Browsing by Subject "Perovskite"

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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
Effect of processing options on ultra-low-loss lead-magnesium-niobium titanate thin films for high density capacitors
(Elsevier, 2013) Chen W.; McCarthy, K.G.; O'Brien, S.; Çopuroǧlu, Mehmet; Cai, M.; Winfield, R.; Mathewson, A.
This work studies the impact of annealing temperatures on PMNT (lead-magnesium niobate-lead titanate, Pb(Mg0.33Nb 0.67)0.65Ti0.35O3) thin films grown on a silicon substrate. The electrical properties of the thin films, such as dielectric constant and loss tangent, are shown to depend strongly on the annealing temperature, with the best electrical properties being achieved at the highest annealing temperature. It is seen that the perovskite phase is highest in the sample annealed at 750 C indicating that a relatively high temperature is necessary for complete transition of PMNT to the perovskite phase. The sample annealed at 400 C exhibits the lowest loss tangent of approximately 0.007 at a frequency of 1 MHz. © 2012 Elsevier B.V.
Open Access
Electronic structure of conventional slater type antiferromagnetic insulators: AIrO3 (A=Sr, Ba) perovskites
(Institute of Physics, 2022) Koc, Husnu; Mamedov, Amirullah M.; Özbay, Ekmel
The structural, mechanical, and electronic properties of Perovskite BaIrO3 and SrIrO3 compounds based on the density functional theory (DFT) have been examined in four different structures (C2/c, R-3m, P6_3/mmc and Pm-3m) and Pnma structure, respectively. The spin polarized generalized gradient approximation has been used for modeling exchange-correlation effects. As a result of spin polarized calculations, it has been observed that BaIrO3 compound showed magnetic properties in C2/c and R-3m structures, but not in Pm-3m and P6_3/mmc structures. SrIrO3 compound also shows magnetic properties in Pnma structure. The elastic constants have been calculated using the strain-stress method and the other related quantities (the bulk modulus, shear modulus, Young's modulus, Poisson's ratio, anisotropy factor, sound velocities, and Debye temperature) have also been estimated. In electronic band structure calculations, while Pm-3m and P6_3/mmc structures of NaIrO3 compound are metallic and semiconductor (Eg = 1.190 eV indirect), respectively, while C2/c and R-3m structures showing magnetic properties are metallic in spin down state and semiconductor (Eg=0.992 eV indirect and Eg=0.665 eV direct, respectively) in the spin up state. The Pmna structure in the SrIrO3 compound is a semiconductor in both spin states (Eg=0.701 eV “0.632 eV” indirect in the spin up “spin down”). © 2022 Institute of Physics Publishing. All rights reserved.
Open Access
N-O activation on precious metal-free metal oxide based NOx removal systems
(2022-01) Ercan, Kerem Emre
Elevated operational costs of platinum group metal (PGM) based environmental catalytic systems shift the focus of catalysis research towards cost-effective materials. In search for PGM-free alternative catalytic materials for NOx removal, high catalytic performance and long catalyst lifetime emerge as two important technical challenges. Within the scope of this dissertation, novel B-site mixed perovskites LaCoxMn1-xO3 (x = 0.1-0.9) and Fe and/or Co based CeO2 catalysts were synthesized, investigated and optimized as high performance, PGM-free, and durable catalyst alternatives for NOx removal systems. The perovskite based catalytic architectures can be utilized as diesel oxidation catalyst (DOC) oxidizing NO/CO to NO2/CO2, which can be coupled with selective catalytic reduction (SCR) catalysts to reduce NOx species to N2. On the other hand, Fe/Co based CeO2 systems can be exploited as catalyst candidates in SCR of NOx. In both of these NOx aftertreatment systems, NO activation is required. A simple and reproducible synthetic protocol was utilized to obtain perovskite-based DOC catalysts whose comprehensive structural characterization was carried out via XRD, N2 adsorption-desorption isotherm, ICP-MS, TEM, H2-TPR, ex-situ and in-situ XANES, EXAFS, in-situ FTIR, XPS, and TPD techniques. The oxidative catalytic performance of the perovskites for CO and NO oxidation was determined in flow-mode catalytic activity tests. It was demonstrated that bulk-oxygen vacancies have a strong influence on the redox activity of the B-site mixed perovskites with the ABO3 structure (where A = La, B = Co, Mn) allowing them to efficiently switch between high and low oxidation states in a reversible fashion under relatively moderate redox conditions without requiring elevated temperatures for regeneration, unlike conventional LaMnO3 and LaCoO3-based simple perovskite systems. La1.01Co0.75Mn0.24O2.97 and La1.04Co0.65Mn0.31O2.97 were found to reveal the best NO and CO oxidation performances among the currently investigated perovskites (La1.01Co0.75Mn0.24O2.97, La1.04Co0.65Mn0.31O2.97, La0.97Co1.03O2.91, and La0.97Mn1.03O3.17), which were on par with a conventional precious-metal benchmark catalyst (i.e., 1 wt. % Pt/Al2O3). Influence of Fe and Co loading on monometallic (Fe or Co) or bimetallic (Fe- Co) catalysts with different CeO2 support materials were studied in SCR of NO to N2. The flow-mode NO reduction experiments point out that 4 wt. % Co/CeO2 is the best catalyst in the studied group of catalysts based on its high N2 selectivity at relatively low temperatures. Detailed structural characterization experiments conducted via XRD, N2 adsorption-desorption isotherm, ATR-FTIR, Raman, and in-situ FTIR techniques indicate correlations between catalyst structure and SCR functionality. Our experimental findings indicate that 4 wt. % Co/CeO2 has relatively higher catalytic performance under excess H2(g) concentrations. The NO activation performance of both La1.01Co0.75Mn0.24O2.97 and La1.04Co0.65Mn0.31O2.97 B-site mixed perovskites and 4 wt. % Co/CeO2 were tested under significantly harsh conditions indicating their strong potential to be used not only in mobile applications but also in stationary NOx removal systems.
Open Access
Novel hybrid perovskite catalysts for DE-NOx applications
(2015-09) Ercan, Kerem Emre
The main purpose of this study is to identify the nature of hybrid perovskites in the form of LaCoxMn1-xO3 (x=0.0-1.0) for catalytic De-NOx applications. Characteristic structure, thermal stability and NOx/SOx adsorption/release properties of perovskites were studied by XRD, BET, XPS, in-situ FTIR, ex-situ FTIR, TEM, BET, TPD and TPR. LaCo0.8Mn0.2 and LaCo0.7Mn0.3O3 were found to yield the highest NOx storage Capacity (NSC) among other investigated perovskites due to their optimized B-site composition. NOx and SOx adsorption experiments pointed out that B-site substitution did not have a significant alteration on adsorption geometries of corresponding adsorbates. NOx uptakes of the investigated perovskites were observed to be enhanced via H2 reduction as verified by IR results. Furthermore, N2 (28 a.m.u) release monitored by QMS during NOx TPD revealed direct N-O bond activation and complete reduction of NOx species under certain conditions. SOx adsorption and reduction experiments suggested that SOx reduction via H2 is more effective for Mn-enrich perovskites, since Co-enriched materials formed irreversible sulfate species. It was observed that adsorbed NOx species can be readily replaced by SOx species in the co-presence of NOx and SOx. It was also demonstrated that the oxygen-defect density and the surface oxygen concentration of hybrid perovskites can be modified by fine-tuning the substitution at the B-site. Based on ex-situ FTIR results, it was established that Co-O linkages could be gradually replaced with Mn-O linkages by increasing the Mn loading in the perovskite composition. Furthermore, specific surface areas (SSA) of hybrid perovskites were found to be enhanced by increasing the Mn loading. Current results suggest that hybrid perovskites are promising novel catalytic architectures for De-NOx applications due to their high NSC and versatile chemical structure which can be fine-tuned to enhance SOx tolerance, redox properties and thermal stability.
Open Access
Preparation, surface state and band structure studies of SrTi (1-X)Fe (x)O (3-δ) (x = 0-1) perovskite-type nano structure by X-ray and ultraviolet photoelectron spectroscopy
(2012) Ghaffari, M.; Shannon, M.; Hui H.; Tan O.K.; Irannejad, A.
In this report, SrTi (1 - x)Fe (x)O (3 - δ) photocatalyst powder was synthesized by a high temperature solid state reaction method. The morphology, crystalline structures of obtained samples, was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscopy (TEM), respectively. The electronic properties and local structure of the perovskite STF x (0 ≤ x ≤ 1) systems have been probed by extended X-ray absorption fine structure (EXAFS) spectroscopy. The effects of iron doping level x (x = 0-1) on the crystal structure and chemical state of the STF x have been investigated by X-ray photoelectron spectroscopy and the valence band edges for electronic band gaps were obtained for STF x by ultraviolet photoelectron spectroscopy (UPS). A single cubic perovskite phase of STF x oxide was successfully obtained at 1200 °C for 24 h by the solid state reaction method. The XPS results showed that the iron present in the STF x perovskite structure is composed of a mixture of Fe 3+ and Fe 4+ (SrTi (1 - x)[Fe 3+, Fe 4+] (x)O (3 - δ)). When the content x of iron doping was increased, the amount of Fe 3+ and Fe 4+ increased significantly and the oxygen lattice decreased on the surface of STF x oxide. The UPS data has confirmed that with more substitution of iron, the position of the valence band decreased. © 2011 Elsevier B.V. All rights reserved.
Open Access
Pt-free perovskite based oxidation catalysts for automotive applications
(2013) Doğaç, Merve
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.
Open Access
Sulfur poisoning and regeneration behavior of perovskite-based NO oxidation catalysts
(Springer New York LLC, 2017) Kurt M.; Say, Z.; Ercan, K. E.; Vovk, E. I.; Kim, C. H.; Ozensoy, E.
SOxuptake and release properties of LaMnO3, Pd/LaMnO3, LaCoO3and Pd/LaCoO3perovskites were investigated via in situ Fourier transform infrared (FTIR) spectroscopy, temperature programmed desorption and X-ray photoelectron spectroscopy. Sulfation of the perovskite leads to the formation of surface sulfite/sulfate and bulk-like sulfate species. Pd addition to LaMnO3and LaCoO3significantly increases the sulfur adsorption capacity. Pd/LaMnO3sample accumulates significantly more sulfur than LaMnO3; however it can also release a larger fraction of the accumulated SOxspecies in a reversible fashion at elevated temperatures in vacuum. This is not the case for Co-based materials, where thermal regeneration of bulk sulfates on poisoned LaCoO3and Pd/LaCoO3is extremely ineffective under similar conditions. However, in the presence of an external reducing agent such as H2(g), Pd/LaMnO3requires much lower temperature (873ï¿½K) for complete sulfur regeneration as compared to that of Pd/LaCoO3(973ï¿½K). Sequential CO and SOxadsorption experiments performed via in situ FTIR indicate that in the presence of carbonyls and/or carbonates, Pd adsorption sites may have a stronger affinity for SOxas compared to that of the perovskite surface, particularly in the early stages of sulfur poisoning.
Open Access
Transition metal catalysis for aerobic C-H oxidation reactions and for the synthesis of fluoranthene derivatives
(2021-01) Şahin, Yeşim
Within the past two decades, a powerful class of new reactions that introduces oxidized functionality to (sp3) C-H bonds has emerged and gained tremendous attention since it can revolutionize the chemical industry by placing reactive functional groups directly in a molecule. Usually, precious metals (e.g., Pd, Pt, Ru etc.) are used for the activation of C-H bonds, and finding alternative ways that use less expensive and less toxic first row transition metals to replace precious metal catalysts is necessary. In this work, we have developed a reductive pretreatment system to increase the activity of precious metal-free LaMnO3 perovskites for C-H oxidation reactions of alkylarenes to ketones or oxidative dimerization of naphthols under mild conditions. Furthermore, a bimetallic nickel-manganese based hydroxide catalyst was synthesized as well and it was proven to oxidize a variety of alkylarenes and alcohols. Using molecular oxygen as the sole oxidant in C-H oxidation reactions is another advantage of our method since it is green, inexpensive and readily available in nature. In the second part, two novel methods have been developed for the synthesis of fluoranthenes which are important polycyclic skeletons. They can be found in many natural products, organic electronics, dyes and various materials. These methods employ Pd-catalyzed cross-coupling reactions such as Suzuki-Miyaura and Sonogashira reactions in the first steps using 1,8-dihalonaphthalenes and then use intramolecular Diels-Alder reactions for the formation of tetracyclic ring in the fluoranthene core. Our methods also provide a modular pathway for the synthesis of multi-substituted fluoranthene derivatives from simple molecules because it is designed as a three-component system and each component can be readily prepared or functionalized allowing easy modification.