Browsing by Subject "Oxygen vacancies"

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Open Access
The effect of gadolinium doping on the structural, magnetic and photoluminescence properties of electrospun bismuth ferrite nanofibers
(Elsevier Ltd, 2015) George Philip G.; Senthamizhan, A.; Srinivasan Natarajan, T.; Chandrasekaran G.; Annal Therese H.
Gadolinium (Gd) doped Bismuth ferrite (BFO) nanofibers (Bi1-xGdxFeO3 (x=0.0, 0.05, 0.10, 0.15 and 0.20)) were synthesized via electrospinning. Scanning Electron Microscope (SEM) analysis showed that the diameter of the nanofibers ranged from 150 to 250 nm. X-Ray Diffraction (XRD) analysis revealed a structural phase transition with varying 'x', the compositions with x≤0.10 have crystal structures with space group R3c, while the compositions with x > 0.10 have crystal structures with space group Pnma. Vibrating Sample Magnetometer (VSM) analysis exhibited the weak ferromagnetic nature of the BFO nanofibers. However an increase in the saturated magnetic moment with increase in Gd dopant concentration was observed. The Photoluminescence (PL) spectra of the Bi:1-x :x nanofibers show enhanced Near Band Emission (NBE) intensity at x=0.10 due to the passivation of oxygen vacancies by Gd doping. © 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Open Access
Gold catalysts supported on ceria doped by rare earth metals for water gas shift reaction: influence of the preparation method
(2009) Andreeva, D.; Ivanov, I.; Ilieva, L.; Abrashev, M. V.; Zanella, R.; Sobczak, J. W.; Lisowski, W.; Kantcheva, M.; Avdeev, G.; Petrov, K.
Gold catalysts based on ceria, doped by various RE metals (La, Sm, Gd, Yb, Y) were studied. The influence of the preparation methods on structure, properties and catalytic activity in the WGS reaction was investigated. The catalysts' supports were prepared using two different methods: co-precipitation (CP) and mechanochemical activation (MA). The catalysts were tested in a wide temperature interval without and after reactivation. All samples were characterized using a combination of X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy (RS) and X-ray photoelectron spectroscopy (XPS) and TPR. It was found that the catalytic activity of MA catalysts is higher than CP ones. The gold catalysts based on ceria doped by Yb and Sm exhibited the highest activity. After reactivation in air the MA samples almost kept the WGS activity same, while the CP catalysts increased it. The catalysts of a single- and double-phase structure are formed as a result of CP and MA preparation, respectively. There are no big differences in the gold particles size (2-3 nm) depending on dopants and on the preparation techniques. The RS spectra analysis indicates that most probably the oxygen vacancies are adjacent to Me3+ dopant and the ceria structure seems to be better ordered than in the case of alumina as a dopant. There is no distinct correlation between reducibility and WGS activity. The XPS analysis disclose positively charged gold particles in addition to metallic gold within a surface region of fresh samples and only metallic gold on the samples after catalytic processing. There is no simple correlation between the concentration of Ce3+ in the samples and their WGS activity.
Open Access
Investigation of local structure effect and X-ray absorption characteristics (EXAFS) of Fe (Ti) K-edge on photocatalyst properties of SrTi (1-x)Fe xO (3-δ)
(2012) Ghaffari, M.; Liu, T.; Huang H.; Tan O.K.; Shannon, M.
In this study, the STF x photocatalyst powder was synthesized with a high temperature solid state reaction. The microstructures and surface of samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The electronic properties and local structure of the perovskite STF x (0 ≤ x ≤ 1) systems were probed by extended X-ray absorption fine structure (EXAFS) spectroscopy. The XPS results revealed that with increasing iron doping, the amount of Fe 3+ and Fe 4+ increased significantly. The X-ray absorption data are discussed in detail with respect to the Fe (Ti) K-edge. The substitution of iron by titanium increased the Ti (Fe)-O first shell disorder factors that can be explained by increasing the oxygen vacancies. Oxygen vacancies or defects act as electron traps, which could capture the photo induced electrons and thus could effectively inhibit the recombination of the photo induced electrons and holes. Moreover due to the substitution of Ti with Fe, lattice shrinkage was observed and the largest derivation from the Gaussian distribution in STF x was from those samples with x = 0.6 and x = 0.8. The substitution of iron by titanium increased the iron valence state, hence the formation of the Jahn-Teller Fe 4+ ion. With increasing iron dopant the [Ti(Fe)-O] ave decreased and bond length of [Ti-O] and the consequent [Ti-O-Ti] increased and this phenomenon affected the photocatalyst and photo degradation properties of material and also decreased its efficiency. © 2012 Elsevier B.V. All rights reserved.
Open Access
Morphological control of mesoporosity and nanoparticles within Co3O4-CuO electrospun nanofibers: quantum confinement and visible light photocatalysis performance
(American Chemical Society, 2017-09) Pradhan, A. C.; Uyar, Tamer
The one-dimensional (1D) mesoporous and interconnected nanoparticles (NPs) enriched composite Co3O4-CuO nanofibers (NFs) in the ratio Co:Cu = 1/4 (Co3O4-CuO NFs) composite have been synthesized by electrospinning and calcination of mixed polymeric template. Not merely the mesoporous composite Co3O4-CuO NFs but also single mesoporous Co3O4 NFs and CuO NFs have been produced for comparison. The choice of mixed polymer templates such as polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) for electrospinning is responsible for the formation of 1D mesoporous NFs. The HR-TEM result showed evolution of interconnected nanoparticles (NPs) and creation of mesoporosity in all electrospun NFs. The quantum confinement is due to NPs within NFs and has been proved by the surface-enhanced Raman scattering (SERS) study and the UV-vis-NRI diffuse reflectance spectra (DRS). The high intense photoluminescence (PL) spectra showing blue shift of all NFs also confirmed the quantum confinement phenomena. The lowering of PL spectrum after mixing of CuO in Co3O4 nanofibers framework (Co3O4-CuO NFs) proved CuO as an efficient visible light response low cost cocatalyst/charge separator. The red shifting of the band gap in composite Co3O4-CuO NFs is due to the internal charge transfer between Co2+ to Co3+ and Cu2+, proved by UV-vis absorption spectroscopy. Creation of oxygen vacancies by mixing of CuO and Co3O4 also prevents the electron-hole recombination and enhances the photocatalytic activity in composite Co3O4-CuO NFs. The photocurrent density, Mott-Schottky (MS), and electrochemical impedance spectroscopy (EIS) studies of all NFs favor the high photocatalytic performance. The mesoporous composite Co3O4-CuO NFs exhibits high photocatalytic activity toward phenolic compounds degradation as compared to the other two NFs (Co3O4 NFs and CuO NFs). The kinetic study of phenolic compounds followed first order rate equation. The high photocatalytic activity of composite Co3O4-CuO NFs is attributed to the formation of mesoporosity and interconnected NPs within NFs framework, quantum confinement, extended light absorption property, internal charge transfer, and effective photogenerated charge separations.
Open Access
Oxygen partial pressure dependence of magnetic, optical and magneto-optical properties of epitaxial cobalt-substituted SrTiO3 films
(OSA - The Optical Society, 2015) Onbaşli, M.C.; Goto, T.; Tang, A.; Pan, A.; Battal, E.; Okyay, Ali Kemal; Dionne G.F.; Ross, C.A.
Cobalt-substituted SrTiO3 films (SrTi0.70Co0.30O3-δ) were grown on SrTiO3 substrates using pulsed laser deposition under oxygen pressures ranging from 1 μTorr to 20 mTorr. The effect of oxygen pressure on structural, magnetic, optical, and magneto-optical properties of the films was investigated. The film grown at 3 μTorr has the highest Faraday rotation (FR) and magnetic saturation moment (Ms). Increasing oxygen pressure during growth reduced Ms, FR and optical absorption in the nearinfrared. This trend is attributed to decreasing Co2+ ion concentration and oxygen vacancy concentration with higher oxygen partial pressure during growth. © 2015 Optical Society of America.
Open Access
Rational synthesis of Na and S co-catalyst TiO2-based nanofibers: presence of surface-layered TiS3 shell grains and sulfur-induced defects for efficient visible-light driven photocatalysis
(Royal Society of Chemistry, 2017) Ranjith, K. S.; Uyar, Tamer
Surface-modified TiO2 nanofibers (NFs) with tunable visible-light photoactive catalysts were synthesised through electrospinning, followed by a sulfidation process. The utilization of sodium-based sulfidation precursors effectively led to the diffusion and integration of sulfur impurities into TiO2, modifying its band function. The optical band function of the sulfur-modified TiO2 NFs can be easily manipulated from 3.17 eV to 2.28 eV through surface modification, due to the creation of oxygen vacancies through the sulfidation process. Sulfidating TiO2 NFs introduces Ti-S-based nanograins and oxygen vacancies on the surface that favor the TiO2-TiS3 core-shell interface. These defect states extend the photocatalytic activity of the TiO2 NFs under visible irradiation and improve effective carrier separation and the production of reactive oxygen species. The surface oxygen vacancies and the Ti-S-based surface nanograins serve as charge traps and act as adsorption sites, improving the carrier mobility and avoiding charge recombination. The diffused S-modified TiO2 NFs exhibit a degradation rate of 0.0365 cm-1 for RhB dye solution, which is 4.8 times higher than that of pristine TiO2 NFs under visible irradiation. By benefiting from the sulfur states and oxygen vacancies, with a narrowed band gap of 2.3 eV, these nanofibers serve as suitable localized states for effective carrier separation.
Open Access
Role of zinc interstitials and oxygen vacancies of ZnO in photocatalysis: a bottom-up approach to control the defect density
(Royal Society of Chemistry, 2014-06-09) Kayaci, F.; Vempati S.; Donmez, I.; Bıyıklı, Necmi; Uyar, Tamer
Oxygen vacancies (VOs) in ZnO are well-known to enhance photocatalytic activity (PCA) despite various other intrinsic crystal defects. In this study, we aim to elucidate the effect of zinc interstitials (Zn i) and VOs on PCA, which has applied as well as fundamental interest. To achieve this, the major hurdle of fabricating ZnO with controlled defect density requires to be overcome, where it is acknowledged that defect level control in ZnO is significantly difficult. In the present context, we fabricated nanostructures and thoroughly characterized their morphological (SEM, TEM), structural (XRD, TEM), chemical (XPS) and optical (photoluminescence, PL) properties. To fabricate the nanostructures, we adopted atomic layer deposition (ALD), which is a powerful bottom-up approach. However, to control defects, we chose polysulfone electrospun nanofibers as a substrate on which the non-uniform adsorption of ALD precursors is inevitable because of the differences in the hydrophilic nature of the functional groups. For the first 100 cycles, Znis were predominant in ZnO quantum dots (QDs), while the presence of VOs was negligible. As the ALD cycle number increased, VOs were introduced, whereas the density of Zni remained unchanged. We employed PL spectra to identify and quantify the density of each defect for all the samples. PCA was performed on all the samples, and the percent change in the decay constant for each sample was juxtaposed with the relative densities of Znis and VOs. A logical comparison of the relative defect densities of Znis and VOs suggested that the former are less efficient than the latter because of the differences in the intrinsic nature and the physical accessibility of the defects. Other reasons for the efficiency differences were elaborated.
Open Access
Selective isolation of the electron or hole in photocatalysis: ZnO–TiO2 and TiO2–ZnO core–shell structured heterojunction nanofibers via electrospinning and atomic layer deposition
(Royal Society of Chemistry, 2014-02-06) Kayaci, F.; Vempati S.; Ozgit Akgun, C.; Donmez, I.; Bıyıklı, Necmi; Uyar, Tamer
Heterojunctions are a well-studied material combination in photocatalysis studies, the majority of which aim to improve the efficacy of the catalysts. Developing novel catalysts begs the question of which photo-generated charge carrier is more efficient in the process of catalysis and the associated mechanism. To address this issue we have fabricated core-shell heterojunction (CSHJ) nanofibers from ZnO and TiO2 in two combinations where only the 'shell' part of the heterojunction is exposed to the environment to participate in the photocatalysis. Core and shell structures were fabricated via electrospinning and atomic layer deposition, respectively which were then subjected to calcination. These CSHJs were characterized and studied for photocatalytic activity (PCA). These two combinations expose electrons or holes selectively to the environment. Under suitable illumination of the ZnO-TiO 2 CSHJ, e/h pairs are created mainly in TiO2 and the electrons take part in catalysis (i.e. reduce the organic dye) at the conduction band or oxygen vacancy sites of the 'shell', while holes migrate to the core of the structure. Conversely, holes take part in catalysis and electrons diffuse to the core in the case of a TiO2-ZnO CSHJ. The results further revealed that the TiO2-ZnO CSHJ shows ∼1.6 times faster PCA when compared to the ZnO-TiO2 CSHJ because of efficient hole capture by oxygen vacancies, and the lower mobility of holes.
Open Access
Surface ionic states and structure of titanate nanotubes
(Royal Society of Chemistry, 2015) Vempati S.; Kayaci-Senirmak, F.; Ozgit Akgun, C.; Bıyıklı, Necmi; Uyar, Tamer
Here we present an investigation on Zn-Ti-O ternary (zinc titanate) nanostructures which were prepared by a combination of electrospinning and atomic layer deposition. Depending on the ZnO and TiO2 molar ratio, two titanates and one mix phased compound were synthesized by varying the post-annealing temperatures. Specifically Zn2TiO4, ZnTiO3 and ZnO/TiO2 nanostructures were fabricated via thermal treatments (900, 700, 800 °C, respectively). Structural studies unveiled the titanate phase of the nanostructures. Furthermore, the ionic states of the titanate nanostructures on the surface are revealed to be Ti3+ and Zn2+. Spin-orbit splitting of Zn2p and Ti2p doublets were, however, not identical for all titanates which vary from 23.09-23.10 eV and 5.67-5.69 eV respectively. Oxygen vacancies were found on the surface of all titanates. The valance band region was analyzed for Zn3d, Ti3p, O2s and O2p and their hybridization, while the edge (below Fermi level) was determined to be at 2.14 eV, 2.00 eV and 1.99 eV for Zn2TiO4, ZnTiO3 and ZnO/TiO2 respectively.
Open Access
Three-dimensional interaction force and tunneling current spectroscopy of point defects on rutile TiO2(110)
(American Institute of Physics Inc., 2016) Baykara, M. Z.; Mönig, H.; Schwendemann, T. C.; Ünverdi, Ö.; Altman, E. I.; Schwarz, U. D.
The extent to which point defects affect the local chemical reactivity and electronic properties of an oxide surface was evaluated with picometer resolution in all three spatial dimensions using simultaneous atomic force/scanning tunneling microscopy measurements performed on the (110) face of rutile TiO2. Oxygen atoms were imaged as protrusions in both data channels, corresponding to a rarely observed imaging mode for this prototypical metal oxide surface. Three-dimensional spectroscopy of interaction forces and tunneling currents was performed on individual surface and subsurface defects as a function of tip-sample distance. An interstitial defect assigned to a subsurface hydrogen atom is found to have a distinct effect on the local density of electronic states on the surface, but no detectable influence on the tip-sample interaction force. Meanwhile, spectroscopic data acquired on an oxygen vacancy highlight the role of the probe tip in chemical reactivity measurements.
Open Access
ZnO nanostructures on electrospun nanofibers by atomic layer deposition/hydrothermal growth and their photocatalytic activity
(Materials Research Society, 2014) Kayaci, Fatma; Vempati, Sesha; Ozgit-Akgun, Cagla; Biyikli, Necmi; Uyar, Tamer
A hierarchy of nanostructured-ZnO was fabricated on the electrospun nanofibers by atomic layer deposition (ALD) and hydrothermal growth, subsequently. Firstly, we produced poly(acrylonitrile) (PAN) nanofibers via electrospinning, then ALD process provided a highly uniform and conformai coating of polycrystalline ZnO with a precise control on the thickness (50 nm). In the last step, this ZnO coating depicting dominant oxygen vacancies and significant grain boundaries was used as a seed on which single crystalline ZnO nanoneedles (average diameter and length of ∼25 nm and ∼600 nm, respectively) with high optical quality were hydrothermally grown. The detailed morphological and structural studies were performed on the resulting nanofibers, and the photocatalytic activity (PCA) was tested with reference to the degradation of methylene blue. The results of PCA were discussed in conjunction with photoluminescence response. The nanoneedle structures supported the vectorial transport of photo-charge carriers, which is crucial for high catalytic activity. The enhanced PCA, structural stability and reusability of the PAN/ZnO nanoneedles indicated that this hierarchical structure is a potential candidate for waste water treatment.