Electronic Structure and Size of TiO2 Nanoparticles of Controlled Size Prepared by Aerosol Methods

Summary.  A complete characterization of nanostructures has to deal both with electronic structure and dimensions. Here we present the characterization of TiO₂ nanoparticles of controlled size prepared by aerosol methods. The electronic structure of these nanoparticles was probed by X-ray absorption spectroscopy (XAS), the particle size by atomic force microscopy (AFM). XAS spectra show that the particles crystallize in the anatase phase upon heating at 500°C, whereas further annealing at 700°C give crystallites of 70% anatase and 30% rutile phases. Raising the temperature to 900°C results in a complete transformation of the particles to rutile. AFM images reveal that the mean size of the anatase particles formed upon heating at 500°C is 30 nm, whereas for the rutile particles formed upon annealing at 900°C 90 nm were found. The results obtained by these techniques agree with XRD data. Received October 5, 2001. Accepted (revised) December 6, 2001     

Biosynthesis and Photocatalytic Properties of SnO<Subscript>2</Subscript> Nanoparticles Prepared Using Aqueous Extract of Cauliflower

This work reports the biosynthesis of Sn(OH)₂ using aqueous extract of fresh cauliflower (Brassica oleracea L. var. botrytis), and the subsequent preparation of SnO₂ nanoparticles at two different annealing temperatures of 300 and 450 °C for 2 h. The obtained SnO₂ nanoparticles were denoted as S1 and S2 for the samples prepared at 300 and 450 °C, respectively. XRD analysis identified rutile tetragonal phase of SnO₂ nanoparticles and TEM results gave a quasispherical and spherical morphologies for S1 and S2 respectively of the size range 3.62–6.34 nm. The optical properties were studied with UV–vis and photoluminescence (PL) spectroscopies, and the nanoparticles showed blue shift in their absorption edges. The observed emission peak in the PL spectra found around 419 nm is attributable to oxygen vacancies and defects. Photocatalytic activities of the nanoparticles (S1 and S2) were studied using methylene blue (MB) under ultraviolet light irradiation and the results reveal 91.89 and 88.23% degradation efficiency of MB by S1 and S2 respectively over a period of 180 min.     

Thermal and hydrothermal stability of flame hydrolytically synthesized SiO2/TiO2 mixed oxides

The phase stability of the two TiO₂ modifications (anatase and rutile) in fumed SiO₂/TiO₂ nano-composites (0–24.8 wt-% silica) under thermal and hydrothermal conditions was investigated by X-ray powder diffraction, transmission electron microscopy (TEM) and gas adsorption methods (BET). The results show that the phase transformation from anatase to rutile type of structure and the growth of anatase crystallites are significantly retarded by mixing small amounts of SiO₂ into TiO₂, while the specific surface area is maintained. The SiO₂/TiO₂-composites reveal a remarkable shift in the anatase to rutile transformation temperature from approx. 500 °C (pure TiO₂) to approx. 1000 °C (samples with SiO₂ contents of more than 10%). The rate of phase transformation from anatase to rutile is enhanced under hydrothermal conditions compared to conventional thermal treatment, e.g. pure titania (AEROXIDE^® TiO₂ P25) annealed under hydrothermal conditions (100 g/m³ absolute humidity, 4 h at 600 °C) had a rutile content of 85%, while the same specimens annealed in absence of humidity contained only 46% rutile. However, the difference in rate of phase transformation became less pronounced when the silica content in SiO₂/TiO₂-composites was further increased.TEM results showed that the surface of the anatase crystallites was covered with silica. This averts coalescence of anatase crystallites and keeps them under a critical size during the annealing process. When the crystal domains grew larger, a rapid conversion to rutile took place. The critical size of anatase crystallites for the phase transformation was estimated to be 15–20 nm.     

Synthesis and Characterization of SnO2 Nanopowder Prepared by Precipitation Method

Tetragonal SnO₂ nanopowder of the range ～8 nm has been successfully synthesized by precipitation method. The prepared powder was characterized by thermogravimetry analysis (TGA), x-ray diffraction (XRD), transmission electron microscopy (TEM), Infrared spectroscopy (FTIR), x-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS), and room temperature photoluminescence (PL) spectroscopy. Experimental results show that the prepared powder was phase pure SnO₂ of tetragonal rutile structure without any impurities. The optical band gap was determined to be 4.26 eV, using diffuse reflectance technique with the aid of Kubelka-Munk relation. The blue shift of the band gap was attributed to the quantum size confinement effect.     

Preparation of nanoparticles and hollow spheres of ��-Fe2O3 and their properties

Uniform nanoparticles and hollow microspheres of hematite (??-Fe₂O₃) were obtained via a hydrothermal method by using iron (III) chloride as a precursor. The effects of reactant concentration, reaction time and temperature on the morphology of the samples were studied. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and superconducting quantum interference device magnetometer (SQUID) measurement. ??-Fe₂O₃ nanoparticles show a superparamagnetic behavior and the average size of the spherical particles was around 60 nm. However, hollow microspheres show a normal ferromagnetic behavior at room temperature with remanent magnetization and coercivity of 0.2482 emu/g and 2,516 Oe, respectively, and their average diameter was around 2 ??m. The effects of reactant concentration and reaction temperature on the formation of the products were investigated. The experimental results reveal that the magnetic properties of hematite can be tuned by controlling the morphology.     

Concurrent synthesis of SnO/SnO<Subscript>2</Subscript> nanocomposites and their enhanced photocatalytic activity

The SnO/SnO₂ nanocomposites were synthesized using semisolvothermal reaction technique. These nanocomposites were prepared using different combination of solvents viz., ethanol, water, and ethylene glycol at 180 °C for 24 h. The synthesized nanocomposites were analyzed with various characterization techniques. Structural analysis indicates the formation of tetragonal phase of SnO₂ for the sample prepared in ethanol, whereas for other solvent combinations, the mixture of SnO and SnO₂ having tetragonal crystal structures were observed. The optical study shows enhanced absorbance in the visible region for all the prepared SnO/SnO₂ nanocomposites. The observed band gap was found to be in the range of 3.0 to 3.25 eV. Microstructural determinations confirm the formation of nanostructures having spherical as well as rod-like morphology. The size of nanoparticles in ethanol-mediated solvent was found to be in the range of 5 to 7 nm. Thermogravimetric analysis indicate the weight gain around 1.3 wt% confirming the conversion of SnO to SnO₂ material. The photocatalytic activity of synthesized nanocomposites was evaluated by following the aqueous methylene blue (MB) degradation. The sample prepared in ethylene glycol-mediated solvent showed highest photoactivity having apparent rate constant (K_app) 0.62 × 10^?2 min^?1.     

Time‐Resolved Phase Transitions of the Nanocrystalline Cubic to Submicron Monoclinic Phase in Zirconia

The nanocrystalline cubic, tetragonal, and submicron monoclinic phases of pure zirconia were prepared by thermal decomposition of carbonate and hydroxide precursors. The crystallization and isothermal phase transformations of the oxide were studied using high temperature X‐ray diffraction, X‐ray diffraction and Raman spectra of quenched samples. Cubic zirconia formed first, and then progressively transformed to tetragonal and monoclinic phases at temperatures as low as 320°C. The cubic, tetragonal, and monoclinic phases for ZrO₂ were found to be distinct functions of crystallite size, indicating the nanocrystalline nature of these phases. They were found to exist within critical size ranges of 50 to 140 Å, 100 to 220 Å and 190 to 420 Å (±5 Å), respectively. Thus, as the crystallites grow during annealing, they first transform from cubic to tetragonal and then from tetragonal to monoclinic at critical sizes. The classical Avrami equation for nucleation and growth was applied to the tetragonal to monoclinic phase transition.     

DSC investigation of nanocrystalline TiO<Subscript>2</Subscript> powder

The aim of the article is to investigate the influence of particle size on titanium dioxide phase transformations. Nanocrystalline titanium dioxide powder was obtained through a hydrothermal procedure in an aqueous media at high pressure (in the range 25–100 atm) and low temperature (≤200 °C). The as-prepared samples were characterized with respect to their composition by ICP (inductive coupled plasma), structure and morphology by XRD (X-ray diffraction), and TEM (transmission electron microscopy), thermal behavior by TG (thermogravimetry) coupled with DSC (differential scanning calorimetry). Thermal behavior of nanostructured TiO₂ was compared with three commercial TiO₂ samples. The sequence of brookite–anatase–rutile phase transformation in TiO₂ samples was investigated. The heat capacity of anatase and rutile in a large temperature range are reported.     

The influence of concentration of doping elements on anatase–rutile transformation at the synthesis of rutile pigments (Ti,Cr,Nb)O2 and their pigmentary properties

An analysis of the effects of dopants concentration and different starting titanium compounds on the anatase to rutile phase transformation at the synthesis of rutile pigments Ti_1?3xCr_xNb_2xO_2±δ is presented in this study. The main goal was to analyze reaction mixtures for x = 0.05 (previous study) and 0.30 by simultaneous TG–DTA analysis and to determine the temperature of anatase–rutile transition. For x = 0.05, initial temperatures 760–830 °C are needful for a formation of rutile structure. The temperature is the lowest for the hydrated Na₂Ti₄O₉ paste (760 °C) and similar for other starting compounds of titanium. But for x = 0.30, the anatase–rutile transition begins at higher temperatures 910–1,030 °C because of high-Nb content, which is the inhibitor of this modification change. In addition, we found the influence of calcination temperatures (850, 900, 950, 1000, 1050, 1100, and 1150 °C) on color properties and particle size distribution of these materials prepared from anatase TiO₂ and with x = 0.30. Selected pigments were also analyzed by X-ray powder diffraction.     

Controllable Synthesis of Covellite Nanoparticles via Thermal Decomposition Method

In this study, covellite (CuS) nanoparticles were synthesized through a facile and low temperature thermal decomposition method using [Cu(sal)₂]- oleylamine complex, (sal = salicylaldehydeato, prepared in situ from [Cu(sal)₂] and oleylamine as the precursors), and sulfur as the Cu²⁺ source and S source, respectively. Scanning electron microscope, transmission electron microscope, electron diffraction and ultraviolet–visible absorption (UV–Vis) spectra were used for the characterization of the products. The effect of reaction parameters, such as the copper:sulfur molar ratio, the reaction temperature and the reaction time on the shape, size and phase of CuS nanostructures, was investigated. The results showed that the, covellite (hexagonal structure of CuS) with an average size between 20 and 45 nm could be obtained with the Cu:S molar ratio of 1: 3 at 105 °C for 60 min. With increasing the reaction temperature from 105 to 200 °C, non-stoichiometric Cu_1.65S with the average size of 25–50 nm was obtained due to the different existing state of the released Cu²⁺ ions from the copper-oleylamine complex.     

Solvothermal Synthesis and Characterization of PbSe Nanostructures with the Aid of Schiff-base Ligand

In this work, Pb(II)N,N-bis(salicylidene)-ethylenediamine; [Pb(salen)]; was applied as lead precursor to synthesis PbSe nanostructures. Besides [Pb(salen)], SeCl₄ and reducing agents like N₂H₄·H₂O have been employed for the production of PbSe nanostructures via a solvothermal route at 180 °C for 3 h in propylene glycol. The effect of preparation factors such as temperature, reaction time, and surfactant on the morphology of PbSe nanostructures was investigated. The experimental results indicated that PbSe synthesized at 150 and 210 °C was composed of agglomerated particles. On the other hand, the use of KBH₄ as reducing agent led to produce PbSe with higher particle size and agglomeration. The as-prepared PbSe nanostructures were characterized by XRD, SEM, TEM, EDS, and FT-IR.     

Simple Hydrothermal Synthesis of Nickel Hydroxide Flower-Like Nanostructures

α-Ni(OH)₂ flower-like nanostructures were successfully synthesized through one-step hydrothermal method with nickel acetate tetrahydrate, ethylene-1,2-diamine (en), hexamethylenetetramine (HMT) and cetyltrimethylammonium bromide (CTAB) as morphology-directing agents. Optimum conditions to obtain high yield and pure phase α-Ni(OH)₂ were identified by varying experimental parameters such as: en, HMT and CTAB concentration and reaction temperature. The products were characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared and thermogravimetric analysis. These results indicated that the α-nickel hydroxide contains water molecules and anions. The hierarchical NiO nanostructures were obtained by the as-synthesized α-Ni(OH)₂ nanostructures annealed at 300 °C for 4 h.     

Characterization and thermal analysis of thiourea and bismuth trichloride complex

A complex of thiourea and bismuth trichloride has been synthesized. Its composition is Bi₃Cl₉[SC(NH₂)₂]₇. Crystallographic data are a = 7.141(2) Å, b = 8.820(3) Å, c = 16.365(5) Å, α = 99.389(4)°, β = 95.422(4)°, γ = 106.177(4)°, triclinic system. There are the mononuclear anion [BiCl₅SC(NH₂)₂]^2? and the dinuclear cation {Bi₂Cl₄[SC(NH₂)₂]₆}²⁺ with the Bi–Cl–Bi bridge bonds in the complex. The electric conductance of the absolute methanol solution contained the complex indicates that the complex is an ionic compound. Raman spectra indicate that the bismuth ion is coordinated by the sulfur atoms of the thiourea. The thermal analysis verifies the structure of complex. The TG–MASS curves show the structure rearrangement in the complex at about 118 °C. The DSC curves and calculation means that the structure rearrangement is irreversible.     

Synthesis and Characterization of Zinc Oxide Nano-particles by Solid State Chemical Reaction Method

Several important synthetic parameters such as precursor concentration, reaction time are found to determine the growth of ZnO nanostructures. These reaction parameters can be tuned to produce a variety size of nanostructures. In this work we show the importance of these parameters on the size of synthesized zinc oxide nano-powders. ZnO nanoparticles are synthesized by the solid-state reaction using ZnSO₄·7H₂O and NaOH as the reagents. In this method Zn(OH)₂ is the intermediate product of the reaction, we show that by adjusting the molar ratio of the reagents and grinding time, we can be removed this unwanted component in the final product so for obtaining pure ZnO nanostructures the calcinations process is not necessary, also we can tune the size of ZnO nanoparticles. XRD spectra of the nanoparticles demonstrate typical diffraction peaks of a well-crystalline Wurtzite ZnO structure transmission electron microscopic observations show that these nanoparticles are of hexagonal phase ZnO mostly in round shapes and he composition analysis by EDX indicate that final product is pure ZnO. In the optimum conditions by XRD analysis we see that the mean grain size of synthesized zinc oxide nano-particles is about 44 nm.     

Microstructure and optical properties of Ag-doped ZrO2 thin films prepared by sol gel method

Ag doped ZrO₂ thin films were deposited on quartz substrates by sol–gel dip coating technique. The effect of Ag doping on tetragonal to monoclinic phase transformation of ZrO₂ at a lower temperature (500 °C) was investigated by X-ray diffraction. It is found that the Ag doping promotes the phase transformation. The phase transformation can be attributed to the increase in the tetragonal grain size and concentration of oxygen vacancies in the presence of the Ag dopant. Accumulation of the Ag atoms at the film surface and surface morphology changes in the films were observed by AFM as a function of varying Ag concentration. X-ray photoelectron spectroscopy gave Ag 3d and O 1s spectra on Ag doped thin film. The chemical states of Ag have been identified as the monovalent state of Ag⁺ ions in ZrO₂. The Ag doped ZrO₂ thin films demonstrated the tailoring of band gap values. It is also found that the intensity of room temperature photoluminescence spectra is suppressed with Ag doping.     

One-step synthesis of nanocrystalline N-doped TiO2 powders and their photocatalytic activity under visible light irradiation

Nanocrystalline N-doped TiO₂ powders were successfully prepared by hydrothermal reaction for 2 h at low temperature (120 °C) and at an applied pressure of 3 MPa. The grain size of the powders (calculated by use of Scherrer’s method) ranged from 8.2 to 10.2 nm. The BET specific surface area ranged from 151.0 to 220.0 m²/g. A significant shift of the light absorption edge toward the visible light zone was observed in the UV–visible spectra. XPS results showed that nitrogen atoms were incorporated into the TiO₂ lattice. The photocatalytic activity of the synthesized N-doped TiO₂ powders was evaluated by measurement of photodegradation of methylene blue (MB) in aqueous solution under visible light irradiation. The amount of MB degraded increased with increasing illumination intensity.     

A study on the effect of starting material phase on the production of trititanate nanotubes

Mixed phase TiO₂ powders of different composition and particle size were subjected to the hydrothermal reaction with 10 M NaOH. It was found that the anatase phase component of the starting material is easily converted to trititanate nanotubes at 140 °C. At this temperature the rutile phase remains unreacted, however at 170 °C it reacts to form trititanate plates and belts. When the reaction time is increased to 7 days, all the TiO₂ is converted to trititanate and the morphology is exclusively nanoplates and belts, with the tube phase destroyed. Many researchers have observed some heterogeneity in their reaction products, but have mainly focussed on the nanotubes. We observed that the tubes are only prepared from the anatase phase component of a TiO₂ precursor, whereas the rutile component produces trititanate plates and sheets, irrespective of the reaction length. The particle size affects the rate of reaction, resulting in the phase transition being more easily visible in the reactions starting with the larger TiO₂ particle size.     

Single‐microemulsion‐based Hydrothermal Approach to In(OH)3 and In2O3 Nanocubes

Well‐defined indium hydroxide [In(OH)₃] nanocubes have been successfully prepared through a facile single‐microemulsion‐mediated hydrothermal process at a relatively low temperature. Calcination of the In(OH)₃ precursor at 400°C in a furnace yielded In₂O₃ crystals with the same morphology. X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FE‐SEM), and transmission electron microscopy (TEM) were used to characterize the samples. The effects of reaction parameters on the formation of nanostructures were also discussed, and the nucleation, aggregation and anisotropic growth mechanism was proposed. Room temperature photoluminescence (PL) spectra as well as the ultraviolet‐visible (UV‐vis) absorbance spectra were carried out on the In₂O₃ crystals to investigate their optical properties.     

Phase transformation and crystalline growth of 4 mol% yttria partially stabilized zirconia

The phase transformation and crystalline growth of 4 mol% yttria partially stabilized zirconia (4Y-PSZ) precursor powders have been investigated using the coprecipitation route, using zirconium oxide chloride octahydrate (ZrOCl₂·8H₂O) and yttrium nitrate (Y(NO₃)₃·6H₂O) as the initial materials. Differential thermal analysis (DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), nano beam electron diffraction (NBED), and high resolution TEM (HRTEM) were utilized to characterize the behavior of phase transformation and crystalline growth of the 4Y-PSZ precursor powders after calcined. Tetragonal ZrO₂ crystallization occurred at about 718.2 K. The activation energy of tetragonal ZrO₂ crystallization was 227.0 ± 17.4 kJ/mol, obtained by a non-isothermal method. The growth morphology parameter (n) and growth mechanism index were close to 2.0, showing that tetragonal ZrO₂ had a plate-like morphology. The crystalline size of tetragonal ZrO₂ increased from 7.9 to 27.6 nm when the calcination temperature was increased from 973 to 1,273 K. The activation energies of tetragonal ZrO₂ growth were 14.97 ± 0.33 and 84.46 ± 6.65 kJ/mol when precursor powders after calcined from 723–973 and 973–1,273 K, respectively.     

FT-IR spectra of NaCl�CH2O in the region from near to beyond the critical state

Water and NaCl?CH₂O solutions and their molecular spectra at high temperatures and pressures were observed and examined using a new design of hydrothermal diamond anvil cell (HDAC) connected to both a light and an infrared microscope. We have modified the diamond window of the HDAC to have a wide angle to allow the infrared beam to pass the window. Fourier-transform infrared (FT-IR) spectra of NaCl?CH₂O?CD₂O were examined at high temperatures and pressures up to 850 °C and 3 GPa. The effect of increasing temperature on water spectra differed from that of increasing pressure. The O?CH stretching frequency of water molecules increases with increasing temperature (from 20 to 600 °C), and also with increasing salinity of the solution.