Browsing by Subject "Barium"

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Open Access
Direct evidence for the instability and deactivation of mixed-oxide systems: influence of surface segregation and subsurface diffusion
(2011) Emmez, E.; Vovk, E. I.; Bukhtiyarov V. I.; Ozensoy, E.
In the current contribution, we provide a direct demonstration of the thermally induced surface structural transformations of an alkaline-earth oxide/transition metal oxide interface that is detrimental to the essential catalytic functionality of such mixed-oxide systems toward particular reactants. The BaOx/TiO2/Pt(111) surface was chosen as a model interfacial system where the enrichment of the surface elemental composition with Ti atoms and the facile diffusion of Ba atoms into the underlying TiO2 matrix within 523 873 K leads to the formation of perovskite type surface species (BaTiO3/Ba2TiO4/BaxTiyOz). At elevated temperatures (T > 973 K), excessive surface segregation of Ti atoms results in an exclusively TiO2/TiOx-terminated surface which is almost free of Ba species. Although the freshly prepared BaOx/TiO2/Pt(111) surface can strongly adsorb ubiquitous catalytic adsorbates such as NO2 and CO2, a thermally deactivated surface at T > 973 K practically loses all of its NO2/CO2 adsorption capacity due to the deficiency of surface BaOx domains.
Open Access
Fe promoted NOx storage materials: structural properties and NOx uptake
(American Chemical Society, 2010) Kayhan, E.; Andonova, S. M.; Şentürk, G. S.; Chusuei, C. C.; Ozensoy, E.
Fe promoted NOx storage materials were synthesized in the form of FeOx/BaO/Al2O3 ternary oxides with varying BaO (8 and 20 wt %) and Fe (5 and 10 wt %) contents. Synthesized NOx storage materials were investigated via TEM, EELS, BET, FTIR, TPD, XRD, XPS, and Raman spectroscopy, and the results were compared with the conventional BaO/Al2O3 NOx storage system. Our results suggest that the introduction of Fe in the BaO/Al2O3 system leads to the formation of additional NOx storage sites which store NOx mostly in the form of bidentate nitrates. NO2 adsorption experiments at 323 K via FTIR indicate that, particularly in the early stages of the NOx uptake, the NOx storage mechanism is significantly altered in the presence of Fe sites where a set of new surface nitrosyl and nitrite groups were detected on the Fe sites and the surface oxidation of nitrites to nitrates is significantly hindered with respect to the BaO/Al2O3 system. Evidence for the existence of both Fe3+ as well as reduced Fe2+/(3-x)+ sites on the freshly pretreated materials was detected via EELS, FTIR, Raman, and XRD experiments. The influence of the Fe sites on the structural properties of the synthesized materials was also studied by performing ex situ annealing protocols within 323-1273 K followed by XRD and Raman experiments where the temperature dependent changes in the morphology and the composition of the surface domains were analyzed in detail. On the basis of the TPD data, it was found that the relative stability of the stored NOx species is influenced by the morphology of the Ba and Fe containing NOx-storage domains. The relative stabilities of the investigated NOx species were found to increase in the following order: N2O3/NO+ < nitrates on γ-Al2O3 < surface nitrates on BaO < bidentate nitrates on FeOx sites < bulk nitrates on BaO.
Open Access
Fine-tuning the dispersion and the mobility of BaO domains on NO x storage materials via TiO2 anchoring sites
(American Chemical Society, 2010) Andonova, S. M.; Şentürk, G. S.; Ozensoy, E.
In an attempt to control the surface dispersion and the mobility of BaO domains on NOx storage materials, TiO2/TiOx anchoring sites were introduced on/inside the conventional γ-Al 2O3 support matrix. BaO/TiO2/Al 2O3 ternary oxide materials were synthesized via two different sol-gel preparation techniques, with varying surface compositions and morphologies. The synthesized NOx storage materials were studied via XRD, Raman spectroscopy, BET surface area analysis, TPD, XPS, SEM, EDX-mapping, and in situ FTIR spectroscopy of adsorbed NO2. NOx uptake properties of the BaO/TiO2/Al2O3 materials were found to be strongly influenced by the morphology and the surface structure of the TiO2/TiOx domains. An improved Ba surface dispersion was observed for the BaO/TiO2/Al2O3 materials synthesized via the coprecipitation of alkoxide precursors, which was found to originate mostly from the increased fraction of accessible TiO 2/TiOx sites on the surface. These TiO2/ TiOx sites function as strong anchoring sites for surface BaO domains and can be tailored to enhance surface dispersion of BaO. TPD experiments suggested the presence of at least two different types of NOx species adsorbed on the TiO2/TiOx sites, with distinctively different thermal stabilities. The relative stability of the NOx species adsorbed on the BaO/TiO2/Al2O3 system was found to increase in the following order: NO+/N2O 3 on alumina ≪ nitrates on alumina < surface nitrates on BaO < bridged/bidentate nitrates on large/isolated TiO2 clusters < bulk nitrates on BaO on alumina surface and bridged/bidentate nitrates on TiO2 crystallites homogenously distributed on the surface < bulk nitrates on the BaO sites located on the TiO2 domains. © 2010 American Chemical Society.
Open Access
Investigation of the adsorption behavior of cesium, barium and phenol onto modified humic acid and iron nanopraticles
(2007) Çelebi, Oğuzhan
Open Access
Nature of the Ti-Ba interactions on the BaO/TiO2/Al 2O3 NOx storage system
(2009) Andonova, S. M.; Şentürk, G. S.; Kayhan, E.; Ozensoy, E.
A ternary oxide-based NO* storage material in the form of BaOZTiO2Zy-Al2O3 was synthesized and characterized. Thermally induced structural changes occurring on the surfaces of the TiO2Zy-Al2O3 and BaOZ TiO 2Zy-Al2O3 systems were studied in a comparative manner within 300-1273 K via X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, and BET surface area analysis. The surface acidity of the studied oxide systems was also investigated via pyridine adsorption monitored by in-situ Fourier transform infrared (FTIR) spectroscopy. BaO/TiO2γ-Al 2O3 ternary oxide was synthesized by incorporating different loadings of (8-20 wt %) BaO onto the TiO2/γ Al 2O3 support material, which was originally prepared using the sol-gel method. In the TiO2Zy-Al2O3 binary oxide support material, anatase phase exhibited a relatively high thermal stability at T < 1073 K. The presence of TiO2 domains on the surface of the alumina particles was found to alter the surface acidity of alumina by providing new medium-strength Lewis acid sites. SEMZEDX results indicate that in the BaO/TiO2γ-Al2O3 system, TiO2 domains present a significant affinity toward BaO and/or Ba(NO3) 2 resulting in a strong Ti-Ba interaction and the formation of overlapping domains on the surface. The presence of TiO2 also leads to a decrease in the decomposition temperature of the Ba(N03) 2 phase with respect to the Ti-free Ba(N03) 2ZyAl2O3 system. Such a destabilization is likely to occur due to a weaker interaction between Ba(N03) 2 and y-Al203 domains in the ternary oxide as well as due to the change in the surface acidity in the presence of TiO 2. At relatively high temperatures (e.g., 873-1273 K) formation of complex structures in the form of BaTiO3, Ba1.23Al 2.46Ti5.54O16, BaTiO5, andor Ba x:AlyTizOn., were also observed. © 2009 American Chemical Society.
Open Access
Peculiar piezoelectric properties of soft two-dimensional materials
(American Chemical Society, 2016-06) Sevik, C.; Çakır, D.; Gülseren, O.; Peeters, F. M.
Group II-VI semiconductor honeycomb monolayers have a noncentrosymmetric crystal structure and therefore are expected to be important for nano piezoelectric device applications. This motivated us to perform first-principles calculations based on density functional theory to unveil the piezoelectric properties (i.e., piezoelectric stress (e11) and piezoelectric strain (d11) coefficients) of these monolayer materials with chemical formula MX (where M = Be, Mg, Ca, Sr, Ba, Zr, Cd and X = S, Se, Te). We found that these two-dimensional materials have peculiar piezoelectric properties with d11 coefficients 1 order of magnitude larger than those of commercially utilized bulk materials. A clear trend in their piezoelectric properties emerges, which originates mainly from their mechanical properties. We establish a simple correlation between the piezoelectric strain coefficients and the physical properties, as the natural elemental polarizabilities, the Bader charges, and lattice constants of the individual M/X atoms and MX monolayers.
Open Access
Radiochemical and spectroscopic studies of cesium, barium, and cobalt sorption on some natural clays
(2000-08) Shahwan, Talal
The wide growth in the nuclear activities results in an increasing subsequent influx of radioactive wastes into the environment. This problem has manifested a great deal of interest aiming at finding out ways through which those wastes can be harmlessly isolated from the human environment. Geological disposal is considered as one of the most promising solutions that ensures a safe storage of radioactive wastes as long as their activities are above the accepted levels. Clay minerals are proposed as backfill buffering materials in the geological repositories that can delay the migration of the radionuclides through sorption and thus decrease the contamination of underground waters. The extent of retardation of the radionuclide migration is dependent on factors like time of contact, pH and Eh of groundwater, concentration, temperature and grain size of the mineral particles. In this study radiochemical, spectroscopic (ToF-SIMS, XPS), and X-ray diffraction techniques were applied to examine different aspects of the sorption behavior of cesium, barium and cobalt on three natural clay minerals containing primarily kaolinite, illite-chlorite, and bentonite. The elements cesium (Z=55), barium (Z=56), and cobalt (Z=27) have the radioactive isotopes superscript 137 Cs (half-life=30.17 years), superscript 140 Ba (half-life=12.79 days), and superscript 60 Co (half-life=5.3 y) which are important in radioactive waste management. The first two radionuclides are produced in high yields in nuclear fission, whereas the third is an activation product. The natural clay samples that were used in this study originated from natural mineralogical beds at Sindırgı, Afyon, and Giresun regions in Turkey. The characterization of these clay samples showed that the primary clay minerals were kaolinite in Sındırgı clay, chlorite and illite in Afyon clay, and montmorillonite in Giresun clay. Each of these clays possesses different structural properties that result in different sorption capabilities. Radiochemical batch experiments were carried out to examine the effects of time, concentration, and temperature on the sorption of cesium, barium and cobalt on clays. Solutions of these cations spiked with several microliters of the radionuclides 137 CS (half-life=30.1 y), 133 Ba (half-life=10.7 y), and 60 Co (half-life=5.3 y) were monitored using gamma-ray spectroscopy prior to and after each sorption experiment. These results showed that equilibrium is achieved within two days in all cases. The sorption data was adequately described by Freundlich and Dubinin-Radushkevich isotherm models. Based on the parameters of those isotherm models, it was found that sorption was nonlinear, and that bentonite showed the highest sorption affinity and sorption capacity towards the sorbed ions. The thermodynamic parameters indicated that while sorption of cesium and barium on the three clays is exothermic that of cobalt is endothermic. The obtained values of Gibbs free energy change, Delta G degrees, were generally in the 8-16 (kJ/mol) energy range that corresponds to ion exchange type sorption mechanism. Since sorption is mainly a surface phenomenon, part of our sorption studies were carried out using the surface sensitive techniques; Time of Flight- Secondary Ion Mass Spectroscopy (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS). In addition, depth profiling up to 70 angstroms was performed using ToF-SIMS to investigate cesium, barium and cobalt concentrations through the clay surface. ToF-SIMS and XPS studies were helpful in figuring out the surface composition of different clays prior to and after sorption. Quantification of the depletion of different alkali and alkaline-earth metals initially contained within the analyzed clay surface showed that ion exchange plays a primary role in the sorption process. In addition, X-Ray Diffraction (XRD) technique was applied to figure out the mineralogical composition of the clay minerals used and examine any structural change a accompanying the sorption process. XRD spectra of the clay samples after sorption showed that -apart from some intensity reductions in some clay features-, no primary changes were detected in the sorption cases of cesium and cobalt. In barium sorption, however, features belonging to barium carbonate were present in the spectra corresponding to sorption on chlorite-illite and bentonite.
Open Access
Radiochemical studies of the sorption behavior of strontium and barium
(Kluwer Academic Publishers, 1995) Göktürk, H.; Eylem, C.; Hatipoĝlu, S.; Erten, H. N.
The sorption behavior of strontium and barium on kaolinite, bentonite and chlorite-illite mixed clay was studied by radioanalytical techniques using the batch method.90Sr (29.1 y) and133Ba (10.5 y) were used as radiotracers. Characterization of the solid matrices was done by FTIR and XRD spectrometries and specific surface area measurements. Synthetic groundwater was used as the aqueous phase. The variation of the distribution ratio Rd, as a function of metal ion loading was examined. The sorption isotherms were fitted to various isotherm models. The sorption energies were calculated to be in the range of 8-10 kJ/mol suggesting an ion exchange type of sorption mechanism. In detailed experiments, chlorite-illite mixed clay was first presaturated with K+, Sr2+, Ca2+ and Al3+ ions, respectively, prior to sorption studies with Ba2+ ions. The results of Ca2+ pretreated chlorite-illite were very similar to those of natural chlorite-illite, suggesting that the Ba2+ ion exchanges primarily with the Ca2+ ion on the clay minerals. © 1995 Akadémiai Kiadó.
Open Access
A radiotracer study of the adsorption behavior of aqueous Ba2+ ions on nanoparticles of zero-valent iron
(2007) Çelebi O.; Üzüm, C.; Shahwan, T.; Erten H.N.
Recently, iron nanoparticles are increasingly being tested as adsorbents for various types of organic and inorganic pollutants. In this study, nanoparticles of zero-valent iron (NZVI) synthesized under atmospheric conditions were employed for the removal of Ba2+ ions in a concentration range 10-3 to 10-6 M. Throughout the study, 133Ba was used as a tracer to study the effects of time, concentration, and temperature. The obtained data was analyzed using various kinetic models and adsorption isotherms. Pseudo-second-order kinetics and Dubinin-Radushkevich isotherm model provided the best correlation with the obtained data. Observed thermodynamic parameters showed that the process is exothermic and hence enthalpy-driven. © 2007 Elsevier B.V. All rights reserved.
Open Access
Sorption behavior of Co2+, Zn2+ and Ba2+ ions on alumina, kaolinite and magnesite
(Kluwer Academic Publishers, 1994) Erten, H. N.; Gokmenoglu, Z.
The sorption behavior of Ba2+, Co2+ and Zn2+ ions on alumina, kaolinite and magnesite have been investigated using the batch method.60Co,65Zn and133Ba were used as radiotracers. The mineral samples were separated into different particle size fractions using an Andreasen Pipette. The particle sizes used in the sorption experiments were all less than 38 μm. Synthetic groundwaters were used which had compositions similar to those from the regions where the minerals were recovered. The samples were shaken with a lateral shaker at 190 rpm, the phases were separated by centrifuging and adioactivity counted using a NaI(Tl) detector. Kinetic studies indicated that sorption onto the minerals took place in two stages with the slower process dominating. The highest sorption was observed on alumina. Both Freundlich and Dubinin-Radushkevich type isotherms were found to describe the sorption process well. The distribution ratio, Rd was found to be a function of the liquid volume to solid mass ratio. The Rd's for sorption on binary mixtures of minerals were experimentally determined and compared with those predicted from Rd values of each individual mineral. © 1994 Akadémiai Kiadó.
Open Access
Sorption of barium on kaolinite, montmorillonite and chlorite
(Royal Society of Chemistry, 1989) Eylem, C.; Erten, H. N.; Göktürk, H.
The sorption characteristics of the Ba2+ ion on kaolinite, montmorillonite and chloritetype clays were studied using the batch method. Barium-133 was used as a tracer. The Ba2+ ion concentrations ranged from 10-8 to 10-5 mol l-1; synthetic groundwater was used and the grain size of all the solid particles was <40 μm. About 6, 8 and 12 d of shaking were necessary to reach equilibrium for chlorite, kaolinite and montmorillonite, respectively. The sorption isotherms were described best by Freundlich and Dubinin - Radushkevich type isotherms. Sorption was predominantly reversible for kaolinite and partly reversible for montmorillonite and chlorite.
Open Access
Sorption of Cs+ and Ba2+ on magnesite
(Cambridge University Press, 1998) Shahwan, Talal; Süzer, Şefik; Erten, Hasan N.
Sorption behavior of Cs and Ba ions on magnesite was studied using the radiotracer method complemented by X-ray photoelectron spectroscopy. Cs and Ba were used as radiotracers. The sorption of Cs is seen to be temperature dependent, whereas Ba sorption is not much affected by temperature changes. It was found that Freundlich type isotherms provide an adequate description of the sorption process. The magnitude of the free energy of sorption are seen to be within the 8-16 kj/mol range. It can be remarked that the sorption of Cs and Ba on magnesite is a fast process suggesting an ion exchange type mechanism, mainly taking place at the surface of mineral particles.
Open Access
Sorption studies of cesium and barium on magnesite using radiotracer and x-ray photoelectron spectroscopy
(1997-06) Shahwan, Talal
As the consumption of the radioactive materials is continuously increasing, the problem of disposing the resulting v^^astes safely is becoming more challenging. One way through which these radioactive wastes could be isolated from the biological environment is by disposing them in deep geological formations. Clay minerals are proposed as backfill buffering materials that can delay the migration of the radionuclides and thus decrease the contamination of underground waters. The extent of retardation of the radionuclide migration is dependent on factors like time of contact, pH and Eh of groundwater, concentration, temperature and grain size of the mineral particles. Up to now, several studies were carried out to examine the effect of such parameters on the sorption behavior of different radionuclides on various kinds of minerals. This study was conducted to investigate the effects of time, concentration and temperature on the sorption behavior of cesium and barium ions on magnesite. Cesium 137 140 and barium have the radioactive isotopes Cs (t^^^ = 30.1 y) and Ba (t^^^ = 12.8 d) 1/2 produced in high yields during the fission process which are important in radioactive waste considerations. Magnesite is a mineral composed mainly of magnesium carbonate 2+ together with minor amounts of quartz and has a single exchangeable cation. Mg . The radiotracer method and x-ray photoelectron spectroscopy, which is a powerful surface sensitive tool, were used in this study. The results obtained from both methods complemented each others and were in good agreement. Kinetic studies of the sorption process show that equilibrium was approached within one day of contact for both of cesium and barium ions. The data of the sorption of both cations using different concentrations at various temperatures were most adequately described by the Freundlich type isotherms which correspond to multilayer adsorption on heterogeneous surfaces. The values of the Freundlich constants k and n imply that barium ions have slightly larger adsorption affinity and adsorption intensity than cesium ions. The adsorption data at low concentrations were also observed to obey the Dubinin-Radushkevich type isotherms which describe monolayer adsorption on heterogeneous or homogeneous surfaces. The adsorption data were very poorly described by the Langmuir type isotherms. Thermodynamic parameters such as enthalpy change, AH°, entropy change, AS° and free energy change of adsorption, AG°, were calculated from the sorption data of cesium and barium ions at different temperatures. The values obtained for AH° and AS° were -37 kJ/moL, -0.09 kJ/moL.K and -13 kJ/moL, -0.009 kJ/moL.K for cesium and barium ions respectively. The negative AH° values indicate the exothermic nature of adsorption which means that low temperatures are favored. The decrease in entropy upon adsorption implied by the negative AS° values is indicative of the stability of adsorption for both cations. The values of AG° at different temperatures were all negative indicating the spontaneity of the adsorption process for both cesium and barium ions. The magnitudes of AG° were seen to be within the 8-16 kJ/moL range which is the energy range of ion- exchange type processes.
Open Access
Sorption studies of Cs+ and Ba2+ cations on magnesite
(Elsevier, 1998-05-11) Shahwan, T.; Süzer, Şefik; Erten, H. N.
The adsorption behavior of Cs+ and Ba2+ cations on magnesite has been studied as a function of time, cation concentration and temperature, utilizing both the radiotracer method and X-ray photoelectron spectroscopy (XPS). Saturation was approached in about I day for both cations. The sorption data were found to follow Freundlich type isotherms. Sorption of both Cs+ and Ba2+ cations were found to be exothermic in nature with ΔH0 (kJ/mol) of -37, -13 and ΔS0 (kJ/mol·K) of -0.09, -0.009, respectively. Negative ΔG0 values were obtained for both cations, indicating the spontaneity of their sorption on magnesite. The magnitude of ΔG0 suggest that ion exchange is the dominating sorption mechanism. The adsorption behavior of Cs+ and Ba2+ cations on magnesite has been studied as a function of time, cation concentration and temperature, utilizing both the radiotracer method and X-ray photoelectron spectroscopy (XPS). Saturation was approached in about 1 day for both cations. The sorption data were found to follow Freundlich type isotherms. Sorption of both Cs+ and Ba2+ cations were found to be exothermic in nature with ΔH0 (kJ/mol) of -37, -13 and ΔS0 (kJ/mol·K) of -0.09, -0.009, respectively. Negative ΔG0 values were obtained for both cations, indicating the spontaneity of their sorption on magnesite. The magnitude of ΔG0 suggest that ion exchange is the dominating sorption mechanism.
Open Access
Sorption studies of Cs+, Ba2+, and Co2+ ions on bentonite using radiotracer, ToF-SIMS, and XRD techniques
(De Gruyter Oldenbourg, 2001) Shahwan, T.; Erten H. N.
The sorption behaviour of Cs+, Ba2+, and Co2+ ions on bentonite were investigated using the radiotracer method, Time of Flight-Secondary Ion Mass Spectroscopy (ToF-SIMS), and X-Ray Diffraction (XRD). The sorption of Cs+ and Ba2+ were exothermic while sorption of Co2+ was endothermic. The sorption data were well described by Freundlich and Dubinin-Radushkevich isotherms. According to ToF-SIMS results Na+ and Mg2+ were the primary exchanging ions in bentonite. The XRD spectra showed that no structural changes were associated with the sorption of Cs+ and Co2+, and BaCO3 precipitate was formed upon the sorption of Ba2+ on bentonite.
Open Access
Structural, microstructural and thermal properties of lead-free bismuth-sodium-barium-titanate piezoceramics synthesized by mechanical alloying
(2013) Amini, R.; Ghazanfari, M.R.; Alizadeh, M.; Ardakani H.A.; Ghaffari, M.
Bismuth-sodium-barium-titanate piezoceramics with a composition of (Bi 0.5Na0.5)0.94Ba0.06TiO3 (BNBT) were prepared by mechanical alloying (MA). Structural analysis and phase identification were performed by X-ray diffraction (XRD). Microstructural studies and chemical composition homogeneity were performed by scanning electron microscope (SEM) coupled with energy dispersive X-ray analysis (EDX). Furthermore, thermal properties of the as-milled powders were evaluated by thermogravimetry/differential thermal analysis (TG/DTA). During the initial milling, the constituents were transformed to the perovskite, pyrochlore, and BNT phases; in addition, partial amorphization of the structure appeared during the milling cycle. As MA progressed, transformation of pyrochlore-to-perovskite and crystallization of the amorphous phase occurred and also, the BNBT phase was significantly developed. It was found that the MA process has the ability to synthesize the BNBT powders with a submicron particle size, regular morphology, and uniform elemental distribution. © 2012 Elsevier Ltd.