Spectroscopic and thermal investigations on Zn2+ and Ba2+ ions modified 30TeO2-39.5B2O3-(30-x)ZnO-xBaO-0.5V2O5 (0 ≤ x ≤ 30 mol %) glass system.

Melt quenching technique was employed to prepare glasses with compositional formula 30TeO2-39.5B2O3-(30-x)ZnO-xBaO-0.5V2O5 (0 ≤ x ≤ 30 mol%). Various characterization tools viz., X-ray diffraction (XRD), Energy dispersive X-ray (EDX) includes color mapping images, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR), Raman, Differential scanning calorimetry (DSC), UV-Vis absorption and Electron paramagnetic resonance (EPR) were used in this investigation for the characterization of these glasses. The XRD patterns together with DSC thermograms asserted the amorphous nature of all glasses. FTIR and Raman vibrational analyses has unveiled the formation of B-O--Ba2+-O- and Te-O---Ba2+-O- wherein the bonds with Ba2+ ions are mostly ionic. DSC investigations disclosed that the increase of BaO at the cost of ZnO declined the crystal phases and favored the amorphosity and this behavior causes these glasses more advantageous for fiber drawing. The Urbach energy (ΔE) lies in between 0.28 and 0.57 eV and suggested the glasses containing high ZnO has less defects. EPR data validated that Ba2+ ions might surround V4+ ions as Ba2+-O-V4+=O by replacing Zn2+-O-V4+=O linkages. The other optical properties were discussed in detail by correlating the structural variations noticed from both FTIR and Raman data analyses.

One-pot hydrothermal preparation and defect-enhanced photocatalytic activity of Bi-doped CdWO4 nanostructures.

In the field of photocatalysis, the suppression of electron-hole recombination through various defects has been an emerging trend to enhance photocatalytic activity. The separation efficiency of electron-hole recombination of well-explored wolframite structured monoclinic CdWO4, prepared using the one-pot hydrothermal method, was further improved by Bi3+ doping in CdWO4. Studies using the partial density of states illustrated that Bi 6s and 6p orbitals altered the electronic band structure to the extent of lowering the band gap, resulting in more photon absorption. The positron annihilation lifetime studies unveiled the formation of cluster defects such as oxygen (V0o, Vo1+, Vo2+) along with cadmium vacancies () in Bi-doped CdWO4. The coexistence and synergy of more adsorption sites of V0o, Vo1+, Vo2+, VCd for dye and O2 molecules, suitable oxide/redox band potentials, the modified electronic band structure especially owing to W-O1-Bi-O2-W linkages, together with high surface area endowed Bi-doped CdWO4 to form ˙O2- radicals played a predominant role in the methyl orange degradation. All the experimental findings demonstrated conclusively that Bi3+ doping at Cd2+ facilitated CdWO4 to exhibit superior photocatalytic activity.

Structural, thermal and optical properties of TeO2-ZnO-CdO-BaO glasses doped with VO(2+).

The glasses with composition 64TeO2-15ZnO-(20-x)CdO-xBaO-1V2O5 (0⩽x⩽20 mol%) were prepared by conventional melt quenching technique. X-ray diffraction analysis was used to confirm the amorphous nature of the glasses. The optical absorption studies revealed that the cut-off wavelength (λα) decreases while optical band gap energy (Eopt) and Urbach energy (ΔE) values increase with an increase of BaO content. Refractive index (n) evaluated from Eopt was found to decrease with an increase of BaO content. The physical parameters such as density (ρ), molar volume (Vm), oxygen packing density (OPD), optical basicity (Λ), molar refraction (Rm), and metallization criterion (M) evaluated and discussed. FTIR and Raman spectroscopic studies showed that the glass network consists of TeO4, TeO3+1/TeO3 and ZnO4 units as basic structural units. The glass transition temperature (Tg) of glass sample, onset crystallization temperature (To) and thermal stability ΔT were determined from Differential Scanning Calorimetry (DSC). Using electron paramagnetic resonance (EPR) spectra of vanadium glasses the spin Hamiltonian parameters and dipolar hyperfine coupling parameters of VO(2+) ions were calculated. It was found that V(4+) ions in these glasses exist as VO(2+) in octahedral coordination with a tetragonal distortion and have C4V symmetry with ground state dxy. Tetragonality (Δg∥/Δg⊥) of vanadium ion sites exhibited non-linear variation with BaO content.

Raman spectroscopy, thermal and optical properties of TeO2-ZnO-Nb2O5-Nd2O3 glasses.

The glasses with composition 75TeO2-10ZnO-(15-x)Nb2O5-xNd2O3 (0≤x≤9 mol%) were prepared using melt quenching method and their physical properties such as density (ρ), molar volume (VM), average crosslink density (nc¯), oxygen packing density (OPD) and number of bonds per unit volume (nb) were determined. Raman spectroscopic studies showed that the glass network consists of TeO4, TeO3+1, TeO3 and NbO6 units as basic structural units. The glass transition temperature (Tg), crystallization onset (To) and thermal stability (ΔT) were determined from DSC thermograms. The Raman and DSC results were found to be correlated with the physical properties. In the optical absorption spectra six absorption bands were observed with different relative intensities at around 464, 522, 576, 742, 801 and 871 nm which are assigned to the transition of electrons from (ground state) 4I9/2→G11/2; 4I9/2→2K3/2, 2G7/2; 4I9/2→4G5/2, 4G7/2; 4I9/2→4S3/2; 4F7/2→2H9/2, 4F5/2 and 4I9/2→2F3/2 respectively. From optical absorption data the energy band gap (Eopt) and Urbach energy (ΔE) were calculated.

Structure, glass transition temperature and spectroscopic properties of 10Li2O-xP2O5-(89-x)TeO2-1CuO (5≤x≤25 mol%) glass system.

X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), energy dispersive X-ray spectrometry (EDS), differential scanning calorimetry (DSC), infrared (IR), Raman, electron paramagnetic resonance (EPR) and optical absorption studies on 10Li2O-xP2O5-(89-x)TeO2-1CuO glasses (where x=5, 10, 15, 20 and 25 mol%) have been carried out. The amorphous nature of the glasses was confirmed using XRD and FESEM measurements. The glass transition temperature (Tg) of glass samples have been estimated from DSC traces and found that the Tg increases with increasing P2O5 content. Both the IR and Raman studies have been showed that the present glass system consists of [TeO3], [TeO4], [PO3] and [PO4] units. The spin-Hamiltonian parameters such as g∥, g⊥, and A∥ have been determined from EPR spectra and it was found that the Cu2+ ion is present in tetragonal distorted octahedral site with [Formula: see text] as the ground state. Bonding parameters and bonding symmetry of Cu2+ ions have been calculated by correlating EPR and optical data and were found to be composition dependent.