Ethylene glycol-assisted solvothermal fabrication of ZnWO4 nanostructures with tunable size,optical properties,and photocatalytic activities

Large scale of uniform small ZnWO₄ nanocrystals and ZnWO₄ nanorods with tunable size have been fabricated in ethylene glycol (EG)-assisted solvothermal process, ZnWO₄ samples ranging in shape from tiny nanocrystals to nanorods were dependent on the volume ratio of EG and water (H₂O). The optical properties of ZnWO₄ nanocrystals and nanorods were investigated by photoluminescence (PL) spectroscopy, showing longer ZnWO₄ nanorods own the increased PL intensity in comparison with that of shorter ones and small ZnWO₄ nanocrystals. The photocatalytic performance of ZnWO₄ nanostructures was studied also, which indicated that the increased size of ZnWO₄ nanorods resulted the degradation of photocatalytic performance in aqueous solution.     

Structure and NLO property relationship in a novel chalcone co-crystal

Single crystals of a chalcone co-crystal (C₁₈H₁₉NO₄/C₁₇H₁₆NO₃Br; 0.972/0.028) have been grown by slow evaporation from solution. The powder second harmonic generation (SHG) efficiency of this chalcone co-crystal is 7 times that of urea. The dependence of second harmonic (SH) intensity on particle size revealed the existence of phase matching direction in this crystal. The large SHG efficiency observed is mainly due to the unidirectional alignment of molecular dipoles, in which the dipole moment of each molecule adds to establish a net polarization. The weak N–H⋅⋅⋅O hydrogen-bond interactions help to stabilize the noncentrosymmetric crystal packing and also contribute partly to the SHG. The better thermal stability, transparency and high laser damage resistance (>1.5 GW cm⁻² at 532 nm, 8 ns) of this chalcone co-crystal indicate that it is a promising material for frequency doubling of diode lasers down to 470 nm. This molecule also shows a third-order NLO response and good optical limiting property of 8 ns laser pulses at 532 nm. The mechanism for optical limiting in this chalcone was attributed to two-photon induced excited state absorption that leads to reverse saturable absorption. The structure–property relationship in this chalcone and related compounds is discussed based on the experimental results and semiempherical hyperpolarizability calculations.     

Impurities in Magnetic Insulators Studied by Low-Temperature Nuclear Orientation

Although the effects of impurities in metallic magnets have been extensively studied there have been far fewer experiments on impurities in insulating magnets, and, in an effort to understand this problem, we have investigated the effect of impurities in various systems. In MnCl₂⋅4H₂O samples doped with 1.6, 4.0 and 6.2% Co, the ⁵⁴Mn NMRON line is significantly broadened compared to the line in the pure crystal and shows structure on the low frequency side. The nuclear spin-lattice relaxation time is also lower by an order of magnitude. ⁵⁴Mn has also been doped into FeCl₂⋅4H₂O for which a 4-sublattice structure has been proposed and some details of this structure have been obtained. This revised version was published online in September 2006 with corrections to the Cover Date.     

Structure and magnetic properties of Zn<Subscript>0.9</Subscript>Co<Subscript>0.1</Subscript>O nanorods synthesized by a simple sol–gel method using metal acetylacetonate and poly(vinyl alcohol)

Room-temperature ferromagnetism was observed in Zn_0.9Co_0.1O nanorods with diameters and lengths of ∼100–200 nm and ∼200–1000 nm, respectively. Nanorods were synthesized by a simple sol–gel method using metal acetylacetonate powders of Zn and Co and poly(vinyl alcohol) gel. The XRD, FT-IR and SAED analyses indicated that the nanorods calcined at 873–1073 K have the pure ZnO wurtzite structure without any significant change in the structure affected by Co substitution. Optical absorption measurements showed absorption bands indicating the presence of Co²⁺ in substitution of Zn²⁺. The specific magnetization of the nanorods appeared to increase with a decrease in the lattice constant c of the wurtzite unit cell with the highest value being at 873 K calcination temperature. This magnetic behavior is similar to that of Zn_0.9Co_0.1O nanoparticles prepared by polymerizable precursor method. We suggest that this behavior might be related to hexagonal c-axis being favorable direction of magnetization in Co-doped ZnO and the 873 K (energy of 75 meV) being close to the exciton/donor binding energy of ZnO.     

Hydrothermal preparation and characterization of Cd0.9Mn0.1S nanorods

Cd_0.9Mn_0.1S semiconductor nanorods were successfully prepared by the hydrothermal reaction of CdCl₂·2.5H₂O and MnCl₂·5H₂O with (NH₄)₂S in aqueous solution. Atomic absorption spectrometry (AAS) and energy dispersive spectroscopy (EDS) were used to determine the Mn contents of these complex nanorods. The samples were characterized by scanning electron microscopy (SEM-EDS), X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-vis absorption spectra, photoluminescence (PL) and compared with the undoped CdS nanorods. The results showed that nanostructured multiplex compounds with high aspect ratio were obtained via hydrothermal method. The products showed almost totally rod-like morphology with approximately identical diameter about 20 nm and the maximal length up to 200 nm.     

Modification of the optical spectra of mixed K2CoxNi1–x(SO4)2?6H2O crystals

We propose a new method for obtaining K₂Co _x Ni_1–x (SO₄)₂⋅6H₂O (x = 0, 0.4, 0.8, 1) crystals, involving the use of the chlorides (CoCl₂⋅6H₂O and NiCl₂⋅6H₂O) in an aqueous solution instead of the widely used sulfates. We have studied the transmission spectra of the grown single crystals in the range λ = 200–900 nm and the IR reflectance spectra in the 2.5–20 μm region. We have observed a change in the position and intensity of the absorption bands as a function of the composition of the crystals. Based on the Tanabe–Sugano diagrams, we determined the crystal field splitting (D_q) and its dependence on the nickel concentration. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 126–130, January–February, 2009.     

Preparation and characterization of SrSnO3 nanorods

Perovskite strontium stannate (SrSnO₃) nanorods were prepared by annealing the precursor SnSr(OH)₆ nanorods at 600 °C for 3 h. The precursor nanorods were hydrothermally synthesized at 160 °C for 16 h using Sr(NO₃)₂ and SnCl₄·5H₂O as starting materials in the presence of surfactant cetyltrimethyl ammonium bromide (CTAB). As-prepared samples were characterized by X-ray diffraction (XRD), thermogravimetric-differential thermal analysis (TG-DTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and infrared ray spectroscopy (IR). The results show that the as-synthesized powders are made of SrSnO₃ one-dimensional nanorods of about 0.2-1 μm length and 100-150 nm diameter. Possible formation mechanism of SrSnO₃ with nanorod structure under certain conditions was preliminarily analyzed, in which it was thought that CTAB played an important role in the formation process of the nanorod structure. Electrochemical performance of the samples versus Li metal was also evaluated for possible use in lithium-ion batteries.     

Synthesis and photocatalytic activity of porous polycrystalline NiO nanowires

Porous polycrystalline NiO nanowires were prepared via thermal decomposition of the nickelous precursor synthesized via the hydrothermal reaction of nickel chloride with trisodium citrate dehydrate (C₆H₅Na₃O₇⋅2H₂O) in ethanol–H₂O binary solution. The porous polycrystalline nanowires with the diameters of 350 to 450 nm were constructed from NiO nanocrsystals with the cubic structure and the sizes of 8 to 12 nm. The photocatalytic activity of the as-prepared porous NiO nanowires for the degradation of acid scarlet dye was studied. It was found that their photocatalytic activity was stronger than that of NiO powders.     

Selective Synthesis of Wurtzite CdSe Nanorods and Zinc Blend CdSe Nanocrystals through a Convenient Solvothermal Route

By simply changing the reactants’ compositions, wurtzite CdSe nanorods and zinc blend CdSe nanoparticles were selectively synthesized through a convenient solvothermal route with the reaction of cadmium nitrate (Cd(NO₃)₂· 4H₂O), hydrazine hydrate (N₂H₄· H₂O), and Se in ethylenediamine (en) at 140°C. Effects of temperature and composition of the reactants were detected and the amount and gaining rate of Se²⁻ ions were found to determine the morphology and structure of the final product. Dong Wu and Guo-Qiao Lai contributed equally to this paper     

Sodium dodecyl sulfate-assisted synthesis of CoWO4 nanorods

CoWO₄ nanorods were synthesized at 453 K for 12 h by a hydrothermal technology from Na₂WO₄ · 2H₂O and CoCl₂ · 6H₂O in the presence of sodium dodecyl sulfate (SDS). The as-synthesized CoWO₄ nanorods were characterized by various techniques of X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and X-ray detector. Luminescent properties of the samples were measured at room temperature. The results showed that CoWO₄ products are nanorods with diameters of about 20 nm, and lengths ranging between 100 and 200 nm. CoWO₄ nanorods display a very strong PL peak at 453 nm with the excitation wavelength 300 nm. The possible formation mechanism of CoWO₄ nanorods was suggested.     

Application of benzophenones to elucidate the photochemical reaction pathways of hydrogen peroxide with dimethylsulfoxide

Benzophenone ((C₆H₅)₂CO) and decafluorobenzophenone ((C₆F₅)₂CO) were applied to elucidate the photochemical reaction pathway of hydrogen peroxide (H₂O₂) with dimethylsulfoxide (DMSO). When a solution of benzophenone in DMSO was excited with the 355 nm laser light, three transient species were observed in the time-resolved electron paramagnetic resonance spectra: benzophenone ketyl (C₆H₅)₂COH^⋅, methyl^⋅CH₃, and methylsulfinic methyl^⋅CH₂SOCH₃ radicals. However, when decafluoro-benzophenone was used with DMSO, only ketyl and methylsulfinic methyl radicals were observed under the same experimental conditions. When the reaction of benzophenone and DMSO was carried out in the presence of H₂O₂, different time profiles of^⋅CH₃ radicals were observed. In the reaction of decafluorobenzophenone-DMSO-H₂O₂, the time profiles of the radicals were not affected by the presence of H₂O₂. Thus, these results verify that^⋅CH₃ radicals are regenerated in a cyclic pathway, in which^⋅CH₃ radicals attack H₂O₂. The regeneration pathway allows us to observe f-pair polarization throughout the lifetime of^⋅CH₃ radicals, which last several microseconds, an order of magnitude longer than theT ₁ relaxation time of^⋅CH₃ radicals.     

Synthesis of crystalline SrMoO4 nanowires from polyoxometalates

Crystalline SrMoO₄ nanowires were synthesized via a facile hydrothermal process at 180 °C for 10 h. α-(NH₄)₆-P₂Mo₁₈O₆₂·nH₂O, one of polyoxometalates with Dawson structure, was employed as the source of molybdates. The diameter and length of the obtained SrMoO₄ nanowires are about 20 nm and 5-10 μm, respectively. HRTEM results show that the SrMoO₄ nanowires are of high crystallinity with rough surface. However, when Na₂MoO₄·2H₂O was used, there are only SrMoO₄ nanorods with smaller aspect ratio (200/70 nm) in the similar hydrothermal process. The probable growth mechanism was discussed.     

Intramolecular and intermolecular hydrogen bonds in aminophenols

IR-Fourier spectroscopy methods are adopted to study intramolecular and intermolecular hydrogen bonds that form in CCl₄ solutions of aminophenol derivatives and in a solid phase of these compounds pressed in KBr. If a hydroxyl group is present in the molecule in the ortho-position to an amino group, then intramolecular interactions between OH and NH groups will take place in aminophenol solutions. Intramolecular O–H⋅⋅⋅O=S=O and N–H⋅⋅⋅O=S=O hydrogen bonds are found in solutions of compounds containing a sulfonamide fragment. Additional acylation of the amino group causes an intramolecular O–H⋅⋅⋅O=C hydrogen bond to form in solutions. Functional groups OH, NH, SO₂, and C=O interact with one another in various ways in the solid phase to form intermolecular hydrogen bonds in aminophenols.     

Chemical, morphological and chromatic behavior of mural paintings under Er:YAG laser irradiation

Several pigments (malachite CuCO₃⋅Cu(OH)₂, azurite 2CuCO₃⋅Cu(OH)₂, yellow ochre (goethite α-FeOOH, gypsum CaSO₄⋅2H₂O), St. John’s white CaCO₃ formed from slaked lime) and respective mural paintings specimens were subjected to the free-running Er:YAG laser radiation in order to study their damage thresholds, in a broad range of laser fluences, both in dry and wet conditions. The specimens’ damage thresholds were evaluated by spectroscopic methods, colorimetric measurements and microscopic observation. The pigments containing –OH groups were found to be more sensitive than St. John’s white; hence the most sensitive paint layers in dry conditions are those containing malachite, azurite (both 1.3 J/cm²) and yellow ochre (2.5 J/cm²) as compared to the ones containing St. John’s white (15.2 J/cm²). The presence of wetting agents (w.a.) attenuated the pigments chemical alteration. The damage thresholds of all the paint layers, in presence of w.a., were found to be around 2.5 J/cm². The alteration was caused by thermo-mechanical damage and by binding medium ablation of a fresco and a secco prepared specimens, respectively.     

Electrochemical properties of polyaniline-modified sodium vanadate nanomaterials

Sodium vanadate nanomaterials were synthesized at different pH-values of a sodium hydroxide solution of vanadium pentoxide. Polyaniline-modified sodium vanadate nanomaterials were prepared at room temperature and at 3°C by a chemical polymerization method. The crystal structure and phase purity of the samples have been examined by powder XRD. The samples were identified as HNaV₆O₁₆⋅4H₂O and Na_1.1V₃O_7.9. The electrochemical measurements show that polyaniline-modified sodium vanadate hydrated nanomaterials provide higher current density than the sodium vanadate nanomaterials.     

Hydrogen bonds of anti-HIV active aminophenols

Analysis of IR-Fourier spectra from solutions and crystals of antiviral sulfo-containing aminophenols has shown that various types of intramolecular and intermolecular interactions can occur in molecules of these compounds. Three types of intramolecular hydrogen bonds (O–H⋅⋅⋅N, O–H⋅⋅⋅O=S=O, and N–H⋅⋅⋅O=S=O) are formed in CCl₄ solutions of the sulfo-containing aminophenols. The formation of intermolecular H-bonds involving the NH- and OH-groups and the preservation of the intramolecular O–H⋅⋅⋅O=S=O H-bond are characteristic of the anti-HIV active aminophenol crystals. Spectral attributes are determined in order to distinguish between the anti-HIV active and inactive sulfo-containing aminophenols.     

Thermal analysis of InP-based quantum cascade lasers for efficient heat dissipation

We have theoretically investigated the thermal characteristics of double-channel ridge–waveguide InGaAs/InAlAs/InP quantum cascade lasers (QCLs) using a two-dimensional heat dissipation model. The temperature distribution, heat flow, and thermal conductance (G _th) of QCLs were obtained through the thermal simulation. A thick electroplated Au around the laser ridges helps to improve the heat dissipation from devices, being good enough to substitute the buried heterostructure (BH) by InP regrowth for epilayer-up bonded lasers. The effects of the device geometry (i.e., ridge width and cavity length) on the G _th of QCLs were investigated. With 5 μm thick electroplated Au, the G _th is increased with the decrease of ridge width, indicating an improvement from G _th=177 W/K⋅cm² at W=40 μm to G _th=301 W/K⋅cm² at W=9 μm for 2 mm long lasers. For the 9 μm×2 mm epilayer-down bonded laser with 5 μm thick electroplated Au, the use of InP contact layer leads to a further improvement of 13% in G _th, and it was totally raised by 45% corresponding to 436 W/K⋅cm² compared to the epilayer-up bonded laser with InGaAs contact layer. It is found that the epilayer-down bonded 9 μm wide BH laser with InP contact layer leads to the highest G _th=449 W/K⋅cm². The theoretical results were also compared with available obtained experimentally data.     

A new isomorph of ferrous chloride tetrahydrate: A Fe Mössbauer and X-ray crystallography study

This paper outlines the discovery of a newly characterised isomorph of ferrous chloride tetrahydrate, Fe(H₂O)₆·FeCl₄(H₂O)₂, which was initially identified by X-ray crystallography and confirmed by Mössbauer spectroscopy. The X-ray analysis identified the space group as P2₁/c with essentially the same unit cell dimensions as the well-known isomorph, FeCl₂·4H₂O, except that one edge is doubled due to two discrete [Fe(H₂O)₆]²⁺ and [FeCl₄(H₂O)₂]²⁻ species per unit cell. Time-series Mössbauer studies revealed this new isomorph to be unstable upon atmospheric exposure, decaying to the well-known structure over a period of days. Density functional theory calculations support an energetically favourable catalytic interconversion involving adsorbed water. A high-precision redetermination on the FeCl₂·4H₂O crystal structure, which is also in space group P2₁/c, is also reported, providing the unit cell parameters: a=5.8765(3) Å, b=7.1100(3) Å, c=8.4892(5) Å and β=111.096(1)°.     

Charge compensation on the luminescence properties of ZnWO4:Tb phosphors via hydrothermal synthesis

A phosphor Tb³⁺-doped ZnWO₄ (ZWO:Tb) phosphors were prepared by a hydrothermal method. X-ray powder diffraction (XRD) analysis revealed that the as-obtained sample is pure ZnWO₄ phase. The excitation and emission spectra indicated that the phosphor could be well excited by ultraviolet light (272 nm) and emit blue light at about 491 nm and green light at about 545 nm. Significant energy transfer from WO₄²⁻ groups to Tb³⁺ ions has been observed. Two approaches to charge compensation are investigated: (a) 2Zn²⁺ = Tb³⁺ + M⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ acting as a charge compensator; (b) 3Zn²⁺ = 2Tb³⁺ + vacancy. Compared with two charge compensation patterns in the ZnWO₄:Tb³⁺, it has been found that ZnWO₄:Tb³⁺ phosphors used Li⁺ as charge compensation show greatly enhanced bluish-green emission under 272 nm excitation.     

Microwave-assisted synthesis and magnetic property of magnetite and hematite nanoparticles

Nanoparticles of magnetite (Fe₃O₄) and hematite (α-Fe₂O₃) have been prepared by a simple microwave heating method using FeCl₃, polyethylene glycol and N₂H₄·H₂O. The amount of N₂H₄·H₂O has an effect on the final phase of Fe₃O₄. The morphology of α-Fe₂O₃ was affected by the heating method. Crystalline α-Fe₂O₃ agglomerates were formed immediately at room temperature and most of these nanoparticles within agglomerates show the same orientation along [110] direction. After microwave heating, ellipsoidal α-Fe₂O₃ nanoparticles were formed following an oriented attachment mechanism. Both Fe₃O₄ and α-Fe₂O₃ nanoparticles exhibit a small hysteresis loop at room temperature.