Effect of manganese ions concentration on the anatase–rutile phase transformation of TiO2 films

The phase structures of Ti_1?xMn_xO₂ (0?x<0.08) films synthesized by sol–gel spin coating have been investigated. The effect of Mn dopants on the stability of titanium dioxide (TiO₂) was studied by X-ray diffraction and Raman spectra for isochronally annealed samples. The increased Mn dopant concentration decreased the onset temperature of anatase–rutile (A–R) phase transformation. The calculated activation energy for the phase transformation decreased from 173.6 to 89.4 kJ/mol with Mn dopants concentration increasing from 0% to 7.51%. The Mn ions incorporated into the TiO₂ lattice reduce the rutile nucleation barrier and promote the nucleation rate.     

Structural analysis and band gap tailoring of Fe3+-doped Zn–TiO2 nanoparticles

We report on the analysis of morphology and electronic structure of Fe³⁺-doped Zn–TiO₂ nanoparticles. Crystalline nature, phase, and preferred growth direction of the nanoparticles were all determined. Due to size effects and OH⁻–(TiO₄) ⁿ complexes, variation in the energy gap with metallic and semiconducting characters on the same sample was found. The variation in the energy gap decreased, and the bang gap decayed exponentially with Fe doping and independent of the supporting substrates. Simultaneous effect of the OH⁻ ligands on the electronic structure and the formation mechanism of nanorods and nanosheets as manifested by the rutile TiO₆ octahedra units edge- and corner-shared bonding was discussed.     

Enhanced photocatalytic performance of TiO2 particles via effect of anatase–rutile ratio

In the present work anatase–rutile transformation temperature and its effect on physical/chemical properties as well as photocatalytic activity of TiO₂ particles were investigated. The characterisation of the synthesised and annealed TiO₂ particles were determined by X-Ray Powder Diffraction (XRD), scanning electron microscope (SEM), dynamic light scattering (DLS) and Brunauer–Emmett–Teller surface area analysis (BET). The refraction in the ultraviolet–visible (UV–vis) range was assessed using a dual-beam spectrophotometer. The photocatalytic performance of the particles was tested on methylene blue solution. The XRD data indicated that the percentage of rutile increased with the annealing temperature and almost 100% of anatase transformed to rutile at 1000 °C. In addition, the phase transformation was a linear function of annealing temperature so phase composition of TiO₂ can be controlled by changing the annealing temperature. The SEM and BET results presented the increase of agglomerate size and the decrease of specific surface area with the increasing annealing temperature. This proved that anatase has smaller particle size and higher surface area than rutile. The photocatalytic activity of the annealed TiO₂ powders reduced with the increase of annealing temperature. The samples annealed at 900 °C and 925 °C with anatase: rutile ratio of 92:8 and 77:23, respectively, showed the best activity. These results suggested that the photocatalytic activity of TiO₂ particles is a function of phase composition. Thus it can be enhanced by changing its phase composition which can be controlled by annealing temperature.     

The phase stability of Ca2TiO4 and related Ruddlesden–Popper phases

The Ruddlesden–Popper phases of the Ca–Ti–O system, Ca_n+1Ti_nO_3n+1, are investigated by means of atomistic simulations employing empirical pair potentials. The stability of the phases is examined in terms of various reaction schemes: the formation from the binary oxides, the addition of the perovskite oxide to a given phase, and the reaction between perovskite and rock-salt oxides. The energies of these reactions are compared with results previously obtained for the Ruddlesden–Popper phases of the Sr–Ti–O system. The importance of the disproportionation reaction of the various R–P phases in both Ca and Sr systems is also emphasized. The results obtained are in good agreement with experimental observations regarding both systems.     

Synthesis of TiO2 nanoparticles and spectroscopic upconversion luminescence of Nd3+-doped TiO2–SiO2 composite glass

Nd³⁺-doped TiO₂–SiO₂ composites were prepared by sol–gel method. Optical properties such as radiative life-time (τ), stimulated emission cross-section (σ_p) and branching ratio (β) were calculated using Judd–Ofelt theory. Violet to blue upconversion emissions at 380 nm (⁴D_3/2→⁴I_11/2), 399 nm (²P_3/2→⁴I_11/2), 420 nm (²D_5/2→⁴I_9/2) and 452 nm (²P_3/2→⁴I_13/2) were obtained under 578 nm xenon-lamp excitation. The choice of 578 nm is justified by the absorption spectra of the same samples, which shows a strong absorption peak at 578 nm. This 578 nm excitation pump produces upconversion in Nd³⁺ by a sequential two-photon absorption process.     

Study of the structural phase transformation,and optical behavior of the as synthesized ZnO–SnO2–TiO2 nanocomposite

Bulk nanocomposites ZnO–SnO₂–TiO₂ were synthesized by solid-state reaction method. The X-ray diffraction patterns and Raman spectra of bulk nanocomposite as a function of sintering temperature (700 °C–1300 °C) indicate that the structural phases of SnO₂ and TiO₂ depend on the sintering temperature while the ZnO retains its hexagonal wurtzite phase at all sintering temperatures and SnO₂ started to transform into SnO at 900 °C and completely converted into SnO at 1100 °C, whereas the titanium dioxide (TiO₂) exhibits its most stable phase such as rutile at low sintering temperature (≤900°C) and it transforms partially into brookite phase at high sintering temperature (≥ 900 °C). The optical band gap of nanocomposite ZnO–SnO₂–TiO₂ sintered at 700 °C, 900 °C, 1100 °C and 1300 °C for 16 hours is calculated using the transformed diffuse reflectance ultra violet visible near infra red (UV–VisNIR) spectra and has been found to be 3.28, 3.29, 3.31 and 3.32 eV, respectively.     

Structural, conductivity, and dielectric characterization of PEO–PEG blend composite polymer electrolyte dispersed with TiO2 nanoparticles

A solid polymer electrolyte (SPE) composites consisting blend of poly(ethylene oxide) (PEO) and poly(ethylene glycol) (PEG) as the polymer host with LiCF₃SO₃ as a Li⁺ cation salt and TiO₂ nanoparticle which acts as a filler were prepared using solution-casting technique. The SPE films were characterized by X-ray diffraction and Fourier transform infrared analysis to ensure complexation of the polymer composites. Frequency-dependent impedance spectroscopy observation was used to determine ionic conductivity and dielectric parameters. Ionic conductivity was found to vary with increasing salt and filler particle concentrations in the polymer blend complexes. The optimum ambient temperature conductivity achieved was 2.66?×?10^?4?S?cm^?1 for PEO (65 %), PEG (15 %), LiCF₃SO₃ (15 %), ethylene carbonate (5 %), and TiO₂ (3 %) using weight percentage. The dielectric relaxation time obtained from a loss tangent plot is fairly consistent with the conductivity studies. Both Arrhenius and VTF behaviors of all the composites confirm that the conductivity mechanism of the solid polymer electrolyte is thermally activated.     

Fabrication and analysis of the structural phase transition of ZrO2 nanoparticles using modified facile sol–gel route

The synthesis of zirconia nanoparticles is achieved through a modified facile sol–gel route. The as-prepared gel is analyzed thermally using TGA and DTA techniques to spot the crystallization process of zirconia nanoparticles. The prepared gel is then annealed at different temperatures and the structure was found to change between tetragonal and monoclinic crystal systems. The first stable tetragonal phase is achieved after annealing for 2?h at 400°C. The annealed powders between 600°C and 800°C demonstrate mixed tetragonal/monoclinic phases. Annealing at 1000°C and higher temperatures up to 1200°C resulted in pure monoclinic phase. Cubic phase was not detected within the annealing temperature range in this study. The elemental analysis of the annealed powder confirmed the formation of zirconia nanoparticles with the chemical formula ZrO₂. The FTIR spectra of the annealed samples introduced a variation in the vibrational bands especially around the phase transition temperature. HR-TEM images reported the formation of nano-zirconia crystals with apparently large particle sizes. The optical energy gap of zirconia nanoparticles is investigated and determined.     

First-principles study of the electronic and optical properties of the （Y,N）-codoped anatase TiO2 photocatalyst

First-principles plane-wave pseudopotential calculations are performed to study the geometrical structures,formation energies,and electronic and optical properties of Y-doped,N-doped,and(Y,N)-codoped TiO 2.The calculated results show that Y and N codoping leads to lattice distortion,easier separation of photogenerated electron-hole pairs and band gap narrowing.The optical absorption spectra indicate that an obvious red-shift occurs upon Y and N codoping,which enhances visible-light photocatalytic activity.     

Characterisation of the Fermi surface and phase transitions of (BEDO-TTF)2 ReO4·(H2O) by physical property measurements and electronic band structure calculations

The electronic properties of the organic superconductor (BEDO-TTF)₂ ReO₄·(H₂O) were investigated by temperature dependent resistivity, ESR, Hall effect and magnetoresistance measurements. Shubnikov-de Haas (SdH) oscillations were observed in magnetic fields up to 24 T in the temperature range 0.5 K to 4.2 K. The electronic band structure of (BEDO-TTF)₂ ReO₄·(H₂O) was calculated by employing the extended Hückel tight binding method on the basis of its room temperature crystal structure. The two observed SdH frequencies of 75 T and 37 T correspond very well with two cross-sectional areas of the hole and electron Fermi surface pockets obtained from the tight binding calculation. From the temperature dependence of the SdH oscillation amplitudes, the cyclotron effective mass (m_c) belonging to the larger and smaller pockets were found to be 0.9 m₀ and m_c=1.15 m₀ respectively. Measurements of the angular dependence of the SdH frequencies show no deviation from that expected for a cylindrical Fermi surface. In terms of our tight binding calculations and experimental measurements, probable causes for the 213 K and 35 K phase transitions are discussed. The calculations show that (BEDO-TTF)₂ ReO₄·(H₂O) is a two dimensional semimetal but possesses a hidden nesting. The latter is likely to cause an SDW instability leading to the 35 K transition. The resistivity drop associated with the 213 K transition is likely to be induced by an abrupt increase in the relaxation time. The excellent agreement between the calculated and experimentally observed Fermi surface implies that, with decreasing temperature below 35 K, (BEDO-TTF)₂ ReO₄·(H₂O) gradually gets out of the SDW state and re-enters the original metallic state, in which it becomes superconducting below 2.4 K.Reported at the 13th Genral Conference of the Condensed Matter Division of the European Physical Society, Regensburg, March 1993     

Development of the IR laser pyrolysis for the synthesis of iron–doped TiO2 nanoparticles: Structural properties and photoactivity

The preparation of TiO₂-based nanoparticles of closely controlled sizes and purity gives rise to considerable interest in the frame of environmental applications, e.g. in photocatalysis. When nanoparticles instead of their bulk counterpart are used the synthesis method plays a fundamental role in defining specific structural properties. Between the different gas-phase synthesis techniques, the CO₂ laser pyrolysis is a versatile method allowing for the preparation of nanostructures of various chemical compositions. Here we demonstrate that pure and Fe–doped TiO₂ nanoparticles with rather low Fe concentration may be prepared by applying the sensitized IR laser pyrolysis to a gas mixtures containing titanium tetrachloride, air and iron pentacarbonyl (vapors). The structures of TiO₂-based particles were systematically investigated by X-ray diffraction, transmission electron microscopy, high-resolution electron microscopy, selected area electron diffraction and X-ray Photoelectron Spectroscopy. Depending on the synthesis parameters, the nanoparticle system contains mixtures of anatase and rutile, with a preponderance of the anatase phase. Higher rutile proportion was found in the iron-doped samples. Mean particle diameters of around 14 nm and 12 nm were estimated for undoped and doped anatase titania, respectively. From UV–Vis diffuse reflectance spectra, higher absorbance and red shifted absorption were evidenced at higher amount of doped iron. Preliminary evaluation tests of the UV photoactivity of samples were performed by using the scanning electrochemical microscopy for determining the evolution of the oxygen consumption in the presence of IV-chlorophenol. They show that the undoped nano titania samples perform better than the reference P25 Degussa sample. A drop of the nano-titania photoactivity as a consequence of Fe doping was observed. Possible reasons of this effect are tentatively discussed.     

Effect of calcination temperature on the structure and performance of CeOx–MnOx/TiO2 nanoparticles for the catalytic combustion of chlorobenzene

Journal of Nanoparticle Research - Janus droplets with two opposite faces of different physical or chemical properties have great potentials in many fields. This paper reports a new method for...     

Structural and luminescence properties of Nd3+-doped PbO–B2O3–TiO2–AlF3 glass for 1.07 μm laser applications

Trivalent neodymium doped multi-component lead borate titanate aluminumfluoride (LBTAFNd) glasses were prepared and characterized as a function of Nd³⁺ ions concentration through optical absorption, NIR luminescence and decay measurements. The intensity (Ω_2,4,6) and other radiative parameters were determined within the frame work of Judd–Ofelt theory. The intensities of absorption bands were expressed in terms of experimental oscillator strengths. Reasonably small root mean square deviation of ±0.384×10^?6 obtained between the experimental and calculated oscillator strengths indicates the validity of intensity parameters. Upon 805 nm laser excitation, the NIR emissions at 0.92 μm (⁴F_3/2→⁴I_9/2), 1.07 μm (⁴F_3/2→⁴I_11/2) and 1.35 μm (⁴F_3/2→⁴I_13/2) were observed. The spectroscopic quality factor has been determined from the Ω₄ and Ω₆ intensity parameters as well as the intensities of emission bands centered at 1.07 and 1.35 μm. The decay curves of the ⁴F_3/2 excited state were recorded by monitoring the emission and excitation wavelengths at 1.07 μm and 805 nm, respectively. The decay curves exhibit single exponential behavior for all the glasses. The laser characteristic parameters of ⁴F_3/2→⁴I_11/2 (1.07 μm) transition were determined and compared with other reported glasses.     

Exploration of the molecular ro-vibrational energy structure: on the perspective of Yb2 and Cd2 internal cooling,and 171Yb-version of Einstein–Podolsky–Rosen experiment

ABSTRACT

Schemes for internal ro-vibrational cooling in Yb₂ and Cd₂, as well as ¹⁷¹Yb Bohm's spin-1/2 particle version of the Einstein?Podolsky?Rosen experiment based on photo-dissociation of (¹⁷¹Yb)₂ are presented. The schemes are based on exploration of the rotational and vibrational energy structures using both theoretical and experimental approaches.     

Grain boundary effect on structural,optical, and electrical properties of sol–gel synthesized Fe-doped SnO_2 nanoparticles

Tin oxide(SnO_2) and iron-doped tin oxide(Sn_(1-x)Fe_xO_2,x=0.05 wt%,0.10 wt%) nanoparticles are synthesized by the simple sol-gel method.The structural characterization using x-ray diffraction(XRD) confirms tetragonal rutile phases of the nanoparticles.The variations in lattice parameters and relative intensity with Fe-doping concentration validate the incorporation of iron into the lattice.The compressive strain present in the lattice estimated by using peak profile analysis through using Williamson-Hall plot also exhibits the influence of grain boundary formation in the lattice.The radiative recombination and quenching observed in optical characterization by using photoluminescence spectrum(PL) and the shift in the band gap estimated from UV-visible diffused reflectance spectrum corroborate the grain boundary influence.Raman spectrum and the morphological analysis by using a field emission scanning electron microscope(FESEM) also indicate the formation of grain boundaries.The compositional analysis by using energy dispersive x-ray spectrum(EDAX) confirms Fe in the SnO_2 lattice.The conductivity studies exhibit that the impendence increases with doping concentration increasing and the loss factor decreases at high frequencies with doping concentration increasing,which makes the Sn_(1-x)Fe_xO_2 a potential candidate for device applications.     

Investigations of the optical band positions,EPR parameters and defect structure for the trigonal Cr3+–Li+ centre in CsMgCl3 crystal

A unified calculation of optical band positions and electron paramagnetic resonance (EPR) (or spin-Hamiltonian) parameters for the trigonal Cr³⁺–Li⁺ centre in CsMgCl₃ crystal is made by using the complete diagonalisation (of energy matrix) method based on the two-spin–orbit-parameter model. In this model, the contributions from the spin–orbit parameter of central dⁿ ion and that of ligand ion are included. From the calculation, the 11 observed optical and EPR data (eight optical band positions and three EPR parameters g_//, g_⊥, D) are reasonably explained with five adjustable parameters and the defect structure of the Cr³⁺–Li⁺ centre (which is consistent with the expectation based on the electrostatic interaction) in CsMgCl₃ is acquired. The results are discussed.     

Sol–gel route of synthesis of nanoparticles of MgFe2O4 and XRD,FTIR and VSM study

Nanoparticles of MgFe₂O₄ are synthesized using sol–gel autocombustion method. Structural studies are carried out using X-ray diffraction (XRD). The XRD pattern of MgFe₂O₄ provides information about single-phase formation of spinel structure with cubic symmetry. The grain size and lattice constant are obtained using XRD data. The cation distribution is also proposed theoretically. The change in site preference of cations in nano-MgFe₂O₄ is compared with its bulk counterpart. The structural morphology of the nanoparticles is studied using Scanning Electron Microscopy (SEM). Formation of spinel structure is conformed using Fourier transform infrared spectroscopy (FTIR), which also lends support for the cation distribution proposed using XRD data. The effect of nanoregime on parameters such as bond length, vibration frequency and force constant are discussed with the help of FTIR data. The M–H loop of MgFe₂O₄ has been traced using the Vibrating Sample Magnetometer (VSM) and magnetic parameters such as saturation magnetization (M_S), coercivity (H_C) and retentivity (M_R) are obtained from VSM data.