Browsing by Subject "Complexation"
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Item Open Access Effects of ions on the liquid crystalline mesophase of transition-metal salt: surfactant (CnEOm)(American Chemical Society, 2004) Dag, Ö.; Alayoǧlu, S.; Uysal, İ.The transition-metal aqua complex salts [M(H2O) x]Y2 (where M is some of the first- and second-row transitionmetal ions and Y is Cl-, NO3-, and ClO4- counteranions) form liquid crystalline (LC) mesophases with oligo(ethylene oxide) nonionic surfactants (CnH 2n+1(CH2CH2O)mOH, denoted as C nEOm). The structure of the [M(H2O) x]Y2:CnEOm mesophase is usually 2D hexagonal in nitrate systems, cubic in perchlorate systems, and absent in the chloride systems. The solubility of the metal aqua complex salt follows the Hofmeister series in a [M(H2O)x]Y2:C nEOm mesophase. However, the nitrate ion interacts with the metal center as a bidentate and/or unidentate ligand, therefore reducing the ion density (and/or ionic strength) of the LC medium and further enhancing the solubility of nitrate salt in the LC systems. The cobalt chloride salt is the only soluble chloride salt that undergoes ligand-exchange reactions in the [Co(H2O)6]Cl2:CnEOm system. In an LC mesophase, anions have a greater influence on the hydrophilicity of nonionic surfactants than do cations. The structure and stability of the LC mesophase can be controlled by controlling either the hydrophilicity of the nonionic surfactant (by choosing the right anion type) or the ion density of the medium (by either influencing the equilibrium between the free and coordinated anions or balancing between the coordinating and noncoordinating anions in the medium).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 Flexible organic-inorganic core-shell nanofibers by electrospinning and atomic layer deposition(CRC Press, 2012) Kayacı, Fatma; Çağla, Özgit-Akgün; Dönmez, İnci; Bıyıklı, Necmi; Uyar, TamerOrganic-inorganic core-shell nanofibers were fabricated by combining electrospinning and atomic layer deposition (ALD). In the first step, nylon66 (polymeric organic core) nanofibers having different average fiber diameters (∼100 nm, ∼250 nm and ∼650 nm) were electrospun by using different solvent systems and polymer concentrations. In the second step, uniform and conformal layer of zinc oxide (ZnO) (inorganic shell) with precise thickness (∼90 nm) and composition on the round surface of the nylon nanofibers were deposited by ALD. The core-shell nylon66-ZnO nanofibers have shown unique properties such as structural flexibility due to the polymeric core and photocatalytic activity due to the ZnO shell layer.Item 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, TamerThe 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.Item Open Access Phase separation in liquid crystalline mesophases of [Co(H 2O)6]X2: P65 Systems (X = NO3-, Cl-, or ClO4-)(2007) Albayrak, C.; Gülten, G.; Dag, Ö.Transition-metal aqua complex salts [M(H2O)6]X 2 (where M is Mn(II), Co(II), Ni(II), Zn(II), or Cd(II) and X is NO3-, Cl-, or ClO4-) can be dissolved in triblock poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) copolymers (Pluronics, such as P65) to form homogeneous liquid crystalline (LC) mesophases. However, the [Co-(H2O) 6]X2:P65 LC mesophases slowly undergo phase separation into a disordered ion-free phase and an ordered ion-rich LC mesophase. The phase separation also takes place in the two-salt systems [Co(H2O) 6](NO3):[Co(H2O)6]-(ClO 4)2:P65 in which the ion-free disordered domains separate out from the initially ordered homogeneous mesophase. The phase separation results in a physical mixture of a hexagonal nitrate-rich and cubic perchlorate-rich LC and disordered ion-free domains in the mixed salt systems. The driving force in the phase separation in the [Co(H2O) 6]-X2:P65 system is Co(II)-catalyzed aerobic oxidation of P65 into ester and/or other oxidation products. The separation of ions in the [Co(H2O)6](NO3)2:[Co(H 2O)6](ClO4)2:P65 system is related to the mesostructures of the two-salt systems that are different, hexagonal in the [Co(H2O)6](NO3)2:P65 system and cubic in the [Co(H2O)6](ClO4)2:P65 system. There is no visible phase separation in the other transition-metal salt:P65 systems. The phase separation in the [Co-(H2O) 6]X2:P65 systems can also be eliminated by keeping the mesophase under a N2 atmosphere. © 2007 American Chemical Society.Item Open Access Quercetin/β-cyclodextrin inclusion complex embedded nanofibres: slow release and high solubility(Elsevier, 2016-04) Aytac Z.; Kusku, S. I.; Durgun, Engin; Uyar, TamerElectrospinning of polyacrylic acid (PAA) nanofibres (NF) incorporating β-cyclodextrin inclusion complex (β-CD-IC) of quercetin (QU) was performed. Here, β-CD was used as not only the crosslinking agent for PAA nanofibres but also as a host molecule for inclusion of QU. The phase solubility test showed enhanced solubility of QU due to the inclusion complexation; in addition, the stoichiometry of QU/β-CD-IC was determined to be 1:1. Computational modelling studies confirmed that 1:1 and 1:2 complex formation are desirable; 1:1 complex formation was chosen to have higher weight loading of QU. SEM images showed that PAA/QU/β-CD-IC-NF were bead-free and uniform. XRD indicated that PAA/QU/β-CD-IC-NF were amorphous in nature without the crystalline peaks of QU. Comparative results revealed that the release profile of QU from PAA/QU/β-CD-IC-NF was much slower but greater in total than from PAA/QU/β-CD-IC-film. Moreover, high antioxidant activity and photostability of QU was achieved in PAA/QU/β-CD-IC-NF.Item Open Access Routes of formation and composition of NOx complexes adsorbed on palladium-promoted tungstated zirconia(2006) Kantcheva, M.; Cayirtepe, I.Surface species obtained during the adsorption of NO and NO/O2 coadsorption at room temperature on Pd-free (WZ) and Pd-promoted tungstated zirconia (Pd/WZ) are identified by means of in situ FT-IR spectroscopy. The WZ and Pd/WZ samples have a tetragonal structure and contain randomly distributed mesoporous phase. Dispersed palladium(II) species are present in two different environments: (i) Pd2+ ions, which have only Zr4+ ions in their second coordination sphere and (ii) Pd2+ ions, which are linked to both zirconium and tungsten ions via oxygen bridges. On the Pd/WZ sample, NO undergoes oxidation to various NOx species depending on the temperature. The compounds formed at room-temperature oxidation are adsorbed N2O3 and products of its self-ionization, NO+ and NO2-. In this process W(VI) is involved, being reduced to W(IV). At high temperature N2O3 decomposes, restoring the WO species. Under these conditions, NO undergoes oxidation to NO2 by the Pd(II) ions, which are reduced to Pd(I). The nitrosyls of Pd(I) display high thermal stability and do not disappear upon evacuation at 623 K. During NO/O2 coadsorption on the Pd/WZ catalyst at room temperature, the amounts of surface nitrates and NO2/N2O4 formed in the gas phase are significantly lower than those observed under identical conditions in the presence of tungstated zirconia. It is concluded that promotion of tungstated zirconia with palladium(II) suppresses the oxidation of NO by molecular oxygen at room temperature due to the elimination of acidic protons involved in the process. © 2005 Elsevier B.V. All rights reserved.Item Open Access Systematic hydrolysis of PIM-1 and electrospinning of hydrolyzed PIM-1 ultrafine fibers for an efficient removal of dye from water(Elsevier, 2017-12) Satilmis, B.; Budd, P. M.; Uyar, TamerIn this study, the Polymer of Intrinsic Microporosity (PIM-1) was systematically hydrolyzed in the presence of sodium hydroxide by varying the concentration of base, washing procedure and the time of the reaction. The chemical structure analyses confirmed that PIM-1 could be hydrolyzed by 65% up to 99% conversion depending on the synthesis procedure. The hydrolyzed PIM-1 samples have shown improved solubility which facilitates the fabrication of hydrolyzed PIM-1 ultrafine fibers by electrospinning technique. Extensive optimization studies were performed for the electrospinning of uniform and bead-free fibers from hydrolyzed PIM-1 with different degree of hydrolysis (65%, 86%, 94% and 99%). The electrospun hydrolysed PIM-1 fibrous samples have average fiber diameters (AFD) ranging from 0.58 ± 0.15 μm to 1.21 ± 0.15 μm, depending on the polymer concentration and applied electrospinning parameters. After electrospinning, self-standing hydrolyzed PIM-1 fibrous membranes were obtained which is useful as a filtering material for the adsorption of organic dyes from wastewater. Here, the capability of hydrolyzed PIM-1 electrospun fibrous membranes for the removal of dyes from aqueous solutions was investigated by using a batch adsorption process. The maximum adsorption capacity of fully hydrolyzed PIM-1 fibers was found 157 ± 16 mg g− 1 for Methylene Blue and 4 mg g− 1 for Congo red when the adsorption was conducted by 20 mg L− 1 dye solution without using any dilution. Moreover, maximum dye adsorption was also studied by using concentrated Methylene Blue solutions showing up to 272 mg g− 1 adsorption maximum. In addition, the self-standing fibrous hydrolyzed PIM-1 membrane was employed to separate Methylene Blue from an aqueous system by filtration without the necessity of additional driving force. The results indicate that hydrolyzed PIM-1 electrospun nanofibrous membranes can be a promising filtering material for wastewater treatmentItem Open Access Variation of stability constants of thorium and uranium oxalate complexes with ionic strength(De Gruyter Oldenbourg, 1994) Erten, H. N.; Mohammed, A. K.; Choppin, G. R.The extraction of Th(IV) and UO!+ by a solution of TTA and HDEHP, respectively in toluene has been used to obtain stability constants of their oxalate complexes at 298 Κ in 1, 3, 5, 7 and 9 Μ ionic strength (NaC104) solutions. The complexes formed were the MOx, MHOx, MOx2 and M(HOx)2 (M = Th, U02) species. The values were analyzed by the Specific Interaction Theory and agreed to / < 3 Μ but required an additional term for fitting at / > 3 M.Item Open Access Variation of stability constants of thorium citrate complexes with ionic strength(De Gruyter Oldenbourg, 1996) Choppin, G. R.; Erten, H. N.; Xia, Yuan-XiaCitrate is among the organic anions which are expected to be present in the wastes planned for deposition in the WIPP repository. In this study, a solvent extraction method has been used to measure the stability constants of Th(IV) with citrate anions in aqueous solutions with (a) NaClO4 and (b) NaCI as the back-ground electrolytes. The ionic strengths were varied up to 5 m (NaCl) and 14 m (NaClO4). The data from the NaClO4 solutions at varying pH values were used to calculate thermodynamic stability constants through the use of Specific Ion Interaction Theory (SIT).