Enhancing photocatalytic properties of rutile TiO2 by codoping with N and metals - Ab initio study

Substitutional N to O and M to Ti (M = Pt, V, Sb) codoped rutile TiO2 was investigated using density functional theory (OFT) based calculations with both standard and hybrid exchange-correlation functionals. The band gaps calculated using generalized gradient approximation (GGA) exhibited narrowing compared to the pure rutile TiO2 in all the investigated cases. In contrast, the results obtained with hybrid exchange-correlation functional showed that there was no band gap narrowing, but doping induced localized states within the band gap just above the valence band, as well as below the conduction band for Pt doped TiO2. The presence of broad intermediate states (IS) in the band gap could enhance visible light absorption through a two step optical transition from the valence to the conduction band via the IS and at the same time lower recombination of the photo-generated charges. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved

A Three - Detector High Resolution TDPAC Spectrometer

An advanced fast-slow coincidence scintillation spectrometer for the Timx Differential Perturbed y-y Angular Correlation (TDPAC) experiments is presented. It consists of three detectors with BaF2 scintillators and was developed in the Group for Hyperfine Interactions in the Institute for Nuclear Sciences in Vinca. The spectrometer is characterized with high detection efficiency, excellent time resolution, high counting rate performance and is operating in the temperature range 78-1300 K

Structural deformation in Hf2Ni observed by TDPAC method

The electric quadrupole interaction in Hf2Ni was measured at 181Ta probe using the time-differential perturbed angular correlation method (TDPAC) in the temperature range 78 to 1314 K. Analysis of the obtained spectra revealed the presence of a single nuclear quadrupole interaction (NQI) and its linear descending dependence with increasing temperature. In the region 1134 to 1314 K, the presence of structural deformation is evident from the coincidence spectra.YUCOMAT 2007 : 9th Annual Conference YUCOMAT 2007 : Programme and the book of abstracts; September 10-14, 2007; Herceg Novi, Montenegr

A study of defect structures in Fe-alloyed ZnO: Morphology, magnetism, and hyperfine interactions

In order to study the effect of Fe cation substitution on the local structure, defect formation, and hyperfine interactions in ZnO, Mössbauer spectroscopy measurements of the microwave processed Zn1−xFexO (x=0.05, 0.10, 0.15, and 0.20) nanoparticles, together with ab initio calculations, were performed. Complementary information on the distribution of particle size and morphology, as well as magnetic properties, were obtained by X-ray diffraction, transmission electron microscopy, and squid-magnetometry. The selected model for analyzing the Mössbauer spectra of our samples is a distribution of quadrupole splittings. The fitting model with two Lorentz doublets was rejected due to its failure to include larger doublets. The Fe3+ ions do not yield magnetic ordering in the samples at room temperature. The results from first-principles calculations confirm that the major component of the Mössbauer spectra corresponds to the Fe-alloyed ZnO with Zn vacancy in the next nearest neighbor environment. The magnetic measurements are consistent with the description of the distribution of iron ions over the randomly formed clusters in the ZnO host lattice. While at room temperature all the samples are paramagnetic, magnetic interactions cause a transition into a cluster spin-glass state at low temperatures

Hyperfine interactions at 181Ta solute in ferromagnetic Hf-Ni alloys with low concentration of Hf atoms

We have measured hyperfine interactions of 181Ta probe in the polycrystalline 0.2at.%Hf-Ni, 2at.%Hf-Ni and 5at.%Hf-Ni alloys, by the time differential perturbed angular correlation (TDPAC) method at room temperature (RT). The hyperfine magnetic field (Hhf) in 0.2at.%Hf-Ni alloy at the 181Ta probe is 8.66(1)T, where the small atomic concentrations of Hf atoms mainly substitute on Ni host lattice sites. Three hyperfine interactions were detected in two other alloys. In the 2at.%Hf-Ni alloy, we found existence of Larmor precession frequency ωL (1)=536(2)Mrad/s at the 181Ta probe surrounded by Ni atoms and the second electric quadrupole interaction (EQI) ωQ (2)=2.20(2)Mrad/s at the 181Ta probe in new formed HfNi5 intermetallic phase. The third EQI ωQ (3)=137.4(1)Mrad/s corresponds to the small amount of monoclinic HfO2 phase contamination at T<900K. In the 5at%Hf-Ni alloy, magnetic dipole interaction (MDI) at the 181Ta probe is ωL (1)=536(6)Mrad/s, while the second EQI at the site of the same probe in HfNi5 is ωQ (2)=2.24(2)Mrad/s. The presence of ωQ (3)=128(1)Mrad/s at the 181Ta probe originating from HfO2 contamination is in good accordance with earlier published results for this phase.52. konferencija ETRAN-a : Jun 8-12, Palić, 2008

Crystalline phases in Zr9Ni11 and Hf9Ni11 intermetallics; Investigations by perturbed angular correlation spectroscopy and ab initio calculations

Crystalline phases formed in stoichiometric Zr9Ni11 and Hf9Ni11 have been studied by perturbed angular correlation (PAC) spectroscopy, XRD and TEM/SAED measurements. In Zr9Ni11, the phases Zr9Ni11 (∼89%) and Zr8Ni21 (∼11%) have been found at room temperature from PAC measurements. At 773 K, Zr9Ni11 partially decomposes to Zr7Ni10 and at 973 K, it is completely decomposed to ZrNi and Zr7Ni10. In Hf9Ni11, a predominant phase (∼81%) due to HfNi is found at room temperature while the phase Hf9Ni11 is produced as a minor phase (∼19%). No compositional phase change at higher temperature is found in Hf9Ni11. Phase components found from XRD and TEM/SAED measurements are similar to those observed from PAC measurements. Electric field gradients in Zr9Ni11 and Hf9Ni11 have been calculated by density functional theory (DFT) using all electron full potential (linearized) augmented plane wave plus local orbitals [FP-(L)APW+lo] method in order to assign the phase components.This is the preprint version of the following article: Dey, S. K., C. C. Dey, S. Saha, G. Bhattacharjee, J. Belošević-Čavor, and D. Toprek. "Crystalline phases in Zr9Ni11 and Hf9Ni11 intermetallics; investigations by perturbed angular correlation spectroscopy and ab initio calculations." Journal of Solid State Chemistry (2018). http://dx.doi.org/10.1016/j.jssc.2018.10.00

Hyperfine interactions at 181Ta solute in ferromagnetic Hf-Ni alloys with low concentration of Hf atoms

We have measured hyperfine interactions of 181Ta probe in the polycrystalline 0.2at.%Hf-Ni, 2at.%Hf-Ni and 5at.%Hf-Ni alloys, by the time differential perturbed angular correlation (TDPAC) method at room temperature (RT). The hyperfine magnetic field (Hhf) in 0.2at.%Hf-Ni alloy at the 181Ta probe is 8.66(1)T, where the small atomic concentrations of Hf atoms mainly substitute on Ni host lattice sites. Three hyperfine interactions were detected in two other alloys. In the 2at.%Hf-Ni alloy, we found existence of Larmor precession frequency ωL (1)=536(2)Mrad/s at the 181Ta probe surrounded by Ni atoms and the second electric quadrupole interaction (EQI) ωQ (2)=2.20(2)Mrad/s at the 181Ta probe in new formed HfNi5 intermetallic phase. The third EQI ωQ (3)=137.4(1)Mrad/s corresponds to the small amount of monoclinic HfO2 phase contamination at T<900K. In the 5at%Hf-Ni alloy, magnetic dipole interaction (MDI) at the 181Ta probe is ωL (1)=536(6)Mrad/s, while the second EQI at the site of the same probe in HfNi5 is ωQ (2)=2.24(2)Mrad/s. The presence of ωQ (3)=128(1)Mrad/s at the 181Ta probe originating from HfO2 contamination is in good accordance with earlier published results for this phase.52. konferencija ETRAN-a : Jun 8-12, Palić, 2008

Tuning the optical, electrical and photoelectrocatalytic properties of Zno materials by varying of intrinsic defects concentration

During the last decade zinc oxide (ZnO) has attracted considerable attention as a promising material for electronic, optoelectronic and spintronic devices. ZnO has a wide bandgap (3.37 eV at room temperature) and relatively large exciton binding energy (60 meV) which enables multifunctional application. Until now ZnO-based materials have been used as UV and blue light emitters, varistors, thermistors, semiconductors, photoanodes, and other. Various approaches have been applied to improve functional properties of zinc oxide, such as: fabrication of ZnO-based heterojunction particles, particles’ surface sensitization, hydrogenation, etc. It has been found that intrinsic defects (vacancies, interstitials and antisites) in the crystal structure of a ZnO strongly influenced its electrical and optical properties. Thus, correlation of the intrinsic defects concentration with optical and electrical properties of ZnO materials is of great importance for their further application in opto-electronic devices. In this study we investigated the influence of intrinsic defects concentration on the optical, electrical and photoelectrocatalytic properties of ZnO materials. To obtain ZnO powder with a high concentration of intrinsic defects microwave processing of precipitate was employed, while for further varying of defects concentration, the powder was thermally treated in three different atmospheres: air, argon and oxygen. The ZnO powder was uniaxially pressed (P = 100 MPa) in cylindrical compacts (R= 6 mm and h approx. 3 mm) which were sintered in different atmospheres by heating rate of 10 °/min up to 1100 °C, and with dwell time of 1 h. To study a crystal structure of ZnO samples XRD and Raman spectroscopy were used, while for microstructural investigation field emission scanning electron micrographs were recorded. Optical properties were studied using UV–Vis diffuse reflectance spectroscopy. To reveal the role of intrinsic defects in ZnO crystal lattice on functional properties, XPS, photoluminescence, electroluminescence and electrochemical impedance spectra were analyzed. A detailed analysis of the experimental results imply that a high concentration of intrinsic defects, in particular oxygen vacancies, is of the greatest importance for tunable light-emitting diode application and significant for the photoanode properties. To support our experimental observation we performed ab initio calculations based on density functional theory (DFT)

Influence of point defects concentration on optical and photocatalytic properties of ZnO ceramics

Zinc oxide is one of the most studied materials due to its wide bandgap (3.37 eV) and large exciton binding energy (60 meV) which enables application in electronics, optoelectronics and spintronics. In the forms of single crystal and thin-film ZnO are used as UV and blue light emitter, while sintered ZnO-based ceramics are important as varistors, thermistors or semiconductors. It has been found that point defects in the crystal structure of a ZnO strongly influenced its electrical and optical properties. Neutral oxygen vacancies are considered to be a major component of the defect structure of ZnO. Thus, correlation of the oxygen vacancies concentration with band gap energy of ZnO product is important to its application in optoelectronic devices. In this study we investigated the influence of point defects concentration in ZnO crystal structure on its optical and photocatalytic properties. We analyzed ZnO powders prepared by different techniques: (a) microwave processing of precipitate and (b) hydrothermal processing, which yield different ordered crystal structure. To increase a concentration of the point defects in the crystal structure, the powders were sintered in air atmosphere by heating rate of 10 °/min up to 1100 °C, with dwell time of 1 h. The crystal structure, average crystallite size and phase purity of the ZnO ceramics were determined by X-ray diffraction and Raman spectroscopy. The optical properties, in particular, absorption capacity and bang gap energy, were studied using UV–Vis diffuse reflectance spectroscopy. To reveal the role of microstructures and point defects in ZnO crystal lattice, which are receptive for luminescence and photocatalytic activity of this functional oxide, photoluminescence (PL), photoluminescence excitation (PLE) and EPR spectra were analyzed. The influence of point defects concentration in the ZnO crystal structure on photocatalytic properties was examined via decolorization of methylene blue under direct sunlight irradiation. Correlation between amount of the point defects, absorption capacity and photocatalytic efficiency were established. In order to clarify the experimental results ab initio calculations based on density functional theory (DFT) were performed

Influence of Point Defects Concentration on Densification Process and Optical Properties of Sintered ZnO Ceramics

Zinc oxide is one of the most studied materials due to its potential applications in electronics, optoelectronics and spintronics. In the forms of single crystal and thin-film ZnO could be used as UV and blue light emitter, while sintered ZnO-based ceramics are important as varistors, thermistors or wide-band gap semiconductors. Intrinsic defects, such as vacancies, interstitials and antisites, in the crystal structure of a ZnO strongly influenced its electrical and optical properties. Thus, understanding the behavior of intrinsic defects during densification of ZnO ceramics as well as correlation of the defects with band gap energy of final product is important to its application in opto-electronic devices. In this study, the influence of point defects concentration on the densification process and optical properties of ZnO sintered ceramics was investigated. To obtain ZnO sintered ceramics with variety of point defects concentration we employed two starting powders with a different crystal structure ordering, as well different morphology and specific surface area. Sinterability of the powders was investigated by thermo mechanical analyzer; shrinkage data, collected in axial (h) direction during non-isothermal sintering with heating rates of 5, 10 and 20 °/min, were used to calculate activation energy of sintering process. Sintering of uniaxially pressed (P = 100 MPa) cylindrical compacts (ø 6 mm and h ≈ 3 mm) were done in air atmosphere by heating rate of 10 °/min up to 1100 and 1200 °C, and dwell time of 2 h. To study a crystal structure of the sintered samples XRD and Raman spectroscopy were used, for microstructural investigation field emission scanning electron micrographs were recorded while optical properties were determined by UV-Vis diffuse reflectance and photoluminescence spectroscopy. A detailed study shows that point defect strongly influenced densification process as well optical properties. Sintered ZnO ceramic with a high crystal defect concentration and nanosized grains shows band gap energy of about 2 eV while band gap energy increased with a decrease of defect concentration