Browsing by Author "Vempati S."
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Item Open Access Amorphous to tetragonal zirconia anostructures and evolution of valence and core regions(American Chemical Society, 2015) Vempati S.; Kayaci-Senirmak, F.; Ozgit-Akgun, C.; Bıyıklı, Necmi; Uyar, TamerIn this report, we study the evolution of valence band (VB) structure during a controlled amorphous to tetragonal transformation of ZrO2 core-shell nanostructures fabricated from electrospun nanofiber template (at 130, 200, and 250 °C). Shell-ZrO2 was formed with atomic layer deposition. X-ray diffraction and transmission electron microscopy are employed to unveil the transformation of amorphous to crystalline structure of ZrO2. O 1s core-level spectra indicated chemisorbed oxygen (OCh) of almost invariant fraction for the three samples. Zr 3s level suggested that the sample deposited at 130 °C has depicted a peak at relatively higher binding energy. Analyses on Zr 3d spectra indicated the presence of metallic-Zr (Zr+ζ, 0 ≤ |ζ| < 4), the fraction of which decreases with increasing template temperature. VB region is analyzed until ∼64 eV below the Fermi level (EF). The region close to EF depicted features that are dissimilar to the literature. This discrepancy is explained on the basis of the analyses from O 1s, Zr 3d, and Zr 4p levels including hybridization of orbitals from chemisorbed species. These levels were analyzed in terms of peak characteristics such as spectral position, area under the peak, etc. The results of this study would enhance the understanding of the evolution of various bands in the presence of OCh and changes to the crystallinity enabling the functionalities that are not available in the single-phase ZrO2.Item Open Access Controlling the photoconductivity: graphene oxide and polyaniline self assembled intercalation(American Institute of Physics Inc., 2015) Vempati S.; Ozcan, S.; Uyar, TamerWe report on controlling the optoelectronic properties of self-assembled intercalating compound of graphene oxide (GO) and HCl doped polyaniline (PANI). Optical emission and X-ray diffraction studies revealed a secondary doping phenomenon of PANI with -OH and -COOH groups of GO, which essentially arbitrate the intercalation. A control on the polarity and the magnitude of the photoresponse (PR) is harnessed by manipulating the weight ratios of PANI to GO (viz., 1:1.5 and 1:2.2 are abbreviated as PG1.5 and PG2.2, respectively), where ±PR = 100(RDark - RUV-Vis)/RDark and R corresponds to the resistance of the device in dark or UV-Vis illumination. To be precise, the PR from GO, PANI, PG1.5, and PG2.2 are +34%, -111%, -51%, and +58%, respectively.Item Open Access Enhanced photocatalytic activity of homoassembled ZnO nanostructures on electrospun polymeric nanofibers: a combination of atomic layer deposition and hydrothermal growth(Elsevier, 2014) Kayaci, F.; Vempati S.; Ozgit Akgun, C.; Bıyıklı, Necmi; Uyar, TamerWe report on the synthesis and photocatalytic activity (PCA) of electrospun poly(acrylonitrile) (PAN) nanofibrous mat decorated with nanoneedles of zinc oxide (ZnO). Apart from a detailed morphological and structural characterization, the PCA has been carefully monitored and the results are discussed elaborately when juxtaposed with the photoluminescence. The present hierarchal homoassembled nanostructures are a combination of two types of ZnO with diverse optical qualities, i.e. (a) controlled deposition of ZnO coating on nanofibers with dominant oxygen vacancies and significant grain boundaries by atomic layer deposition (ALD), and (b) growth of single crystalline ZnO nanoneedles with high optical quality on the ALD seeds via hydrothermal process. The needle structure (~25. nm in diameter with an aspect ratio of ~24) also supports the vectorial transport of photo-charge carriers, which is crucial for high catalytic activity. Furthermore, it is shown that enhanced PCA is because of the catalytic activity at surface defects (on ALD seed), valence band, and conduction band (of ZnO nanoneedles). PCA and durability of the PAN/ZnO nanofibrous mat have also been tested with aqueous solution of methylene blue and the results showed almost no decay in the catalytic activity of this material when reused.Item Open Access Excitation dependent recombination studies on SnO2/TiO2 electrospun nanofibers(Royal Society of Chemistry, 2015) Babu, V. J.; Vempati S.; Ertas Y.; Uyar, TamerPoly(vinyl acetate) (PVAc)/TiO2 nanofibers, PVAc/SnO2 nanoribbons and PVAc/SnO2-TiO2 nanoribbons were produced via electrospinning. TiO2 nanofibers and SnO2 nanoribbons were obtained by removal of the polymeric matrix (PVAc) after calcination at 450 °C. Interestingly, PVAc/SnO2-TiO2 nanoribbons were transformed into SnO2-TiO2 nanofibers after calcination under the similar conditions. Fiber morphology and elemental mapping confirmed through SEM and TEM microscope techniques respectively. The X-ray diffraction measurements suggested the presence of anatase TiO2 and rutile SnO2 and both were present in the SnO2-TiO2 mixed system. Systematic photoluminescence studies were performed on the electrospun nanostructures at different excitation wavelengths (λex1 = 325, λex2 = 330, λex3 = 350, λex4 = 397 and λex5 = 540 nm). We emphasize that the defects in the SnO2-TiO2 based on the defect levels present in TiO2 and SnO2 and anticipate that these defect levels may have great potential in understanding and characterizing various semiconducting nanostructures.Item Open Access Fabrication of flexible polymer–GaN core–shell nanofibers by the combination of electrospinning and hollow cathode plasma-assisted atomic layer deposition(Royal Society of Chemistry, 2015) Ozgit Akgun, C.; Kayaci, F.; Vempati S.; Haider A.; Celebioglu A.; Goldenberg, E.; Kizir S.; Uyar, Tamer; Bıyıklı, NecmiHere we demonstrate the combination of electrospinning and hollow cathode plasma-assisted atomic layer deposition (HCPA-ALD) processes by fabricating flexible polymer-GaN organic-inorganic core-shell nanofibers at a processing temperature much lower than that needed for the preparation of conventional GaN ceramic nanofibers. Polymer-GaN organic-inorganic core-shell nanofibers fabricated by the HCPA-ALD of GaN on electrospun polymeric (nylon 6,6) nanofibers at 200 °C were characterized in detail using electron microscopy, energy dispersive X-ray analysis, selected area electron diffraction, X-ray diffraction, X-ray photoelectron spectroscopy, photoluminescence measurements, and dynamic mechanical analysis. Although transmission electron microscopy studies indicated that the process parameters should be further optimized for obtaining ultimate uniformity and conformality on these high surface area 3D substrates, the HCPA-ALD process resulted in a ∼28 nm thick polycrystalline wurtzite GaN layer on polymeric nanofibers of an average fiber diameter of ∼70 nm. Having a flexible polymeric core and low processing temperature, these core-shell semiconducting nanofibers might have the potential to substitute brittle ceramic GaN nanofibers, which have already been shown to be high performance materials for various electronic and optoelectronic applications.Item Open Access Non-universal behavior of leaky surface waves in a one dimensional asymmetric plasmonic grating(American Institute of Physics Inc., 2015) Vempati S.; Iqbal, T.; Afsheen, S.We report on a non-universal behavior of leaky surface plasmon waves on asymmetric (Si/Au/analyte of different height) 1D grating through numerical modelling. The occurrence of the leaky surface wave was maximized (suppressing the Fabry-Perot cavity mode), which can be identified in a reflection spectrum through characteristic minimum. Beyond a specific analyte height (h), new sets of surface waves emerge, each bearing a unique reflection minimum. Furthermore, all of these minima depicted a red-shift before saturating at higher h values. This saturation is found to be non-universal despite the close association with their origin (being leaky surface waves). This behavior is attributed to the fundamental nature and the origin of the each set. Additionally, all of the surface wave modes co-exit at relatively higher h values. © 2015 AIP Publishing LLC.Item Open Access Optoelectronic properties of layered titanate nanostructure and polyaniline impregnated devices(Wiley - V C H Verlag GmbH & Co. KGaA, 2016) Vempati S.; Ertas Y.; Babu, V. J.; Uyar, TamerIntegrated structure of titanate nanotubes and nanosheets is investigated for their optical, electronic and optoelectronic properties when combined with HCl doped polyaniline (PANI). HR-TEM, SEM and XRD were employed for detailed morphological and microstructural understanding of the orthorhombic titanate nanostructure. Chemisorbed oxygeneous groups are probed with Raman spectroscopy which are found to desorb under UV-Vis treatment. We note a blue shift of Ti-O-Ti Raman frequency in contrast to Na-O-Ti stretching. Valence band region of titanate is analyzed for contribution of O2p, O2s, Na2p and Ti3p. Photoluminescence with different excitation energies revealed the presence of oxygen vacancy related defects in titanate. The highly occupied electronic states of PANI were also analyzed until 40 eV below the Fermi energy. XPS core-level analyses revealed ∼25 % doping density in PANI. Edges of valence band and HOMO are determined to be at 2.45 eV and 2.54 eV below Fermi energy for titanate and PANI, respectively. ITO/PANI/ITO has depicted negative photoresponse and the magnitude of which is reduced ∼4 times after combining with titanate nanostructure. Essentially the nanoscale architecture separates the emeraldine base and salt regions of PANI. This separation channelizes the charge carriers before trapping which reduces the magnitude of the negative photoresponse.Item Open Access Reduced recombination and enhanced UV-assisted photocatalysis by highly anisotropic titanates from electrospun TiO2-SiO2 nanostructures(Royal Society of Chemistry, 2014) Babu, V. J.; Vempati S.; Ramakrishna, S.The surface areas of electrospun fibers/rice grain-shaped nanostructures of TiO2-SiO2 composites were further enhanced after transforming them into thorn or sponge shaped titanates via selective leaching of SiO2, which was reported by our group previously [RSC Adv., 2012, 2, 992]. In this study, we report on their application in photocatalytic activity (PCA) when juxtaposed with photoluminescence (PL). Two defect related bands are observed in PL and their origin is discussed in relation to calcination, crystallization and nucleation effects. The relative PL intensity for sponge shapes was the lowest and hence had the lowest radiative recombination, which suggests carrier trapping at defect centers. This enables the charge carriers to migrate to the surface and participate in the PCA. The results of PCA suggested that the sponge-shaped titanate exhibits the highest degradation rate among all samples. A plausible mechanism for the differences in PCA is proposed based on the variation in the defect-densities. This journal is © the Partner Organisations 2014.Item Open Access Review of one-dimensional and two-dimensional nanostructured materials for hydrogen generation(Royal Society of Chemistry, 2015) Babu, V. J.; Vempati S.; Uyar, Tamer; Ramakrishna, S.Hydrogen is an attractive alternative to fossil fuels in terms of environmental and other advantages. Of the various production methods for H2, photocatalysis requires further development so that it can be applied economically on an industrial scale. One- and two-dimensional nanostructures in both pristine and modified forms have shown great potential as catalysts in the generation of H2. We review here recent developments in these nanostructure catalysts and their efficiency in the generation of H2 under UV/visible/simulated solar light. Despite much research effort, many photocatalysts do not yet meet the practical requirements for the generation of H2, such as visible light activity. H2 production is dependent on a variety of parameters and factors. To meet future energy demands, several challenges in H2 production still need to be solved. We address here the factors that influence the efficiency of H2 production and suggest alternatives. The nanostructures are classified based on their morphology and their efficiency is considered with respect to the influencing parameters. We suggest effective ways of engineering catalyst combinations to overcome the current performance barriers.Item 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, TamerOxygen 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.Item 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, TamerHeterojunctions 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.Item Open Access Sensitive surface states and their passivation mechanism in CdS quantum dots(American Chemical Society, 2013) Vempati S.; Ertas, Y.; Uyar, TamerWe report on phase sensitive surface states of CdS quantum dots (QDs), where it is noticed that a simple phase change from dispersion to solid has shown significant influence on the emission spectrum. As the solvent evaporates from the dispersion, apparently yellow dispersion transforms into a white light emitter because of the conformal changes in the polymer that surrounds the QDs. In turn, these changes catalyze the emission from three specific wavelengths in the blue region of the spectrum, shifting the surface defects closer to the conduction band of CdS. In the phase change from dispersion to solid, flexible and dangling polymer chains are transformed into rigid moieties that can be treated as a modified chemical environment. Furthermore, to ascertain the origin of the new emission lines, we have studied a dipole interaction-based passivation mechanism between QDs and the polymer. The proposed mechanism may be valuable for designing future QD-based fluorophores and explains the sensitivity of the surface states in the case of CdS. © 2013 American Chemical Society.Item 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, TamerHere 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.Item Open Access Transformation of polymer-ZnO core-shell nanofibers into ZnO hollow nanofibers: Intrinsic defect reorganization in ZnO and its influence on the photocatalysis(Elsevier, 2015) Kayaci, F.; Vempati S.; Ozgit Akgun, C.; Donmez, I.; Bıyıklı, Necmi; Uyar, TamerPhotocatalytic activity (PCA) on semiconductors is known to be majorly influenced by specific surface area and intrinsic lattice defects of the catalyst. In this report, we tested the efficiencies of 1D ZnO catalysts of varying fiber diameter (80. nm and 650. nm of inner diameter) in two formats, viz. core-shell and hollow nanofibers, where the former is calcined to yield the latter. These nanofibrous catalysts were produced by combining electrospinning and atomic layer deposition processes which were then subjected to thorough characterization including photoluminescence (PL) unveiling the details of intrinsic defects/densities. During the thermal treatment, intrinsic defects are reorganized and as a result a new PL band is observed apart from some significant changes in the intensities of other emissions. The densities of various intrinsic defects from PL are compared for all samples and juxtaposed with the PCA. Careful scrutiny of the various results suggested an anti-correlation between surface area and PCA; i.e., higher surface area does not necessarily imply better PCA. Beyond a limit, the most deterministic factor would be the density of surface defects rather than the specific surface area. The results of this study enable the researchers to fabricate 1D semiconductor photocatalysts while striking the balance between surface area and density of defects.Item Open Access Water-soluble non-polymeric electrospun cyclodextrin nanofiber template for the synthesis of metal oxide tubes by atomic layer deposition(Royal Society of Chemistry, 2014) Celebioglu A.; Vempati S.; Ozgit Akgun, C.; Bıyıklı, Necmi; Uyar, TamerWe report on the suitability of water-soluble non-polymeric electrospun cyclodextrin (CD) nanofiber templates by using atomic layer deposition (ALD) to yield metal oxide tubes. To demonstrate this, water-soluble electrospun CD nanofibers were chosen as template to produce metal oxide tubes where we have tested two examples of ALD coatings, namely, Al2O3 and ZnO. After the ALD coating on the CD nanofibers, the CD core is simply dissolved in water to yield metal oxide tubes. Morphological investigations suggested that Al2O3 is smoother in contrast to ZnO which shows a grainy structure. Structural characterization evidenced amorphous Al2O3 and highly crystalline ZnO. Given the applicability of Al2O3 and ZnO in various contexts the ionic states of Al, Zn and O are also investigated. After the washing step to remove the CD core, Al2O3 developed some hydroxylation, while ZnO hosts various oxygen related functional groups.