Hydrothermal synthesis and characterization of nanocrystalline Zn-Mn spinel

Hydrothermal method had been used to successfully synthesize the nanocrystalline spinel zinc manganese oxide (ZnMn₂O₄) directly from Zn(CH₃COO)₂·2H₂O, NaOH, Mn(NO₃)₂ and H₂O₂ at 170 °C for the reaction time of 48 h. The effects of the synthesis conditions, such as the Zn/Mn molar ratio, the reaction temperature, the reaction time, the zinc source and the concentrations of NaOH and H₂O₂, on the formation of the Zn-Mn spinel were investigated. The products were characterized by means of X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The results indicated that the compositions of the Zn-Mn spinel with the tetragonal structure were Zn_1.14Mn_1.86O₄. Scanning electron microscope (SEM) and transmission electron microscopy (TEM) images showed that the products at 170 °C were with square-shaped nanocrystalline spinel with the particle size of about 20-50 nm. The thermal behaviors of the products were investigated by thermogravimetric analysis (TG).     

Catalyst efficiency, photostability and reusability study of ZnO nanoparticles in visible light for dye degradation

Polydispersed ZnO nanoparticles (ZnO1000 and ZnO600) with two different windows of particle size distributions (∼120 and 30 nm) were synthesized using citrate gel route and different annealing treatments (1000 and 600 °C, respectively). Photocatalytic efficiency of these samples was compared with TiO₂ in its commercial form-P25, on two dyes, Methylene blue (MB) and Methyl orange (MO). The X-ray diffraction data showed wrutzite ZnO and anatase and rutile phases of P25. UV-visible absorbance spectra of ZnO1000 showed broad absorption range from UV-to-visible (from 382 to 700 nm), as against sharp absorption peaks in UV range for both ZnO600 and P25. The microstructural morphology as seen through scanning electron micrographs showed ZnO1000 with tetrapod-like structures while the ZnO600 showed almost spherical morphologies. Upon subjecting these catalysts to dye solutions in sunlight it was found that both the dyes were completely decolorised within 20 min by ZnO1000, as against partial decolorisation by ZnO600 and P25 ( 53% and 78% for MO and 77% and 88% for MB samples). The effect of catalyst loading (from 125 mg to 1 g) on decolorisation showed that ZnO1000 had good efficiency for all concentrations which was followed by P25 and then by ZnO600. Small perturbations are attributed to the competition between sunlight scattering-induced, reduced irradiation field and the exposed surface area offered by catalyst, which work as active sites for decolorisation. The reusability of the catalysts when studied on fresh dye samples (4 trials), the decolorisation efficiency decreased merely from 99.2% to 99.12% for ZnO1000 as compared to ZnO600 (53.3% to 19.94%) and P25 (78.3% to 31.42%), indicating the efficient reusability of ZnO1000. The effective half life of the catalysts, in terms of number of reuses, were calculated and found to be ∼3 for both ZnO600 and P25 and was >3000 for ZnO1000, which justifies its extremely high reuse. The byproduct analysis (compared with standards prescribed by World Health Organisation (WHO) and Central Pollution Control Board of India (CPCB)) showed cleavage of the chromophore and of other bonds with opening of benzene rings, indicating degradation of the dyes in concurrence with decolorisation, in the stipulated time. Further, cytotoxicity studies performed on SiHa cell lines showed non-toxicity of the byproducts with ZnO1000 as compared to ZnO600 and P25.     

Synthesis and characterization of the SnO2-pillared layered titanate nanohybrid

SnO₂-pillared titanate nanohybrid has been prepared by reacting the exfoliated layered titanate sheets with the nanosized SnO₂ sol particles. The stable two-dimensional colloidal nanosheets could be obtained by intercalating tetrabutylammonium cation into the layered protonic titanate, H_xTi_2−x/4□_x/4O₄·H₂O (x=0.67) with a lepidocrocite-like structure, and by successive exfoliation process in an aqueous solution. Monodispersed SnO₂ nano sol particles were prepared by hydrolysis of SnCl₄·5H₂O in the presence of sodium hydroxide, and then the exfoliated titanate suspension was mixed with SnO₂ nano sol solution until the flocculated products formed. The final product was heated at various temperatures in order to complete the grafting reaction of intercalated SnO₂ nano sol on the interlayer surface of layered titanate. Inductive coupled plasma, X-ray diffraction, thermal analysis and N₂-adsorption-desorption isotherms were carried out to study the hybridizing process and the structure of SnO₂-pillared titanate nanohybrid.     

Green synthesis of ZnO nanoparticles in a room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Nanoparticles of ZnO with the wurtzite structure have been successfully synthesized via a microwave through the decomposition of zinc acetate dihydrate in an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, as a solvent. Fundamental characterizations including X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were conducted for the ZnO nanostructures.To explore the growth mechanism, the samples have been prepared in different irradiation time and also cetyltrimethylammonium bromide (CTAB) has been used as the capping reagent.     

Thermal, optical, mechanical and dielectric properties of nonlinear optical crystal 4-methoxy benzaldehyde-N-methyl 4-stilbazolium tosylate

We have grown organic nonlinear optical 4-methoxy benzaldehyde-N-methyl-4-stilbazolium tosylate (MBST) crystals by slow evaporation technique. The grown crystals were analyzed by powder XRD, FTIR, NMR, UV, Thermal, mechanical and dielectric measurements. Lattice parameters and crystallinity of the crystal is confirmed by the XRD studies. The FTIR and NMR studies give the details about the various functional groups present. In order to study the optical quality of the crystal, the UV-vis absorption spectrum was recorded and cut-off wavelength was determined. Melting point of the crystal is found from the differential scanning calorimetry. The powder SHG studies were done with the Kurtz powder technique and the NLO efficiency is 17.2 times greater than that of urea. The surface of the grown crystal was analyzed with etching. Laser damage threshold studies have been carried out for the crystal using a Q-switched Nd:YAG laser of 10 ns pulses.     

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.     

Influence of initial pH on the particle size and fluorescence properties of the nano scale Eu(III) doped yttria

Europium doped ytrrium oxide (Eu:Y₂O₃) was synthesized by a chemical wet method in the presence of tween-80 and ?-caprolactam in pH range 4-10. It has been observed that the variation in surface area, pore size, and pore volume of the final product, was strongly dependent on the initial pH of the solution. The powder with a large surface area (∼230 m²/g) and low pore diameter (∼16 nm) was obtained when the powder was processed at pH ∼4. The crystallite sizes of the powders processed at pH ∼4 and 10, were found to be 35 and 198 nm, respectively. The structural, chemical and thermal studies of the powders were characterized by X-ray diffraction (XRD), Fourier transformed infrared spectrophotometer (FTIR), Carbon analyzer and Thermogravimetry (TGA). High resolution transmission electron microscopic (HRTEM) study of heat treated powders showed a polygonal morphology with particle size of 40 nm when powder was derived at pH ∼4. Observations of fluorescence suggested that the ⁵D₀→⁷F₂ transition within europium was found to be highly dependent on the initial pH.     

Effect of co-dopant on the formation and properties of anatase-type titania solid solutions doped with niobium

The effect of co-dopant M (M=gallium (Ga), aluminum (Al), and scandium (Sc)) on the formation, crystallite growth, optical band gap, photocatalytic activity, and phase stability of anatase-type titanium dioxide solid solutions (Ti_1−2XNb_XM_XO₂) containing the same amount of dopant niobium (Nb) that were directly formed as nanoparticles under mild hydrothermal conditions at 180 °C for 5 h was investigated. The composition range X of the anatase-type solid solutions (Ti_1−2XNb_XM_XO₂) depended on the co-dopant M, i.e., X=0.15-0.20 for M=Ga and Al, and X=0.33 for M=Sc. A remarkable increase in the lattice parameter c₀ was detected in the solid solutions co-doped with M=Sc. The increase in the amount of co-dopant M=Ga and Al enhanced the crystallite growth of the anatase-type solid solutions under the hydrothermal conditions. The photocatalytic activity of the solid solutions (Ti_0.80Nb_0.10M_0.10O₂) co-doped with M=Sc, Ga, and Al increased in that order. The co-dopant M=Ga promoted the anatase-to-rutile phase transformation of the solid solutions at lower temperature.     

Synthesis and investigation of nonlinear optical properties of semiconductor ZnS nanoparticles

ZnS nanoparticles were prepared by a simple chemical method and using PVP (poly vinylpyrrolidone) as capping agent. The sample was characterized by UV-vis spectrophotometer, X-ray diffraction (XRD) and Z-scan technique. XRD pattern showed that the ZnS nanoparticles had zinc blende structure with an average size of about 2.18 nm. The value of band gap of these nanoparticles was measured to be 4.20 eV. The nonlinear optical properties of ZnS nanoparticles in aqueous solution were studied by Z-scan technique using CW He-Ne laser at 632.8 nm. The nonlinear absorption coefficient (β) was estimated to be as high as 3.2×10⁻³ cm/W and the nonlinear refractive index (n₂) was in order of 10⁻⁸ cm²/W. The sign of the nonlinear refractive index obtained negative that indicated this material exhibits self-defocusing optical nonlinearity.     

Effect of aluminium doping and annealing on structural and optical properties of cerium oxide nanocrystals

Nanocrystalline fluorite-like structures of Ce_1−xAl_xO_2−δ compounds were prepared by the chemical precipitation method using cerium chloride and aluminium chloride as precursors. The prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and diffuse reflectance spectroscopy (DRS). The effects of aluminium doping concentration and annealing on particle size, lattice parameter and band gap energies were investigated. The particle size of Al-doped CeO₂ samples were found to decrease with Al concentration and it increases from 6 to 20 nm as annealing temperature increases to 900 °C.     

Effect of iron doping and annealing on structural and optical properties of cerium oxide nanocrystals

Nanocrystalline fluorite-like structures of Ce_1−xFe_xO_2−δ compounds were prepared by chemical precipitation method using cerium chloride and iron chloride as precursors. The prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and diffuse reflectance spectroscopy (DRS). The effects of iron doping concentration and annealing on particle size, lattice parameter and band gap energies were investigated. The particle size of Fe-doped CeO₂ samples were found to decrease with iron concentration and it increases from 9 to 26 nm as annealing temperature increases to 900 °C.     

Studies on nanocrystalline (Sr,Pb)TiO3 solid solutions prepared via a facile self-propagating combustion method

Macroporous nanocrystalline (Sr,Pb)TiO₃ solid solutions were prepared by a facile self-propagating combustion method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy dispersive X-ray spectrum (EDS) and X-ray photoelectron spectroscopy (XPS). (Sr,Pb)TiO₃ solid solutions showed enhanced photocatalytic activity for the degradation of methyl orange (MO) than pure SrTiO₃ and an optimum performance was observed for Sr_29/32Pb_3/32TiO₃. The possible mechanism for the enhanced photocatalytic activity on (Sr,Pb)TiO₃ solid solutions was proposed.     

The first synthesis of a graphite bis(oxalato)borate intercalation compound

A new graphite intercalation compound containing the bis(oxalato)borate anion, B[OC(O)C(O)O]₂⁻, is prepared for the first time by chemical oxidation of graphite with fluorine gas in the presence of a solution containing the intercalate anion in anhydrous hydrofluoric acid. The products of stage 1-3 compounds are characterized by powder X-ray diffraction, thermogravimetric analysis, and elemental analyses. X-ray diffraction data indicate a standing-up orientation for the borate anion, with long axis perpendicular to the graphene sheets. Elemental analyses provide x and δ for the nominal composition of C_xB[OC(O)C(O)O]₂·δF, where the chelate borate and fluoride are co-intercalates, and indicate a low borate, and high fluoride, intercalate content as compared to anion packing in other graphite intercalation compounds.     

Shape-controlled synthesis of Cu2O nano/microcrystals and their antibacterial activity

Uniform cuprous oxides with different morphologies have been successfully synthesized using polyvinylpyrrolidone (PVP) as a capping agent. X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–vis spectrophotometer, Fourier transform infrared spectrometer (FTIR) and X-ray photoelectron spectroscopy were employed to characterize the structure and morphology of cuprous oxides. It was found that the reaction conditions such as PVP, reducing agent and complexing agent played important roles in the formation of regular cuprous oxide crystals. In addition, their antibacterial activity against Bacillus subtilis (B. subtilis), Staphylococcus aureus (S. aureus), Escherichia coli (E. coli) and Pseudomonas aeruginosa (P. aeruginosa) was also investigated by the Oxford cup method. Results suggested that cuprous oxides are selective in their antibacterial action. They display effective antibacterial activity against S. aureus, B. subtilis and P. aeruginosa. There is no bactericidal ability against E. coli in the tested concentration range, which indicates that E. coli may be a Cu(I)-tolerant bacterium.     

Synthesis of dimethyl carbonate from methyl carbamate and methanol catalyzed by mixed oxides from hydrotalcite-like compounds

A series of mixed oxides calcined from hydrotalcite-like compounds with different cations were prepared and their catalytic activities were studied by the synthesis of dimethyl carbonate (DMC) from methyl carbamate and methanol. Among them, ZnFe mixed oxide possessed the best catalytic ability. Furthermore, the zinc-based mixed oxides as well as the corresponding hydrotalcite-like compounds were characterized by using ICP, TGA, CO₂-TPD and N₂ adsorption/desorption techniques.     

A general and low-cost synthetic route to high-surface area metal oxides through a silica xerogel template

Porous metal oxides with a large surface area are synthesised by means of a procedure based on the templating approach. An inexpensive porous silica xerogel synthesised at moderate temperatures (∼100 °C) in order to preserve the silanol superficial groups was used as template. In a first step, the silica porosity was filled with a concentrated solution containing a metallic salt. Then, the impregnated sample was calcined in air at a temperature of 600 °C. Under these conditions, the metal oxides were synthesised within the confined space provided by the silica pores. Finally, the product was recovered after dissolution of the silica framework in 2 M NaOH solution. The materials obtained by this procedure are made up of aggregates of nanoparticles and/or 3D solid structures containing confined pores. In this work, the synthetic route proposed is illustrated by the preparation of various binary metal oxides (i.e. Fe₂O₃, Cr₂O₃, NiO, CeO₂, Mn₂O₃, Co₂O₃ and Al₂O₃). The BET surface areas measured for these materials are in the range of 100-270 m² g⁻¹. The proposed method is not restricted to the binary metal oxides. It can also be used in the preparation of other inorganic materials such as metal sulphides or mixed metal oxides.     

Synthesis and characterization of micrometric ceramic powders for electro-rheological fluids

Micrometric lamellar ceramic powders of the displacive ferroelectric oxide Bi₄Ti₃O₁₂ were synthesized by co-precipitation of bismuth nitrate and ammonia titanyl solutions followed by a heat treatment. It was found that a complete thermal decomposition is reached at 1000 °C. Structural and thermal evolution of these ceramic powders were studied by X-ray diffraction, thermogravimetry and differential thermal analysis. The homogeneity in size and morphology of these ferroelectric particles are appropriate to prepare electro-rheological fluids. One of these fluids was prepared by dispersing the powders in silicone oil; the complex cluster structure formed by the particles, under an applied AC electric field, was observed.     

Nitrogen containing barium titanate: Preparation and characterisation

The purpose of this work is to study the incorporation of nitrogen into barium titanate at oxygen sites by ammonolysis. The nitrogen content of the resulting barium titanate powders strongly depends on the flow rate of ammonia and the ratio Ba/Ti. The amount of resulting oxygen vacancies is lowered by co-doping with fluoride and tantalum.By avoiding an excess of BaO and exchanging 10 mol% Ti by Ta it is possible to produce powders with nitrogen content of more than 1 wt%. Partial substitution of barium oxide by barium fluoride also increases the nitrogen content. The nitrogen containing powders are colored and show an additional absorption at 500 nm measured in the UV/vis reflectance spectrum. The concentrations of nitrogen and fluorine in the samples were determined using ion-sensitive electrodes. X-ray powder diffraction shows the composition of the powders. The thermal stability was investigated by thermogravimetric analysis, and in order to calculate the specific surface area the three-point BET method was used.     

Preparation, conversion, and comparison of the photocatalytic property of Cd(OH)2, CdO, CdS and CdSe

In this paper, we report the hydrothermal preparation of Cd(OH)₂ nanowires and further conversion to CdO nanobelts, CdS nanowires and CdSe nanoparticles through thermal treatment, solvothermal and mixed-solvothermal routes, respectively. The as-obtained products were characterized by means of powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FEMSEM). Research showed that four cadmium compounds were good photocatalysts for the degradation of organic dyes such as Safranine T and Pyronine B, under irradiation of 365 nm UV light. The order of catalytic activity of different materials was found to be Cd(OH)₂<CdO<CdS<CdSe.