Electron density in lead bromine and chlorine hilgardites on the basis of precise x‐ray diffraction data and ab‐initio calculations and correlation with the properties

By a precise X‐ray diffraction experiment carried out on grown crystals of lead bromine and chlorine hilgardites (Pb₂B₅O₉Br and Pb₂B₅O₉Cl) we solved the structure of Pb₂B₅O₉Cl and refined the structure of Pb₂B₅O₉Br. The electron density distribution in the Pb₂B₅O₉Br was analyzed and its spatial distribution was linked to the unusually high optical nonlinearity of the Pb₂B₅O₉Br. Ab‐initio calculations confirmed the role of the lead atoms as the major contributors to the optical nonlinearity. By the Bader critical point approach, we analyzed the coordination polyhedrons of lead and halogen atoms, we showed that despite a long distance the bonding between lead and halogen atoms exists indeed. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hydrothermal synthesis and formation of 4ZnO·B2O3·H2O whiskers via a new route

4ZnO·B₂O₃·H₂O whiskers were prepared from 2ZnO·3B₂O₃·3.5H₂O under hydrothermal process at 160 °C for 10 h. The synthesized product was characterized by XRD, SEM, TG‐DSC and FT‐IR. SEM results showed that the synthesized 4ZnO·B₂O₃·H₂O whiskers' length was about 3–10 μm and the diameter was 0.2–0.3 μm. Further study on the whiskers' growth process and mechanism showed that the formation of the whiskers went through three stages and the morphology of 4ZnO·B₂O₃·H₂O changed from irregular particles to rod‐like structures and finally to whiskers. The variation of the morphology of the 4ZnO·B₂O₃·H₂O whisker with the concentration of the starting material was investigated. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A new nonlinear optical borate, Na0.5Pb2[B5O9](OH)1.5 · 0.5H2O, from the orthorhombic hilgardite family

A new polar representative of the hilgardite structural family, Na_0.5Pb₂[B₅O₉](OH)_1.5 · 0.5H₂O (space group Pnn2), is synthesized under hydrothermal conditions. The crystal structure of the compound synthesized is similar to the structure of the previously studied polar compound Na_0.5Pb₂[B₅O₉]Cl(OH)_0.5 and is intermediate between the latter compound and the centrosymmetric hydrate Pb₂[B₅O₉](OH) · 0.5H₂O. The additional peak revealed in the electron density in the vicinity of the Pb(1) atom is attributed to the stereochemically active lone electron pair of this atom. The lone electron pair is oriented toward the two most distant oxygen atoms involved in the Pb(1) coordination environment, namely, O(7) and O(2), which are located in a boron-oxygen framework layer in the ac plane, not toward the (00_z) channel occupied by water molecules. The nonequivalence in the stereochemical activity of two lead atoms [Pb(1) > Pb(2)] is similar to that observed in the nonlinear optical borate Pb₂[B₄O₅(OH)₄](OH)₂ · H₂O related to BiB₃O₆.     

Magnetic properties and X‐ray photoelectron spectroscopy of nanocrystalline Ho3Al5O12

Nanocrystalline holmium aluminium garnet (Ho₃Al₅O₁₂) has been prepared for the first time by modified Pechini's reaction after sintering the precursor gel at 1223 K. The nanomaterial has been characterized by X‐ray diffraction (XRD), selected area electron diffraction (SAED) and high resolution transmission electron microscopy (HRTEM). The XRD pattern confirms the formation of single‐phase Ho₃Al₅O₁₂; the average size of the nanoparticles has also been determined. X‐ray photoelectron spectroscopy (XPS) has been used to study the chemical composition and bonding in the as‐prepared samples. The binding energies of core‐level electrons in Ho, Al and O in the title material have been found slightly shifted compared to the values of the respective elements. DC magnetic susceptibility has been measured in the temperature range 2 – 260 K. Low effective magnetic moment of Ho³⁺, μ_eff = 1.35 µ_B and Weiss constant have been derived from the inverse magnetic susceptibility–temperature linear plot. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of LaBGeO5 crystal fibers by the micro‐pulling down technique

The LaBGeO₅ compound (LBGO) was prepared by solid state reaction at 1050°C and characterized by XRD and DTA analysis. The direct growth of LBGO fibers from the melt using micro‐pulling down technique was unsuccessful because of its high viscosity. The study of the LBGO‐LiF phase diagram showed that LiF could be considered as a convenient flux to reduce viscosity of the melt during the growth process. Several crystal fibers were then grown and characterized by Raman spectroscopy. To decrease the high volatility of LiF, B₂O₃ was added to the melt. A white cloudy fiber was obtained from LiF‐B₂O₃ flux and checked by Raman spectroscopy and scanning electron microscopy.     

Room‐temperature synthesis and characterization of cross‐like Pr2(C2O4)3·10H2O micro‐particles

Cross‐like Pr₂(C₂O₄)₃·10H₂O micro‐particles were synthesized through a simple precipitation method at room temperature. The products were characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), field‐emission scanning electron microscopy (FESEM), thermogravimetry–differential thermal analysis (TG‐DTA) and photoluminescence (PL). The possible formation mechanism of the cross‐like Pr₂(C₂O₄)₃·10H₂O micro‐particles was discussed, and Pr₆O₁₁ with similar morphology was obtained by calcining the oxalate precursor. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The influence of low-temperature annealings on the structural and superconducting properties of Bi 2212 and Bi 2201 whiskers

The influence of post-growth short-term low-temperature annealings (O₂, 400°C, 5–15 min) on the composition, crystal structure, and superconductivity of Bi₂Sr₂CaCu₂O_{8 + δ} and Bi₂Sr₂CuO_{6 + δ} oxycuprate whiskers freely grown in gas cavities has been investigated. The optimal conditions for growth in closed gas cavities in a flux and post-growth annealing in oxygen were found, making it possible to obtain high-quality superconducting Bi 2212 and Bi 2201 whiskers in a wide doping range (from heavily underdoped to optimally doped) with a small rocking curve half-width (～0.1^°–0.2^°) and narrow superconducting transition (ΔT = 1.5–2 K).     

Ag@Fe3O4 nanowire: fabrication,characterization and peroxidase‐like activity

With a facile solvothermal method, Ag@Fe₃O₄ nanowire was successfully prepared and characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The obtained Ag@Fe₃O₄ nanowire posses enhanced peroxidase‐like activity with good stability and high absorbance. The optimization of pH, H₂O₂ concentration and loading capacity were carried out. The result of kinetic analysis indicates that the catalyzed reaction followed a Michaelis‐Menten behavior. The good peroxidase‐like activity makes Ag@Fe₃O₄ nanowire be promising for real application in biomedicine.     

Influence of polymerizing agent on structure and spectroscopic properties of nano‐crystalline La0.8Sr0.2MnO3 powders

Strontium‐doped lanthanum manganite (La_1‐xSr_xMnO₃ or LSM) is the material most widely used on solid oxide fuel cells cathode. In this work, nano‐scale La_0.8Sr_0.2MnO₃ powders have been synthesized by polymeric precursor‐based methods using different polymerizing agents with the aim of evaluating the influence of this change in the final powder. The powders calcined at 700 °C for 2 h have been characterized by X‐ray diffraction (XRD), scanning electron microscopy (FE‐SEM) and Fourier transform infrared spectroscopy (FTIR) in order to investigate the quality of both synthesis routes. It is shown that the crystal structure and morphology of the particles are significantly dependent on the preparation conditions. Single phase and La_0.8Sr_0.2MnO₃ nano‐crystalline particles less than 30 nm were obtained using ethylene glycol as polymerizing agent. FTIR results have been indicated that only the powder obtained using gelatin presented small traces of hydroxyl groups on its surface. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

α‐Fe2O3 nanospindles loaded with ZnO nanocrystals: Synthesis and improved gas sensing performance

ZnO/α‐Fe₂O₃ nanocomposites were fabricated through a two‐step hydrothermal method. The morphology and composition of the as‐synthesized products were characterized by X‐ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), energy‐dispersive X‐ray spectroscopy (EDS), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). The gas sensing properties of the fabricated products were investigated towards ethanol, acetone, propanol, isopropanol, formaldehyde, chloroform and so on. The results demonstrated that the ZnO/α‐Fe₂O₃ nanocomposites exhibited excellent sensing properties and showed remarkably higher sensing responses and much lower optimum operating temperature compared to individual ZnO and α‐Fe₂O₃. In addition, the ZnO/α‐Fe₂O₃ nanocomposites have some selectivity for ethanol, propanol and isopropanol. The possible gas sensing mechanism was also proposed. Our studies demonstrate that our fabricated materials could be widely used in the future.     

Capsule‐like α‐Fe2O3 nanoparticles: Synthesis,characterization, and growth mechanism

Uniform capsule‐like α‐Fe₂O₃ particles were synthesized via a simple hydrothermal method, employing FeCl₃ and CH₃COONa as the precursors and sodium dodecyl sulfate (SDS) as soft template. X‐ray powder diffraction (XRD), field emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), and high‐resolution transmission electron microscopy were used to characterize the structure of synthesized products. Some factors influencing the formation of capsule‐like α‐Fe₂O₃ particles were systematically investigated, including different kinds of surfactants, the concentration of SDS, and reaction times. The investigation on the evolution formation reveals that SDS was critical to control the morphology of final products, and a possible five‐step growth mechanism was presented by tracking the structures of the products at different reaction stages.     

Crystal structure of the lead bromo-borate Pb<Subscript>2</Subscript>[B<Subscript>5</Subscript>O<Subscript>9</Subscript>]Br from precision single-crystal X-ray diffraction data and the problem of optical nonlinearity of hilgardites

The structural features responsible for the high nonlinear optical activity of crystals of the hilgardite-like anhydrous bromo-borate Pb₂[B₅O₉]Br (space group Pnn2) are analyzed with the use of data obtained from two (precision and conventional) single-crystal X-ray diffraction experiments. The electron-density peaks associated with the stereochemically active lone electron pair are located in free space at two equally probable positions in the vicinity of the Pb(2) atom on the side of the two most distant atoms, Br(1) and Br(2). The stereochemical activity of two nonequivalent lead atoms in the crystal structure increases upon changing over from the Pb(1) atom to the Pb(2) atom. This is in agreement with the behavior of the lone electron pairs in the hilgardite-like hydrated borate Na_0.5Pb₂[B₅O₉](OH)_1.5 · 0.5H₂O and another nonlinear optical borate, namely, Pb₂[B₄O₅(OH)₄](OH)₂ · H₂O, which is related to the compound BiB₃O₆. The most pronounced nonlinear optical properties of the lead bromo-borate Pb₂[B₅O₉]Br as compared to other orthorhombic hilgardites and lead borates are associated with the presence of highly polarized Pb-Br bonds. In this case, the electron density of the lone electron pair of the Pb(2) atom enhances the polarization effect.     

Synthesis and properties of α‐Fe2O3 nanorods

We report synthesis of α‐Fe₂O₃ (hematite) nanorods by reverse micelles method using cetyltrimethyl ammonium bromide (CTAB) as surfactant and calcined at 300 °C. The calcined α‐Fe₂O₃ nanorods were characterized by X‐ray diffraction (XRD), high‐resolution scanning electron microscopy (HRSEM), transmission electron microscopy (TEM), energy dispersive spectrometer (EDS), fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometer (VSM). The result showed that the α‐Fe₂O₃ nanorods were hexagonal structure. The nanorods have diameter of 30‐50 nm and length of 120‐150 nm. The weak ferromagnetic behavior was observed with saturation magnetization = 0.6 emu/g, coercive force = 25 Oe and remanant magnetization = 0.03 emu/g. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Vanadium pentoxide nanobelts: One pot synthesis and its lithium storage behavior

In this paper, we report a synthesis, characterization and electrochemical properties of V₂O₅ nanobelts. V₂O₅ nanobelts have been prepared via hydrothermal treatment of commercial V₂O₅ in acidic (HCl/H₂SO₄) medium at relatively low temperature (160 °C). The hydrothermally derived products have been characterized by powder X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR), Raman spectroscopy, X‐ray photo electron spectroscopy (XPS), UV‐Vis spectroscopy, Scanning/Transmission electron microscopy (SEM/TEM). XRD pattern of V₂O₅ nanobelts show an orthorhombic phase. From the FTIR spectrum, the peak observed at 1018 cm⁻¹ is characteristic of the stretching vibration mode of the terminal vanadyl, V = O. The UV‐Vis absorption spectrum of V₂O₅ nanobelts show maximum absorbance at 430 nm, which was blue‐shifted compared to that of bulk V₂O₅. TEM micrographs reveal that the products consist of nanobelts of 40‐200 nm in thickness and several tens of micrometers in length. The electrochemical analysis shows an initial discharge capacity of 360 mAh g⁻¹ and its almost stabilized capacity is reached to 250 mAh g⁻¹ after 55 cycles. A probable reaction mechanism for the formation of orthorhombic V₂O₅ nanobelts is proposed.     

Calculation of thermodynamic parameters of melts from experimentally determined liquidus‐curves

Thermodynamic parameters of melts (ΔH_S, A₀, A₁) in the system Anorthite‐Diopside and Bi₂O₃‐Bi₄B₂O₉ have been calculated by a rigorous application of solution thermodynamics. The data are internally consistent and yield values of ΔH_S for Anorthite = 133 kJ/mole, Diopside = 81 kJ/mole, Bi₂O₃ = 19 kJ/mole and Bi₄B₂O₉ = 39 kJ/mole. The activity of Anorthite and Diopside in an anorhtitic melt deviates negative from ideality, whereas a diopsidic melt behaves almost ideal. In a “Bi₂O₃” melt the activity of the Bi₂O₃ component is strongly positive, that of Bi₄B₂O₉ is strongly negative. The opposite is observed for the “Bi₄B₂O₉” melt. All calculated liquidi except the Bi₄B₂O₉ liquidus closely match the experimental ones. In contrast to the experimental liquidus the calculated Bi₄B₂O₉ liquidus has an inflection point. The crest of the metastable spinode (solvus) for a “Bi₂O₃” melt is close to the liquidus indicating melt separation at undercooling. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Rapid synthesis of dendrite‐ and platelet‐like α‐Fe2O3 via a hydrothermal oxidation route

Dendrite and platelet‐like α‐Fe₂O₃ microcrystals were synthesized by the oxidation reaction of K₄Fe(CN)₆and NaClO₃ through a simple hydrothermal method. The structures and morphologies of the as‐prepared samples were characterized in detail by X‐ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The experiment results show that NaOH played an important role in controlling the morphology of the final products. The possible mechanism was discussed to elucidate the formation of different morphologies of the α‐Fe₂O₃ microstructures. Besides, the magnetic property of the dendrite α‐Fe₂O₃ microstructure was characterized by a vibrating sample magnetometer (VSM). (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Room,low, and high temperature dehydration and phase transitions of kernite in vacuum and in air

Kernite Na₂B₄O₆(OH)₂·3H₂O dehydration in air at high temperature and in vacuum at room temperature has been studied. It was found that kernite easily dehydrates forming a new phase‐I both on heating and in vacuum. The chemical formula Na₂B₄O₆(OH)₂·1.5H₂O of the new phase‐I has been estimated on the basis of thermogravity analysis. It is triclinic with the unit cell parameters a = 7.047(8), b = 8.76(1), c = 13.08(2) Å, α = 93.40(9), β = 95.32(9), γ = 90.28(9)° changing slightly on pressure reduction. Due to the relatively low temperature (353 K) and reversibility of the kernite ⟷ phase‐I transition an anion of the new phase‐I likely consists of the same chains [B₄O₆(OH)₂]^2– like in kernite structure. The high anisotropy of kernite thermal expansion was explained by approaching of NaO chains due to the initial removing of water molecules from kernite crystal structure. The behaviour of the new phase‐I at low temperatures in vacuum was also investigated. A formation of an additional new phase II has been detected at the temperature of 93 K. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal growth of barium aluminum (gallium) borates

Crystals listed in the JCPDS card in the BaO‐B₂O₃‐Al₂O₃ and BaO‐B₂O₃‐Ga₂O₃ systems are of interest from a viewpoint of the Second Harmonic Generation (SHG). Ba₅Al₄B₁₂O₂₉ and Ba₅Ga₄B₁₂O₂₉ are promising new crystals with SHG activity and with congruent melting mode. These crystals can be grown by the Czochralski method with a size of 3 × 3 × 0.1‐1mm. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterization of SHG candidate crystals in barium aluminum (gallium) borates

Crystals listed in the JCPDS card in BaO‐B₂O₃‐Al₂O₃ and BaO‐B₂O₃‐Ga₂O₃ systems were synthesized by means of a solid‐state reaction method and a liquid‐state reaction method. Synthesized crystals were characterized from a viewpoint of Second Harmonic Generation (SHG) and crystal growth possibility. Ba₅Al₄B₁₂O₂₉ and Ba₅Ga₄B₁₂O₂₉ are promising new candidate crystals from the viewpoint of SHG activity and congruent melting behavior. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electrospinning synthesis and photocatalytic property of CaFe2O4/MgFe2O4 heterostructure for degradation of tetracycline

CaFe₂O₄/MgFe₂O₄ nanowires with heterostructure had been successfully synthesized by electrospinning method. The obtained samples were systematically characterized by scanning electron microscopy (SEM), X‐Ray diffraction (XRD), UV–Vis diffuse reflectance spectra (UV‐Vis DR) and Environment scanning electron microscopy (ESEM). The novel CaFe₂O₄/MgFe₂O₄ nanowires exhibit an enhanced photocatalytic activity for degrading of tetracycline (TC) under visible light. Compared with bare CaFe₂O₄ or MgFe₂O₄ samples, the prepared CaFe₂O₄/MgFe₂O₄ (Ca:Mg:Fe = 3:2:10) composited nanowires show the best photocatalytic performance with a degradation efficiency of 40% after 150 min reaction time. This enhancement is attributed to the heterostructure of CaFe₂O₄/MgFe₂O₄ nanowires, which effectively repress the recombination of photo‐generated electrons and holes. Based on heterostructure and energy band positions, the enhancement of mechanism under visible‐light enhances the photocatalytic activity.