Synthesis of nanocrystalline and mesoporous zinc sulphide from a single precursor Zn(SOCCH3)2Lut2 complex

We report the formation of mesoporous zinc sulphide, composed by the fine network of nanoparticles, which was formed via a single precursor Zn(SOCCH₃)₂Lut₂ complex. The complex was chemically synthesized using zinc carbonate basic, 3,5-lutidine and thioacetic acid, in air. The metal precursor complex was characterized using different conventional techniques. Thermogravimetric analysis (TGA) result indicates that the decomposition of the complex starts at 100 °C and continues up to 450 °C, finally yielding ZnS. ZnS nanocrystals were characterized by powder X-ray diffraction (XRD) technique, field emission scanning electron microscopy (FESEM), N₂-sorption isotherm, UV-vis spectroscopy and photoluminescence (PL) spectroscopy. The grain diameter of nanocrystals was found to be 4-5 nm. The material followed Type-IV N₂-sorption isotherm, which is the characteristic of mesoporous materials. The band gap energy, as obtained from optical measurements was around 3.8 eV.     

Improved dielectric properties of (Pb,Ca)TiO3 thin films prepared by metal-organic decomposition method

(Pb,Ca)TiO₃ (PCT) thin films have been deposited on Pt/Ti/SiO₂/Si substrate by metal-organic decomposition (MOD) technique. The film processing parameters such as drying and annealing temperatures have been optimized to obtain good-quality PCT films. Compositional analysis of the film has been studied by X-ray photoelectron spectroscopy (XPS). The effect of the annealing temperature on the crystalline structure, microstructure and electrical properties have been investigated by X-ray diffraction, atomic force microscopy (AFM) and impedance analyzer, respectively. Amorphous PCT films form at 350 °C and crystallize in the perovskite phase following the isothermal annealing at ?650 °C for 3 h in oxygen ambient. Typical tetragonal structure of the PCT film is evidenced from X-ray diffraction pattern. The grain size in the PCT films increases with an increase in annealing temperature. Significant improvement in the dielectric constant value is observed as compared to other reported work on PCT films. The observed dielectric constant and dissipation factor at 100 kHz for 650 °C annealed PCT films are 308 and 0.015, respectively. The correlation of the film microstructural features and electrical behaviors is described.     

Structural and electrical impedance study of Pb(Sr1/3Nb2/3)O3

Lead-based ceramic Pb(Sr_1/3Nb_2/3)O₃ (PSN) is prepared by the columbite precursor method and structurally characterized using XRD. The X-ray diffraction shows a perovskite structure with cubic pyrochlore phase. Detailed studies of ε′ and ε″ of the compounds show that the compounds exhibit dielectric anomaly. Impedance spectroscopy is used to characterize the electrical behaviour. Results indicate that the relaxation mechanism of the material is temperature dependent and has dominant bulk contribution in different temperature ranges. Modulus spectroscopic data were used to gain an insight into the electrical properties of the samples and with a view to observe the relaxations in them. Frequency dependence dielectric permittivity shows typical Debye-type dielectric dispersion. Temperature-dependent DC resistivity shows that resistance decreases with the increase in temperature and follows Arrhenius behaviour in different temperature regions.     

Synthesis of earth-abundant Cu2SnS3 powder using solid state reaction

Cu₂SnS₃ (CTS) powder has been synthesized at 200 °C by solid state reaction of pastes consisting of Cu and Sn salts and different sulphur compounds in air. The compositions of the products is elucidated from XRD and only thiourea is found to yield CTS without any unwanted CuS_x or SnS_y. Rietveld analysis of Cu₂SnS₃ is carried out to determine the structure parameters. XPS shows that Cu and Sn are in oxidation states +1 and +4, respectively. Morphology of powder as revealed by SEM shows the powder to be polycrystalline with porous structure. The band gap of CTS powder is found to be 1.1 eV from diffuse reflectance spectroscopy. Cu₂SnS₃ pellets are p-type with electrical conductivity of 10⁻² S/cm. The thermal degradation and metal–ligand coordination in CTS precursor are studied with TGA/DSC and FT-IR, respectively, and a probable mechanism of formation of CTS has been suggested.     

Orientation-dependent dielectric properties of Ba(Sn0.15Ti0.85)O3 thin films prepared by sol-gel method

The orientation-dependent dielectric properties of barium stannate titanate (Ba(Sn_0.15Ti_0.85)O₃, BTS) thin films grown on (1 0 0) LaAlO₃ single-crystal substrates through sol-gel process were investigated. The nonlinear dielectric properties of the BTS films were measured using an inter-digital capacitor (IDC). The results show that the in-plane dielectric properties of BTS films exhibited a strong sensitivity to orientation. The upward shift of Curie temperature (T_c) of the highly (1 0 0)-oriented BTS thin films is believed to be attributing to a tensile stress along the in-plane direction inside the film. A high tunability of 47.03% was obtained for the highly (1 0 0)-oriented BTS films, which is about three times larger than that of the BTS films with random orientation, measured at a frequency of 1 MHz and an applied electric field of 80 kV/cm. This work clearly reveals the highly promising potential of BTS films for application in tunable microwave devices.     

Multicomponent GeSe2-CdI2-TeO2 (Bi2O3) systems: glass formation and properties

The glass-forming regions of the GeSe₂-CdI₂-TeO₂ (I), GeSe₂-CdI₂-Bi₂O₃ (II) and GeSe₂-TeO₂-Bi₂O₃ (III) systems have been determined. The obtained glassy phases have been characterized by their basic physicochemical parameters such as temperatures of glass transition, crystallization, and melting, density and microhardness. The phase T-X diagram of the GeSe₂-CdI₂ system, which is the basic joint line for systems I and II, has been specified. Three non-variant equilibria (two eutectic and one syntectic) have been observed at temperatures 350, 280 and 375 °C for compositions containing 15, 95 and 33.3 mol% GeSe₂, respectively. A new intermediate phase with probable composition of 2CdI₂·GeSe₂ has been formed.     

Photocatalytic abilities of gel-derived P-doped TiO2

P-doped TiO₂ nanoparticles were synthesized through hydrolysis and condensation of Ti(OC₂H₅)₄ with H₃PO₄ additions. Effects of [H₃PO₄]/[Ti(OC₂H₅)₄] molar ratios on the anatase-to-rutile phase transformation, crystallite sizes, surface areas, and photocatalytic abilities of the gel-derived P-doped TiO₂ were investigated. The P-doped TiO₂ nanoparticles prepared by [H₃PO₄]/[Ti(OC₂H₅)₄]=0.03 were composed of anatase monophase even at 900 ^oC and possessed very strong photocatalytic ability. Kinetic studies on the P-doped TiO₂ to photocatalytically decompose methylene blue under irradiation of 365 nm UV light found that the P-doped TiO₂ prepared by [H₃PO₄]/[Ti(OC₂H₅)₄]=0.03 and calcined at 800 ^oC had the specific reaction rates, at 25 °C, k_A,m=0.76 m³/(kg min) (based on the mass of P-doped TiO₂) and k_A,BET=46.2×10⁻⁶ m/min (based on the BET surface area of P-doped TiO₂), which is superior to the performance of a commercial product, P25 (k_A,m=0.22 m³/(kg min) and k_A,BET=4.8×10⁻⁶ m/min).     

Characterization, sintering and dielectric properties of nanocrystalline zinc oxide prepared by a citric acid-based combustion route

Nanosized zinc oxide has been synthesized through a novel single step solution combustion route using citric acid as fuel. The X-ray diffraction (XRD) analysis revealed that the synthesized ZnO nanopowder has the pure wurtzite structure. The phase purity of the nanopowder has been confirmed using differential thermal analysis (DTA), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR). The morphology and crystalline size of the as-prepared nanopowder characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that the powder consisted of a mixture of nanoparticles and nanorods. The nanocrystalline ZnO could be sintered to ∼97% of the theoretical density at 1200 °C in 4 h. The dielectric constant (ε_r) and dielectric loss (ε_i) of sintered ZnO pellets at 5 MHz were 1.38 and 9×10⁻², respectively, at room temperature.     

Preparation and characterization of NiFe2O4/NiO composite film via a single-source precursor route

NiFe₂O₄/NiO nanocomposite thin films have been successfully prepared through a facile route using nickel iron layered double hydroxide (NiFe-LDH) as a single-source precursor. This synthetic approach mainly involves the formation of NiFe-LDH film by casting the slurry of NiFe-LDH precursor on the α-Al₂O₃ substrate, followed by high-temperature calcination. The composition, microstructure and properties of the films were characterized in detail by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX) and vibrating sample magnetometer (VSM). The results indicate that NiFe₂O₄/NiO composite film was composed of granules with diameter less than 100 nm, and the thickness of the film was in the range 1-2 μm. The magnetization of the film can be tuned by alternating the Ni/Fe molar ratio of LDH precursor. In addition, the method developed should be easily extended to fabricate other MFe₂O₄/MO composite film systems with specific applications just by an appropriate combination of divalent/trivalent composition in the precursor of LDHs.     

Particle size distribution and electrochemical properties of LiFePO4 prepared by a freeze-drying method

The electrochemical performance of carbon-coated nanocrystalline LiFePO₄ prepared by a freeze-drying method is examined. This method is based on the thermal decomposition of homogeneous phosphate-formate precursors. Structural and morphological characterization of LiFePO₄ is carried out by powder XRD, BET measurements, SEM and XPS analyses. The electrochemical behaviour is tested in model lithium cells using galvanostatic mode. By changing the solution concentration, the freeze-drying method allows preparing LiFePO₄ with mean particle sizes between 60 and 100 nm and different particle size distributions. The content of carbon appearing mainly on the particle surface depends on both the solution concentration and the annealing temperature. The effect of particle size distribution on the voltage profile of LiFePO₄ is also demonstrated. The specific capacity is mainly determined by the amount of carbon deposited on the particle surfaces.     

Influence of lithium phosphate concentration and temperature on the electrical conduction of (76V2O5-24P2O5)1−X (Li3PO4)X glasses

Characterization of the (76V₂O₅-24P₂O₅)_1−X (Li₃PO₅)_X, where X=0.0,0.01,0.02,0.10 and 0.15, glass has been done using X-ray diffraction and differential thermal analysis (DTA). The dc conductivity of the glass samples was studied over a temperature range from 300 to 593 K. The temperature dependence of dc conductivity shows two regions. One at relatively high temperature range, above θ_D/2, and the other at relatively low temperature range, below θ_D/2. The I-V characteristics of the glasses have been studied as a function of both temperature and Li₃PO₄ content. The I-V characteristics exhibits threshold switching with differential negative resistance. It's found that both the threshold voltage (V_th) and threshold current (I_th) are dependent on the temperature and lithium phosphate concentration.     

Preparation and characterization of the layered hybrids (CnH2n+1NH3)2FeCl4

The series of the hybrids (C_nH_2n+1NH₃)₂FeCl₄, where n=2, 4, 6, 8, 10 and 12, were synthesized in HCl solutions. The optimum conditions of synthesis were investigated including the sequence of adding reactants, the stoichiometric ratio of the reactants, the reaction time and the drying procedures. The results demonstrate that the order of adding reactants, the drying temperature and drying time have little effect on the structures of the products. But for the hybrids of n?10, longer reaction time is needed to form the layered structures. The X-ray diffraction (XRD) patterns and the images of scanning electron microscopy of the products demonstrate that the hybrids crystallize well with typical layered structures. Chemical analysis of C, H and N confirms that the hybrids consist of the elements in the ratio of the molecular formulas. The d values, the interlayer distance between the two adjacent inorganic sheets of each hybrid, are obtained from the XRD patterns and they suggest that the organic chains interdigitate between the inorganic sheets. The longer the organic chains are, the more interdigitations there are. This can be explained by the different interaction strengths between the organic species when the chain lengths change. These different interactions can also explain the phenomena observed in the synthesis and the decomposing temperatures of the hybrids.     

Effect of AgNO3 additive/doping on microstructure and superconductivity of the Pb doped Hg: 1223 thin film prepared through spray pyrolysis

We report successful fabrication of Ag doped Hg:1223 films by reacting Ba₂Ca_2.3Cu_3.3O_z(Ag_y): y=0, 0.02, 0.025, 0.05, 0.1 and 0.2 precursors deposited by spray pyrolysis on SrTiO₃ (100) substrates, in controlled Hg+Pb ambient, in an evacuated sealed quartz tube at 820 °C for 4 h. The effects of AgNO₃ addition on the superconducting properties of Hg/(Pb):1223 films are studied. The addition of low concentration of silver e.g. y≈0.025 results in a slight increase in T_c (R=0) from 125 to 126 K and the dc critical current density (J_c) decreases with the increasing Ag in Hg(Pb):1223 (Ag_y) films. The microstructural details exhibit the curious characteristics of spiral like features for lower concentrations of silver i.e. up to y=0.05. These improvements are believed to be due to the liberation of oxygen through the dissociation of AgNO₃ at higher temperature and passivation of weak link effects through the segregation of silver at these grain boundaries. The addition of silver content y≥0.05 resulted in the decrease in transition temperature. The J_c is observed to decrease steadily with increasing Ag content. The microstructural features, e.g. spiral are also found to deteriorate with increasing silver content. The deterioration in superconducting properties at high Ag content is believed to be mainly due to the formation of Ag-Hg amalgam.     

Preparation and photocatalytic activity of nitrogen-doped TiO2 hollow nanospheres

TiO₂ hollow nanospheres were prepared using silicon oxide as a template. N-doped titanium oxide hollow spheres, TiO_2−xN_x were synthesized by reacting TiO₂ hollow spheres with thiourea at 500 °C. XRD and XPS data showed that oxygen was successfully substituted by nitrogen through the nitrogen-doping reaction, and finally N-doped TiO₂ hollow spheres were formed. The N-doped TiO₂ hollow spheres showed new absorption shoulder in visible light region so that they were expected to exhibit photocatalytic activity in the visible light. The photocatalytic activity of N-doped TiO₂ hollow spheres under visible light was similar to that of normal spherical TiO_2−xN_x in spite of the structural difference.     

Nanocrystalline Sr2FeMoO6 prepared by citrate-gel method

Double perovskite Sr₂FeMoO₆ powders with small crystallite size have been synthesised with citrate-gel method. The starting solution pH was varied between 1.5 and 9.0 resulting in large differences in the phase composition and ordering of B^′/B^″ sites. The samples prepared at 975 °C had crystallite sizes under 40 nm whereas crystallite sizes of the samples prepared at 1050 °C were between 78 and 239 nm. The XRD patterns were refined with spacegroup I 4/m, which gave good results for both batches, although clearly better results were obtained with monoclinic P 2₁/n spacegroup for the 975 °C batch. The ordering and the saturation magnetization agreed well with each other after treatment at 1050 °C, but the samples prepared at 975 °C had a strongly reduced saturation magnetization from that given by the ordering.     

Structural deformation monitored by vibrational properties and orbital modeling in (Pb,Sm)TiO3 systems

Pb_1−xSm_xTiO₃ (PST) powders with x varying from 0 to 0.1 were obtained by the polymeric precursor method, a soft chemical route. The vibrational properties relating tetragonal to pseudo-cubic phase transition were studied by Raman spectroscopy. The results obtained showed that the phase transition is extremely dependent upon the samarium content and presents a diffuse behavior. Monitoring of the oxygen 2p and titanium 3d orbitals was performed by the periodic mechanical quantum method, revealing the changes that occur with the distribution and contribution of the hybrid orbitals due to the samarium influence.     

Photocatalytic H2 evolution under visible light irradiation on AgIn5S8 photocatalyst

A new visible-light-driven photocatalyst AgIn₅S₈ was prepared by a simple two-step process, which involves the first co-precipitation process at room temperature and subsequently heat-treatment process at 750 °C under pure argon flow protection. The obtained AgIn₅S₈ sample showed high activity for the evolution of hydrogen under visible light irradiation (λ?420 nm) from aqueous solution containing S²⁻ and SO₃²⁻ ions as sacrificial electron donors. It was found that several experimental parameters, such as the concentration of sacrificial reagents and the loading of Pt co-catalyst, play important roles on the evolution rate of H₂ under visible light irradiation.     

Structural study by X-ray diffraction and Mössbauer spectroscopy of a new synthetic iron phosphate: K4MgFe3(PO4)5

A new iron phosphate K₄MgFe₃(PO₄)₅ has been synthesized by the flux method and characterized by single-crystal X-ray diffraction and Mössbauer spectroscopy. It crystallizes in the tetragonal system with the space group and the unit cell parameters a=9.714(3) Å and c=9.494(5) Å. The crystal structure is of a new type. It exhibits a three-dimensional framework built up from corner-sharing MO₅ (M=0.75Fe+0.25Mg) trigonal bipyramids and PO₄ tetrahedra. The K⁺ ions are occupying large eight-sided tunnels running along c. A room temperature Mössbauer study confirmed the +3 valence state of iron and its five-coordination.     

Synthesis and characterization of a new monophosphate [2,5-(CH3)2C6H3NH3]H2PO4

Chemical preparation, calorimetric studies, crystal structure and spectroscopic investigations are given for a new noncentrosymmetric organic cation monophosphate [2,5-(CH₃)₂C₆H₃NH₃]H₂PO₄. This compound is orthorhombic P2₁2₁2₁ with the following unit-cell parameters: a=5.872(4), b=20.984(3), c=8.465(1) Å, Z=4, V=1043.0(5) Å³ and D_x=1.396 g cm⁻³. Crystal structure has been solved and refined to R=0.048 using 2526 independent reflections. Structure can be described as an inorganic layer parallel to (a,b) planes between which organic groups [2,5-(CH₃)₂C₆H₃NH₃]⁺ are located. Multiple hydrogen bonds connecting the different entities of compound thrust upon three-dimensional network a noncentrosymmetric configuration.     

Synthesis and enhanced photocatalytic activity of NaNbO3 prepared by hydrothermal and polymerized complex methods

We prepared NaNbO₃ by several methods, namely solid-state reaction (SSR), hydrothermal (HT) and polymerized complex (PC) methods, and investigated the relationships between the photocatalytic activity and the particle size and morphology. The photocatalytic activity was evaluated by H₂ evolution from an aqueous methanol solution and pure water splitting in the presence of the Pt(0.5 wt%)/NaNbO₃ and RuO₂(1.25 wt%)/NaNbO₃, respectively. It is found that the sample prepared by PC with smallest particles exhibits the highest photocatalytic activity in both reactions. Moreover, the HT sample with the cubic and rectangular shape also shows the enhanced photocatalytic activity for H₂ evolution from an aqueous methanol solution in comparison with that of the sample prepared by SSR.