallization. The structures of the produced compounds were elucidated using various spectroscopic analyses (¹H NMR, ¹³C NMR, GC–MS). The catalyst is readily recovered by simple magnetic decantation and can be recycled several times with no discernible loss of catalytic activity. Furthermore, the prepared chalcone derivatives were evaluated for their anti‐tumour activity against three human tumour cell lines, namely HCT116 (colon cancer), MCF7 (breast cancer) and HEPG2 (liver cancer), and showed a good activity against colon cancer. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation of ZnSe Nanoparticles via Low‐Temperature Solid Phase Process

ZnSe nanoparticles were prepared from ZnCl₂, Se and KBH₄ in the presence of cetyltrimethyl ammonium bromide (CTAB) through a room temperature solid phase process. The products were characterized with x‐ray diffraction (XRD), transmission electron microscope (TEM), and energy dispersive analysis of x‐ray (EDAX). The results show that the cubic zincblende phase ZnSe nanoparticles can be obtained using this simple method. The size of nanoparticles was evaluated to be from 8 to 30 nm.     

Green Synthesis of Magnetic Zeolite LTA using NaOH Activated Fly Ash

The magnetic zeolite LTA was successfully synthesized using NaOH activated fly ash. The properties of the magnetic zeolite LTA were characterized by XRD, FTIR, SEM, TEM, BET, and VSM. We can be concluded that the synthesized composite consists of zeolite LTA and magnetic Fe₃O₄ nanoparticle. The nitrogen adsorption technique confirmed that the magnetic zeolite LTA exhibits a specifific surface area of 10.0183 m² · g^–1, which is much larger than that of the fly ash. VSM result confirms that the magnetization saturation value of the magnetic zeolite LTA is 10.06 emu · g^–1. Therefore, the magnetic zeolite LTA could be easily separated from the liquid phase using a magnet.