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Sample records for charged cations ti

  1. Interfacial Cation-Defect Charge Dipoles in Stacked TiO2/Al2O3 Gate Dielectrics.

    Science.gov (United States)

    Zhang, Liangliang; Janotti, Anderson; Meng, Andrew C; Tang, Kechao; Van de Walle, Chris G; McIntyre, Paul C

    2018-02-14

    Layered atomic-layer-deposited and forming-gas-annealed TiO 2 /Al 2 O 3 dielectric stacks, with the Al 2 O 3 layer interposed between the TiO 2 and a p-type germanium substrate, are found to exhibit a significant interface charge dipole that causes a ∼-0.2 V shift of the flat-band voltage and suppresses the leakage current density for gate injection of electrons. These effects can be eliminated by the formation of a trilayer dielectric stack, consistent with the cancellation of one TiO 2 /Al 2 O 3 interface dipole by the addition of another dipole of opposite sign. Density functional theory calculations indicate that the observed interface-dependent properties of TiO 2 /Al 2 O 3 dielectric stacks are consistent in sign and magnitude with the predicted behavior of Al Ti and Ti Al point-defect dipoles produced by local intermixing of the Al 2 O 3 /TiO 2 layers across the interface. Evidence for such intermixing is found in both electrical and physical characterization of the gate stacks.

  2. Coordination Environments of Highly Charged Cations (Ti, Cr, and Light REE's) in Borosilicate Glass/Melts to 1120C

    Energy Technology Data Exchange (ETDEWEB)

    Farges, Francois; /Museum Natl. Hist. Natur. /Stanford U., Geo. Environ. Sci.; Brown, Gordon E., Jr.; /Stanford U., Geo. Environ Sci. /SLAC, SSRL

    2007-01-02

    The local environments around Ti, Cr, and several light rare-earth elements (La, Ce, and Nd) were investigated by in-situ XANES spectroscopy in a number of complex borosilicate glasses and melts (to 1120 C) that are used for nuclear waste storage. Examination of the high-resolution XANES spectra at the Ti K-edge shows that the average coordination of Ti changes from {approx}5 to {approx}4.5. Cr is dominantly trivalent in the melts studied. However, its average coordination is probably lower in the melt (tetrahedral ?) as revealed by the more intense Cr-K pre-edge feature. Ce also changes its average valence from dominantly +4 to +3.5 upon glass melting. These changes are reversible at T{sub g}, the glass transition temperature ({approx}500-550 C for these glasses). In contrast, the local environments of Nd, Pr, and La are unaffected by melting. Therefore, structural reorganization of these borosilicate glass/melts above T{sub g} is variable, not only in terms of valence (as for Ce) but also speciation (Ti and Cr). Both the ability of B to adopt various coordination geometries (triangular and tetrahedral) and the chemical complexity of the glass/melts explain these changes.

  3. New TiO2/DSAT Immobilization System for Photodegradation of Anionic and Cationic Dyes

    Directory of Open Access Journals (Sweden)

    Wan Izhan Nawawi Wan Ismail

    2015-01-01

    Full Text Available A new immobilized TiO2 technique was prepared by coating TiO2 solution onto double-sided adhesive tape (DSAT as a thin layer binder without adding any organic additives. Glass plate was used as support material to immobilized TiO2/DSAT. Two different charges of dyes were applied, namely, anionic reactive red 4 (RR4 and cationic methylene blue (MB dyes. Photocatalytic degradation of RR4 and MB dyes was observed under immobilized TiO2/DSAT with the degradation rate slightly lower and higher, respectively, compared with TiO2 in suspension mode. It was observed that DSAT is able to provide a very strong intact between glass and TiO2 layers thus making the reusability of immobilized TiO2/DSAT be up to 30 cycles. In fact, a better photodegradation activity was observed by number of cycles due to increasing formation of pores on TiO2 surface observed by SEM analysis.

  4. Inversion of membrane surface charge by trivalent cations probed with a cation-selective channel.

    Science.gov (United States)

    Gurnev, Philip A; Bezrukov, Sergey M

    2012-11-13

    We demonstrate that the cation-selective channel formed by gramicidin A can be used as a reliable sensor for studying the multivalent ion accumulation at the surfaces of charged lipid membranes and the "charge inversion" phenomenon. In asymmetrically charged membranes with the individual leaflets formed from pure negative and positive lipids bathed by 0.1 M CsCl solutions the channel exhibits current rectification, which is comparable to that of a typical n/p semiconductor diode. We show that even at these highly asymmetrical conditions the channel conductance can be satisfactorily described by the electrodiffusion equation in the constant field approximation but, due to predictable limitations, only when the applied voltages do not exceed 50 mV. Analysis of the changes in the voltage-dependent channel conductance upon addition of trivalent cations allows us to gauge their interactions with the membrane surface. The inversion of the sign of the effective surface charge takes place at the concentrations, which correlate with the cation size. Specifically, these concentrations are close to 0.05 mM for lanthanum, 0.25 mM for hexaamminecobalt, and 4 mM for spermidine.

  5. Adsorption of cations onto positively charged surface mesopores.

    Science.gov (United States)

    Neue, Uwe; Iraneta, Pamela; Gritti, Fabrice; Guiochon, Georges

    2013-11-29

    Uwe Neue developed a theoretical treatment to account for the adsorption of ions on mesopores of packing materials the walls of which are bonded to ionic ligands but left this work unfinished. We elaborated upon this treatment and refined it, based on the equivalence that he suggested between charged surface particles and a membrane that separates two ionic solutions but is impermeable to one specification. He had written that the electro-chemical potentials in both ionic solutions are equal (Donnan equilibrium). The equilibrium between the surface and the pore concentrations is accounted for by an homogeneous electrostatically modified Langmuir (EML) isotherm model. The theoretical results are presented for four different charge surface concentrations σ0=0, 0.001, 0.002, and 0.003C/m(2), using a phosphate buffer (W(S)pH=2.65) of ionic strength I=10mM. The average pore size, the specific surface area, and the specific pore volume of the stationary phase were Dp=140Å, Sp=182m(2)/g, and Vp=0.70cm(3)/g, respectively. The theoretical results provide the quantitative difference between the ionic strength, the pH, and the concentrations of all the ions in the pores and in the bulk eluent. The theory predicts (1) that the retention times of cations under linear conditions is lower and (2) that their band widths under overloaded conditions for a given retention factor shrinks when the surface charge density σ0 is increased. These theoretical results are in good agreement with experimental results published previously and explain them. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Cation vacancies in ferroelectric PbTiO3 and Pb(Zr,Ti)O3 : A positron annihilation lifetime spectroscopy study

    Science.gov (United States)

    Keeble, D. J.; Singh, S.; Mackie, R. A.; Morozov, M.; McGuire, S.; Damjanovic, D.

    2007-10-01

    Positron annihilation lifetime spectroscopy measurements identify A - and B -site cation vacancies in ferroelectric perovskite oxides (ABO3) . Crystal PbTiO3 and ceramic lead zirconium titanate (PZT) were studied and gave consistent values for the lifetime resulting from positron localization at lead vacancies VPb . Positron trapping to B -site vacancies was inferred in PZT. Temperature dependent studies showed that the defect specific trapping rate was higher for VB compared to VPb , consistent with the larger negative charge. Doping PZT with Fe increased the fraction positron trapping to VB compared to VPb -type defects.

  7. Antimony(3) ethylenediaminetetraacetate complexes with single- and doubly charged cations

    International Nuclear Information System (INIS)

    Davidovich, R.L.; Logvinova, V.B.; Kajdalova, T.A.

    1998-01-01

    The antimony(3) ethylenediaminetetraacetate complexes with alkaline and bivalent metals cations of the M + Sb(Edta) · H 2 O (M + = K, Rb, Cs, NH 4 ), M 2+ [Sb(Edta)] 2 · 8H 2 O (M 2+ = Mg, Ca, Sr, Co, Cd) composition are synthesized. Roentgenographic and IR-spectroscopic characteristics of the synthesized substances are determined. Two groups of the isostructural compounds: M + Sb(Edta) · H 2 O (M + = K, Rb, NH 4 ) and M 2+ [Sb(Edta)] 2 · 8H 2 O (M 2+ = Mg, Ca, Sr, Mn, Co, Cd) are established [ru

  8. Charge transfers in complex transition metal alloys (Ti2Fe)

    International Nuclear Information System (INIS)

    Abramovici, G.

    1998-01-01

    We introduce a new non-orthogonal tight-binding model, for complex alloys, in which electronic structure is characterized by charge transfers. We give the analytic calculation of a charge transfer, in which overlapping two-center terms are rigorously taken into account. Then, we apply numerically this result to an approximant phase of a quasicrystal of Ti 2 Fe alloy. This model is more particularly adapted to transition metals, and gives realistic densities of states. (orig.)

  9. Effect of charge of quaternary ammonium cations on lipophilicity and electroanalytical parameters : Task for ion transfer voltammetry

    NARCIS (Netherlands)

    Poltorak, L.; Sudholter, E.J.R.; de Smet, L.C.P.M.

    2017-01-01

    The electrochemical behavior of three differently charged drug molecules (zwitter-ionic acetylcarnitine, bi-cationic succinylcholine and tri-cationic gallamine) was studied at the interface between two immiscible electrolyte solutions. Tetramethylammonium was used as a model mono cationic

  10. Adsorption of cationic surfactants on silica surface: 1. Adsorption isotherms and surface charge

    NARCIS (Netherlands)

    Goloub, T.P.; Koopal, L.K.; Sidorova, M.P.

    2004-01-01

    Adsorption isotherms of cationic surfactant, dodecylpyridinium chloride, on an Aerosil OX50 and isotherms of surface charge against the background of 0.001- and 0.1-M KCl solutions at pH 7 and 9 were measured and analyzed. Different forms of adsorption isotherms of surfactants at low and high

  11. Stability and aggregation of nanoscale titanium dioxide particle (nTiO2): Effect of cation valence, humic acid, and clay colloids.

    Science.gov (United States)

    Tang, Zhong; Cheng, Tao

    2018-02-01

    Fate and transport of engineered nanoscale titanium dioxide (nTiO 2 ) have received much attention during the past decade. The aggregation and stability of nTiO 2 in water with complicated components, however, have not been fully examined. The objective of this paper is to determine the individual and synergistic effect of cation valence, humic acid, and clay colloids on nTiO 2 stability and aggregation, and elucidate the related mechanisms. We conducted systematic laboratory experiments to determine nTiO 2 stability and aggregation in NaCl and MgCl 2 solutions, both in the absence and presence of humic acid and illite colloids. Results showed that Mg 2+ , in comparison to Na + , could make the zeta potential of nTiO 2 more positive, and shift the point of zero charge of nTiO 2 (pH pzc,TiO2 ) towards higher pH. We also found that nTiO 2 are destabilized by illite colloids at pH < pH pzc,TiO2 through formation of illite-nTiO 2 hetero-aggregates, but are not interfered by illite colloids at higher pH. HA was found to make nTiO 2 stable via electrostatic and steric effects, both in the absence and presence of illite colloids. Calculated interaction energy based on DLVO theory revealed that instability of the nTiO 2 suspensions is mainly caused by primary minima, and that secondary minima normally do not destabilize the suspension, even though they are found to promote aggregation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Effects of cation contaminants in conductive TiO2 ceramics

    Science.gov (United States)

    Yan, M. F.; Rhodes, W. W.

    1982-12-01

    Ten cation contaminants, namely Al, Ga, Co, Fe, Mg, Zn, Zr, Ca, Sr, and Ba were investigated for their effects on the electrical properties, microstructures, and discoloration of conductive TiO2 ceramics. It was found that Al, Ga, Co, Fe, and Mg cause discoloration and increase the electrical resistivity by a factor of 104 to 106 in Nb-doped TiO2 ceramics. The other dopants do not introduce such changes in TiO2. The electrical properties, microstructures, and discoloration were measured in specimens of AlxNb0.007Ti0.993-xO2 with 0≤x≤0.01. When the Al content exceeds a critical value, ranging from 0.48% at 1400 °C to 0.25% at 1200 °C, the electrical resistivities and grain size increase rapidly, and the specimen is discolored from the original black to an ivory white color. Color boundary migration induced by Al diffusion in Nb-doped TiO2 was quantitatively measured. From the kinetics of the boundary migration, the Al diffusivity (D) was calculated to be D=2.67 exp(-53.3 kcal/mole/RT) cm2/s in the temperature range of 1200 to 1400 °C. The rapid diffusion of the small cations, namely Al, Ga, Co, Fe, and Mg, results from an interstitial diffusion mechanism. However, other cations, having a radius larger than the interstitial channel (˜0.77 Å radius), cannot diffuse by this mechanism. Defect reactions are proposed to explain the increase in the electrical resistivity and microstructural changes due to Al diffusion. These defect reactions also show that the problem of acceptor contamination cannot be avoided by adding an excess quantity of donor dopant if the solubility of the donor is much less than that of the acceptor contaminant.

  13. Relating saturation capacity to charge density in strong cation exchangers.

    Science.gov (United States)

    Steinebach, Fabian; Coquebert de Neuville, Bertrand; Morbidelli, Massimo

    2017-07-21

    In this work the relation between physical and chemical resin characteristics and the total amount of adsorbed protein (saturation capacity) for ion-exchange resins is discussed. Eleven different packing materials with a sulfo-functionalization and one multimodal resin were analyzed in terms of their porosity, pore size distribution, ligand density and binding capacity. By specifying the ligand density and binding capacity by the total and accessible surface area, two different groups of resins were identified: Below a ligand density of approx. 2.5μmol/m 2 area the ligand density controls the saturation capacity, while above this limit the accessible surface area becomes the limiting factor. This results in a maximum protein uptake of around 2.5mg/m 2 of accessible surface area. The obtained results allow estimating the saturation capacity from independent resin characteristics like the saturation capacity mainly depends on "library data" such as the accessible and total surface area and the charge density. Hence these results give an insight into the fundamentals of protein adsorption and help to find suitable resins, thus limiting the experimental effort in early process development stages. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Naked (C5Me5)(2)M cations (M = Sc, Ti, and V) and their fluoroarene complexes

    NARCIS (Netherlands)

    Bouwkamp, MW; Budzelaar, PHM; Gercama, J; Morales, ID; de Wolf, J; Meetsma, A; Troyanov, SI; Teuben, JH; Hessen, B; Budzelaar, Peter H.M.; Hierro Morales, Isabel Del; Troyanov, Sergei I.

    2005-01-01

    The ionic metallocene complexes [Cp*M-2][BPh4] (CP* = C5Me5) of the trivalent 3d metals Sc, Ti, and V were synthesized and structurally characterized. For M Sc, the anion interacts weakly with the metal center through one of the phenyl groups, but for M = Ti and V, the cations are naked. They each

  15. Overcoming the inhibitory effect of serum on lipofection by increasing the charge ratio of cationic liposome to DNA.

    Science.gov (United States)

    Yang, J P; Huang, L

    1997-09-01

    Since cationic liposome was first developed as a lipofection reagent, a drawback has been noted in that the efficiency of lipofection decreases dramatically after addition of serum to the lipofection medium. This drawback hampers the application of cationic liposome for systematic delivery of genes. In the present studies, we found that the effect of serum on DC-chol liposome-mediated lipofection is dependent on the charge ratio of liposome to DNA. Serum inhibited lipofection activity of the lipoplex at low charge ratios, whereas it enhanced the lipofection activity at high charge ratios. This phenomenon was observed using DOTAP/DOPE but not lipofectamine. Measurement of cellular association of DNA showed that serum could reduce the binding of lipoplex to cells at all tested charge ratios, i.e. 0-10.6. Removal of negatively charged proteins from serum by DEAE Sephacel column abolished the inhibitory effect of serum on lipofection. The fraction contained only negatively charged serum proteins which strongly inhibited lipofection at low charge ratios but not at higher charge ratios. Furthermore, preincubation of serum with positively charged polylysine, which neutralized negatively charged serum proteins, eliminated the inhibitory effect of serum on lipofection. In summary, inactivation of cationic liposome by serum is due to negatively charged serum proteins and it can be overcome by increasing charge ratio of cationic liposome-DNA lipoplexes or by neutralizing the serum with polylysine.

  16. Tetracyanidoborates with triply charged rare earth metal cations and their optical properties

    Energy Technology Data Exchange (ETDEWEB)

    Hackbarth, Liisa

    2015-11-24

    The aim of this thesis is the description of the synthesis and characterization of a new group of tetracyanidoborates: tetracyanidoborates with trivalent rare earth metal cations. Their optical properties in the ultraviolet and visible range are also discussed. Common synthetic routes for tetracyanidoborates are adapted and applied to the preparation of the rare earth tetracyanidoborate hydrates. They are accessible with high yields and high purity through a reaction between the tetracyanidoboronic acid and rare earth hydroxides. It is shown that the rare earth tetracyanidoborates form isostructural groups, like the [LRE(H{sub 2}O){sub 5}][B(CN){sub 4}]{sub 3}.0.5 H{sub 2}O, where LRE{sup 3+} is La, Ce, Pr, Nd, Sm, Eu and Gd, the [HRE(H{sub 2}O){sub 7}][B(CN){sub 4}]{sub 3} and the [HRE(H{sub 2}O){sub 8}][B(CN){sub 4}]{sub 3}.3 H{sub 2}O, where HRE{sup 3+} is Tb, Dy, Ho, Er, Tm, Yb, Lu and Y. Furthermore, the coordination number 9 is noticed to be common among the light rare earth cations, whereas the minor coordination number 8 is prevalent for the heavy rare earth cations in their tetracyanidoborates. This different construction of the coordination spheres between light and heavy rare earth cations leads to different structures depending on the energetic efficiency of the structural arrangement. Generally, the rare earth tetracyanidoborate hydrates are found to crystallize in the monoclinic crystal system. Moreover, other different crystal structures are observed depending on the crystallization temperature and the type of coordinated ligands and co-crystallized solvent molecules. The tetracyanidoborate hydrates with triply charged rare earth cations are characterized comprehensively by X-ray diffraction, vibrational spectroscopy, NMR-spectroscopy as well as by thermal analysis. Furthermore, the optical properties of some dehydrated rare earth tetracyanidoborates are investigated by UV-spectroscopy and luminescence measurements. The results of the optical

  17. Tetracyanidoborates with triply charged rare earth metal cations and their optical properties

    International Nuclear Information System (INIS)

    Hackbarth, Liisa

    2015-01-01

    The aim of this thesis is the description of the synthesis and characterization of a new group of tetracyanidoborates: tetracyanidoborates with trivalent rare earth metal cations. Their optical properties in the ultraviolet and visible range are also discussed. Common synthetic routes for tetracyanidoborates are adapted and applied to the preparation of the rare earth tetracyanidoborate hydrates. They are accessible with high yields and high purity through a reaction between the tetracyanidoboronic acid and rare earth hydroxides. It is shown that the rare earth tetracyanidoborates form isostructural groups, like the [LRE(H_2O)_5][B(CN)_4]_3.0.5 H_2O, where LRE"3"+ is La, Ce, Pr, Nd, Sm, Eu and Gd, the [HRE(H_2O)_7][B(CN)_4]_3 and the [HRE(H_2O)_8][B(CN)_4]_3.3 H_2O, where HRE"3"+ is Tb, Dy, Ho, Er, Tm, Yb, Lu and Y. Furthermore, the coordination number 9 is noticed to be common among the light rare earth cations, whereas the minor coordination number 8 is prevalent for the heavy rare earth cations in their tetracyanidoborates. This different construction of the coordination spheres between light and heavy rare earth cations leads to different structures depending on the energetic efficiency of the structural arrangement. Generally, the rare earth tetracyanidoborate hydrates are found to crystallize in the monoclinic crystal system. Moreover, other different crystal structures are observed depending on the crystallization temperature and the type of coordinated ligands and co-crystallized solvent molecules. The tetracyanidoborate hydrates with triply charged rare earth cations are characterized comprehensively by X-ray diffraction, vibrational spectroscopy, NMR-spectroscopy as well as by thermal analysis. Furthermore, the optical properties of some dehydrated rare earth tetracyanidoborates are investigated by UV-spectroscopy and luminescence measurements. The results of the optical measurements indicate that the tetracyanidoborates with rare earth metal cations

  18. Ionic charge transport between blockages: Sodium cation conduction in freshly excised bulk brain tissue

    Energy Technology Data Exchange (ETDEWEB)

    Emin, David, E-mail: emin@unm.edu [Department of Physics and Astronomy, University of New Mexico, Albuquerque, NM 87131 (United States); Akhtari, Massoud [Semple Institutes for Neuroscience and Human Behavior, David Geffen School of Medicine, University of California at Los Angeles, Los Angeles, CA 90095 (United States); Ellingson, B. M. [Department of Radiology, David Geffen School of Medicine, University of California at Los Angeles, Los Angeles, CA 90095 (United States); Mathern, G. W. [Department of Neurosurgery, David Geffen School of Medicine, University of California at Los Angeles, Los Angeles, CA 90095 (United States)

    2015-08-15

    We analyze the transient-dc and frequency-dependent electrical conductivities between blocking electrodes. We extend this analysis to measurements of ions’ transport in freshly excised bulk samples of human brain tissue whose complex cellular structure produces blockages. The associated ionic charge-carrier density and diffusivity are consistent with local values for sodium cations determined non-invasively in brain tissue by MRI (NMR) and diffusion-MRI (spin-echo NMR). The characteristic separation between blockages, about 450 microns, is very much shorter than that found for sodium-doped gel proxies for brain tissue, >1 cm.

  19. Varying the charge of small cations in liquid water: Structural, transport, and thermodynamical properties

    Science.gov (United States)

    Martelli, Fausto; Vuilleumier, Rodolphe; Simonin, Jean-Pierre; Spezia, Riccardo

    2012-10-01

    In this work, we show how increasing the charge of small cations affects the structural, thermodynamical, and dynamical properties of these ions in liquid water. We have studied the case of lanthanoid and actinoid ions, for which we have recently developed accurate polarizable force fields, and the ionic radius is in the 0.995-1.250 Å range, and explored the valency range from 0 to 4+. We found that the ion charge strongly structures the neighboring water molecules and that, in this range of charges, the hydration enthalpies exhibit a quadratic dependence with respect to the charge, in line with the Born model. The diffusion process follows two main regimes: a hydrodynamical regime for neutral or low charges, and a dielectric friction regime for high charges in which the contraction of the ionic radius along the series of elements causes a decrease of the diffusion coefficient. This latter behavior can be qualitatively described by theoretical models, such as the Zwanzig and the solvated ion models. However, these models need be modified in order to obtain agreement with the observed behavior in the full charge range. We have thus modified the solvated ion model by introducing a dependence of the bare ion radius as a function of the ionic charge. Besides agreement between theory and simulation this modification allows one to obtain an empirical unified model. Thus, by analyzing the contributions to the drag coefficient from the viscous and the dielectric terms, we are able to explain the transition from a regime in which the effect of viscosity dominates to one in which dielectric friction governs the motion of ions with radii of ca. 1 Å.

  20. Novel doubly charged cation based electrolytes for non-aqueous supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Jaenes, Alar; Kurig, Heisi; Romann, Tavo; Lust, Enn [Institute of Chemistry, University of Tartu, 14a Ravila Street, 50411 Tartu (Estonia)

    2010-04-15

    The electrochemical characteristics for the electrical double layer capacitors based on the titanium carbide derived carbon (CDC-TiC) electrodes in 0.4 M N,N-dimethyl-1,4-diazabicyclo[2,2,2]octanediium tetrafluoroborate (DMDABCO(BF{sub 4}){sub 2}), 0.2 M DMDABCO(BF{sub 4}){sub 2} + 0.2 M triethylmethylammonium tetrafluoroborate (TEMABF{sub 4}), and 0.4 M TEMABF{sub 4} in {gamma}-butyrolactone ({gamma}-BL) have been studied using cyclic voltammetry, constant current charging/discharging and electrochemical impedance spectroscopy. The ideal electrical double layer capacitor behaviour was observed in a wide region of cell voltages (U {<=} 3.0 V) for the CDC-TiC electrodes in 0.4 M DMDABCO(BF{sub 4}){sub 2} in {gamma}-BL. The geometry of solvation shells around DMDABCO{sup 2+}, TEMA{sup +}, and BF{sub 4}{sup -} have been optimized with molecular dynamics calculations and the coordination numbers equal to 15, 7 or 8, respectively, have been proposed and compared with electrochemical and gas sorption data for CDC-TiC. The gravimetric capacitance (129 F g{sup -1}), high gravimetric energy (40.6 Wh kg{sup -1}) and power (93 kW kg{sup -1}) were established for the CDC-TiC electrodes in 0.4 M DMDABCO(BF{sub 4}){sub 2} {gamma}-BL solution. (author)

  1. Influence of polymer charge on the shear yield stress of silica aggregated with adsorbed cationic polymers.

    Science.gov (United States)

    Zhou, Ying; Yu, Hai; Wanless, Erica J; Jameson, Graeme J; Franks, George V

    2009-08-15

    Flocs were produced by adding three cationic polymers (10% charge density, 3.0x10(5) g/mol molecular weight; 40% charge density, 1.1x10(5) g/mol molecular weight; and 100% charge density, 1.2x10(5) g/mol molecular weight) to 90 nm diameter silica particles. The shear yield stresses of the consolidated sediment beds from settled and centrifuged flocs were determined via the vane technique. The polymer charge density plays an important role in influencing the shear yield stresses of sediment beds. The shear yield stresses of sediment beds from flocs induced by the 10% charged polymer were observed to increase with an increase in polymer dose, initial solid concentration and background electrolyte concentration at all volume fractions. In comparison, polymer dose has a marginal effect on the shear yield stresses of sediment beds from flocs induced by the 40% and 100% charged polymers. The shear yield stresses of sediments from flocs induced by the 40% charged polymer are independent of salt concentration whereas the addition of salt decreases the shear yield stresses of sediments from flocs induced by the 100% charged polymer. When flocculated at the optimum dose for each polymer (12 mg/g silica for the 10% charged polymer at 0.03 M NaCl, 12 mg/g for 40% and 2 mg/g for 100%), shear yield stress increases as polymer charge increases. The effects observed are related to the flocculation mechanism (bridging, patch attraction or charge neutralisation) and the magnitude of the adhesive force. Comparison of shear and compressive yield stresses show that the network is only slightly weaker in shear than in compression. This is different than many other systems (mainly salt and pH coagulation) which have shear yield stress much less than compressive yield stress. The existing models relating the power law exponent of the volume fraction dependence of the shear yield stress to the network fractal structure are not satisfactory to predict all the experimental behaviour.

  2. Influence of cation disorder on the magnetic properties of ball-milled ilmenite (FeTiO3)

    DEFF Research Database (Denmark)

    Mørup, Steen; Rasmussen, Helge Kildahl; Brok, Erik

    2012-01-01

    We have investigated the evolution of crystal structure, cation disorder and magnetic properties of ilmenite (FeTiO3) after increasing time of high-energy ball-milling in an inert atmosphere. Refinement of X-ray diffraction data show that the hexagonal crystal structure of ilmenite is maintained...

  3. Iodide Ion Pairing with Highly Charged Ruthenium Polypyridyl Cations in CH3CN.

    Science.gov (United States)

    Swords, Wesley B; Li, Guocan; Meyer, Gerald J

    2015-05-04

    A series of three highly charged cationic ruthenium(II) polypyridyl complexes of the general formula [Ru(deeb)3-x(tmam)x](PF6)2x+2, where deeb is 4,4'-diethyl ester-2,2'-bipyridine and tmam is 4,4'-bis[(trimethylamino)methyl]-2,2'-bipyridine, were synthesized and characterized and are referred to as 1, 2, or 3 based on the number of tmam ligands. Crystals suitable for X-ray crystallography were obtained for the homoleptic complex 3, which was found to possess D3 symmetry over the entire ruthenium complex. The complexes displayed visible absorption spectra typical of metal-to-ligand charge-transfer (MLCT) transitions. In acetonitrile, quasi-reversible waves were assigned to Ru(III/II) electron transfer, with formal reduction potentials that shifted negative as the number of tmam ligands was increased. Room temperature photoluminescence was observed in acetonitrile with quantum yields of ϕ ∼ 0.1 and lifetimes of τ ∼ 2 μs. The spectroscopic and electrochemical data were most consistent with excited-state localization on the deeb ligand for 1 and 2 and on the tmam ligand for 3. The addition of tetrabutylammonium iodide to the complexes dissolved in a CH3CN solution led to changes in the UV-vis absorption spectra consistent with ion pairing. A Benesi-Hildebrand-type analysis of these data revealed equilibrium constants that increased with the cationic charge 1 10(8) s(-1). The possible relevance of this work to solar energy conversion and dye-sensitized solar cells is discussed.

  4. Suppression of the two-dimensional electron gas in LaGaO3/SrTiO3 by cation intermixing

    KAUST Repository

    Nazir, S.; Amin, B.; Schwingenschlö gl, Udo

    2013-01-01

    Cation intermixing at the n-type polar LaGaO 3 /SrTiO 3 (001) interface is investigated by first principles calculations. Ti"Ga, Sr"La, and SrTi"LaGa intermixing are studied in comparison to each other, with a focus on the interface stability. We

  5. Effect of Cation Rotation on Charge Dynamics in Hybrid Lead Halide Perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Gélvez-Rueda, María C.; Cao, Duyen H.; Patwardhan, Sameer; Renaud, Nicolas; Stoumpos, Constantinos C.; Schatz, George C.; Hupp, Joseph T.; Farha, Omar K.; Savenije, Tom J.; Kanatzidis, Mercouri G.; Grozema, Ferdinand C.

    2016-08-04

    Organic-inorganic hybrid halide perovskites are a promising class of materials for photovoltaic application with reported power efficiencies over similar to 22%. However, not much is known about the influence of the organic dipole rotation and phase transitions on charge carrier dynamics. Here, we report substantial changes in mobility and lifetime of charge carriers in CH3NH3PbI3 after the low-temperature tetragonal (beta) to orthorhombic (gamma) phase transition. By using microwave conductivity measurements, we observed that the mobility and lifetime of ionized charge carriers increase as the temperature decreases and a sudden increment is seen after the beta-gamma phase transition. For CH3NH3PbI3, the mobility and the half-lifetime increase by a factor of 36 compared with the values before the beta-gamma phase transition. We attribute the considerable change in the dynamics at low temperature to the decrease of the inherent dynamic disorder of the organic cation (CH3NH3+) inside the perovskite crystal structure.

  6. IR spectroscopy of cationized aliphatic amino acids: Stability of charge-solvated structure increases with metal cation size

    NARCIS (Netherlands)

    Drayss, M. K.; Armentrout, P. B.; Oomens, J.; Schaefer, M.

    2010-01-01

    Gas-phase structures of alkali metal cationized (Li+, Na+,K+, Rb+, and Cs+) proline (Pro) and N-methyl alanine have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy utilizing light generated by a free electron laser and computational modeling. Measured IRMPD spectra

  7. IR spectroscopy of cationized aliphatic amino acids: Stability of charge-solvated structure increases with metal cation size

    NARCIS (Netherlands)

    Drayß, M.K.; Armentrout, P.B.; Oomens, J.; Schäfer, M.

    2010-01-01

    Gas-phase structures of alkali metal cationized (Li+, Na+, K+, Rb+, and Cs+) proline (Pro) and N-methyl alanine have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy utilizing light generated by a free electron laser and computational modeling. Measured IRMPD

  8. Surface charge density determines the efficiency of cationic gemini surfactant based lipofection.

    Science.gov (United States)

    Ryhänen, Samppa J; Säily, Matti J; Paukku, Tommi; Borocci, Stefano; Mancini, Giovanna; Holopainen, Juha M; Kinnunen, Paavo K J

    2003-01-01

    The efficiencies of the binary liposomes composed of 1,2-dimyristoyl-sn-glycero-3-phosphocholine and cationic gemini surfactant, (2S,3R)-2,3-dimethoxy-1,4-bis(N-hexadecyl-N,N-dimethylammonium)butane dibromide as transfection vectors, were measured using the enhanced green fluorescent protein coding plasmid and COS-1 cells. Strong correlation between the transfection efficiency and lipid stoichiometry was observed. Accordingly, liposomes with X(SR-1) > or = 0.50 conveyed the enhanced green fluorescent protein coding plasmid effectively into cells. The condensation of DNA by liposomes with X(SR-1) > 0.50 was indicated by static light scattering and ethidium bromide intercalation assay, whereas differential scanning calorimetry and fluorescence anisotropy of diphenylhexatriene revealed stoichiometry dependent reorganization in the headgroup region of the liposome bilayer, in alignment with our previous Langmuir-balance study. Surface charge density and the organization of positive charges appear to determine the mode of interaction of DNA with (2S,3R)-2,3-dimethoxy-1,4-bis(N-hexadecyl-N,N-dimethylammonium)butane dibromide/1,2-dimyristoyl-sn-glycero-3-phosphocholine liposomes, only resulting in DNA condensation when X(SR-1) > 0.50. Condensation of DNA in turn seems to be required for efficient transfection.

  9. Nanocapsule of cationic liposomes obtained using "in situ" acrylic acid polymerization: stability, surface charge and biocompatibility.

    Science.gov (United States)

    Scarioti, Giovana Danieli; Lubambo, Adriana; Feitosa, Judith P A; Sierakowski, Maria Rita; Bresolin, Tania M B; de Freitas, Rilton Alves

    2011-10-15

    In this work, didecyldimethylammonium bromide (DDAB) and 1,2-dioleoyl-sn-glycero-3-phosphatidylethanolamine (DOPE) (2.5:1) were used to prepare liposomes coated with polyacrylic acid (PAA) using "in situ" polymerization with 2.5, 5 and 25 mM of acrylic acid (AA). The PAA concentrations were chosen to achieve partially to fully covered capsules, and the polymerization reaction was observed with real-time monitoring using dynamic light scattering (NanoDLS). The DDAB:DOPE liposomes showed stability in the tested temperature range (25-70°C), whereas the results confirmed the success of the polymerization according to superficial charge (zeta potential of +66.7±1.2 mV) results and AFM images. For the liposomes that were fully coated with PAA (zeta potential of +0.3±3.9 mV), cytotoxicity was independent of the concentration of albumin. Cationic liposomes and nanocapsules of the stable liposomes coated with PAA were obtained by controlling the surface charge, which was the most important factor related to cytotoxicity. Thus, a potential, safe drug nanocarrier was successfully developed in this work. Copyright © 2011 Elsevier B.V. All rights reserved.

  10. Suppression of the two-dimensional electron gas in LaGaO3/SrTiO3 by cation intermixing

    KAUST Repository

    Nazir, S.

    2013-12-03

    Cation intermixing at the n-type polar LaGaO 3 /SrTiO 3 (001) interface is investigated by first principles calculations. Ti"Ga, Sr"La, and SrTi"LaGa intermixing are studied in comparison to each other, with a focus on the interface stability. We demonstrate in which cases intermixing is energetically favorable as compared to a clean interface. A depopulation of the Ti 3d xy orbitals under cation intermixing is found, reflecting a complete suppression of the two-dimensional electron gas present at the clean interface.

  11. Characterization of ParTI Phoswiches Using Charged Pion Beams

    Science.gov (United States)

    Churchman, Emily; Zarrella, Andrew; Youngs, Michael; Yennello, Sherry

    2017-09-01

    The Partial Truncated Icosahedron (ParTI) detector array consists of 15 phoswiches. Each phoswich is made of two scintillating components - a thallium-doped cesium iodide (CsI(Tl)) crystal and an EJ-212 scintillating plastic - coupled to a photomultiplier tube. Both materials have different scintillation times and are sensitive to both charged and neutral particles. The type of particle and amount of energy deposited determine the shape of the scintillation pulse as a function of time. By integrating the fast and slow signals of the scintillation pulses, a ``Fast vs. Slow Integration'' plot can be created that produces particle identification lines based on the energy deposited in the scintillating materials. Four of these phoswiches were taken to the Paul Scherrer Institute (PSI) in Switzerland where π + , π-, and proton beams were scattered onto the phoswiches to demonstrate their particle identification (PID) capabilities. Using digitizers to record the detector response waveforms, pions can also be identified by the characteristic decay pulse of the muon daughters.

  12. Theoretical study of oxygen adsorption on pure Au-n+1(+) and doped MAun+ cationic gold clusters for M = Ti, Fe and n=3-7

    DEFF Research Database (Denmark)

    Torres, M. Begona; Fernandez Sanchez, Eva; Balbas, Luis C.

    2008-01-01

    A comparative study of the adsorption of an O-2 molecule on pure Au-n+1(+) and doped MAun+ cationic gold clusters for n = 3-7 and M = Ti, Fe is presented. The simultaneous adsorption of two oxygen atoms also was studied. This work was performed by means of first principles calculations based...... with adsorption energies of 0.56 and 0.69 eV, respectively. The ground-state geometry of Au-n(+) is almost unperturbed after O-2 adsorption. The electronic charge flows towards O-2 when the molecule is adsorbed in bridge positions and towards the gold cluster when O-2 is adsorbed on top of An atoms, and both...... with size n are rationalized in terms of O-O and O-M bond distances, as well as charge transfer between oxygen and cluster substrates. The spin multiplicity of those (MAunO2+)(ad) complexes with the highest O-2 adsorption energy is a maximum (minimum) for M = Fe (Ti), corresponding to parallel (anti...

  13. Spectroscopic study of the charge-transfer complexes TiCl4/styrene and TiCl4/polystyrene

    Science.gov (United States)

    Gonçalves, Norberto S.; Noda, Lúcia. K.

    2017-10-01

    In this work, solutions of TiCl4/styrene and TiCl4/polystyrene charge-transfer complexes in CHCl3 or CDCl3 were investigated by UV-vis, resonance Raman and 1H NMR spectroscopies in order to study their molecular and electronic structures. Both show a yellow colour due to absorption in the 400 nm region, related to a charge-transfer transition. In Raman spectra, as the excitation approaches the resonance region, the primary enhancement of aromatic ring modes was mainly observed, rather than intensification of the vinylic double-bond stretch. Under the experimental conditions it was observed that formation of polystyrene takes place, as showed by 1H NMR spectra, and the most significant interaction occurs at the aromatic ring, as supported by the results from interaction of TiCl4 with polystyrene, as indicated by the charge-transfer band and resonant intensification of the aromatic ring modes.

  14. Rotationally resolved state-to-state photoionization and photoelectron study of titanium carbide and its cation (TiC/TiC⁺).

    Science.gov (United States)

    Luo, Zhihong; Huang, Huang; Chang, Yih-Chung; Zhang, Zheng; Yin, Qing-Zhu; Ng, C Y

    2014-10-14

    Titanium carbide and its cation (TiC/TiC(+)) have been investigated by the two-color visible (VIS)-ultraviolet (UV) resonance-enhanced photoionization and pulsed field ionization-photoelectron (PFI-PE) methods. Two visible excitation bands for neutral TiC are observed at 16,446 and 16,930 cm(-1). Based on rotational analyses, these bands are assigned as the respective TiC((3)Π1) ← TiC(X(3)Σ(+)) and TiC((3)Σ(+)) ← TiC(X(3)Σ(+)) transition bands. This assignment supports that the electronic configuration and term symmetry for the neutral TiC ground state are …7σ(2)8σ(1)9σ(1)3π(4) (X(3)Σ(+)). The rotational constant and the corresponding bond distance of TiC(X(3)Σ(+); v″ = 0) are determined to be B0″ = 0.6112(10) cm(-1) and r0″ = 1.695(2) Å, respectively. The rotational analyses of the VIS-UV-PFI-PE spectra for the TiC(+)(X; v(+) = 0 and 1) vibrational bands show that the electronic configuration and term symmetry for the ionic TiC(+) ground state are …7σ(2)8σ(1)3π(4) (X(2)Σ(+)) with the v(+) = 0 → 1 vibrational spacing of 870.0(8) cm(-1) and the rotational constants of B(e)(+) = 0.6322(28) cm(-1), and α(e)(+) = 0.0085(28) cm(-1). The latter rotational constants yield the equilibrium bond distance of r(e)(+) = 1.667(4) Å for TiC(+)(X(2)Σ(+)). The cleanly rotationally resolved VIS-UV-PFI-PE spectra have also provided a highly precise value of 53 200.2(8) cm(-1) [6.5960(1) eV] for the adiabatic ionization energy (IE) of TiC. This IE(TiC) value along with the known IE(Ti) has made possible the determination of the difference between the 0 K bond dissociation energy (D0) of TiC(+)(X(2)Σ(+)) and that of TiC(X(3)Σ(+)) to be D0(Ti(+)-C) - D0(Ti-C) = 0.2322(2) eV. Similar to previous experimental observations, the present state-to-state PFI-PE study of the photoionization transitions, TiC(+)(X(2)Σ(+); v(+) = 0 and 1, N(+)) ← TiC((3)Π1; v', J'), reveals a strong decreasing trend for the photoionization cross section as |ΔN(+)| = |N

  15. Rotationally resolved state-to-state photoionization and photoelectron study of titanium carbide and its cation (TiC/TiC+)

    International Nuclear Information System (INIS)

    Luo, Zhihong; Huang, Huang; Chang, Yih-Chung; Zhang, Zheng; Ng, C. Y.; Yin, Qing-Zhu

    2014-01-01

    Titanium carbide and its cation (TiC/TiC + ) have been investigated by the two-color visible (VIS)-ultraviolet (UV) resonance-enhanced photoionization and pulsed field ionization-photoelectron (PFI-PE) methods. Two visible excitation bands for neutral TiC are observed at 16 446 and 16 930 cm −1 . Based on rotational analyses, these bands are assigned as the respective TiC( 3 Π 1 ) ← TiC(X 3 Σ + ) and TiC( 3 Σ + ) ← TiC(X 3 Σ + ) transition bands. This assignment supports that the electronic configuration and term symmetry for the neutral TiC ground state are …7σ 2 8σ 1 9σ 1 3π 4 (X 3 Σ + ). The rotational constant and the corresponding bond distance of TiC(X 3 Σ + ; v″ = 0) are determined to be B 0 ″ = 0.6112(10) cm −1 and r 0 ″ = 1.695(2) Å, respectively. The rotational analyses of the VIS-UV-PFI-PE spectra for the TiC + (X; v + = 0 and 1) vibrational bands show that the electronic configuration and term symmetry for the ionic TiC + ground state are …7σ 2 8σ 1 3π 4 (X 2 Σ + ) with the v + = 0 → 1 vibrational spacing of 870.0(8) cm −1 and the rotational constants of B e + = 0.6322(28) cm −1 , and α e + = 0.0085(28) cm −1 . The latter rotational constants yield the equilibrium bond distance of r e + = 1.667(4) Å for TiC + (X 2 Σ + ). The cleanly rotationally resolved VIS-UV-PFI-PE spectra have also provided a highly precise value of 53 200.2(8) cm −1 [6.5960(1) eV] for the adiabatic ionization energy (IE) of TiC. This IE(TiC) value along with the known IE(Ti) has made possible the determination of the difference between the 0 K bond dissociation energy (D 0 ) of TiC + (X 2 Σ + ) and that of TiC(X 3 Σ + ) to be D 0 (Ti + −C) − D 0 (Ti−C) = 0.2322(2) eV. Similar to previous experimental observations, the present state-to-state PFI-PE study of the photoionization transitions, TiC + (X 2 Σ + ; v + = 0 and 1, N + ) ← TiC( 3 Π 1 ; v′, J′), reveals a strong decreasing trend for the photoionization cross

  16. Adsorption of tetrabutylammonium cations on negatively charged surfaces of the Hg, Ga, In-Ga, Tl-Ga electrodes

    International Nuclear Information System (INIS)

    Damaskin, B.B.; Baturina, O.A.; Vykhodtseva, L.N.; Emets, V.V.; Kazarinov, V.E.

    1999-01-01

    The differential capacitance curves in the 0.05M Na 2 SO 4 + [(C 4 H 9 ) 4 N]BF 4 aqueous solutions on the electrodes of mercury gallium and also of the In-Ga and Tl-Ga alloys are obtained. The adsorption parameters of the tetrabutylammonium cations on each of the electrodes within the frames of two parallel condensers model, supplemented by the Frumkin isotherm are calculated. The conclusion is made that different adsorption behaviour of the (C 4 H 9 ) 4 N + cations on the gallium subgroup metals by the electrodes high negative charges is related to nonuniform electrochemical work of the output electrons [ru

  17. What Is the Structure of the Naphthalene-Benzene Heterodimer Radical Cation? Binding Energy, Charge Delocalization, and Unexpected Charge-Transfer Interaction in Stacked Dimer and Trimer Radical Cations.

    Science.gov (United States)

    Attah, Isaac K; Platt, Sean P; Meot-Ner Mautner, Michael; El-Shall, M Samy; Peverati, Roberto; Head-Gordon, Martin

    2015-04-02

    The binding energy of the naphthalene(+•)(benzene) heterodimer cation has been determined to be 7.9 ± 1 kcal/mol for C10H8(+•)(C6H6) and 8.1 ± 1 kcal/mol for C10H8(+•)(C6D6) by equilibrium thermochemical measurements using the mass-selected drift cell technique. A second benzene molecule binds to the C10H8(+•)(C6D6) dimer with essentially the same energy (8.4 ± 1 kcal/mol), suggesting that the two benzene molecules are stacked on opposite sides of the naphthalene cation in the (C6D6)C10H8(+•)(C6D6) heterotrimer. The lowest-energy isomers of the C10H8(+•)(C6D6) and (C6D6)C10H8(+•)(C6D6) dimer and trimer calculated using the M11/cc-pVTZ method have parallel stacked structures with enthalpies of binding (-ΔH°) of 8.4 and 9.0 kcal/mol, respectively, in excellent agreement with the experimental values. The stacked face-to-face class of isomers is calculated to have substantial charge-transfer stabilization of about 45% of the total interaction energy despite the large difference between the ionization energies of benzene and naphthalene. Similarly, significant delocalization of the positive charge is found among all three fragments of the (C6D6)C10H8(+•)(C6D6) heterotrimer, thus leaving only 46% of the total charge on the central naphthalene moiety. This unexpectedly high charge-transfer component results in activating two benzene molecules in the naphthalene(+•)(benzene)2 heterotrimer cation to associate with a third benzene molecule at 219 K to form a benzene trimer cation and a neutral naphthalene molecule. The global minimum of the C10H8(+•)(C6H6)2 heterotrimer is found to be the one where the naphthalene cation is sandwiched between two benzene molecules. It is remarkable, and rather unusual, that the binding energy of the second benzene molecule is essentially the same as that of the first. This is attributed to the enhanced charge-transfer interaction in the stacked trimer radical cation.

  18. Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

    Energy Technology Data Exchange (ETDEWEB)

    Gibson, John K.; Marcalo, Joaquim; Santos, Marta; Pires de Matos, Antonio; Haire, Richard G.

    2008-12-08

    The gas-phase reactivity of doubly-charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly-charged organometallic ions?adducts or species formed via metal-ion-induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons?and singly-charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly-charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers.

  19. Effect of alterations in glomerular charge on deposition of cationic and anionic antibodies to fixed glomerular antigens in the rat.

    Science.gov (United States)

    Adler, S; Baker, P; Pritzl, P; Couser, W G

    1985-07-01

    Reduction of the negative charge of the glomerular capillary wall alters its charge- and size-selective properties. To investigate the effect of alteration in glomerular charge properties on antibody localization, we prepared cationic and anionic fractions of antibodies to subepithelial and glomerular basement membrane (GBM) antigens, and compared their deposition in normal rats and rats treated with protamine sulfate or aminonucleoside of puromycin to reduce capillary wall charge. IgG antibodies were eluted from kidneys of rats with active Heymann's nephritis (AICN), passive Heymann's nephritis (PHN), or anti-GBM nephritis (NTN), separated into cationic and anionic fractions, and radiolabeled with iodine 125 or iodine 131. Relative antibody content of each fraction was determined by incubation with an excess of glomerular antigen. Varying amounts of cationic and anionic IgG eluted from kidneys of rats with AICN or PHN were injected into 24 normal or protamine sulfate-treated rats. Glomerular binding of all antibodies was highly correlated with IgG delivery to the kidney. The ratio of cationic to anionic antibody deposited in the glomeruli of normal rats after 4 hours was 1.08 +/- 0.07 for AICN eluate and 0.37 +/- 0.04 for PHN eluate. The ratios were not significantly different in animals pretreated with protamine sulfate (1.15 +/- 0.06 and 0.44 +/- 0.06, respectively; P greater than 0.05). Varying amounts of cationic and anionic IgG eluted from kidneys of rats with NTN were injected into 10 normal rats and four rats treated with aminonucleoside of puromycin. Glomerular binding of antibody was again highly correlated with IgG delivery to the kidney. The ratio of cationic to anionic antibody deposited in the glomeruli of normal rats after 1 hour was 1.03 +/- 0.06, and was not significantly altered in rats treated with aminonucleoside of puromycin (1.05 +/- 0.03, P greater than 0.5). Proteinuria in PHN rats was also unaffected by treatment with protamine sulfate for

  20. Silica-grafted ionic liquids for revealing the respective charging behaviors of cations and anions in supercapacitors.

    Science.gov (United States)

    Dou, Qingyun; Liu, Lingyang; Yang, Bingjun; Lang, Junwei; Yan, Xingbin

    2017-12-19

    Supercapacitors based on activated carbon electrodes and ionic liquids as electrolytes are capable of storing charge through the electrosorption of ions on porous carbons and represent important energy storage devices with high power delivery/uptake. Various computational and instrumental methods have been developed to understand the ion storage behavior, however, techniques that can probe various cations and anions of ionic liquids separately remain lacking. Here, we report an approach to monitoring cations and anions independently by using silica nanoparticle-grafted ionic liquids, in which ions attaching to silica nanoparticle cannot access activated carbon pores upon charging, whereas free counter-ions can. Aided by this strategy, conventional electrochemical characterizations allow the direct measurement of the respective capacitance contributions and acting potential windows of different ions. Moreover, coupled with electrochemical quartz crystal microbalance, this method can provide unprecedented insight into the underlying electrochemistry.

  1. Actinide cation-cation complexes

    International Nuclear Information System (INIS)

    Stoyer, N.J.; Seaborg, G.T.

    1994-12-01

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO 2 + ) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO 2 + ; therefore, cation-cation complexes indicate something unique about AnO 2 + cations compared to actinide cations in general. The first cation-cation complex, NpO 2 + ·UO 2 2+ , was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO 2 + species, the cation-cation complexes of NpO 2 + have been studied most extensively while the other actinides have not. The only PuO 2 + cation-cation complexes that have been studied are with Fe 3+ and Cr 3+ and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO 2 + ·UO 2 2+ , NpO 2 + ·Th 4+ , PuO 2 + ·UO 2 2+ , and PuO 2 + ·Th 4+ at an ionic strength of 6 M using LIPAS are 2.4 ± 0.2, 1.8 ± 0.9, 2.2 ± 1.5, and ∼0.8 M -1

  2. Cation-mediated conversion of the state of charge in uranium arene inverted-sandwich complexes

    Energy Technology Data Exchange (ETDEWEB)

    Camp, Clement; Mougel, Victor; Pecaut, Jacques; Mazzanti, Marinella [Laboratoire de Reconnaissance Ionique et Chimie de Coordination, SCIB, UMR-E3 CEA-UJF, INAC, CEA-Grenoble (France); Maron, Laurent [LCPNO, CNRS and INSA, UPS, Universite de Toulouse (France)

    2013-12-16

    Two new arene inverted-sandwich complexes of uranium supported by siloxide ancillary ligands [K{U(OSi(OtBu)_3)_3}{sub 2}(μ-η{sup 6}:η{sup 6}-C{sub 7}H{sub 8})] (3) and [K{sub 2}{U(OSi(OtBu)_3)_3}{sub 2}(μ-η{sup 6}:η{sup 6}-C{sub 7}H{sub 8})] (4) were synthesized by the reduction of the parent arene-bridged complex [{U(OSi(OtBu)_3)_3}{sub 2}(μ-η{sup 6}:η{sup 6}-C{sub 7}H{sub 8})] (2) with stoichiometric amounts of KC{sub 8} yielding a rare family of inverted-sandwich complexes in three states of charge. The structural data and computational studies of the electronic structure are in agreement with the presence of high-valent uranium centers bridged by a reduced tetra-anionic toluene with the best formulation being U{sup V}-(arene{sup 4-})-U{sup V}, KU{sup IV}-(arene{sup 4-})-U{sup V}, and K{sub 2}U{sup IV}-(arene{sup 4-})-U{sup IV} for complexes 2, 3, and 4 respectively. The potassium cations in complexes 3 and 4 are coordinated to the siloxide ligands both in the solid state and in solution. The addition of KOTf (OTf=triflate) to the neutral compound 2 promotes its disproportionation to yield complexes 3 and 4 (depending on the stoichiometry) and the U{sup IV} mononuclear complex [U(OSi(OtBu){sub 3}){sub 3}(OTf)(thf){sub 2}] (5). This unprecedented reactivity demonstrates the key role of potassium for the stability of these complexes. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Thickness dependent charge transport in ferroelectric BaTiO3 heterojunctions

    Science.gov (United States)

    Singh, Pooja; Rout, P. K.; Singh, Manju; Rakshit, R. K.; Dogra, Anjana

    2015-09-01

    We have investigated the effect of ferroelectric barium titanate (BaTiO3) film thickness on the charge transport mechanism in pulsed laser deposited epitaxial metal-ferroelectric semiconductor junctions. The current (I)-voltage (V) measurements across the junctions comprising of 20-500 nm thick BaTiO3 and conducting bottom electrode (Nb: SrTiO3 substrate or La2/3Ca1/3MnO3 buffer layer) demonstrate the space charge limited conduction. Further analysis indicates a reduction in the ratio of free to trapped carriers with increasing thickness in spite of decreasing trap density. Such behaviour arises the deepening of the shallow trap levels (I-V curves implies a bipolar resistive switching behaviour, which can be explained in terms of charge trapping and de-trapping process.

  4. Charge transfer in photorechargeable composite films of TiO2 and polyaniline

    Science.gov (United States)

    Nomiyama, Teruaki; Sasabe, Kenichi; Sakamoto, Kenta; Horie, Yuji

    2015-07-01

    A photorechargeable battery (PRB) is a photovoltaic device having an energy storage function in a single cell. The photoactive electrode of PRB is a bilayer film consisting of bare porous TiO2 and a TiO2-polyaniline (PANi) mixture that work as a photovoltaic current generator and an electrochemical energy storage by ion dedoping, respectively. To study the charge transfer between TiO2 and PANi, the photorechargeable quantum efficiency QE ([electron count on discharge]/[incident photon count on photocharge]) was measured by varying the thickness LS of the TiO2-PANi mixture. The quantum efficiency QEuv for UV photons had a maximum of ˜7% at LS ˜ 7 µm. The time constant τTP for the charge transfer was about 10-1 s, which was longer ten times or more than the lifetime of excited electrons within TiO2. These facts reveal that the main rate-limiting factor in the photocharging process is the charge transfer between TiO2 and PANi.

  5. Emergence of charge density waves and a pseudogap in single-layer TiTe2.

    Science.gov (United States)

    Chen, P; Pai, Woei Wu; Chan, Y-H; Takayama, A; Xu, C-Z; Karn, A; Hasegawa, S; Chou, M Y; Mo, S-K; Fedorov, A-V; Chiang, T-C

    2017-09-11

    Two-dimensional materials constitute a promising platform for developing nanoscale devices and systems. Their physical properties can be very different from those of the corresponding three-dimensional materials because of extreme quantum confinement and dimensional reduction. Here we report a study of TiTe 2 from the single-layer to the bulk limit. Using angle-resolved photoemission spectroscopy and scanning tunneling microscopy and spectroscopy, we observed the emergence of a (2 × 2) charge density wave order in single-layer TiTe 2 with a transition temperature of 92 ± 3 K. Also observed was a pseudogap of about 28 meV at the Fermi level at 4.2 K. Surprisingly, no charge density wave transitions were observed in two-layer and multi-layer TiTe 2 , despite the quasi-two-dimensional nature of the material in the bulk. The unique charge density wave phenomenon in the single layer raises intriguing questions that challenge the prevailing thinking about the mechanisms of charge density wave formation.Due to reduced dimensionality, the properties of 2D materials are often different from their 3D counterparts. Here, the authors identify the emergence of a unique charge density wave (CDW) order in monolayer TiTe 2 that challenges the current understanding of CDW formation.

  6. Nongeminate radiative recombination of free charges in cation-exchanged PbS quantum dot films

    Energy Technology Data Exchange (ETDEWEB)

    Marshall, Ashley R. [National Renewable Energy Laboratory, 15013 Denver West Pkwy., Golden, CO 80401 (United States); Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309 (United States); Beard, Matthew C.; Johnson, Justin C. [National Renewable Energy Laboratory, 15013 Denver West Pkwy., Golden, CO 80401 (United States)

    2016-06-01

    Highlights: • Photoluminescence and transient absorption are used to probe PbS QD films. • Cation-exchanged PbS QDs show room-temperature PL emission. • Bimolecular recombination is shown for the first time in coupled, PbS QD films. - Abstract: Using photoluminescence (PL) spectroscopy we explore the radiative recombination pathways in PbS quantum dots (QDs) synthesized by two methods. We compare conventionally synthesized PbS from a PbO precursor to PbS synthesized using cation-exchange from CdS QDs. We show that strongly coupled films of PbS QDs from the cation-exchange luminesce with significant efficiency at room temperature. This is in stark contrast to conventional PbS QDs, which have exceedingly weak room temperature emission. Moreover, the power dependence of the emission is quadratic, indicating bimolecular radiative recombination that is reasonably competitive with trap-assisted recombination, a feature previously unreported in coupled PbS QD films. We interpret these results in terms of a greatly reduced defect concentration for cation-exchanged QDs that mitigates the influence of trap-assisted recombination. Cation-exchanged QDs have recently been employed in highly efficient and air-stable lead chalcogenide QD devices, and the reduced number of trap states inferred here may lead to improved current collection and higher open circuit voltage.

  7. Controllable Charge Transfer in Ag-TiO2 Composite Structure for SERS Application

    Directory of Open Access Journals (Sweden)

    Yaxin Wang

    2017-06-01

    Full Text Available The nanocaps array of TiO2/Ag bilayer with different Ag thicknesses and co-sputtering TiO2-Ag monolayer with different TiO2 contents were fabricated on a two-dimensional colloidal array substrate for the investigation of Surface enhanced Raman scattering (SERS properties. For the TiO2/Ag bilayer, when the Ag thickness increased, SERS intensity decreased. Meanwhile, a significant enhancement was observed when the sublayer Ag was 10 nm compared to the pure Ag monolayer, which was ascribed to the metal-semiconductor synergistic effect that electromagnetic mechanism (EM provided by roughness surface and charge-transfer (CT enhancement mechanism from TiO2-Ag composite components. In comparison to the TiO2/Ag bilayer, the co-sputtered TiO2-Ag monolayer decreased the aggregation of Ag particles and led to the formation of small Ag particles, which showed that TiO2 could effectively inhibit the aggregation and growth of Ag nanoparticles.

  8. Charge transfer-type fluorescence of Ti-doped Ca{sub 14}Al{sub 10}Zn{sub 6}O{sub 35}

    Energy Technology Data Exchange (ETDEWEB)

    Satoh, Yuta; Takemoto, Minoru, E-mail: takemoto@chem.kanagawa-it.ac.jp

    2017-05-15

    The calcium aluminum zincates Ca{sub 14}(Al{sub 1-2x}Ti{sub x}Zn{sub x}){sub 10}Zn{sub 6}O{sub 35}, in which Al{sup 3+} sites in the host material Ca{sub 14}Al{sub 10}Zn{sub 6}O{sub 35} are simultaneously substituted by Ti{sup 4+} and Zn{sup 2+}, were synthesized by a polymerized complex method. Al{sup 3+} ions could be replaced up to an x value of 0.1. The host material does not exhibit fluorescence, while the cation-substituted samples show an emission band centered at 383 nm under excitation by UV light at 243 nm. The emission intensity increases with x up to 0.1 and then gradually decreases as x is further increased. The emission wavelength also becomes longer with increasing temperature. Based on the properties of other Ti{sup 4+}-containing fluorescent materials, the emission of Ca{sub 14}(Al{sub 1-2x}Ti{sub x}Zn{sub x}){sub 10}Zn{sub 6}O{sub 35} is attributed to charge transfer-type fluorescence resulting from [TiO{sub 6}] octahedra.

  9. Effect of cation size and charge on the interaction between silica surfaces in 1:1, 2:1, and 3:1 aqueous electrolytes.

    Science.gov (United States)

    Dishon, Matan; Zohar, Ohad; Sivan, Uri

    2011-11-01

    Application of two complementary AFM measurements, force vs separation and adhesion force, reveals the combined effects of cation size and charge (valency) on the interaction between silica surfaces in three 1:1, three 2:1, and three 3:1 metal chloride aqueous solutions of different concentrations. The interaction between the silica surfaces in 1:1 and 2:1 salt solutions is fully accounted for by ion-independent van der Waals (vdW) attraction and electric double-layer repulsion modified by cation specific adsorption to the silica surfaces. The deduced ranking of mono- and divalent cation adsorption capacity (adsorbability) to silica, Mg(2+) cation bare size as well as cation solvation energy but does not correlate with hydrated ionic radius or with volume or surface ionic charge density. In the presence of 3:1 salts, the coarse phenomenology of the force between the silica surfaces as a function of salt concentration resembles that in 1:1 and 2:1 electrolytes. Nevertheless, two fundamental differences should be noticed. First, the attraction between the silica surfaces is too large to be attributed solely to vdW force, hence implying an additional attraction mechanism or gross modification of the conventional vdW attraction. Second, neutralization of the silica surfaces occurs at trivalent cation concentrations that are 3 orders of magnitude smaller than those characterizing surface neutralization by mono- and divalent cations. Consequently, when trivalent cations are added to our cation adsorbability series the correlation with bare ion size breaks down abruptly. The strong adsorbability of trivalent cations to silica contrasts straightforward expectations based on ranking of the cationic solvation energies, thus suggesting a different adsorption mechanism which is inoperative or weak for mono- and divalent cations.

  10. Charge transport in anodic TiO.sub.2./sub. nanotubes studied by terahertz spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Krbal, M.; Kuchařík, Jiří; Sopha, H.; Němec, Hynek; Macák, J. M.

    2016-01-01

    Roč. 10, č. 9 (2016), s. 691-695 ISSN 1862-6254 R&D Projects: GA ČR GA13-12386S Institutional support: RVO:68378271 Keywords : terahertz spectroscopy * charge transport * TiO2 nanotubes Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.032, year: 2016

  11. Charge transfer properties and photoelectrocatalytic activity of TiO{sub 2}/MWCNT hybrid

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Liaochuan [Nano Science Research Center, School of Chemistry and Chemical Engineering, South China University of Technology, 381 Wushan Road, Guangzhou 510640 (China); Zhang Weide, E-mail: zhangwd@scut.edu.c [Nano Science Research Center, School of Chemistry and Chemical Engineering, South China University of Technology, 381 Wushan Road, Guangzhou 510640 (China)

    2010-12-15

    The vertically aligned multiwalled carbon nanotube (MWCNT) arrays on tantalum foils were successfully coated with TiO{sub 2} nanoparticles by a hydrothermal process. The prepared TiO{sub 2}/MWCNT hybrid was characterized by scanning electron microscopy and transmission electron microscopy. The charge transfer properties and photocatalytic degradation of rhodamine B with and without bias potential under UV irradiation were investigated. The MWCNTs promoted the separation of photoinduced carriers in the TiO{sub 2}, thus enhanced photocatalytic activity. Applying bias potential on the photoanode further enhanced its catalytic activity. The efficient charge transportation and high photoelectrocatalytic activity towards degradation of rhodamine B made this hybrid material promising for photocatalyst and for the development of photoelectrical devices.

  12. Nonmonotonic anisotropy in charge conduction induced by antiferrodistortive transition in metallic SrTiO3

    Science.gov (United States)

    Tao, Qian; Loret, Bastien; Xu, Bin; Yang, Xiaojun; Rischau, Carl Willem; Lin, Xiao; Fauqué, Benoît; Verstraete, Matthieu J.; Behnia, Kamran

    2016-07-01

    Cubic SrTiO3 becomes tetragonal below 105 K. The antiferrodistortive (AFD) distortion leads to clockwise and counterclockwise rotation of adjacent TiO6 octahedra. This insulator becomes a metal upon the introduction of extremely low concentration of n -type dopants. However, signatures of the structural phase transition in charge conduction have remained elusive. Employing the Montgomery technique, we succeed in resolving the anisotropy of charge conductivity induced by the AFD transition, in the presence of different types of dopants. We find that the slight lattice distortion (liquids, the anisotropy has opposite signs for elastic and inelastic scattering. Increasing the concentration of dopants leads to a drastic shift in the temperature of the AFD transition either upward or downward. The latter result puts strong constraints on any hypothetical role played by the AFD soft mode in the formation of Cooper pairs and the emergence of superconductivity in SrTiO3.

  13. Effect of the Cationic Block Structure on the Characteristics of Sludge Flocs Formed by Charge Neutralization and Patching

    Directory of Open Access Journals (Sweden)

    Huaili Zheng

    2017-05-01

    Full Text Available In this study, a template copolymer (TPAA of (3-Acrylamidopropyl trimethylammonium chloride (AATPAC and acrylamide (AM was successfully synthesized though ultrasonic-initiated template copolymerization (UTP, using sodium polyacrylate (PAAS as a template. TPAA was characterized by an evident cationic microblock structure which was observed through the analyses of the reactivity ratio, Fourier transform infrared spectroscopy (FTIR, 1H (13C nuclear magnetic resonance spectroscopy (1H (13C NMR, and thermogravimetry/differential scanning calorimetry (TG/DSC. The introduction of the template could improve the monomer (AATPAC reactivity ratio and increase the length and amount of AATPAC segments. This novel cationic microblock structure extremely enhanced the ability of charge neutralization, patching, and bridging, thus improving the activated sludge flocculation performance. The experiments of floc formation, breakage, and regrowth revealed that the cationic microblock structure in the copolymer resulted in large and compact flocs, and these flocs had a rapid regrowth when broken. Finally, the larger and more compact flocs contributed to the formation of more channels and voids, and therefore the specific resistance to filtration (SRF reached a minimum.

  14. Low-Temperature Synthesis of Anatase TiO2 Nanoparticles with Tunable Surface Charges for Enhancing Photocatalytic Activity

    Science.gov (United States)

    Li, Ye; Qin, Zhenping; Guo, Hongxia; Yang, Hanxiao; Zhang, Guojun; Ji, Shulan; Zeng, Tingying

    2014-01-01

    In this work, the positively or negatively charged anatase TiO2 nanoparticles were synthesized via a low temperature precipitation-peptization process (LTPPP) in the presence of poly(ethyleneimine) (PEI) and poly(sodium4- styrenesulfonate) (PSS). X-ray diffraction (XRD) pattern and high-resolution transmission electron microscope (HRTEM) confirmed the anatase crystalline phase. The charges of the prepared TiO2, PEI-TiO2 and PSS-TiO2 nanoparticles were investigated by zeta potentials. The results showed that the zeta potentials of PEI-TiO2 nanoparticles can be tuned from +39.47 mV to +95.46 mV, and that of PSS-TiO2 nanoparticles can be adjusted from −56.63 mV to −119.32 mV. In comparison with TiO2, PSS-TiO2 exhibited dramatic adsorption and degradation of dye molecules, while the PEI modified TiO2 nanoparticles showed lower photocatalytic activity. The photocatalytic performances of these charged nanoparticles were elucidated by the results of UV-vis diffuse reflectance spectra (DRS) and the photoluminescence (PL) spectra, which indicated that the PSS-TiO2 nanoparticles showed a lower recombination rate of electron-hole pairs than TiO2 and PEI-TiO2. PMID:25506839

  15. Anionic or Cationic S-Doping in Bulk Anatase TiO 2 : Insights on Optical Absorption from First Principles Calculations

    KAUST Repository

    Harb, Moussab

    2013-05-02

    Using first principles calculations, we investigate the structural, electronic, optical, and energetic properties of S-doped anatase TiO2 bulk systems. To ensure accurate band gap predictions, we use the HSE06 exchange correlation functional, and the absorption spectra are obtained with density functional perturbation (DFPT) theory by employing HSE06. Various oxidation states (anionic and cationic) of sulfur are considered depending on the location in bulk TiO2: in interstitial position or in substitution for either oxygen or titanium atoms. Among the explored structures, two anionic and one cationic configurations induce an improved optical absorption response in the visible region as observed experimentally. Moreover, we undertake a thermodynamic analysis as a function of the chemical potential of oxygen and considering three relevant sulfur chemical doping agents (S 2, H2S, and thiourea). It highlights that cationic configurations (S4+ and S6+) are strongly stabilized in a wide range of oxygen chemical potential (including standard conditions), whereas anionic species are stabilized only at very low chemical potential of oxygen. The metastable cationic Ti(1-2x)O2S2x system involving the presence of S4+ species in substitution for Ti 4+, with the formation of SO2 units, should offer the best compromise between the thermodynamic conditions and the expected optical properties. © 2013 American Chemical Society.

  16. Sandia octahedral molecular sieves (SOMS): structural and property effects of charge-balancing the M(IV)-substituted (M = Ti, Zr) Niobate framework.

    Science.gov (United States)

    Nyman, May; Tripathi, Akhilesh; Parise, John B; Maxwell, Robert S; Nenoff, Tina M

    2002-02-27

    Sandia octahedral molecular sieves (SOMS) is an isostructural, variable composition class of ion exchangers with the general formula Na(2)Nb(2-x)M(IV)(x)O (6-x)(OH)(x).H(2)O (M(IV) = Ti, Zr; x = 0.04-0.40) where up to 20% of the framework Nb(V) can be substituted with Ti(IV) or Zr(IV). This class of molecular sieves is easily converted to perovskite through low-temperature heat treatment (500-600 degrees C). This report provides a detailed account of how the charge imbalance of this Nb(V)-M(IV) substitution is compensated. X-ray powder diffraction with Rietveld refinement, infrared spectroscopy, thermogravimetric analysis, (23)Na MAS NMR, and (1)H MAS NMR were used to determine how the framework anionic charge is cation-balanced over a range of framework compositions. All spectroscopic evidence indicated a proton addition for each M(IV) substitution. Evidences for variable proton content included (1) increasing OH observed by (1)H MAS NMR with increasing M(IV) substitution, (2) increased infrared band broadening indicating increased H-bonding with increasing M(IV) substitution, (3) increased TGA weight loss (due to increased OH content) with increasing M(IV) substitution, (4) no variance in population on the sodium sites (indicated by Rietveld refinement) with variable composition, and (5) no change in the (23)Na MAS NMR spectra with variable composition. Also observed by infrared spectroscopy and (23)Na MAS NMR was increased disorder on the Nb(V)/M(IV) framework sites with increasing M(IV) substitution, evidenced by broadening of these spectral features. These spectroscopic studies, along with ion exchange experiments, also revealed the effect of the Nb(V)/M(IV) framework substitution on materials properties. Namely, the temperature of conversion to NaNb(1-x)M(IV)(x)O(3) (M = Ti, Zr) perovskite increased with increasing Ti in the framework and decreased with increasing Zr in the framework. This suggested that Ti stabilizes the SOMS framework and Zr destabilizes

  17. Origin of the charge density wave in 1T-TiSe2

    KAUST Repository

    Zhu, Zhiyong

    2012-06-27

    All-electron ab initio calculations are used to study the microscopic origin of the charge density wave (CDW) in 1T-TiSe2. A purely electronic picture is ruled out as a possible scenario, indicating that the CDW transition in the present system is merely a structural phase transition. The CDW instability is the result of a symmetry lowering by electron correlations occurring with electron localization. Suppression of the CDW in pressurized and in Cu-intercalated 1T-TiSe2 is explained by a delocalization of the electrons, which weakens the correlations and counteracts the symmetry lowering.

  18. Origin of the charge density wave in 1T-TiSe2

    KAUST Repository

    Zhu, Zhiyong; Cheng, Yingchun; Schwingenschlö gl, Udo

    2012-01-01

    All-electron ab initio calculations are used to study the microscopic origin of the charge density wave (CDW) in 1T-TiSe2. A purely electronic picture is ruled out as a possible scenario, indicating that the CDW transition in the present system is merely a structural phase transition. The CDW instability is the result of a symmetry lowering by electron correlations occurring with electron localization. Suppression of the CDW in pressurized and in Cu-intercalated 1T-TiSe2 is explained by a delocalization of the electrons, which weakens the correlations and counteracts the symmetry lowering.

  19. Discoloration of a red cationic dye by supported TiO2 photocatalysis

    International Nuclear Information System (INIS)

    Mounir, B.; Pons, M.N.; Zahraa, O.; Yaacoubi, A.; Benhammou, A.

    2007-01-01

    The degradation under UV, visible and sunlight irradiation of C.I. Basic Red 46 (BR 46) dye used for acrylic fibers dyeing has been studied in a lab-scale continuous system with two different immobilized TiO 2 systems. Catalyst I was based on TiO 2 particles deposited on cellulose fibers; Catalyst II combined TiO 2 particles deposited on a layer of cellulose fibers (as in Catalyst I) with a layer of carbon fibers and finally a layer of cellulose fibers. The treatment of aqueous dye solutions and industrial wastewater contaminated with the same dye has been evaluated in terms of color removal and chemical oxygen demand (COD) decrease. With UV light, aqueous solutions containing dye were decolorized slightly more rapidly with Catalyst II than with Catalyst I. Sunlight was also very effective and experiments involving sunlight irradiation showed Catalyst II to be the more efficient, giving more than 90% discoloration after 20 min of treatment. Comparing the discoloration yield by adsorption or under visible light for both catalysts, it was observed that the difference between them is below 5%. The adsorption kinetics was found to follow a second-order rate law for Catalyst I and a first-order rate law for Catalyst II. The kinetics of photocatalytic degradation under UV or sunlight were found to follow a first-order rate law for both catalytic systems. Under sunlight the COD removal yield for textile wastewater reaches 33% with Catalyst I against 93% with Catalyst II

  20. Adsorption of a cationic dye molecule on polystyrene microspheres in colloids: effect of surface charge and composition probed by second harmonic generation.

    Science.gov (United States)

    Eckenrode, Heather M; Jen, Shih-Hui; Han, Jun; Yeh, An-Gong; Dai, Hai-Lung

    2005-03-17

    Nonlinear optical probe, second harmonic generation (SHG), of the adsorption of the dye molecule malachite green (MG), in cationic form at pH polystyrene microspheres in aqueous solution is used to study the effect of surface charge and composition on molecular adsorption. Three types of polystyrene microspheres with different surface composition are investigated: (1) a sulfate terminated, anionic surface, (2) a neutral surface without any functional group termination, and (3) an amine terminated, cationic surface. The cationic dye was found to adsorb at all three surfaces, regardless of surface charge. The adsorption free energies, DeltaG's, measured for the three surfaces are -12.67, -12.39, and -10.46 kcal/mol, respectively, with the trend as expected from the charge interactions. The adsorption density on the anionic surface, where attractive charge-charge interaction dominates, is determined by the surface negative charge density. The adsorption densities on the neutral and cationic surfaces are on the other hand higher, perhaps as a result of a balance between minimizing repulsive charge interaction and maximizing attractive molecule-substrate and intermolecular interactions. The relative strength of the SH intensity per molecule, in combination of a model calculation, reveals that the C(2) axis of the MG molecule is nearly perpendicular to the surface on the anionic surface and tilts away from the surface norm when the surface is neutral and further away when cationic. Changing the pH of the solution may alter the surface charge and subsequently affect the adsorption configuration and SH intensity.

  1. Charge Carrier Dynamics and pH Effect on Optical Properties of Anionic and Cationic Porphyrin-Graphene Oxide Composites

    Science.gov (United States)

    Bajjou, O.; Bakour, A.; Khenfouch, M.; Baitoul, M.; Mothudi, B.; Maaza, M.; Faulques, E.

    2018-02-01

    Composites of graphene oxide (GO) functionalized with Sn(V) tetrakis (4-pyridyl)porphyrin (SnTPyP2+) and meso-tetrakis(4-phenylsulfonic acid)porphyrin (H4TPPS4 2- ) were prepared at different pH values.Successful synthesis of water-soluble stable suspension of GO-SnTPyP2+ and GO-H4TPPS4 2-was confirmed using various spectroscopic techniques, including scanning electronic microscopy (SEM), Raman spectroscopy, and ultraviolet-visible (UV-Vis) absorption. Variation of the pH was found to strongly influence the optical properties of the GO-SnTPyP2+ and GO-H4TPPS4 2-composites, as demonstrated by the UV-Vis absorption results. Steady-state photoluminescence (PL) and time-resolved PL (TRPL) results for both composites showed PL quenching and decrease in the exciton mean lifetime, suggesting strong excited-state interactions between the different components. Moreover, charge carrier dynamics study revealed that insertion of GO into both porphyrin derivatives led to faster mean lifetime for excitons with a slight advantage in the case of the cationic porphyrin-GO composite, making it a better choice for charge separation applications thanks to the higher efficiency of charge/energy transfer interactions.

  2. Charge Berezinskii-Kosterlitz-Thouless transition in superconducting NbTiN films

    Energy Technology Data Exchange (ETDEWEB)

    Mironov, Alexey Yu.; Silevitch, Daniel M.; Proslier, Thomas; Postolova, Svetlana V.; Burdastyh, Maria V.; Gutakovskii, Anton K.; Rosenbaum, Thomas F.; Vinokur, Valerii V.; Baturina, Tatyana I.

    2018-03-06

    Three decades after the prediction of charge-vortex duality in the critical vicinity of the two-dimensional superconductor-insulator transition (SIT), one of the fundamental implications of this duality-the charge Berezinskii-Kosterlitz-Thouless (BKT) transition that should occur on the insulating side of the SIT-has remained unobserved. The dual picture of the process points to the existence of a superinsulating state endowed with zero conductance at finite temperature. Here, we report the observation of the charge BKT transition on the insulating side of the SIT in 10 nm thick NbTiN films, identified by the BKT critical behavior of the temperature and magnetic field dependent resistance, and map out the magnetic-field dependence of the critical temperature of the charge BKT transition. Finally, we ascertain the effects of the finite electrostatic screening length and its divergence at the magnetic field-tuned approach to the superconductor-insulator transition.

  3. Dynamics of chemical reactions of multiply-charged cations: Information from beam scattering experiments

    Czech Academy of Sciences Publication Activity Database

    Herman, Zdeněk

    2015-01-01

    Roč. 378, FEB 2015 (2015), s. 113-126 ISSN 1387-3806 Institutional support: RVO:61388955 Keywords : Multiply-charged ions * Dynamics of chemical reactions * Beam scattering Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.183, year: 2015

  4. Optimization of charge transfer and transport processes at the CdSe quantum dots/TiO2 nanorod interface by TiO2 interlayer passivation

    International Nuclear Information System (INIS)

    Jaramillo-Quintero, O A; Rincon, M E; Triana, M A

    2017-01-01

    Surface trap states hinder charge transfer and transport properties in TiO 2 nanorods (NRs), limiting its application on optoelectronic devices. Here, we study the interfacial processes between rutile TiO 2 NR and CdSe quantum dots (QDs) using TiO 2 interlayer passivation treatments. Anatase or rutile TiO 2 thin layers were deposited on an NR surface by two wet-chemical deposition treatments. Reduced interfacial charge recombination between NRs and CdSe QDs was observed by electrochemical impedance spectroscopy with the introduction of TiO 2 thin film interlayers compared to bare TiO 2 NRs. These results can be ascribed to in-gap trap state passivation of the TiO 2 NR surface, which led to an increase in open circuit voltage. Moreover, the rutile thin layer was more efficient than anatase to promote a higher photo-excited electron transfer from CdSe QDs to TiO 2 NRs due to a large driving force for charge injection, as confirmed by surface photovoltage spectroscopy. (paper)

  5. Ab initio investigation of sulfur monofluoride and its singly charged cation and anion in their ground electronic state

    International Nuclear Information System (INIS)

    Li Song; Chen Shan-Jun; Chen Yan; Chen Peng

    2016-01-01

    The SF radical and its singly charged cation and anion, SF + and SF − , have been investigated on the MRCI/aug-cc-pVXZ (X = Q, 5, 6) levels of theory with Davidson correction. Both the core–valence correlation and the relativistic effect are considered. The extrapolating to the complete basis set (CBS) limit is adopted to remove the basis set truncation error. Geometrical parameters, potential energy curves (PECs), vibrational energy levels, spectroscopic constants, ionization potentials, and electron affinities of the ground electronic state for all these species are obtained. The information with respect to molecular characteristics of the SF n (n = −1, 0, +1) systems derived in this work will help to extend our knowledge and to guide further experimental or theoretical researches. (paper)

  6. Design of Nickel-Based Cation-Disordered Rock-Salt Oxides: The Effect of Transition Metal (M = V, Ti, Zr) Substitution in LiNi0.5M0.5O2 Binary Systems.

    Science.gov (United States)

    Cambaz, Musa Ali; Vinayan, Bhaghavathi P; Euchner, Holger; Johnsen, Rune E; Guda, Alexander A; Mazilkin, Andrey; Rusalev, Yury V; Trigub, Alexander L; Gross, Axel; Fichtner, Maximilian

    2018-06-20

    Cation-disordered oxides have been ignored as positive electrode material for a long time due to structurally limited lithium insertion/extraction capabilities. In this work, a case study is carried out on nickel-based cation-disordered Fm3 ̅m LiNi 0.5 M 0.5 O 2 positive electrode materials. The present investigation targets tailoring the electrochemical properties for nickel-based cation-disordered rock-salt by electronic considerations. The compositional space for binary LiM +3 O 2 with metals active for +3/+4 redox couples is extended to ternary oxides with LiA 0.5 B 0.5 O 2 with A = Ni 2+ and B = Ti 4+ , Zr 4+ , and V +4 to assess the impact of the different transition metals in the isostructural oxides. The direct synthesis of various new unknown ternary nickel-based Fm3̅ m cation-disordered rock-salt positive electrode materials is presented with a particular focus on the LiNi 0.5 V 0.5 O 2 system. This positive electrode material for Li-ion batteries displays an average voltage of ∼2.55 V and a high discharge capacity of 264 mAhg -1 corresponding to 0.94 Li. For appropriate cutoff voltages, a long cycle life is achieved. The charge compensation mechanism is probed by XANES, confirming the reversible oxidation and reduction of V 4+ /V 5+ . The enhancement in the electrochemical performances within the presented compounds stresses the importance of mixed cation-disordered transition metal oxides with different electronic configuration.

  7. Splitting of the Ti-3d bands of TiSe{sub 2} in the charge-density wave phase

    Energy Technology Data Exchange (ETDEWEB)

    Ghafari, A., E-mail: aa.ghafari@gmail.com [Elettra Sincrotrone Trieste, Strada Statale 14 km 163.5, I-34149, Trieste (Italy); Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109, Berlin (Germany); Petaccia, L. [Elettra Sincrotrone Trieste, Strada Statale 14 km 163.5, I-34149, Trieste (Italy); Janowitz, C. [Institute of Physics, Humboldt-University of Berlin, Newtonst. 15, D-12489, Berlin (Germany)

    2017-02-28

    Highlights: • Angle resolved photoemission spectroscopy (ARPES). • Charge density wave (CDW). • TiSe{sub 2}- Splitting of the conduction bands. Horizontal and vertical polarizations. Temperature dependence. - Abstract: Very high resolution angular resolved photoemission (ARPES) spectra on TiSe{sub 2} in two distinct polarization geometries (vertical and horizontal) at temperatures between 300 K and 22 K enabled the observation of details of bands near the Fermi level not reported so far. Calculations of the electronic band structure based on density functional theory (DFT) using B3LYP hybrid functional and MBJ potential (with and without spin-orbit coupling) were performed to obtain the orbital symmetry and dispersion. Two degenerate conduction bands (CB’s) were observed at the Γ-point, a weak CB- emission at the A-point, and two non degenerate CB’s (i.e. splitting of CB) at the M/L-point of the Brillouin Zone (BZ). The splitting was detected at L for both polarizations, while at M remarkably only for horizontal polarization. These results cannot be fully accounted for by current theories for the charge density wave (CDW) and point to a reduced symmetry of the electronic states, possibly due to the chiral CDW.

  8. Discoloration of a red cationic dye by supported TiO{sub 2} photocatalysis

    Energy Technology Data Exchange (ETDEWEB)

    Mounir, B. [Ecole Superieure de Technologie de Safi, Universite Cadi Ayyad, BP 89, Route Dar Si Aissa, Safi (Morocco); Pons, M.N. [Laboratoire des Sciences du Genie Chimique, CNRS-ENSIC-INPL, 1, rue Grandville, BP 20451, F-54001 Nancy Cedex (France)], E-mail: Marie-Noelle.Pons@ensic.inpl-nancy.fr; Zahraa, O. [Departement de Chimie Physique des Reactions, ENSIC-INPL, 1, rue Grandville, BP 20451, F-54001 Nancy Cedex (France); Yaacoubi, A. [Departement de Chimie, Faculte des Sciences Semlalia, Universite Cadi Ayyad, Boulevard Prince Moulay Abdellah, BP 2390, 40000 Marrakech (Morocco); Benhammou, A. [Laboratoire d' Automatique et d' Etudes des Procedes, Faculte des Sciences Semlalia, Universite Cadi Ayyad, Boulevard Prince Moulay Abdellah, BP 2390, 40000 Marrakech (Morocco)

    2007-09-30

    The degradation under UV, visible and sunlight irradiation of C.I. Basic Red 46 (BR 46) dye used for acrylic fibers dyeing has been studied in a lab-scale continuous system with two different immobilized TiO{sub 2} systems. Catalyst I was based on TiO{sub 2} particles deposited on cellulose fibers; Catalyst II combined TiO{sub 2} particles deposited on a layer of cellulose fibers (as in Catalyst I) with a layer of carbon fibers and finally a layer of cellulose fibers. The treatment of aqueous dye solutions and industrial wastewater contaminated with the same dye has been evaluated in terms of color removal and chemical oxygen demand (COD) decrease. With UV light, aqueous solutions containing dye were decolorized slightly more rapidly with Catalyst II than with Catalyst I. Sunlight was also very effective and experiments involving sunlight irradiation showed Catalyst II to be the more efficient, giving more than 90% discoloration after 20 min of treatment. Comparing the discoloration yield by adsorption or under visible light for both catalysts, it was observed that the difference between them is below 5%. The adsorption kinetics was found to follow a second-order rate law for Catalyst I and a first-order rate law for Catalyst II. The kinetics of photocatalytic degradation under UV or sunlight were found to follow a first-order rate law for both catalytic systems. Under sunlight the COD removal yield for textile wastewater reaches 33% with Catalyst I against 93% with Catalyst II.

  9. Effective charge collection in dye-sensitized nanocrystalline TiO2

    Science.gov (United States)

    Yanagida, Masatoshi; Numata, Youhei; Yoshimatsu, Keiichi; Satoh, Shin; Han, Liyuan

    2013-03-01

    The effective charge collection in dye-sensitized solar cells (DSCs) is an important factor to improve the efficiency. Here, we report the comparison of three types of structures in DSCs. One type of structure is a sandwich-type DSC (SW-DSC), in which the TiO2 film is sandwiched between a TCO glass front electron-collection electrode and a sputtered Ti back collection electrode. The second is a normal DSC (N-DSC), which has no back electrode. The third is a back-contact-type DSC (BC-DSC), in which a sputtered Ti back electrode is deposited on a TiO2 film on the opposite side of the normal glass as an optical window. The photocurrent response of an SW-DSC is the fastest of the three structures due to using intensity modulated photocurrent spectroscopy, which can be explained by the electron diffusion model. The model shows that the SW-DSC is a favorable structure for effective charge collection in DSCs.

  10. Effective charge collection in dye-sensitized nanocrystalline TiO2

    International Nuclear Information System (INIS)

    Yanagida, Masatoshi; Numata, Youhei; Yoshimatsu, Keiichi; Satoh, Shin; Han, Liyuan

    2013-01-01

    The effective charge collection in dye-sensitized solar cells (DSCs) is an important factor to improve the efficiency. Here, we report the comparison of three types of structures in DSCs. One type of structure is a sandwich-type DSC (SW-DSC), in which the TiO 2 film is sandwiched between a TCO glass front electron-collection electrode and a sputtered Ti back collection electrode. The second is a normal DSC (N-DSC), which has no back electrode. The third is a back-contact-type DSC (BC-DSC), in which a sputtered Ti back electrode is deposited on a TiO 2 film on the opposite side of the normal glass as an optical window. The photocurrent response of an SW-DSC is the fastest of the three structures due to using intensity modulated photocurrent spectroscopy, which can be explained by the electron diffusion model. The model shows that the SW-DSC is a favorable structure for effective charge collection in DSCs. (paper)

  11. Integrating high electrical conductivity and photocatalytic activity in cotton fabric by cationizing for enriched coating of negatively charged graphene oxide.

    Science.gov (United States)

    Sahito, Iftikhar Ali; Sun, Kyung Chul; Arbab, Alvira Ayoub; Qadir, Muhammad Bilal; Jeong, Sung Hoon

    2015-10-05

    Electroconductive textiles have attended tremendous focus recently and researchers are making efforts to increase conductivity of e-textiles, in order to increase the use of such flexible and low cost textile materials. In this study, surface conductivity and photo catalytic activity of standard cotton fabric (SCF) was enhanced by modifying its surface charge, from negative to positive, using Bovine Serum Albumin (BSA) as a cationic agent, to convert it into cationised cotton fabric (CCF). Then, both types of fabrics were dip coated with a simple dip and dry technique for the adsorption of negatively charged graphene oxide (GO) sheets onto its surface. This resulted in 67.74% higher loading amount of GO on the CCF making self-assembly. Finally, this coating was chemically converted by vapor reduction using hydrazine hydrate to reduced graphene oxide (rGO) for restoration of a high electrical conductivity at the fabric surface. Our results revealed that with such high loading of GO, the surface resistance of CCF was only 40Ω/sq as compared to 510Ω/sq of the SCF and a 66% higher photo catalytic activity was also achieved through cationization for improved GO coating. Graphene coated SCF and CCF were characterized using FE-SEM, FTIR, Raman, UV-vis, WAXD, EDX and XPS spectroscopy to ascertain successful reduction of GO to rGO. The effect of BSA treatment on adsorption of cotton fabric was studied using drop shape analyzer to measure contact angle and for thermal and mechanical resistance, the fabric was tested for TGA and tensile strength, respectively. rGO coated fabric also showed slightly improved thermal stability yet a minor loss of strength was observed. The high flexibility, photocatalytic activity and excellent conductivity of this fabric suggests that it can be used as an electrode material for various applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Mechanical behavior of NiTi arc wires under pseudoelastic cycling and cathodically hydrogen charging

    Science.gov (United States)

    Sarraj, R.; Hassine, T.; Gamaoun, F.

    2018-01-01

    NiTi wires are mainly used to design orthodontic devices. However, they may be susceptible to a delayed fracture while they are submitted to cyclic loading with the presence of hydrogen in the oral cavity. Hydrogen may cause the embrittlement of the structure, leading to lower ductility and to a change in transformation behavior. The aim of the present study is to predict the NiTi behavior under cyclic loading with hydrogen charging. One the one hand, samples are submitted to superelastic cyclic loading, which results in investigating their performance degradations. On the other hand, after hydrogen charging, cyclic tensile aging tests are carried out on NiTi orthodontic wires at room temperature in the air. During cyclic loading, we notice that the critical stress for the martensite transformation evolves, the residual strain is accumulated in the structure and the hysteresis loop changes. Thus, via this work, we can assume that the embrittlement is due to the diffusion of hydrogen and the generation of dislocations after aging. The evolution of mechanical properties of specimens becomes more significant with hydrogen charging rather than without it.

  13. Cationic membranes complexed with oppositely charged microtubules: hierarchical self-assembly leading to bio-nanotubes

    International Nuclear Information System (INIS)

    Raviv, Uri; Needleman, Daniel J; Safinya, Cyrus R

    2006-01-01

    The self-assembly of microtubules and charged membranes has been studied, using x-ray diffraction and electron microscopy. Polyelectrolyte lipid complexes usually form structures templated by the lipid phase, when the polyelectrolyte curvature is much larger than the membrane spontaneous curvature. When the polyelectrolyte curvature approaches the membrane spontaneous curvature, as in microtubules, two types of new structures emerge. Depending on the conditions, vesicles either adsorb onto the microtubule, forming a 'beads on a rod' structure, or coat the microtubule, which now forms the template. Tubulin oligomers then coat the external lipid layer, forming a lipid protein nanotube. The tubulin oligomer coverage at the external layer is determined by the membrane charge density. The energy barrier between the beads on a rod and the lipid-protein nanotube states depends on the membrane bending rigidity and membrane charge density. By controlling the lipid/tubulin stoichiometry we can switch between lipid-protein nanotubes with open ends to lipid-protein nanotubes with closed end with lipid cups. This forms the basis for controlled drug encapsulation and release

  14. Electrolyte containing lithium cation in squaraine-sensitized solar cells: interactions and consequences for performance and charge transfer dynamics.

    Science.gov (United States)

    Novelli, Vittoria; Barbero, Nadia; Barolo, Claudia; Viscardi, Guido; Sliwa, Michel; Sauvage, Frédéric

    2017-10-18

    By optimizing the lithium concentration in an electrolyte to 50 mmol L -1 and the dye-to-chenodeoxycholic acid ratio in a VG1-based dye solution, we achieved 4.7% power conversion efficiency under standard AM 1.5G conditions. In addition to this performance, we herein discuss the role played by lithium in the electrolyte and its interplay in the charge transfer processes from ms to fs dynamics. Based on electrochemical impedance spectroscopy, photoluminescence and pump-probe transient absorption spectroscopy, we conclude that although lithium increases the electron diffusion length, this has no satisfactory impact on electron injection and even slows dye regeneration. This study provides evidence that lithium is not only specifically adsorbed on the surface of TiO 2 but prompts a molecular reorganization of the self-assembled dye monolayer, forming harmful H-aggregates.

  15. Adsorption of hazardous cationic dye onto the combustion derived SrTiO3 nanoparticles: Kinetic and isotherm studies

    Directory of Open Access Journals (Sweden)

    N.P. Bhagya

    2016-03-01

    Full Text Available In this article we report on solution combustion method to synthesize SrTiO3 nanoparticles (ST-NPs and the removal of malachite green (MG azo dye from the aqueous solution. The synthesized ST-NPs were calcined at 600 °C for 2 h. Powder X-ray diffraction (PXRD, field emission scanning electron microscopy (FE-SEM, transmission electron microscopy (TEM, Fourier transform infrared spectroscopy (FT-IR, and Brunauer–Emmett–Teller (BET were used to characterize the product. Adsorption experiments were performed with cationic malachite green (MG dye. ∼98% dye was adsorbed onto the ST-NPs at pH 10 for 30 min of the contact time. The optimum adsorbent dose was found to be 0.015 g/L of the dye. To study the adsorption kinetics Langmuir Hinshelwood model was used and the first order kinetic best describes the MG adsorption onto the ST-NPs. The adsorption isotherms data of MG onto ST-NPs obtained were analyzed by Langmuir and Freundlich isotherm models and the results describe the best representation of the Langmuir isotherm model.

  16. Rapid charge-discharge property of Li4Ti5O12-TiO2 nanosheet and nanotube composites as anode material for power lithium-ion batteries.

    Science.gov (United States)

    Yi, Ting-Feng; Fang, Zi-Kui; Xie, Ying; Zhu, Yan-Rong; Yang, Shuang-Yuan

    2014-11-26

    Well-defined Li4Ti5O12-TiO2 nanosheet and nanotube composites have been synthesized by a solvothermal process. The combination of in situ generated rutile-TiO2 in Li4Ti5O12 nanosheets or nanotubes is favorable for reducing the electrode polarization, and Li4Ti5O12-TiO2 nanocomposites show faster lithium insertion/extraction kinetics than that of pristine Li4Ti5O12 during cycling. Li4Ti5O12-TiO2 electrodes also display lower charge-transfer resistance and higher lithium diffusion coefficients than pristine Li4Ti5O12. Therefore, Li4Ti5O12-TiO2 electrodes display lower charge-transfer resistance and higher lithium diffusion coefficients. This reveals that the in situ TiO2 modification improves the electronic conductivity and electrochemical activity of the electrode in the local environment, resulting in its relatively higher capacity at high charge-discharge rate. Li4Ti5O12-TiO2 nanocomposite with a Li/Ti ratio of 3.8:5 exhibits the lowest charge-transfer resistance and the highest lithium diffusion coefficient among all samples, and it shows a much improved rate capability and specific capacity in comparison with pristine Li4Ti5O12 when charging and discharging at a 10 C rate. The improved high-rate capability, cycling stability, and fast charge-discharge performance of Li4Ti5O12-TiO2 nanocomposites can be ascribed to the improvement of electrochemical reversibility, lithium ion diffusion, and conductivity by in situ TiO2 modification.

  17. The lightest organic radical cation for charge storage in redox flow batteries.

    Science.gov (United States)

    Huang, Jinhua; Pan, Baofei; Duan, Wentao; Wei, Xiaoliang; Assary, Rajeev S; Su, Liang; Brushett, Fikile R; Cheng, Lei; Liao, Chen; Ferrandon, Magali S; Wang, Wei; Zhang, Zhengcheng; Burrell, Anthony K; Curtiss, Larry A; Shkrob, Ilya A; Moore, Jeffrey S; Zhang, Lu

    2016-08-25

    In advanced electrical grids of the future, electrochemically rechargeable fluids of high energy density will capture the power generated from intermittent sources like solar and wind. To meet this outstanding technological demand there is a need to understand the fundamental limits and interplay of electrochemical potential, stability, and solubility in low-weight redox-active molecules. By generating a combinatorial set of 1,4-dimethoxybenzene derivatives with different arrangements of substituents, we discovered a minimalistic structure that combines exceptional long-term stability in its oxidized form and a record-breaking intrinsic capacity of 161 mAh/g. The nonaqueous redox flow battery has been demonstrated that uses this molecule as a catholyte material and operated stably for 100 charge/discharge cycles. The observed stability trends are rationalized by mechanistic considerations of the reaction pathways.

  18. Fabrication of Tiron-TiO{sub 2} charge-transfer complex with excellent visible-light photocatalytic performance

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Binghua, E-mail: bhyao@xaut.edu.cn [Department of Applied Chemistry, Xi' an University of Technology, Xi' an 710048 (China); The Key Laboratory of Northwest Water Resources and Environmental Ecology of Ministry of Education, Xi' an University of Technology, Xi' an 710048 (China); Peng, Chao; Lu, Pan; He, Yangqing [Department of Applied Chemistry, Xi' an University of Technology, Xi' an 710048 (China); Zhang, Wen, E-mail: wenzhang@uark.edu [Department of Civil Engineering, University of Arkansas, Fayetteville 72701 (United States); Zhang, Qinku [Department of Applied Chemistry, Xi' an University of Technology, Xi' an 710048 (China); The Key Laboratory of Northwest Water Resources and Environmental Ecology of Ministry of Education, Xi' an University of Technology, Xi' an 710048 (China)

    2016-12-01

    A new charge-transfer(CT) complex (Tiron-TiO{sub 2}) was prepared via the 1,2-dihydroxy-3,5-benzenedisulfonic acid disodium salt (Tiron) as chelate sensitizer. The phase structures and morphologies were measured by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results demonstrated that the as-prepared Tiron-TiO{sub 2} is of anatase microspheres with size range between 300 and 350 nm. The analysis of FT-IR and XPS revealed that the binding structure of the Tiron-TiO{sub 2} CT complex is of the characteristic of bidentate binuclear binding-bridging. UV–vis analysis showed that the formation of CT complex on the surface of TiO{sub 2} through Tiron significantly extends the photoresponse of Tiron-TiO{sub 2} nanoparticles to visible light range (400–600 nm). Compared with unmodified TiO{sub 2}, Tiron-modified TiO{sub 2}(Tiron-TiO{sub 2}) exhibited excellent photocatalytic activity for the photocatalytic degradation of methylene blue(MB) and three kind of antibiotics under visible light irradiation (λ > 400 nm). - Highlights: • The Tiron-TiO{sub 2} charge transfer complex was synthesized. • The incorporation of Tiron with TiO{sub 2} extended TiO{sub 2} response to visible light region. • Tiron-TiO{sub 2} exhibited significant photocatalytic degradation for antibiotics. • Tiron-TiO{sub 2} showed the long-term stability and reusability.

  19. Visible Light Absorption of Binuclear TiOCoII Charge-Transfer UnitAssembled in Mesoporous Silica

    Energy Technology Data Exchange (ETDEWEB)

    Han, Hongxian; Frei, Heinz

    2007-01-30

    Grafting of CoII(NCCH3)2Cl2 onto mesoporous Ti-MCM-41 silicain acetonitrile solution affords binuclear Ti-O-CoII sites on the poresurface under complete replacement of the precursor ligands byinteractions with anchored Ti centers and the silica surface. The CoIIligand field spectrum signals that the Co centers are anchored on thepore surface in tetrahedral coordination. FT-infrared action spectroscopyusing ammonia gas adsorption reveals Co-O-Si bond modes at 831 and 762cm-1. No Co oxide clusters are observed in the as-synthesized material.The bimetallic moieties feature an absorption extending from the UV intothe visible to about 600 nm which is attributed to the TiIV-O-CoII?3TiIII-O-CoIII metal-to-metal charge-transfer (MMCT) transition. Thechromophore is absent in MCM-41 containing Ti and Co centers isolatedfrom each other; this material was synthesized by grafting CoII onto aTi-MCM-41 sample with the Ti centers protected by a cyclopentadienylligand. The result indicates that the appearance of the charge-transferabsorption requires that the metal centers are linked by an oxo bridge,which is additionally supported by XANES spectroscopy. The MMCTchromophore of Ti-O-CoII units has sufficient oxidation power to serve asvisible light electron pump for driving multi-electron transfer catalystsof demanding uphill reactions such as water oxidation.

  20. Ab initio investigation of sulfur monofluoride and its singly charged cation and anion in their ground electronic state

    Science.gov (United States)

    Song, Li; Shan-Jun, Chen; Yan, Chen; Peng, Chen

    2016-03-01

    The SF radical and its singly charged cation and anion, SF+ and SF-, have been investigated on the MRCI/aug-cc-pVXZ (X = Q, 5, 6) levels of theory with Davidson correction. Both the core-valence correlation and the relativistic effect are considered. The extrapolating to the complete basis set (CBS) limit is adopted to remove the basis set truncation error. Geometrical parameters, potential energy curves (PECs), vibrational energy levels, spectroscopic constants, ionization potentials, and electron affinities of the ground electronic state for all these species are obtained. The information with respect to molecular characteristics of the SFn (n = -1, 0, +1) systems derived in this work will help to extend our knowledge and to guide further experimental or theoretical researches. Project supported by the National Natural Science Foundation of China (Grant Nos. 11304023 and 11447172), the Young and Middle-Aged Talent of Education Burea of Hubei Province, China (Grant No. Q20151307), and the Yangtze Youth Talents Fund of Yangtze University, China (Grant No. 2015cqr21).

  1. Charge transfer between biogenic jarosite derived Fe3+and TiO2 enhances visible light photocatalytic activity of TiO2.

    Science.gov (United States)

    Chowdhury, Mahabubur; Shoko, Sipiwe; Cummings, Fransciuos; Fester, Veruscha; Ojumu, Tunde Victor

    2017-04-01

    In this work, we have shown that mining waste derived Fe 3+ can be used to enhance the photocatalytic activity of TiO 2 . This will allow us to harness a waste product from the mines, and utilize it to enhance TiO 2 photocatalytic waste water treatment efficiency. An organic linker mediated route was utilized to create a composite of TiO 2 and biogenic jarosite. Evidence of FeOTi bonding in the TiO 2 /jarosite composite was apparent from the FTIR, EFTEM, EELS and ELNEFS analysis. The as prepared material showed enhanced photocatalytic activity compared to pristine TiO 2 , biogenic jarosite and mechanically mixed sample of jarosite and TiO 2 under both simulated and natural solar irradiation. The prepared material can reduce the electrical energy consumption by 4 times compared to pristine P25 for degradation of organic pollutant in water. The material also showed good recyclability. Results obtained from sedimentation experiments showed that the larger sized jarosite material provided the surface to TiO 2 nanoparticles, which increases the settling rate of the materials. This allowed simple and efficient recovery of the catalyst from the reaction system after completion of photocatalysis. Enhanced photocatalytic activity of the composite material was due to effective charge transfer between TiO 2 and jarosite derived Fe 3+ as was shown from the EELS and ELNEFS. Generation of OH was supported by photoluminesence (PL) experiments. Copyright © 2016. Published by Elsevier B.V.

  2. Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals - II. Application to Fe2+ --> Ti4+ charge transfer transitions in oxides and silicates

    Science.gov (United States)

    Sherman, David M.

    1987-01-01

    A molecular orbital description, based on Xα-Scattered wave calculations on a (FeTiO10)14− cluster, is given for Fe2+ → Ti4+ charge transfer transitions in minerals. The calculated energy for the lowest Fe2+ → Ti4+ metal-metal charge transfer transition is 18040 cm−1 in reasonable agreement with energies observed in the optical spectra of Fe-Ti oxides and silicates. As in the case of Fe2+ → Fe3+ charge transfer in mixed-valence iron oxides and silicates, Fe2+ → Ti4+ charge transfer is associated with Fe-Ti bonding across shared polyhedral edges. Such bonding results from the overlap of the Fe(t 2g ) and Ti(t 2g ) 3d orbitals.

  3. Inherent Electrochemistry and Charge Transfer Properties of Few-Layer Two Dimensional Ti3C2Tx MXene

    KAUST Repository

    Nayak, Pranati

    2018-05-25

    We report the effect of Ti3C2Tx MXene flake thickness on its inherent electrochemistry and heterogeneous charge transfer characteristics. It is shown that the Ti3C2Tx undergoes irreversible oxidation in the positive potential window, which strongly depends on the flake thickness and pH of the electrolyte. Few-layer Ti3C2Tx exhibits faster electron transfer kinetics (k0=0.09533 cm/s) with Fe(CN)64−/3− redox mediator compared to multi-layer Ti3C2Tx (k0= 0.00503 cm/s). In addition, few-layer free standing Ti3C2Tx film electrode remains intact after enduring irreversible oxidation.

  4. Inherent Electrochemistry and Charge Transfer Properties of Few-Layer Two Dimensional Ti3C2Tx MXene

    KAUST Repository

    Nayak, Pranati; Jiang, Qiu; Mohanraman, Rajeshkumar; Anjum, Dalaver H.; Hedhili, Mohamed N.; Alshareef, Husam N.

    2018-01-01

    We report the effect of Ti3C2Tx MXene flake thickness on its inherent electrochemistry and heterogeneous charge transfer characteristics. It is shown that the Ti3C2Tx undergoes irreversible oxidation in the positive potential window, which strongly depends on the flake thickness and pH of the electrolyte. Few-layer Ti3C2Tx exhibits faster electron transfer kinetics (k0=0.09533 cm/s) with Fe(CN)64−/3− redox mediator compared to multi-layer Ti3C2Tx (k0= 0.00503 cm/s). In addition, few-layer free standing Ti3C2Tx film electrode remains intact after enduring irreversible oxidation.

  5. Effect of Viscosity and Polar Properties of Solvent on Dynamics of Photoinduced Charge Transfer in BTA-1 Cation — Derivative of Thioflavin T

    Science.gov (United States)

    Gogoleva, S. D.; Stsiapura, V. I.

    2018-05-01

    It was found that the spectral and fluorescent properties of BTA-1C cation in protic and aprotic solvents differ. It was shown that for solutions in long-chain alcohols viscosity is the main factor that determines the dynamics of intramolecular charge transfer in the excited state of the BTA-1C molecule. In the case of aprotic solvents a correlation was found between the rate constant of twisted intramolecular charge transfer (TICT) during rotation of fragments of the molecule in relation to each other in the excited state and the solvent relaxation rate: k TICT 1/τ S .

  6. Hydrogen Charging Effects in Pd/Ti/TiO2/Ti Thin Films Deposited on Si(111 Studied by Ion Beam Analysis Methods

    Directory of Open Access Journals (Sweden)

    K. Drogowska

    2012-01-01

    Full Text Available Titanium and titanium dioxide thin films were deposited onto Si(111 substrates by magnetron sputtering from a metallic Ti target in a reactive Ar+O2 atmosphere, the composition of which was controlled by precision gas controllers. For some samples, 1/3 of the surface was covered with palladium using molecular beam epitaxy. Chemical composition, density, and layer thickness of the layers were determined by Auger electron spectroscopy (AES and Rutherford backscattering spectrometry (RBS. The surface morphology was studied using high-resolution scanning electron microscopy (HRSEM. After deposition, smooth, homogenous sample surfaces were observed. Hydrogen charging for 5 hours under pressure of 1 bar and at temperature of 300°C results in granulation of the surface. Hydrogen depth profile was determined using secondary ion mass spectrometry (SIMS and nuclear Reaction Analysis (N-15 method, using a 15N beam at and above the resonance energy of 6.417 MeV. NRA measurements proved a higher hydrogen concentration in samples with partially covered top layers, than in samples without palladium. The highest value of H concentration after charging was about 50% (in the palladium-covered part and about 40% in titanium that was not covered by Pd. These values are in good agreement with the results of SIMS measurements.

  7. Generation of reactive oxygen species and charge carriers in plasmonic photocatalytic Au@TiO2 nanostructures with enhanced activity.

    Science.gov (United States)

    He, Weiwei; Cai, Junhui; Jiang, Xiumei; Yin, Jun-Jie; Meng, Qingbo

    2018-06-13

    The combination of semiconductor and plasmonic nanostructures, endowed with high efficiency light harvesting and surface plasmon confinement, has been a promising way for efficient utilization of solar energy. Although the surface plasmon resonance (SPR) assisted photocatalysis has been extensively studied, the photochemical mechanism, e.g. the effect of SPR on the generation of reactive oxygen species and charge carriers, is not well understood. In this study, we take Au@TiO2 nanostructures as a plasmonic photocatalyst to address this critical issue. The Au@TiO2 core/shell nanostructures with tunable SPR property were synthesized by the templating method with post annealing thermal treatment. It was found that Au@TiO2 nanostructures exhibit enhanced photocatalytic activity in either sunlight or visible light (λ > 420 nm). Electron spin resonance spectroscopy with spin trapping and spin labeling was used to investigate the enhancing effect of Au@TiO2 on the photo-induced reactive oxygen species and charge carriers. The formation of Au@TiO2 core/shell nanostructures resulted in a dramatic increase in light-induced generation of hydroxyl radicals, singlet oxygen, holes and electrons, as compared with TiO2 alone. This enhancement under visible light (λ > 420 nm) irradiation may be dominated by SPR induced local electrical field enhancement, while the enhancement under sunlight irradiation is dominated by the higher electron transfer from TiO2 to Au. These results unveiled that the superior photocatalytic activity of Au@TiO2 nanostructures correlates with enhanced generation of reactive oxygen species and charge carriers.

  8. Anomalous metallic state with strong charge fluctuations in BaxTi8O16 +δ revealed by hard x-ray photoemission spectroscopy

    Science.gov (United States)

    Dash, S.; Kajita, T.; Okawa, M.; Saitoh, T.; Ikenaga, E.; Saini, N. L.; Katsufuji, T.; Mizokawa, T.

    2018-04-01

    We have studied a charge-orbital driven metal-insulator transition (MIT) in hollandite-type BaxTi8O16 +δ by means of hard x-ray photoemission spectroscopy (HAXPES). The Ti 2 p HAXPES indicates strong Ti3 +/Ti4 + charge fluctuation in the metallic phase above the MIT temperature. The metallic phase is characterized by a power-law spectral function near the Fermi level which would be a signature of bad metal with non-Drude polaronic behavior. The power-law spectral shape is associated with the large Seebeck coefficient of the metallic phase in BaxTi8O16 +δ .

  9. BiOI/TiO{sub 2}-nanorod array heterojunction solar cell: Growth, charge transport kinetics and photoelectrochemical properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Lingyun; Daoud, Walid A., E-mail: wdaoud@cityu.edu.hk

    2015-01-01

    Highlights: • BiOI/TiO{sub 2} photoanodes were fabricated by a simple solvothermal/hydrothermal method. • BiOI/TiO{sub 2} (PVP) showed a 13-fold increase in photocurrent density compared to TiO{sub 2}. • Charge transport kinetics within the BiOI/TiO{sub 2} heterojunctions are discussed. - Abstract: A series of BiOI/TiO{sub 2}-nanorod array photoanodes were grown on fluorine-doped tin oxide (FTO) glass using a simple two-step solvothermal/hydrothermal method. The effects of the hydrothermal process, such as TiO{sub 2} nanorod growth time, BiOI concentration and the role of surfactant, polyvinylpyrrolidone (PVP), on the growth of BiOI, were investigated. The heterojunctions were characterized by X-ray diffraction, UV–vis absorbance spectroscopy and scanning electron microscopy. The photoelectrochemical properties of the as-grown junctions, such as linear sweep voltammetry (LSV) behavior, photocurrent response and incident photon-to-electron conversion efficiency (IPCE) under Xenon lamp illumination, are presented. The cell with BiOI/TiO{sub 2} (PVP) as photoanode can reach a short current density (J{sub sc}) of 0.13 mA/cm{sup 2} and open circuit voltage (V{sub oc}) of 0.46 V vs. Ag/AgCl under the irradiation of a 300 W Xenon lamp. Compared to bare TiO{sub 2}, the IPCE of BiOI/TiO{sub 2} (PVP) increased 4–5 times at 380 nm. Furthermore, the charge transport kinetics within the heterojunction is also discussed.

  10. BiOI/TiO2-nanorod array heterojunction solar cell: Growth, charge transport kinetics and photoelectrochemical properties

    International Nuclear Information System (INIS)

    Wang, Lingyun; Daoud, Walid A.

    2015-01-01

    Highlights: • BiOI/TiO 2 photoanodes were fabricated by a simple solvothermal/hydrothermal method. • BiOI/TiO 2 (PVP) showed a 13-fold increase in photocurrent density compared to TiO 2 . • Charge transport kinetics within the BiOI/TiO 2 heterojunctions are discussed. - Abstract: A series of BiOI/TiO 2 -nanorod array photoanodes were grown on fluorine-doped tin oxide (FTO) glass using a simple two-step solvothermal/hydrothermal method. The effects of the hydrothermal process, such as TiO 2 nanorod growth time, BiOI concentration and the role of surfactant, polyvinylpyrrolidone (PVP), on the growth of BiOI, were investigated. The heterojunctions were characterized by X-ray diffraction, UV–vis absorbance spectroscopy and scanning electron microscopy. The photoelectrochemical properties of the as-grown junctions, such as linear sweep voltammetry (LSV) behavior, photocurrent response and incident photon-to-electron conversion efficiency (IPCE) under Xenon lamp illumination, are presented. The cell with BiOI/TiO 2 (PVP) as photoanode can reach a short current density (J sc ) of 0.13 mA/cm 2 and open circuit voltage (V oc ) of 0.46 V vs. Ag/AgCl under the irradiation of a 300 W Xenon lamp. Compared to bare TiO 2 , the IPCE of BiOI/TiO 2 (PVP) increased 4–5 times at 380 nm. Furthermore, the charge transport kinetics within the heterojunction is also discussed

  11. Measurement of chirality of charge-density-waves in TiSe2 by using STM

    International Nuclear Information System (INIS)

    Ishioka, J.; Liu, Y.H.; Shimatake, K.; Kurosawa, T.; Ichimura, K.; Toda, Y.; Oda, M.; Tanda, S.

    2010-01-01

    We report the chirality of charge density waves (CDW) in 1T-TiSe 2 by using scanning tunneling microscopy (STM) measurements. We found that the CDW intensity becomes Ia 1 :Ia 2 :Ia 3 =1:0.7±0.1:0.5±0.1, where Ia i (i=1, 2, 3) is the amplitude of the tunneling current contributed by the CDWs. We found two states, in which the three intensity peaks of the CDW decrease clockwise and anticlockwise when we index each nesting vector in order of intensity in the Fourier transformation of the STM images. We found that this difference arises from CDW stacking along the c-axis at intervals of 2c 0 /3. This chirality is attributed to the helical stacking such as cholesteric liquid crystals.

  12. Effects of Hydrogen Charging on the Phase Transformation of Martensitic NiTi Shape Memory Alloy Wires

    Science.gov (United States)

    Snir, Yoav; Carl, Matthew; Ley, Nathan A.; Young, Marcus L.

    2017-12-01

    Ti-rich martensitic NiTi shape memory alloy (SMA) wires of 0.5 mm diameter were tested under hydrogen-charging conditions to reveal the effects on phase transformation. Hydrogen charging was performed by immersion testing for several durations. The SMA wires were characterized by differential scanning calorimetry (DSC), scanning electron microscopy with energy dispersive spectroscopy, and synchrotron radiation X-ray diffraction (SR-XRD) for the the as-received, polished, and hydrogen-charged conditions. The DSC revealed the phase-transformation behavior of the NiTi SMA wires. Single and triple heating/cooling cycles in the DSC show the relationship between hydrogen and temperature on the material. Five distinct peaks (peaks I-V) are observed during heating/cooling in the DSC. Peak I corresponds to the martensite-to-austenite (M → A) transformation. Peaks II, III, and IV are related to hydrogen charging. Peak II appears at about 210-230 °C, while peaks III and IV appear at about 350 and 440 °C, respectively. These higher temperature peaks, peaks II-IV, were observed for the first time for a martensitic NiTi SMA due to the large temperature range covered using the DSC. Only one peak (peak V) appears during cooling and corresponds to the austenite-to-martensite transformation peak. Ex situ and in situ SR-XRD revealed the phases and the crystallographic relationship to peaks I-V in the DSC.

  13. Facile synthesis of semi-library of low charge density cationic polyesters from poly(alkylene maleate)s for efficient local gene delivery.

    Science.gov (United States)

    Yan, Huijie; Zhu, Dingcheng; Zhou, Zhuxian; Liu, Xin; Piao, Ying; Zhang, Zhen; Liu, Xiangrui; Tang, Jianbin; Shen, Youqing

    2018-03-30

    Cationic polymers are one of the main non-viral vectors for gene therapy, but their applications are hindered by the toxicity and inefficient transfection, particularly in the presence of serum or other biological fluids. While rational design based on the current understanding of gene delivery process has produced various cationic polymers with improved overall transfection, high-throughput parallel synthesis of libraries of cationic polymers seems a more effective strategy to screen out efficacious polymers. Herein, we demonstrate a novel platform for parallel synthesis of low cationic charge-density polyesters for efficient gene delivery. Unsaturated polyester poly(alkylene maleate) (PAM) readily underwent Michael-addition reactions with various mercaptamines to produce polyester backbones with pendant amine groups, poly(alkylene maleate mercaptamine)s (PAMAs). Variations of the alkylenes in the backbone and the mercaptamines on the side chain produced PAMAs with tunable hydrophobicity and DNA-condensation ability, the key parameters dominating transfection efficiency of the resulting polymer/DNA complexes (polyplexes). A semi-library of such PAMAs was exampled from 7 alkylenes and 18 mercaptamines, from which a lead PAMA, G-1, synthesized from poly(1,4-phenylene bis(methylene) maleate) and N,N-dimethylcysteamine, showed remarkable transfection efficiency even in the presence of serum, owing to its efficient lysosome-circumventing cellular uptake. Furthermore, G-1 polyplexes efficiently delivered the suicide gene pTRAIL to intraperitoneal tumors and elicited effective anticancer activity. Copyright © 2018 Elsevier Ltd. All rights reserved.

  14. Effects of noble-metal ion implantation on corrosion inhibition and charge injection capability of surgical Ti and Ti-6Al-4V

    International Nuclear Information System (INIS)

    Lee, I.S.

    1989-01-01

    Studies are described involving effects of noble-metal ion implantation on corrosion inhibition and charge injection capabilities of surgical Ti and Ti-6Al-4V. With surgical alloys, harmful biological responses are principally due to the type and quantity of metal ions released by the corrosion process. One approach to improve long-term biological performance involves surface modifications to significantly reduce degradation rates. With regard to surface-modifications, one of the most effective methods is through ion implantation. Results are presented for ion-implanted Au, Rh, and Ir. For the static in vitro corrosion properties, the noble-metal ion implanted Ti-6Al-4V and commercially-pure (CP) Ti were investigated in non-passivating acid and passivating saline solutions. It was postulated that during the early stages of corrosion (or during a corrosion pretreatment) the implanted noble-metal would enrich at the surface and significantly reduce subsequent corrosion rates. The observed behavior for the Ir and Rh implanted materials appeared to follow the postulated mechanism, with both initial and time-dependent improvements in corrosion resistance. However, the Au implanted material yielded early benefits, but the enhanced corrosion resistance deteriorated with time. X-ray photoelectron spectroscopy (XPS) analysis indicated that the implanted Au atoms remained as pure metallic Au, while the Ir and Rh atoms were in some oxide state, which gave the good adhesion of the Ir or Rh enriched surface to the Ti substrate. For a stimulating neural electrode, the charge density should be as large as possible to provide adequate stimulation of the nervous system while allowing for miniaturization of the electrode. Activated Ir has been known as having the highest charge injection capability of any material known

  15. The impact of Au doping on the charge carrier dynamics at the interfaces between cationic porphyrin and silver nanoclusters

    KAUST Repository

    Almansaf, Abdulkhaleq A.

    2017-02-04

    We explore the impact of Au doping on the charge transfer dynamics between the positively charged porphyrin (TMPyP) and negatively charged silver nanoclusters (Ag29 NCs). Our transient absorption (TA) spectroscopic results demonstrate that the interfacial charge transfer, the intersystem crossing and the triplet state lifetime of porphyrin can be tuned by the doping of Au atoms in Ag29 NCs. Additionally, we found that the electrostatic interaction between the negative charge of the cluster and the positive charge on the TMPyP is the driving force that brings them close to each other for complex formation and subsequently facilitates the transfer process.

  16. The impact of Au doping on the charge carrier dynamics at the interfaces between cationic porphyrin and silver nanoclusters

    KAUST Repository

    Almansaf, Abdulkhaleq A.; Parida, Manas R.; Besong, Tabot M.D.; Maity, Partha; Bootharaju, Megalamane Siddaramappa; Bakr, Osman; Mohammed, Omar F.

    2017-01-01

    We explore the impact of Au doping on the charge transfer dynamics between the positively charged porphyrin (TMPyP) and negatively charged silver nanoclusters (Ag29 NCs). Our transient absorption (TA) spectroscopic results demonstrate that the interfacial charge transfer, the intersystem crossing and the triplet state lifetime of porphyrin can be tuned by the doping of Au atoms in Ag29 NCs. Additionally, we found that the electrostatic interaction between the negative charge of the cluster and the positive charge on the TMPyP is the driving force that brings them close to each other for complex formation and subsequently facilitates the transfer process.

  17. The cation-deficient Ruddlesden-Popper oxysulfide Y2Ti2O5S2 as a layered sulfide: topotactic potassium intercalation to form KY2Ti2O5S2.

    Science.gov (United States)

    Rutt, Oliver J; Hill, Timothy L; Gál, Zoltán A; Hayward, Michael A; Clarke, Simon J

    2003-12-01

    Potassium intercalation into the cation-deficient n = 2 Ruddlesden-Popper oxysulfide Y(2)Ti(2)O(5)S(2) to form KY(2)Ti(2)O(5)S(2) has been carried out by reaction of the oxysulfide with potassium vapor in sealed metal tubes at 400 degrees C, potassium naphthalide in THF at 50 degrees C, or potassium in liquid ammonia at temperatures as low as -78 degrees C. Insertion of potassium is topotactic, and although a site 12-coordinate by oxide ions is vacant in the perovskite-type oxide slabs of the structure, potassium is too large to enter this site via the 4-coordinate window, and instead enters the rock-salt-type sulfide layers of the structure which necessitates a 30% increase in the lattice parameter c normal to the layers. In contrast with one of the sodium intercalates of Y(2)Ti(2)O(5)S(2) (beta-NaY(2)Ti(2)O(5)S(2)) in which sodium occupies a tetrahedral site in the sulfide layers, potassium favors an 8-coordinate site which necessitates a relative translation of adjacent oxide slabs. KY(2)Ti(2)O(5)S(2) is tetragonal: P4/mmm, a = 3.71563(4) A, c = 14.8682(2) A (at 298 K), Z = 1. Although the resistivity (3.4(1) x 10(3) Omega cm) is larger than would be expected for a metal, temperature independent paramagnetism dominates the magnetic susceptibility, and the material is electronically very similar to the analogous sodium intercalate beta-NaY(2)Ti(2)O(5)S(2) which features reduced-titanium-containing oxide layers of very similar geometry and electron count.

  18. Charge carrier transport mechanisms in perovskite CdTiO3 fibers

    Directory of Open Access Journals (Sweden)

    Z. Imran

    2014-06-01

    Full Text Available Electrical transport properties of electrospun cadmium titanate (CdTiO3 fibers have been investigated using ac and dc measurements. Air annealing of as spun fibers at 1000 °C yielded the single phase perovskite fibers having diameter ∼600 nm - 800 nm. Both the ac and dc electrical measurements were carried out at temperatures from 200 K – 420 K. The complex impedance plane plots revealed a single semicircular arc which indicates the interfacial effect due to grain boundaries of fibers. The dielectric properties obey the Maxwell-Wagner theory of interfacial polarization. In dc transport study at low voltages, data show Ohmic like behavior followed by space charge limited current (SCLC with traps at higher voltages at all temperatures (200 K – 420 K. Trap density in our fibers system is Nt = 6.27 × 1017 /cm3. Conduction mechanism in the sample is governed by 3-D variable range hopping (VRH from 200 K – 300 K. The localized density of states were found to be N(EF = 5.51 × 1021 eV−1 cm−3 at 2 V. Other VRH parameters such as hopping distance (Rhop and hopping energy (Whop were also calculated. In the high temperature range of 320 K – 420 K, conductivity follows the Arrhenius law. The activation energy found at 2 V is 0.10 eV. Temperature dependent and higher values of dielectric constant make the perovskite CdTiO3 fibers efficient material for capacitive energy storage devices.

  19. Quasi-elastic transfer and charge-exchange reactions in collisions of 48Ti on 42Ca and 26Mg

    International Nuclear Information System (INIS)

    Brendel, C.

    1985-01-01

    At the GSI magnetic spectrometer quasi-elastic transfer and charge-exchange reactions of the system 48 Ti + 42 Ca at incident energies E lab = 240, 300, and 385 MeV and additionally at the higher projectile energy the system 48 Ti + 26 Mg were studied each in the excitation energy range up to E x ≅ 80 MeV. The transition strength was for each particle-hole configuration of the final system calculated by means of the DWBA and subsequently folded with a Breit-Wigner distribution. The localization of the strength of the cross section and the specific structure of the energy spectra were at incident energies between 6 and 8 MeV/amu for all angles well reproduced. By an extension of the core-excitation model to many-stage reactions the charge-exchange reaction 48 Ti + 42 Ca → 48 Sc + 42 Sc could be described as sequential two-stage process. In the two-neutron stripping reaction 48 Ti + 42 Ca → 46 Ti + 44 Ca a surprisingly narrow line with a width of the experimental resolution and an excitation energy of E x = 17.8 MeV was measured at angles smaller than the grazing angle. In the 48 Ti + 26 Mg system the corresponding 46 Ti spectra show also under forward angles structures at excitation energies between 8 and 16 MeV. These lines can be explained as two-neutron states with high spin. (orig./HSI) [de

  20. Ab initio computation of the transition temperature of the charge density wave transition in TiS e2

    Science.gov (United States)

    Duong, Dinh Loc; Burghard, Marko; Schön, J. Christian

    2015-12-01

    We present a density functional perturbation theory approach to estimate the transition temperature of the charge density wave transition of TiS e2 . The softening of the phonon mode at the L point where in TiS e2 a giant Kohn anomaly occurs, and the energy difference between the normal and distorted phase are analyzed. Both features are studied as functions of the electronic temperature, which corresponds to the Fermi-Dirac distribution smearing value in the calculation. The transition temperature is found to be 500 and 600 K by phonon and energy analysis, respectively, in reasonable agreement with the experimental value of 200 K.

  1. Plasmon-Sensitized Graphene/TiO2 Inverse Opal Nanostructures with Enhanced Charge Collection Efficiency for Water Splitting.

    Science.gov (United States)

    Boppella, Ramireddy; Kochuveedu, Saji Thomas; Kim, Heejun; Jeong, Myung Jin; Marques Mota, Filipe; Park, Jong Hyeok; Kim, Dong Ha

    2017-03-01

    In this contribution we have developed TiO 2 inverse opal based photoelectrodes for photoelectrochemical (PEC) water splitting devices, in which Au nanoparticles (NPs) and reduced graphene oxide (rGO) have been strategically incorporated (TiO 2 @rGO@Au). The periodic hybrid nanostructure showed a photocurrent density of 1.29 mA cm -2 at 1.23 V vs RHE, uncovering a 2-fold enhancement compared to a pristine TiO 2 reference. The Au NPs were confirmed to extensively broaden the absorption spectrum of TiO 2 into the visible range and to reduce the onset potential of these photoelectrodes. Most importantly, TiO 2 @rGO@Au hybrid exhibited a 14-fold enhanced PEC efficiency under visible light and a 2.5-fold enrichment in the applied bias photon-to-current efficiency at much lower bias potential compared with pristine TiO 2 . Incident photon-to-electron conversion efficiency measurements highlighted a synergetic effect between Au plasmon sensitization and rGO-mediated facile charge separation/transportation, which is believed to significantly enhance the PEC activity of these nanostructures under simulated and visible light irradiation. Under the selected operating conditions the incorporation of Au NPs and rGO into TiO 2 resulted in a remarkable boost in the H 2 evolution rate (17.8 μmol/cm 2 ) compared to a pristine TiO 2 photoelectrode reference (7.6 μmol/cm 2 ). In line with these results and by showing excellent stability as a photoelectrode, these materials are herin underlined to be of promising interest in the PEC water splitting reaction.

  2. Understanding and removing surface states limiting charge transport in TiO2 nanowire arrays for enhanced optoelectronic device performance.

    Science.gov (United States)

    Sheng, Xia; Chen, Liping; Xu, Tao; Zhu, Kai; Feng, Xinjian

    2016-03-01

    Charge transport within electrode materials plays a key role in determining the optoelectronic device performance. Aligned single-crystal TiO 2 nanowire arrays offer an ideal electron transport path and are expected to have higher electron mobility. Unfortunately, their transport is found not to be superior to that in nanoparticle films. Here we show that the low electron transport in rutile TiO 2 nanowires is mainly caused by surface traps in relatively deep energy levels, which cannot be removed by conventional approaches, such as oxygen annealing treatment. Moreover, we demonstrate an effective wet-chemistry approach to minimize these trap states, leading to over 20-fold enhancement in electron diffusion coefficient and 62% improvement in solar cell performance. On the basis of our results, the potential of TiO 2 NWs can be developed and well-utilized, which is significantly important for their practical applications.

  3. Mechanism of biphasic charge recombination and accumulation in TiO2 mesoporous structured perovskite solar cells.

    Science.gov (United States)

    Wang, Hao-Yi; Wang, Yi; Yu, Man; Han, Jun; Guo, Zhi-Xin; Ai, Xi-Cheng; Zhang, Jian-Ping; Qin, Yujun

    2016-04-28

    Organic-inorganic halide perovskite solar cells are becoming the next big thing in the photovoltaic field owing to their rapidly developing photoelectric conversion performance. Herein, mesoporous structured perovskite devices with various perovskite grain sizes are fabricated by a sequential dropping method, and the charge recombination dynamics is investigated by transient optical-electric measurements. All devices exhibit an overall power conversion efficiency around 15%. More importantly, a biphasic trap-limited charge recombination process is proposed and interpreted by taking into account the specific charge accumulation mechanism in perovskite solar cells. At low Fermi levels, photo-generated electrons predominately populate in the perovskite phase, while at high Fermi levels, most electrons occupy traps in mesoporous TiO2. As a result, the dynamics of charge recombination is, respectively, dominated by the perovskite phase and mesoporous TiO2 in these two cases. The present work would give a new perspective on the charge recombination process in meso-structured perovskite solar cells.

  4. Concentration Dependence of Luminescent Properties for Sr2TiO4:Eu3+ Red Phosphor and Its Charge Compensation

    Directory of Open Access Journals (Sweden)

    Zhou Lu

    2012-01-01

    Full Text Available Sr2TiO4:Eu3+ phosphors using M+ (M = Li+, Na+, and K+ as charge compensators were prepared by the solid-state reaction. The powders were investigated by powder X-ray diffraction (XRD and photoluminescence spectra (PL to study the phase composition, structure, and luminescent properties. The results showed that Li+ ion was the best charge compensator. The phase was Sr2TiO4 when the doping concentration was small (x≤10.0%. When x reached 15.0%, the phase turned into Sr3Ti3O7 because of the structure damage. The phosphor could be effectively excited by ultraviolet (365, 395 nm and blue light (465 nm, and thenitemitted intense red light that peaked at around 620 nm (5D0→7F2. In addition, the emission of 700 nm (5D0→7F4 enhanced the red light color purity. The CIE chromaticity coordinates of samples with the higher red emission were between (0.650, 0.344 and (0.635, 0.352. Doped layered titanate Sr2TiO4:Eu3+ is a promising candidate red phosphor for white LEDs which can be suited for both near-UV LED chip and blue LED chip.

  5. A systematic Monte Carlo simulation study of the primitive model planar electrical double layer over an extended range of concentrations, electrode charges, cation diameters and valences

    Science.gov (United States)

    Valiskó, Mónika; Kristóf, Tamás; Gillespie, Dirk; Boda, Dezső

    2018-02-01

    The purpose of this study is to provide data for the primitive model of the planar electrical double layer, where ions are modeled as charged hard spheres, the solvent as an implicit dielectric background (with dielectric constant ɛ = 78.5), and the electrode as a smooth, uniformly charged, hard wall. We use canonical and grand canonical Monte Carlo simulations to compute the concentration profiles, from which the electric field and electrostatic potential profiles are obtained by solving Poisson's equation. We report data for an extended range of parameters including 1:1, 2:1, and 3:1 electrolytes at concentrations c = 0.0001 - 1 M near electrodes carrying surface charges up to σ = ±0.5 Cm-2. The anions are monovalent with a fixed diameter d- = 3 Å, while the charge and diameter of cations are varied in the range z+ = 1, 2, 3 and d+ = 1.5, 3, 6, and 9 Å (the temperature is 298.15 K). We provide all the raw data in the supplementary material (ftp://ftp.aip.org/epaps/aip_advances/E-AAIDBI-8-084802">supplementary material).

  6. A systematic Monte Carlo simulation study of the primitive model planar electrical double layer over an extended range of concentrations, electrode charges, cation diameters and valences

    Directory of Open Access Journals (Sweden)

    Mónika Valiskó

    2018-02-01

    Full Text Available The purpose of this study is to provide data for the primitive model of the planar electrical double layer, where ions are modeled as charged hard spheres, the solvent as an implicit dielectric background (with dielectric constant ϵ = 78.5, and the electrode as a smooth, uniformly charged, hard wall. We use canonical and grand canonical Monte Carlo simulations to compute the concentration profiles, from which the electric field and electrostatic potential profiles are obtained by solving Poisson’s equation. We report data for an extended range of parameters including 1:1, 2:1, and 3:1 electrolytes at concentrations c = 0.0001 − 1 M near electrodes carrying surface charges up to σ = ±0.5 Cm−2. The anions are monovalent with a fixed diameter d− = 3 Å, while the charge and diameter of cations are varied in the range z+ = 1, 2, 3 and d+ = 1.5, 3, 6, and 9 Å (the temperature is 298.15 K. We provide all the raw data in the supplementary material.

  7. Study of the Bulk Charge Carrier Dynamics in Anatase and Rutile TiO2 Single Crystals by Femtosecond Time Resolved Spectroscopy

    KAUST Repository

    Maity, Partha; Mohammed, Omar F.; Katsiev, Khabiboulakh; Idriss, Hicham

    2018-01-01

    as the best model for fundamental studies. Their ultrafast charge carrier dynamics especially on TiO2 anatase single crystal (the most active phase) are unresolved. Here femtosecond time resolved spectroscopy (TRS) was carried out to explore the dynamics

  8. Soft X-ray absorption spectra of aqueous salt solutions with highly charged cations in liquid microjets

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, Craig P.; Uejio, Janel S.; Duffin, Andrew M.; Drisdell, Walter S.; Smith, Jared D.; Saykally, Richard J.

    2010-03-11

    X-ray absorption spectra of 1M aqueous solutions of indium (III) chloride, yttrium (III) bromide, lanthanum (III) chloride, tin (IV) chloride and chromium (III) chloride have been measured at the oxygen K-edge. Relatively minor changes are observed in the spectra compared to that of pure water. SnCl{sub 4} and CrCl{sub 3} exhibit a new onset feature which is attributed to formation of hydroxide or other complex molecules in the solution. At higher energy, only relatively minor, but salt-specific changes in the spectra occur. The small magnitude of the observed spectral changes is ascribed to offsetting perturbations by the cations and anions.

  9. Local-site cation ordering of Eu{sup 3+} ion in doped PbTiO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Mendez-González, Y. [Departamento de Física Aplicada, Instituto de Cibernética, Matemática y Física, ICIMAF, 15 No. 551, Vedado, La Habana 10400 (Cuba); Pentón-Madrigal, A., E-mail: arbelio@fisica.uh.cu [Facultad de Física-Instituto de Ciencia y Tecnología de Materiales, Universidad de La Habana, San Lázaro y L, Vedado, La Habana 10400 (Cuba); Peláiz-Barranco, A. [Facultad de Física-Instituto de Ciencia y Tecnología de Materiales, Universidad de La Habana, San Lázaro y L, Vedado, La Habana 10400 (Cuba); Figueroa, Santiago J.A. [Brazilian Synchrotron Light Laboratory (LNLS)/Brazilian Center of Energy and Materials (CNPEM), CP 6192, 13083-970, Campinas, SP (Brazil); Oliveira, L.A.S. de [Polo Xerém, Universidade Federal do Rio de Janeiro, Estrada de Xerém, 27 Xerém, Duque de Caxias, RJ (Brazil); Concepción-Rosabal, B. [Facultad de Física-Instituto de Ciencia y Tecnología de Materiales, Universidad de La Habana, San Lázaro y L, Vedado, La Habana 10400 (Cuba)

    2014-02-01

    X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS), and scanning electron microscopy experiments were carried out in the (Pb{sub 0.88}Eu{sub 0.08})TiO{sub 3} ferroelectric compound with a perovskite type structure. Qualitative EXAFS analysis has shown that Eu{sup 3+} ions substitute to Pb{sup 2+} and Ti{sup 4+} ions at A and B sites of the ABO{sub 3} structure, respectively. The XRD pattern refinement was consistent with the Eu{sup 3+} substitution at both A and B sites, which provides the formation of donor and acceptor-type defects. The shape of the observed X-ray lines profiles has shown features, which are known for this kind of ferroelectric material to be typical of the ferroelectric domains microstructure. A phenomenological model has been used for fitting the diffraction profiles by the Rietveld method.

  10. Synthesis and characterization of sodium cation-conducting Nax(MyL1-yO2 (M = Ni2+, Fe3+; L = Ti4+, Sb5+

    Directory of Open Access Journals (Sweden)

    Marques, F. M. B.

    2004-06-01

    Full Text Available The Na+-conducting ceramics of layered Na0.8Ni0.4Ti0.6O2, Na0.8Fe0.8Ti0.2O2, Na0.8Ni0.6Sb0.4O2 (structural type O3 and Na0.68Ni0.34Ti0.66O2 (P2 type with density higher than 91% were prepared via the standard solid-state synthesis route and characterized by the impedance spectroscopy, thermal analysis, scanning electron microscopy, structure refinement using X-ray powder diffraction data, measurements of Na+ concentration cell e.m.f., and dilatometry. The conductivity of antimonate Na0.8Ni0.6Sb0.4O2, synthesized first time, was found lower than that of isostructural Na0.8Ni0.4Ti0.6O2 due to larger ion jump distance between Na+ sites. At temperatures above 420 K, transport properties of sodium cationconducting materials are essentially independent of partial water vapor pressure. In the low-temperature range, the conductivity reversibly increases with water vapor pressure varied in the range from approximately 0 (dry air up to 0.46 atm. The sensitivity to air humidity is influenced by the ceramic microstructure, being favored by increasing boundary area. The average thermal expansion coefficients of layered materials at 300-1173 K are in the range (13.7-16.0×10-6 K-1.Se han preparado cerámicas conductoras conteniendo Na+ de composición Na0.8Ni0.4Ti0.6O2, Na0.8Fe0.8Ti0.2O2, Na0.8Ni0.6Sb0.4O2 (tipo estructural O3 y Na0.68Ni0.34Ti0.66O2 (tipo P2 con densidad mayor del 91%. Las vía de preparación fu la ruta de estandard de síntesis en estado sólido. Las composiciones se caracterizaron mediante espectroscopía de impedancia, análisis térmico, microscopía electrónica de barrido, refinamiento de la estructura usando datos de difracción de rayos X en polvo, medidas de concentración de Na+, f.e.m. de la célula y dilatometría. La conductividad del antimoniate, sintetizado por primera vez, Na0.8Ni0.6Sb0.4O2, era menor que la del compuesto isoestructural Na0.8Ni0.4Ti0.6O2 debido a la mayor distancia de salto iónico entre las posiciones de Na

  11. Degradation of TiO2 and/or SiO2 hybrid films doped with different cationic dyes

    International Nuclear Information System (INIS)

    Purcar, Violeta; Caprarescu, Simona; Donescu, Dan; Petcu, Cristian; Stamatin, Ioan; Ianchis, Raluca; Stroescu, Hermine

    2013-01-01

    Hybrid thin films, silica–titanium oxides and silica–aluminum oxides, designed based on the sol–gel process are evaluated as catalysts in the photo-degradation of the cationic dyes. Silica matrices from different precursors with various organic functional groups and cross-linked with titanium or aluminum agents (tetraisopropyl orthotitanate and aluminum sec-butoxide) allow the surface property tailoring related to the high capacity of the dye adsorption respective, high photo-degradation activity. The cationic dyes (methylene blue, rhodamine B, crystal violet, malachite green) embedded on the hybrid silica matrix, under ultraviolet light, have a first order kinetics of photodegradation. The cross-linking agents play a key role in the photocatalytic degradation and silica matrix as dye absorbent. The photo-degradation rate for the binary system derived from methyltriethoxysilane/vinyltriethoxysilane precursors with both cross linkers showed a significant improvement by comparison with other hybrid materials. The significant increasing in the photodecomposition rate is related to the capacity to generate additional oxidizing species by each silica hybrid compounds. - Highlights: ► Dyes display different electrostatic interactions to the silica matrix. ► Cross-linking agent influences the photocatalytic degradation of dyes. ► Photodegradation reaction obeyed the rules of a pseudo-first-order kinetic reaction. ► UV radiation can be the origin of the photodegradation

  12. Positively charged TiO2 particles in non-polar system for electrophoretic display

    International Nuclear Information System (INIS)

    Chang, Young Seon

    2005-02-01

    Electrophoretic display uses a technique called electrophoresis to represent images and letters electronically with electronic ink. Although it has good characteristics such as wide viewing angle, high contrast ratio and extremely low power consumption, there are still several issues to be resolved to improve its performances. Higher mobility and stability of the ink particles are the most important issues among them. In this study, TiO 2 particles coated with acrylamide were found to be effective ink particles that satisfy higher mobility and stability. The TiO 2 particles coated with 5∼40% acrylamide were prepared by dispersion polymerization using monomers of methyl methacrylate (MMA) and acrylamide. The TiO 2 particles coated with acrylamide were dispersed in isopar-G with sorbitan esters such as span 20, span 80 and span 85. The size of the TiO 2 particles were changed from 200±150 nm to 350∼500 nm by the coating process. The morphology of coated particles was observed using a transmission electron microscope (TEM) and thermogravimetric analysis (TGA). From the TGA results, the weight fraction of TiO 2 and polymer in coated particle were calculated. From the zeta potential measurement, it was shown that as acrylamide concentration was increased from 5% to 30%, zeta potential of the coated TiO 2 particles was increased from 50mV to about 230mV. The zeta potential of the coated TiO 2 particles with 40% acrylamide was decreased to 50mV. As a stabilizer, span 85 was the most effective surfactant to improve stability of the TiO 2 particles coated with acrylamide among used surfactants in this study. Span 85 showed best stability in the storage test with TiO 2 particles coated with 10% acrylamide. The mobility of TiO 2 particles coated with acrylamide with span 85 in dye solution (Oil Blue-N dissolved in isopar-G) were measured by ITO cell test. The mobility of TiO 2 particles coated with 10∼30% acrylamide was over 600μm 2 /Vs while the mobility of TiO 2

  13. Contributions of conduction band offset to the enhanced separation efficiency of photoinduced charges for SrTiO3/Bi2O3 heterojunction semiconductor

    International Nuclear Information System (INIS)

    Zhang, Zhenlong; Zhu, Jichun; Li, Shengjun; Mao, Yanli

    2014-01-01

    SrTiO 3 /Bi 2 O 3 heterojunction semiconductor was prepared and characterized by X-ray diffraction, UV–vis absorption spectrum, and scanning electron microscope, surface photovoltage spectroscopy, and photoluminescence spectroscopy. The surface photovoltage spectra indicate that the separation efficiency of photoinduced charges for SrTiO 3 /Bi 2 O 3 was enhanced compared with that of SrTiO 3 or Bi 2 O 3 . The energy band diagram of SrTiO 3 /Bi 2 O 3 heterojunction was directly determined with X-ray photoelectron spectroscopy, and the conduction band offset between SrTiO 3 and Bi 2 O 3 was quantified to be 0.28±0.03 eV. The photoluminescence spectra display that the recombination rate of photoinduced carriers for SrTiO 3 /Bi 2 O 3 decreases compared with that of SrTiO 3 or Bi 2 O 3 , which is mainly due to the energy levels matching between them. Therefore the enhanced separation efficiency of photoinduced charges is resulting from the energy difference between the conduction band edges of SrTiO 3 and Bi 2 O 3 . -- Graphical abstract: Enhanced separation efficiency for SrTiO 3 /Bi 2 O 3 is resulting from the energy difference between the conduction band edges. Highlights: ●Heterojunction semiconductor of SrTiO 3 /Bi 2 O 3 was prepared. ●SrTiO 3 /Bi 2 O 3 presents enhanced separation efficiency. ●Conduction band offset between SrTiO 3 and Bi 2 O 3 is quantified. ●Recombination rate of SrTiO 3 /Bi 2 O 3 decreases compared with single phases

  14. Investigation of exciton photodissociation, charge transport and photovoltaic response of poly(N-vinyl carbazole):TiO2 nanocomposites for solar cell applications

    International Nuclear Information System (INIS)

    Dridi, C; Chaabane, H; Barlier, V; Davenas, J; Ouada, H Ben

    2008-01-01

    The photogeneration of charge carriers in spin-coated thin films of nanocrystalline (nc-)TiO 2 particles dispersed in a semiconducting polymer, poly(N-vinylcarbazole) (PVK), has been studied by photoluminescence and charge transport measurements. The solvent and the TiO 2 particle concentration have been selected to optimize the composite morphology. A large number of small domains leading to a large interface and an improved exciton dissociation could be obtained with tetrahydrofuran (THF). The charge transport mechanism and trap distribution at low and high voltage in ITO/nc-TiO 2 :PVK/Al diodes in the dark could be identified by current-voltage measurements and impedance spectroscopy. The transport mechanism is space charge limited with an exponential trap distribution in the high voltage regime (1-4 V), whereas a Schottky process with a barrier height of about 0.9 eV is observed at low bias voltages ( sc and open circuit voltage V oc for a 30% TiO 2 volume content corresponding to the morphology exhibiting the best dispersion of TiO 2 particles. A degradation of the photovoltaic properties is induced at higher compositions by the formation of larger TiO 2 aggregates. A procedure has been developed to extract the physical parameters from the J-V characteristics in the dark and under illumination on the basis of an equivalent circuit. The variation of the solar cell parameters with the TiO 2 composition confirms that the photovoltaic response is optimum for 30% TiO 2 volume content. It is concluded that the photovoltaic properties of nc-TiO 2 :PVK nanocomposites are controlled by the interfacial area between the donor and the acceptor material and are limited by the dispersion of the TiO 2 nanoparticles in the polymer

  15. High charge carrier density at the NaTaO3/SrTiO3 hetero-interface

    KAUST Repository

    Nazir, Safdar

    2011-08-05

    The formation of a (quasi) two-dimensional electron gas between the band insulators NaTaO3 and SrTiO3 is studied by means of the full-potential linearized augmented plane-wave method of density functional theory. Optimization of the atomic positions points to only small changes in the chemical bonding at the interface. Both the p-type (NaO)−/(TiO2)0 and n-type (TaO2)+/(SrO)0 interfaces are found to be metallic with high charge carrier densities. The effects of O vacancies are discussed. Spin-polarized calculations point to the formation of isolated O 2pmagnetic moments, located in the metallic region of the p-type interface.

  16. Investigating the local structure of B-site cations in (1-x)BaTiO3-xBiScO3 and (1-x)PbTiO3-xBiScO3 using X-ray absorption spectroscopy

    Science.gov (United States)

    Blanchard, Peter E. R.; Grosvenor, Andrew P.

    2018-05-01

    The structural properties of (1-x)BaTiO3-xBiScO3 and (1-x)PbTiO3-xBiScO3 were investigated using powder X-ray diffraction and X-ray absorption spectroscopy. Diffraction measurements confirmed that substituting small amounts of BiScO3 into BaTiO3 initially stabilizes a cubic phase at x = 0.2 before impurity phases begin to form at x = 0.5. BiScO3 substitution also resulted in noticeable changes in the local coordination environment of Ti4+. X-ray absorption near-edge spectroscopy (XANES) analysis showed that replacing Ti4+ with Sc3+ results in an increase in the off-centre displacement of Ti4+ cations. Surprisingly, BiScO3 substitution has no effect on the displacement of the Ti4+ cation in the (1-x)PbTiO3-xBiScO3 solid solution.

  17. Unraveling the charge transfer/electron transport in mesoporous semiconductive TiO2 films by voltabsorptometry.

    Science.gov (United States)

    Renault, Christophe; Nicole, Lionel; Sanchez, Clément; Costentin, Cyrille; Balland, Véronique; Limoges, Benoît

    2015-04-28

    In this work, we demonstrate that chronoabsorptometry and more specifically cyclic voltabsorptometry are particularly well suited techniques for acquiring a comprehensive understanding of the dynamics of electron transfer/charge transport within a transparent mesoporous semiconductive metal oxide film loaded with a redox-active dye. This is illustrated with the quantitative analysis of the spectroelectrochemical responses of two distinct heme-based redox probes adsorbed in highly-ordered mesoporous TiO2 thin films (prepared from evaporation-induced self-assembly, EISA). On the basis of a finite linear diffusion-reaction model as well as the establishment of the analytical expressions governing the limiting cases, it was possible to quantitatively analyse, predict and interpret the unusual voltabsorptometric responses of the adsorbed redox species as a function of the potential applied to the semiconductive film (i.e., as a function of the transition from an insulating to a conductive state or vice versa). In particular, we were able to accurately determine the interfacial charge transfer rates between the adsorbed redox species and the porous semiconductor. Another important and unexpected finding, inferred from the voltabsorptograms, is an interfacial electron transfer process predominantly governed by the extended conduction band states of the EISA TiO2 film and not by the localized traps in the bandgap. This is a significant result that contrasts those previously observed for dye-sensitized solar cells formed of randomly sintered TiO2 nanoparticles, a behaviour that was ascribed to a particularly low density of localized surface states in EISA TiO2. The present methodology also provides a unique and straightforward access to an activation-driving force relationship according to the Marcus theory, thus opening new opportunities not only to investigate the driving-force effects on electron recombination dynamics in dye-sensitized solar cells but also to study the

  18. The titanium tris-anilide cation [Ti(N[(t)Bu]Ar)3](+) stabilized as its perfluoro-tetra-phenylborate salt: structural characterization and synthesis in connection with redox activity of 4,4'-bipyridine dititanium complexes.

    Science.gov (United States)

    Spinney, Heather A; Clough, Christopher R; Cummins, Christopher C

    2015-04-21

    This work explores the reduction of 4,4'-bipyridine using two equivalents of the titanium(iii) complex Ti(N[(t)Bu]Ar)3 resulting in formation of a black, crystalline complex, (4,4'-bipy){Ti(N[(t)Bu]Ar)3}2, for which an X-ray structure determination is reported. The neutral, black, 4,4'-bipyridine-bridged bimetallic was found to be redox active, with mono- and di-anions being accessible electrochemically, and with the mono- and di-cations also being accessible chemically, and isolable, at least when using the weakly coordinating anion [B(C6F5)4](-) as the counter-ion. It proved possible to crystallize the salt [(4,4'-bipy){Ti(N[(t)Bu]Ar)3}2][B(C6F5)4]2 for a single-crystal X-ray structure investigation; in this instance it was revealed that the aromaticity of the 4,4'-bipyridine ligand, that had been disrupted upon reduction, had been regained. A rare cationic d(0) metal tris-amide complex, shown by X-ray crystallography to contain an intriguing pyramidal TiN3 core geometry, namely {Ti(N[(t)Bu]Ar)3}(+), could also be isolated when using [B(C6F5)4] as the essentially non-interacting counter-ion. This highly reactive cation should be considered as a potential intermediate in the plethora of reactions wherein Ti(N[(t)Bu]Ar)3 has been shown to effect the reduction of substrates including halogenated organic molecules, carbonyl compounds, organic nitriles, and metal complexes.

  19. Purification of Anthocyanins with o-Dihydroxy Arrangement by Sorption in Cationic Resins Charged with Fe(III

    Directory of Open Access Journals (Sweden)

    Araceli Castañeda-Ovando

    2014-01-01

    Full Text Available In the present work, a new purification method of anthocyanins with o-dihydroxy arrangement is proposed. This method is based on a ligand-exchange mechanism, using a cationic exchange resin loaded with metallic ions in order to increase the affinity of the resin to the anthocyanin(s with o-dihydroxy arrangement. This method was used to purify the main anthocyanin (cyanidin-3-glucoside; Cy-3-glc from the anthocyanic methanolic extract of blue corn. The best sorption result was using Fe(III in its ion form. The purification procedure begins with the formation of a metal-anthocyanin complex (Cy-3-glc-Fe which was optimal at pH 5, followed by a NaOH 0.1 M elution process in order to eliminate anthocyanins without o-dihydroxy arrangement, sugars, and organic acids. Finally, the pure anthocyanin is obtained by adding HCl 0.1 M which breaks the metal-anthocyanin complex.

  20. Energetic charged particle emission from hydrogen-loaded Pd and Ti cathodes and its enhancement by He-4 implantation

    Energy Technology Data Exchange (ETDEWEB)

    Lipson, A.G.; Miley, G.H. [University of Illinois at Urbana - Champaign, lL (United States); Lipson, A.G.; Lyakhov, B.F. [lnstitute of Physical Chemistry, The Russian Academy of Sciences, Moscow (Russian Federation); Roussetski, A.S. [P. N. Lebedev Physics Institute, The Russian Academy of Sciences Moscow (Russian Federation)

    2006-07-01

    In this paper, we demonstrate reproducible emissions of energetic alphas and protons appearing in an energy range where both cosmic ray interference and possible alpha emissions from contamination (e.g., radon) is assumed to be negligible. We also show that, {sup 4}He doping of Pd and Ti cathodes leads to a significant enhancement of the energetic charged particles emission (ECPE). This measurement of the emissions of energetic (MeV) particles, in a region of low background interference plus their enhancement by {sup 4}He doping provides very strong support for the existence of LENR processes in the crystalline lattice of deuterated metals. (authors)

  1. Energetic Charged Particle Emission from Hydrogen-Loaded pd and ti Cathodes and its Enhancement by He-4 Implantation

    Science.gov (United States)

    Lipson, A. G.; Miley, G. H.; Lipson, A. G.; Lyakhov, B. F.; Roussetski, A. S.

    2006-02-01

    In this paper, we demonstrate reproducible emissions of energetic alphas and protons appearing in an energy range where both cosmic ray interference and possible alpha emissions from contamination (e.g., radon) is assumed to be negligible. We also show that He4 doping of Pd and Ti cathodes leads to a significant enhancement of the energetic charged particles emission (ECPE). This measurement of the emissions of energetic (MeV) particles, in a region of low background interference plus their enhancement by He4 doping provides very strong support for the existence of LENR processes in the crystalline lattice of deuterated metals.

  2. Energetic charged particle emission from hydrogen-loaded Pd and Ti cathodes and its enhancement by He-4 implantation

    International Nuclear Information System (INIS)

    Lipson, A.G.; Miley, G.H.; Lipson, A.G.; Lyakhov, B.F.; Roussetski, A.S.

    2006-01-01

    In this paper, we demonstrate reproducible emissions of energetic alphas and protons appearing in an energy range where both cosmic ray interference and possible alpha emissions from contamination (e.g., radon) is assumed to be negligible. We also show that, 4 He doping of Pd and Ti cathodes leads to a significant enhancement of the energetic charged particles emission (ECPE). This measurement of the emissions of energetic (MeV) particles, in a region of low background interference plus their enhancement by 4 He doping provides very strong support for the existence of LENR processes in the crystalline lattice of deuterated metals. (authors)

  3. Humic acid adsorption onto cationic cellulose nanofibers for bioinspired removal of copper( ii ) and a positively charged dye

    KAUST Repository

    Sehaqui, H.

    2015-01-01

    © The Royal Society of Chemistry. Waste pulp residues are herein exploited for the synthesis of a sorbent for humic acid (HA), which is a major water pollutant. Cellulose pulp was etherified with a quaternary ammonium salt in water thereby introducing positive charges onto the surface of the pulp fibers, and subsequently mechanically disintegrated into high surface area cellulose nanofibers (CNF). CNF with three different charge contents were produced and their adsorption capacity towards HA was investigated with UV-spectrophotometry, quartz crystal microbalance with dissipation, and ζ-potential measurements. Substantial coverage of the CNF surface with HA in a wide pH range led to a reversal of the positive ζ-potentials of CNF suspensions. The HA adsorption capacity and the kinetics of HA uptake were found to be promoted by both acidic pH conditions and the surface charge content of CNF. It is suggested that HA adsorption onto CNF depends on electrostatic interactions between the two components, as well as on the conformation of HA. At pH ∼ 6, up to 310 mg g-1 of HA were adsorbed by the functionalized CNF, a substantially higher capacity than that of previously reported HA sorbents in the literature. It is further shown that CNF-HA complexes could be freeze-dried into "soil-mimicking" porous foams having good capacity to capture Cu(ii) ions and positive dyes from contaminated water. Thus, the most abundant natural polymer, i.e., cellulose could effectively bind the most abundant natural organic matter for environmental remediation purpose.

  4. Interaction of cationic porphyrins with DNA: Importance of the number and position of the charges and minimum structural requirements for intercalation

    International Nuclear Information System (INIS)

    Sari, M.A.; Battioni, J.P.; Dupre, D.; Mansuy, D.; Le Pecq, J.B.

    1990-01-01

    Thirty-three porphyrins or metalloporphyrins corresponding to the general formula [meso-[N-methyl-4(or 3 or 2)-pyridiniumyl] n (aryl) 4-n porphyrin]M (M = H 2 , Cu II , or ClFe III ), with n = 2-4, have been synthesized and characterized by UV-visible and 1 H NMR spectroscopy and mass spectrometry. These porphyrins differ not only in the number (2-4) and position of their cationic charges but also in the steric requirements to reach even temporarily a completely planar geometry. Interaction of these porphyrins or metalloporphyrins with calf thymus DNA has been studied and their apparent affinity binding constants have been determined by use of a competition method with ethidium bromide which was applicable not only for all the free base porphyrins but also for their copper (II) or iron (III) complexes. Whatever their mode of binding may be, their apparent affinity binding constants were relatively high and a linear decrease of log K app with the number of porphyrin charges was observed. Studies of porphyrin-DNA interactions by UV and fluorescence spectroscopy, viscosimetry, and fluorescence energy transfer experiments showed that not only the tetracationic meso-tetrakis[N-methyl-4(or 3)-pyridiniumyl]porphyrins, which both involved four freely rotating meso-aryl groups, but also the corresponding tri- and dicationic porphyrins were able to intercalate into calf thymus DNA. These results show that only half of the porphyrin ring is necessary for intercalation to occur

  5. Rapid analysis of charge variants of monoclonal antibodies using non-linear salt gradient in cation-exchange high performance liquid chromatography.

    Science.gov (United States)

    Joshi, Varsha; Kumar, Vijesh; Rathore, Anurag S

    2015-08-07

    A method is proposed for rapid development of a short, analytical cation exchange high performance liquid chromatography method for analysis of charge heterogeneity in monoclonal antibody products. The parameters investigated and optimized include pH, shape of elution gradient and length of the column. It is found that the most important parameter for development of a shorter method is the choice of the shape of elution gradient. In this paper, we propose a step by step approach to develop a non-linear sigmoidal shape gradient for analysis of charge heterogeneity for two different monoclonal antibody products. The use of this gradient not only decreases the run time of the method to 4min against the conventional method that takes more than 40min but also the resolution is retained. Superiority of the phosphate gradient over sodium chloride gradient for elution of mAbs is also observed. The method has been successfully evaluated for specificity, sensitivity, linearity, limit of detection, and limit of quantification. Application of this method as a potential at-line process analytical technology tool has been suggested. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Positively charged TiO{sub 2} particles in non-polar system for electrophoretic display

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Young Seon

    2005-02-15

    Electrophoretic display uses a technique called electrophoresis to represent images and letters electronically with electronic ink. Although it has good characteristics such as wide viewing angle, high contrast ratio and extremely low power consumption, there are still several issues to be resolved to improve its performances. Higher mobility and stability of the ink particles are the most important issues among them. In this study, TiO{sub 2} particles coated with acrylamide were found to be effective ink particles that satisfy higher mobility and stability. The TiO{sub 2} particles coated with 5∼40% acrylamide were prepared by dispersion polymerization using monomers of methyl methacrylate (MMA) and acrylamide. The TiO{sub 2} particles coated with acrylamide were dispersed in isopar-G with sorbitan esters such as span 20, span 80 and span 85. The size of the TiO{sub 2} particles were changed from 200±150 nm to 350∼500 nm by the coating process. The morphology of coated particles was observed using a transmission electron microscope (TEM) and thermogravimetric analysis (TGA). From the TGA results, the weight fraction of TiO{sub 2} and polymer in coated particle were calculated. From the zeta potential measurement, it was shown that as acrylamide concentration was increased from 5% to 30%, zeta potential of the coated TiO{sub 2} particles was increased from 50mV to about 230mV. The zeta potential of the coated TiO{sub 2} particles with 40% acrylamide was decreased to 50mV. As a stabilizer, span 85 was the most effective surfactant to improve stability of the TiO{sub 2} particles coated with acrylamide among used surfactants in this study. Span 85 showed best stability in the storage test with TiO{sub 2} particles coated with 10% acrylamide. The mobility of TiO{sub 2} particles coated with acrylamide with span 85 in dye solution (Oil Blue-N dissolved in isopar-G) were measured by ITO cell test. The mobility of TiO{sub 2} particles coated with 10∼30

  7. Dynamics of charge at water-to-semiconductor interface: Case study of wet [0 0 1] anatase TiO{sub 2} nanowire

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Shuping [Department of Chemistry, University of South Dakota, Vermillion (United States); College of Chemistry, Fuzhou University, Fuzhou 350116 (China); Department of Chemistry, University of Minnesota, Minneapolis, MN 55455 (United States); Balasanthiran, Choumini [Department of Chemistry, University of South Dakota, Vermillion (United States); Tretiak, Sergei [Center for Integrated Nanotechnologies, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Hoefelmeyer, James D. [Department of Chemistry, University of South Dakota, Vermillion (United States); Kilina, Svetlana V. [Department of Chemistry and Biochemistry, NDSU, Fargo, ND 58108 (United States); Kilin, Dmitri S., E-mail: Dmitri.Kilin@usd.edu [Department of Chemistry, University of South Dakota, Vermillion (United States); Department of Chemistry and Biochemistry, NDSU, Fargo, ND 58108 (United States)

    2016-12-20

    Highlights: • Dynamics of photoexcitations is computed for TiO{sub 2} nanowires in aqueous environment. • Aqueous TiO{sub 2} nanowires gain brighter but short-lived optical transitions. • Relaxation of electrons (holes) is 2 (4) times faster in water than in vacuum. • Calculated and experimental absorption/emission spectra correlate well. - Abstract: The behavior of water molecules on the surfaces of the TiO{sub 2} nanowire grown in [0 0 1] direction has been investigated by combining theoretical calculations and experiments. Calculated UV–visible absorption spectra reproduce the main features of the experimental spectra. Computations predict that a photoexcitation followed by a sequence of relaxation events results in photoluminescence across the gap. TiO{sub 2} nanowires in vacuum and aqueous environment exhibit different dynamics of photo-excited charge carriers. In water, computed relaxation of electrons (holes) is approximately 2 (4) times faster compared with vacuum environment. Faster relaxation of holes vs. electrons and specific spatial localization of holes result to formation of long lived charge transfer excitation with positive charge at the surface of the nanowire. Comparison of relaxation process in TiO{sub 2}/water interfaces focusing on different surfaces and nanostructures has potential in identifying structural characteristics of TiO{sub 2} materials important for efficient photo-electrochemical water splitting.

  8. Enhanced Charge Extraction of Li-Doped TiO2 for Efficient Thermal-Evaporated Sb2S3 Thin Film Solar Cells

    Directory of Open Access Journals (Sweden)

    Chunfeng Lan

    2018-02-01

    Full Text Available We provided a new method to improve the efficiency of Sb2S3 thin film solar cells. The TiO2 electron transport layers were doped by lithium to improve their charge extraction properties for the thermal-evaporated Sb2S3 solar cells. The Mott-Schottky curves suggested a change of energy band and faster charge transport in the Li-doped TiO2 films. Compared with the undoped TiO2, Li-doped mesoporous TiO2 dramatically improved the photo-voltaic performance of the thermal-evaporated Sb2S3 thin film solar cells, with the average power conversion efficiency (PCE increasing from 1.79% to 4.03%, as well as the improved open-voltage (Voc, short-circuit current (Jsc and fill factors. The best device based on Li-doped TiO2 achieved a power conversion efficiency up to 4.42% as well as a Voc of 0.645 V, which are the highest values among the reported thermal-evaporated Sb2S3 solar cells. This study showed that Li-doping on TiO2 can effectively enhance the charge extraction properties of electron transport layers, offering a new strategy to improve the efficiency of Sb2S3-based solar cells.

  9. Enhanced Charge Extraction of Li-Doped TiO2 for Efficient Thermal-Evaporated Sb2S3 Thin Film Solar Cells

    Science.gov (United States)

    Lan, Chunfeng; Luo, Jingting; Lan, Huabin; Fan, Bo; Peng, Huanxin; Zhao, Jun; Sun, Huibin; Zheng, Zhuanghao; Liang, Guangxing; Fan, Ping

    2018-01-01

    We provided a new method to improve the efficiency of Sb2S3 thin film solar cells. The TiO2 electron transport layers were doped by lithium to improve their charge extraction properties for the thermal-evaporated Sb2S3 solar cells. The Mott-Schottky curves suggested a change of energy band and faster charge transport in the Li-doped TiO2 films. Compared with the undoped TiO2, Li-doped mesoporous TiO2 dramatically improved the photo-voltaic performance of the thermal-evaporated Sb2S3 thin film solar cells, with the average power conversion efficiency (PCE) increasing from 1.79% to 4.03%, as well as the improved open-voltage (Voc), short-circuit current (Jsc) and fill factors. The best device based on Li-doped TiO2 achieved a power conversion efficiency up to 4.42% as well as a Voc of 0.645 V, which are the highest values among the reported thermal-evaporated Sb2S3 solar cells. This study showed that Li-doping on TiO2 can effectively enhance the charge extraction properties of electron transport layers, offering a new strategy to improve the efficiency of Sb2S3-based solar cells. PMID:29495612

  10. Enhanced Charge Extraction of Li-Doped TiO₂ for Efficient Thermal-Evaporated Sb₂S₃ Thin Film Solar Cells.

    Science.gov (United States)

    Lan, Chunfeng; Luo, Jingting; Lan, Huabin; Fan, Bo; Peng, Huanxin; Zhao, Jun; Sun, Huibin; Zheng, Zhuanghao; Liang, Guangxing; Fan, Ping

    2018-02-28

    We provided a new method to improve the efficiency of Sb₂S₃ thin film solar cells. The TiO₂ electron transport layers were doped by lithium to improve their charge extraction properties for the thermal-evaporated Sb₂S₃ solar cells. The Mott-Schottky curves suggested a change of energy band and faster charge transport in the Li-doped TiO₂ films. Compared with the undoped TiO₂, Li-doped mesoporous TiO₂ dramatically improved the photo-voltaic performance of the thermal-evaporated Sb₂S₃ thin film solar cells, with the average power conversion efficiency ( PCE ) increasing from 1.79% to 4.03%, as well as the improved open-voltage ( V oc ), short-circuit current ( J sc ) and fill factors. The best device based on Li-doped TiO₂ achieved a power conversion efficiency up to 4.42% as well as a V oc of 0.645 V, which are the highest values among the reported thermal-evaporated Sb₂S₃ solar cells. This study showed that Li-doping on TiO₂ can effectively enhance the charge extraction properties of electron transport layers, offering a new strategy to improve the efficiency of Sb₂S₃-based solar cells.

  11. Charge modulated interfacial conductivity in SrTiO3-based oxide heterostructures

    DEFF Research Database (Denmark)

    Chen, Yunzhong; Stamate, Eugen; Pryds, Nini

    2011-01-01

    When depositing amorphous SrTiO3 (STO) films on crystalline STO substrates by pulsed laser deposition, metallic interfaces are observed, though both materials are band-gap insulators. The interfacial conductivity exhibits strong dependence on oxygen pressure during film growth, which is closely...

  12. Visible-light-driven TiO2/Ag3PO4/GO heterostructure photocatalyst with dual-channel for photo-generated charges separation

    International Nuclear Information System (INIS)

    Lu, Bingqing; Ma, Ni; Wang, Yaping; Qiu, Yiwei; Hu, Haihua; Zhao, Jiahuan; Liang, Dayu; Xu, Sheng; Li, Xiaoyun; Zhu, Zhiyan; Cui, Can

    2015-01-01

    Highlights: • TiO 2 /Ag 3 PO 4 /GO was synthesized with a facile two-step method. • TiO 2 /Ag 3 PO 4 /GO exhibit superior photocatalytic activity and stability. • TiO 2 /Ag 3 PO 4 /GO has dual-channel for photo-generated charges separation. • TiO 2 /Ag 3 PO 4 /GO composite reduces the consumption of Ag. - Abstract: A novel triple-component TiO 2 /Ag 3 PO 4 /graphene oxide (TiO 2 /Ag 3 PO 4 /GO) photocatalyst with dual channels for photo-generated charges separation has been synthesized to improve the photocatalytic activity and stability of Ag 3 PO 4 under visible light. The synthesis involved in-situ growth of Ag 3 PO 4 nanoparticles on GO sheets to form Ag 3 PO 4 /GO, and then deposited TiO 2 nanocrystals on the surface of Ag 3 PO 4 by hydrolysis of Ti(SO 4 ) 2 at low-temperature hydrothermal condition. The TiO 2 /Ag 3 PO 4 /GO exhibited superior photocatalytic activity and stability to bare Ag 3 PO 4 , TiO 2 /Ag 3 PO 4 and Ag 3 PO 4 /GO in degradation of Rhodamine B and phenol solutions under visible light. It is suggested that the photo-generated electrons in the conduction band of Ag 3 PO 4 can be quickly transferred to GO, while the holes in the valence band of Ag 3 PO 4 can be transferred to the valence band of TiO 2 . The dual transfer channels at the interfaces of TiO 2 /Ag 3 PO 4 /GO result in effective charges separation, leading to enhanced photocatalytic activity and stability. Furthermore, the content of noble metal Ag significantly reduces from 77 wt% in bare Ag 3 PO 4 to 55 wt% in the nanocomposite. The concept of establishing dual channels for charges separation in a triple-component heterostructure provides a promising way to develop photocatalysts with high efficiency

  13. New insight for enhancing photocatalytic activity of MWCNT/TiO{sub 2} by decorating palladium nanoparticles as charge-transfer channel

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Feng-Jun, E-mail: zhang-fengjun@hotmail.com [School of Materials and Chemical Engineering, Anhui University of Architecture, Anhui Hefei 230022 (China); Department of Advanced Materials and Science Engineering, Hanseo University, Seosan-si, Chungnam-do 356-706 (Korea, Republic of); Oh, Won-Chun, E-mail: wc_oh@hanseo.ac.kr [Department of Advanced Materials and Science Engineering, Hanseo University, Seosan-si, Chungnam-do 356-706 (Korea, Republic of); Zhang, Kan [Department of Advanced Materials and Science Engineering, Hanseo University, Seosan-si, Chungnam-do 356-706 (Korea, Republic of); Center for Superfunctional Materials, Department of Chemistry, Pohang University of Science and Technology, Hyojadong, Namgu, Pohang 790-784 (Korea, Republic of)

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer A new insight for further improving photoactivity of MWCNT/TiO{sub 2} was reported. Black-Right-Pointing-Pointer The Pd as charge transfer channel trap electrons from MWCNT to TiO{sub 2} surface. Black-Right-Pointing-Pointer The Pd content can also influence photoactivity of MWCNT/TiO{sub 2} photocatalyst. Black-Right-Pointing-Pointer The approach is practically usable for other nanocarbon/semiconductor materials. -- Abstract: A surface bond-grafted multi-walled carbon nanotube (MWCNT)/TiO{sub 2} as supporter, palladium nanoparticles, approximately 3 nm in diameter, are uniformly deposited on the functional MWCNT surface in first, constructing a novel Pd-MWCNT/TiO{sub 2} photocatalyst for photocatalytic solar conversion. The characterization of photocatalysts by a series of joint techniques, including BET surface area, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray (EDX), Raman spectroscopy and ultraviolet/visible (UV/vis) diffuse reflectance spectra, discloses that palladium nanoparticles has a crucial role in enhancement of photocatalytic activity of MWCNT/TiO{sub 2}, that is to act as a charge transfer channel, which helps to trap electrons from MWCNT to TiO{sub 2}.

  14. Redox-Active Star Molecules Incorporating the 4-Benzoylpyridinium Cation - Implications for the Charge Transfer Along Branches vs. Across the Perimeter in Dendrimer

    Science.gov (United States)

    Leventis, Nicholas; Yang, Jinua; Fabrizio,Even F.; Rawashdeh, Abdel-Monem M.; Oh, Woon Su; Sotiriou-Leventis, Chariklia

    2004-01-01

    Dendrimers are self-repeating globular branched star molecules, whose fractal structure continues to fascinate, challenge, and inspire. Functional dendrimers may incorporate redox centers, and potential applications include antennae molecules for light harvesting, sensors, mediators, and artificial biomolecules. We report the synthesis and redox properties of four star systems incorporating the 4-benzoyl-N-alkylpyridinium cation; the redox potential varies along the branches but remains constant at fixed radii. Bulk electrolysis shows that at a semi-infinite time scale all redox centers are electrochemically accessible. However, voltammetric analysis (cyclic voltammetry and differential pulse voltammetry) shows that on1y two of the three redox-active centers in the perimeter are electrochemically accessible during potential sweeps as slow as 20 mV/s and as fast as 10 V/s. On the contrary, both redox centers along branches are accessible electrochemically within the same time frame. These results are explained in terms of slow through-space charge transfer and the globular 3-D folding of the molecules and are discussed in terms of their implications on the design of efficient redox functional dendrimers.

  15. Quantitative determination of charge transfer parameters of photorefractive BaTiO3:Rh from EPR-based defect studies

    International Nuclear Information System (INIS)

    Veber, C; Meyer, M; Schirmer, O F; Kaczmarek, M

    2003-01-01

    Optical absorption bands can be used as fingerprints of defects and their charge states in insulators and semiconductors. On the basis of the photochromicity usually shown by such materials, a method is introduced by which the optical bands are assigned to the defects and their charge states. It is based on simultaneous measurements of the light-induced changes of the optical absorption and of the corresponding EPR signals. Moreover, indirectly optical bands of EPR-silent defects can also be labelled in this way, strongly widening the scope of EPR based defect studies. We apply this method to the infrared-sensitive photorefractive system BaTiO 3 :Rh, where illumination leads to recharging among the valence states Rh 5+ , Rh 4+ and Rh 3+ . The values of all parameters governing the charge transfers responsible are inferred from the magnitude of the absorption bands, the absolute determination of their absorption cross-sections and the kinetics of the absorption changes under illumination. In contrast to previous investigations, these parameters are deduced independently of photorefractive measurements

  16. Study of the de-excitation of the 44Ti nuclei light charged particles

    International Nuclear Information System (INIS)

    Papka, Paul

    2003-01-01

    The deexcitation process of the 44 Ti compound nuclei, produced by fusion-evaporation reactions, has been studied at bombarding energies E lab 44 Ti has been populated through two reactions: 16 O + 28 Si at bombarding energies E lab ( 16 O) = 76, 96 and 112 MeV, and 32 S + 12 C at E lab ( 32 S) = 180 and 225 MeV. The exclusive experimental data, angular and energy distributions, have been analysed with the statistical code CACARIZO. The well identified evaporation channels have been precisely studied to determine the energy distributions of the residual nuclei. The calculations reproduce the sequential emission of α particles in the deexcitation chains, however, the emission of nucleons is partially misunderstood. In both reactions, the energy distribution of the protons indicates a temperature in residual nuclei lower than predicted. The dynamical deformation induced for the highest angular momenta has been quantified with an axis ratio of 2:1. (author) [fr

  17. Structure and cation distribution of (Mn0.5Zn0.5)Fe2O4 thin films on SrTiO3(001)

    Science.gov (United States)

    Welke, M.; Brachwitz, K.; Lorenz, M.; Grundmann, M.; Schindler, K.-M.; Chassé, A.; Denecke, R.

    2017-06-01

    A comprehensive study on growth of ferrimagnetic manganese zinc ferrite (Mn0.5Zn0.5Fe2O4) films on single crystalline strontium titanate(001) (SrTiO3) substrates was carried out. Under the optimized conditions, a thin film with a layer thickness of 200 nm was deposited, and the structural properties were investigated. Contrary to data published in literature, no buffer layer was necessary to achieve epitaxial growth of a poorly lattice-matched layer. This was confirmed for Mn0.5Zn0.5Fe2O4(001) on SrTiO3(001) by x-ray diffraction and the adjoined phi scans, which also revealed a lattice compression of 1.2% of the manganese zinc ferrite film in the out-of-plane direction. Using x-ray photoelectron spectroscopy, the near surface stoichiometry of the film could be shown to agree with the intended one within the uncertainty of the method. X-ray absorption spectroscopy showed an electronic structure close to that published for bulk samples. Additional x-ray magnetic circular dichroism investigations were performed to answer detailed structural questions by a comparison of experimental data with the calculated ones. The calculations took into account ion sites (tetrahedral vs. octahedral coordination) as well as the charge of Fe ions (Fe2+ vs. Fe3+). Contrary to the expectation for a perfect normal spinel that only Fe3+ ions are present in octahedral sites, hints regarding the presence of additional Fe2+ in octahedral sites as well as Fe3+ ions in tetrahedral sites have been obtained. Altogether, the layer could be shown to be mostly in a normal spinel configuration.

  18. Electric charging/discharging characteristics of super capacitor, using de-alloying and anodic oxidized Ti-Ni-Si amorphous alloy ribbons.

    Science.gov (United States)

    Fukuhara, Mikio; Sugawara, Kazuyuki

    2014-01-01

    Charging/discharging behaviors of de-alloyed and anodic oxidized Ti-Ni-Si amorphous alloy ribbons were measured as a function of current between 10 pA and 100 mA, using galvanostatic charge/discharging method. In sharp contrast to conventional electric double layer capacitor (EDLC), discharging behaviors for voltage under constant currents of 1, 10 and 100 mA after 1.8 ks charging at 100 mA show parabolic decrease, demonstrating direct electric storage without solvents. The supercapacitors, devices that store electric charge on their amorphous TiO2-x surfaces that contain many 70-nm sized cavities, show the Ragone plot which locates at lower energy density region near the 2nd cells, and RC constant of 800 s (at 1 mHz), which is 157,000 times larger than that (5 ms) in EDLC.

  19. Charge transfer from TiO2 into adsorbed benzene diazonium compounds

    Science.gov (United States)

    Merson, A.; Dittrich, Th.; Zidon, Y.; Rappich, J.; Shapira, Yoram

    2004-08-01

    Electron transfer from sol-gel-prepared TiO2 into adsorbed benzene diazonium compounds has been investigated using cyclic voltammetry, x-ray photoelectron spectroscopy, contact potential difference, and surface photovoltage spectroscopy. The results show that the potential of maximum electron transfer depends strongly on the dipole moment of the benzene compound. Two reactive surface sites at which electron transfer occurs have been identified.

  20. Anisotropic Metal Deposition on TiO2 Particles by Electric-Field-Induced Charge Separation.

    Science.gov (United States)

    Tiewcharoen, Supakit; Warakulwit, Chompunuch; Lapeyre, Veronique; Garrigue, Patrick; Fourier, Lucas; Elissalde, Catherine; Buffière, Sonia; Legros, Philippe; Gayot, Marion; Limtrakul, Jumras; Kuhn, Alexander

    2017-09-11

    Deposition of metals on TiO 2 semiconductor particles (M-TiO 2 ) results in hybrid Janus objects combining the properties of both materials. One of the techniques proposed to generate Janus particles is bipolar electrochemistry (BPE). The concept can be applied in a straightforward way for the site-selective modification of conducting particles, but is much less obvious to use for semiconductors. Herein we report the bulk synthesis of anisotropic M-TiO 2 particles based on the synergy of BPE and photochemistry, allowing the intrinsic limitations, when they are used separately, to be overcome. When applying electric fields during irradiation, electrons and holes can be efficiently separated, thus breaking the symmetry of particles by modifying them selectively and in a wireless way on one side with either gold or platinum. Such hybrid materials are an important first step towards high-performance designer catalyst particles, for example for photosplitting of water. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Release of DNA from polyelectrolyte multilayers fabricated using 'charge-shifting' cationic polymers: tunable temporal control and sequential, multi-agent release.

    Science.gov (United States)

    Sun, Bin; Lynn, David M

    2010-11-20

    We report an approach to the design of multilayered polyelectrolyte thin films (or 'polyelectrolyte multilayers', PEMs) that can be used to provide tunable control over the release of plasmid DNA (or multiple different DNA constructs) from film-coated surfaces. Our approach is based upon methods for the layer-by-layer assembly of DNA-containing thin films, and exploits the properties of a new class of cationic 'charge-shifting' polymers (amine functionalized polymers that undergo gradual changes in net charge upon side chain ester hydrolysis) to provide control over the rates at which these films erode and release DNA. We synthesized two 'charge-shifting' polymers (polymers 1 and 2) containing different side chain structures by ring-opening reactions of poly(2-alkenyl azlactone)s with two different tertiary amine functionalized alcohols (3-dimethylamino-1-propanol and 2-dimethylaminoethanol, respectively). Subsequent characterization revealed large changes in the rates of side chain ester hydrolysis for these two polymers; whereas the half-life for the hydrolysis of the esters in polymer 1 was ~200 days, the half-life for polymer 2 was ~6 days. We demonstrate that these large differences in side chain hydrolysis make possible the design of PEMs that erode and promote the surface-mediated release of DNA either rapidly (e.g., over ~3 days for films fabricated using polymer 2) or slowly (e.g., over ~1 month for films fabricated using polymer 1). We demonstrate further that it is possible to design films with release profiles that are intermediate to these two extremes by fabricating films using solutions containing different mixtures of these two polymers. This approach can thus expand the usefulness of these two polymers and achieve a broader range of DNA release profiles without the need to synthesize polymers with new structures or properties. Finally, we demonstrate that polymers 1 and 2 can be used to fabricate multilayered films with hierarchical structures that

  2. Charge separation in branched TiO_2 nanorod array homojunction aroused by quantum effect for enhanced photocatalytic decomposition of gaseous benzene

    International Nuclear Information System (INIS)

    Wang, Xiaoxia; Ni, Qian; Zeng, Dawen; Liao, Guanglan; Xie, Changsheng

    2016-01-01

    Highlights: • Charge separation in homojunction based on the broadened band gap by quantum effect. • Absolute charge separation by the passivation effect of TiO_2 nanorod. • Long-distance electron transfer behavior in photocatalysis. • Roughed surface for enhanced light harvesting by light trapping effect. - Abstract: As known, the electron transfer behavior in photocatalysis is short-distance transportation, which leads the photo-induced electrons and holes to be localized. The temporarily separated electrons and holes will recombine with each other in the localized region. In this paper, we successfully achieved electron transfer in a homojunction of branched rutile TiO_2 nanorod @nanoparticle core-shell architecture by quantum confinement effect aroused by the nanoparticle, which is proved by the blue-shifting in UV–vis absorption spectrum of the homojunction. Meanwhile, an absolute charge separation is also achieved by the long-distance electron transfer along the single-crystalline rutile TiO_2 nanorod as uninterrupted high-speed electron transfer channel to FTO substrates. Based on the effective charge separation, the photocatalytic decomposition of gaseous benzene by the homojunction is significantly enhanced, yielding 10 times CO_2 than that of the nanorod array. This homojunction interfacial charge separation, aroused by quantum effect, through long-distance transfer along the single-crystalline nanorod gives us inspiration to achieve efficient charge separation with defect-less interfaces, which might can be utilized for real-time environmental abatement and energy generation simultaneously.

  3. Charge driven metal-insulator transitions in LaMnO3|SrTiO3 (111) superlattices

    KAUST Repository

    Cossu, Fabrizio

    2017-08-01

    Interfaces of perovskite oxides, due to the strong interplay between the lattice, charge and spin degrees of freedom, can host various phase transitions, which is particularly interesting if these transitions can be tuned by external fields. Recently, ferromagnetism was found together with a seemingly insulating state in superlattices of manganites and titanates. We therefore study the (111) oriented $(\\\\text{LaMnO}_3)_{6-x}\\\\vert(\\\\text{SrTiO}_3)_{6+x}~(x = -0.5, 0, 0.5)$ superlattices by means of ab initio calculations, predicting a ferromagnetic ground state due to double exchange in all cases. We shed light on the ferromagnetic coupling in the LaMnO3 region and at the interfaces. The insulating states of specific superlattices can be understood on the basis of Jahn-Teller modes and electron/hole doping.

  4. Charge driven metal-insulator transitions in LaMnO3|SrTiO3 (111) superlattices

    KAUST Repository

    Cossu, Fabrizio; Tahini, Hassan Ali; Singh, Nirpendra; Schwingenschlö gl, Udo

    2017-01-01

    Interfaces of perovskite oxides, due to the strong interplay between the lattice, charge and spin degrees of freedom, can host various phase transitions, which is particularly interesting if these transitions can be tuned by external fields. Recently, ferromagnetism was found together with a seemingly insulating state in superlattices of manganites and titanates. We therefore study the (111) oriented $(\\text{LaMnO}_3)_{6-x}\\vert(\\text{SrTiO}_3)_{6+x}~(x = -0.5, 0, 0.5)$ superlattices by means of ab initio calculations, predicting a ferromagnetic ground state due to double exchange in all cases. We shed light on the ferromagnetic coupling in the LaMnO3 region and at the interfaces. The insulating states of specific superlattices can be understood on the basis of Jahn-Teller modes and electron/hole doping.

  5. Decoupling the Lattice Distortion and Charge Doping Effects on the Phase Transition Behavior of VO2 by Titanium (Ti4+) Doping

    Science.gov (United States)

    Wu, Yanfei; Fan, Lele; Liu, Qinghua; Chen, Shi; Huang, Weifeng; Chen, Feihu; Liao, Guangming; Zou, Chongwen; Wu, Ziyu

    2015-01-01

    The mechanism for regulating the critical temperature (TC) of metal-insulator transition (MIT) in ions-doped VO2 systems is still a matter of debate, in particular, the unclear roles of lattice distortion and charge doping effects. To rule out the charge doping effect on the regulation of TC, we investigated Ti4+-doped VO2 (TixV1-xO2) system. It was observed that the TC of TixV1-xO2 samples first slightly decreased and then increased with increasing Ti concentration. X-ray absorption fine structure (XAFS) spectroscopy was used to explore the electronic states and local lattice structures around both Ti and V atoms in TixV1-xO2 samples. Our results revealed the local structure evolution from the initial anatase to the rutile-like structure around the Ti dopants. Furthermore, the host monoclinic VO2 lattice, specifically, the VO6 octahedra would be subtly distorted by Ti doping. The distortion of VO6 octahedra and the variation of TC showed almost the similar trend, confirming the direct effect of local structural perturbations on the phase transition behavior. By comparing other ion-doping systems, we point out that the charge doping is more effective than the lattice distortion in modulating the MIT behavior of VO2 materials. PMID:25950809

  6. Mechanisms of charge transfer and redistribution in LaAlO3/SrTiO3 revealed by high-energy optical conductivity.

    Science.gov (United States)

    Asmara, T C; Annadi, A; Santoso, I; Gogoi, P K; Kotlov, A; Omer, H M; Motapothula, M; Breese, M B H; Rübhausen, M; Venkatesan, T; Ariando; Rusydi, A

    2014-04-14

    In condensed matter physics the quasi two-dimensional electron gas at the interface of two different insulators, polar LaAlO3 on nonpolar SrTiO3 (LaAlO3/SrTiO3) is a spectacular and surprising observation. This phenomenon is LaAlO3 film thickness dependent and may be explained by the polarization catastrophe model, in which a charge transfer of 0.5e(-) from the LaAlO3 film into the LaAlO3/SrTiO3 interface is expected. Here we show that in conducting samples (≥ 4 unit cells of LaAlO3) there is indeed a ~0.5e(-) transfer from LaAlO3 into the LaAlO3/SrTiO3 interface by studying the optical conductivity in a broad energy range (0.5-35 eV). Surprisingly, in insulating samples (≤ 3 unit cells of LaAlO3) a redistribution of charges within the polar LaAlO3 sublayers (from AlO2 to LaO) as large as ~0.5e(-) is observed, with no charge transfer into the interface. Hence, our results reveal the different mechanisms for the polarization catastrophe compensation in insulating and conducting LaAlO3/SrTiO3 interfaces.

  7. Coexistence of charge density wave and superconductivity in Cu0.10TiSe2

    Science.gov (United States)

    Jat, K. S.; Nagpal, V.; Sagar, A. D.; Neha, P.; Patnaik, S.

    2018-04-01

    We report the synthesis and characterization of Cu intercalated TiSe2 superconductor. The resistivity variation with temperature indicates superconducting transition onset at 3.1K and resistivity drops down to zero at 2.1K. The magnetization measurement provides the diamagnetic transition at 3 K. The upper critical field Hc2, lower critical field Hc1, Ginzburg Landau coherence length (ξ) and penetration depth(λ) are estimated to be 0.93 T, 0.01T, 18.8 nm and 181.5 nm respectively. At 100K, CDW type feature is observed. The coexistence of CDW phase and superconductivity is summarized.

  8. Charge transfer mechanism for the formation of metallic states at the KTaO3/SrTiO3 interface

    KAUST Repository

    Nazir, Safdar

    2011-03-29

    The electronic and optical properties of the KTaO3/SrTiO3 heterointerface are analyzed by the full-potential linearized augmented plane-wave approach of density functional theory. Optimization of the atomic positions points at subordinate changes in the crystal structure and chemical bonding near the interface, which is due to a minimal lattice mismatch. The creation of metallic interface states thus is not affected by structural relaxation but can be explained by charge transfer between transition metal and oxygen atoms. It is to be expected that a charge transfer is likewise important for related interfaces such as LaAlO3/SrTiO3. The KTaO3/SrTiO3 system is ideal for disentangling the complex behavior of metallic interface states, since almost no structural relaxation takes place.

  9. Ti:Pt:Au:Ni thin-film CVD diamond sensor ability for charged particle detection.

    Science.gov (United States)

    Kasiwattanawut, Haruetai; Tchouaso, Modeste Tchakoua; Prelas, Mark A

    2018-05-22

    This work demonstrates the development of diamond sensors with reliable contacts using a new metallization formula, which can operate under high-pressure gas environment. The metallization was created using thin film layers of titanium, platinum, gold and nickel deposited on a single crystal electronic grade CVD diamond chip. The contacts were 2 mm in diameter with thickness of 50/5/20/150 nm of Ti:Pt:Au:Ni. The optimum operating voltage of the sensor was determined from the current-voltage measurements. The sensor was calibrated with 239 Pu and 241 Am alpha radiation sources at 300 V. The energy resolution of the Ti:Pt:Au:Ni diamond sensor was determined to be 7.6% at 5.2 MeV of 239 Pu and 2.2% at 5.48 MeV of 241 Am. The high-pressure gas loading environment under which this sensor was used is discussed. Specifically, experimental observations are described using hydrogen loading of nickel as a means of initiating low energy nuclear reactions. No neutrons, electrons, ions or other ionizing radiations were observed in these experiments. Copyright © 2018 Elsevier Ltd. All rights reserved.

  10. Magnetically controlled space charge capacitance at La{sub 1-x}Sr{sub x}MnO{sub 3}/Sr{sub x}La{sub 1-x}TiO{sub 3} interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, Rainer; Garcia-Barriocanal, Javier; Leon, Carlos; Santamaria, Jacobo [Facultad de Ciencias Fisicas, Dpto. Fisica Aplicada III, Universidad Complutense de Madrid, GFMC (Spain); Unidad Asociada ' ' Laboratorio de Heteroestructuras con Aplicacion en Espintronica' ' , UCM/CSIC, Madrid (Spain); Varela, Maria [Facultad de Ciencias Fisicas, Dpto. Fisica Aplicada III, Universidad Complutense de Madrid, GFMC (Spain); Oak Ridge National Laboratory, Oak Ridge, TN (United States); Instituto Pluridisciplinar, Universidad Complutense de Madrid (Spain); Garcia-Hernandez, Mar [Instituto de Ciencia de Materiales de Madrid - Consejo Superior de Investigaciones Cientificas (ICMM-CSIC), Madrid (Spain)

    2016-08-15

    This work reports on magnetocapacitance (MC) effects in epitaxial heterostructures of nominally 15 unit cells (u.c.) LaMnO{sub 3} (LMO) and 2 u.c. SrTiO{sub 3} (STO) with an alternating layer-repetition rate of 8: (LMO{sub 15}/STO{sub 2}){sub 8}. Epitaxial multilayer growth at high temperatures (900 C) activates a selective inter-diffusion of La{sup 3+} and Sr{sup 2+} cations across the interfaces, which gives rise to Sr p-doping of the LMO and La n-doping of the STO layers. MC effects at the buried La{sub 1-x}Sr{sub x}MnO{sub 3}/Sr{sub x}La{sub 1-x}TiO{sub 3} (LSMO/SLTO) interfaces are probed by frequency, temperature and magnetic field dependent AC impedance spectroscopy. The technique is shown to be appropriate to account for the separate analysis of different resistance and capacitance contributions at the buried interfaces. As a result of the La/Sr inter-diffusion process, Schottky barriers are formed at the LSMO/SLTO interfaces, which give rise to massive MC of up to ∼ -200% in the out-of-plane film direction. The capacitance of the manganite-titanate LSMO/SLTO interfaces may be coupled indirectly to the resistance of the LSMO layers, because the Schottky space-charge layers and their capacitance can be modulated by varying the concentration of highly mobile charge carriers in the LSMO with a magnetic field. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Influence of controlled-charge anodization processes on the morphology of TiO2 nanotubes and their efficiency in dye-sensitized solar cells

    International Nuclear Information System (INIS)

    Vaenas, Naoum; Stergiopoulos, Thomas; Kontos, Athanassios G.; Likodimos, Vlassis; Falaras, Polycarpos

    2013-01-01

    The effect of the electrochemical anodization growth process on the development of self-organized TiO 2 nanotube (NT) films and their efficiency as photoelectrodes in dye sensitized solar cells (DSCs) has been comparatively investigated, by keeping constant the total anodization charge. Slow and rapid potentiostatic anodization processes were accordingly compared to the galvanostatic one, while a two step potentiostatic–galvanostatic technique was applied for the first time for the growth of TiO 2 NT arrays, as a step forward in relation to the existing potentiostatic–potentiostatic (P–P) technique. Scanning electron microscopy and Raman spectroscopy verified the wide diversity in the morphological and structural characteristics of the TiO 2 NTs obtained by the different anodization modes. The novel approach of galvanostatic tube growth on a potentiostatically patterned Ti foil provided the most uniform TiO 2 nanotubular films with clean top surface exempt of nanograss or cracks over extended areas. Evaluation of the TiO 2 NTs performance as photoelectrodes in DSC devices showed distinct differences of their electrical parameters that reflected finely the underlying structure/morphology variations of the different anodic oxidation conditions. Galvanostatic TiO 2 NT films presented the most favorable (open-ordered) structure for DSC photoelectrodes with superior electrical performance, essentially impaired by a relatively low fill factor that requires improvement by appropriate post-treatment. Furthermore, despite the marked differences in morphology, the TiO 2 NT photoelectrodes exhibited comparable overall performance (of the order of 4%), with only exception the P–P samples which presented slightly lower (about 25%) photovoltaic efficiency. These results indicate that the anodization charge is a critical factor that effectively controls the nanotubes behavior when they are used as photoelectrodes in DSCs

  12. Mesoporous anatase TiO_2 microspheres with interconnected nanoparticles delivering enhanced dye-loading and charge transport for efficient dye-sensitized solar cells

    International Nuclear Information System (INIS)

    Chu, Liang; Qin, Zhengfei; Zhang, Qiaoxia; Chen, Wei; Yang, Jian; Yang, Jianping; Li, Xing’ao

    2016-01-01

    Graphical abstract: The photoelectrodes of DSSCs consisted of mesoporous anatase TiO_2 microspheres with interconnected nanoparticles. The interconnected nanoparticles enhance dye-loading capacity and charge transport. - Highlights: • The mesoporous anatase TiO_2 microspheres were synthesized by a template-free, one-step fast solvothermal process. • The mesoporous anatase TiO_2 microspheres with interconnected nanoparticles have the advantages of large surface area and connected-structure for electron transfer. • The mesoporous anatase TiO_2 microspheres were further utilized as efficient photoelectrodes for dye-sensitized solar cells. - Abstract: Mesoporous anatase TiO_2 microspheres with interconnected nanostructures meet both large surface area and connected-structure for electron transfer as ideal nano/micromaterials for application in solar cells, energy storage, catalysis, water splitting and gas sensing. In this work, mesoporous anatase TiO_2 microspheres consisting of interconnected nanoparticles were synthesized by template-free, one-step fast solvothermal process, where urea was used as capping agent to control phase and promote oriented growth. The morphology was assembled by nucleation-growth-assembly-mechanism. The mesoporous anatase TiO_2 microspheres with interconnected nanoparticles were further utilized as efficient photoelectrodes of dye-sensitized solar cells (DSSCs), which were beneficial to capacity of dye loading and charge transfer. The power conversion efficiency (PCE) based on the optimized thickness of TiO_2 photoelectrodes was up to 7.13% under standard AM 1.5 G illumination (100 mW/cm"2).

  13. Screened coulomb hybrid DFT study on electronic structure and optical properties of anionic and cationic Te-doped anatase TiO2

    KAUST Repository

    Harb, Moussab

    2013-06-27

    The origin of the enhanced visible-light optical absorption in Te-doped bulk anatase TiO2 is investigated in the framework of DFT and DFPT within HSE06 in order to ensure accurate electronic structure and optical transition predictions. Various oxidation states of Te species are considered based on their structural location in bulk TiO2. In fact, TiO (2-x)Tex (with isolated Te2- species at Te-Te distance of 8.28 Å), TiO2Tex (with isolated TeO 2- species at Te-Te distance of 8.28 Å), TiO2Te 2x (with two concomitant TeO2- species at Te-Te distance of 4.11 Å), and Ti(1-2x)O2Te2x (with two neighboring Te4+ species at nearest-neighbor Te-Te distance of 3.05 Å) show improved optical absorption responses in the visible range similarly as it is experimentally observed in Te-doped TiO2 powders. The optical absorption edges of TiO(2-x)Tex, TiO 2Tex, and TiO2Te2x are found to be red-shifted by 400 nm compared with undoped TiO2 whereas that of Ti(1-2x)O2Te2x is red-shifted by 150 nm. On the basis of calculated valence and conduction band edge positions of Te-doped TiO2, only TiO(2-x)Tex and Ti (1-2x)O2Te2x show suitable potentials for overall water splitting under visible-light irradiation. The electronic structure analysis revealed narrower band gaps of 1.12 and 1.17 eV with respect to undoped TiO2, respectively, resulting from the appearance of new occupied electronic states in the gap of TiO2. A delocalized nature of the gap states is found to be much more pronounced in TiO (2-x)Tex than that with Ti(1-2x)O 2Te2x due to the important contribution of numerous O 2p orbitals together with Te 5p orbitals. © 2013 American Chemical Society.

  14. Catalytic role of Au-TiO{sub 2} nanocomposite on enhanced degradation of an azo-dye by electrochemically active biofilms: a quantized charging effect

    Energy Technology Data Exchange (ETDEWEB)

    Kalathil, Shafeer; Lee, Jintae; Cho, Moo Hwan, E-mail: mhcho@ynu.ac.kr [Yeungnam University, School of Chemical Engineering (Korea, Republic of)

    2013-01-15

    A green and sustainable approach to azo dye degradation by an electrochemically active biofilm (EAB) with Au-TiO{sub 2} nanocomposite assistance (average size of Au {approx}8 nm) has been developed with high efficiency and mineralization of toxic intermediates. The EAB-Au-TiO{sub 2} system degraded the dye more rapidly than the EAB without the nanocomposite, which indicated the catalytic role of the Au-TiO{sub 2} nanocomposite on the dye degradation. Toxicity measurements showed that the dye wastewater treated by the EAB-Au-TiO{sub 2} system was almost non-toxic while the dye wastewater treated by the EAB without the nanocomposite showed a high toxicity compared to the parent dye. Quantized charging and Fermi level equilibration within the Au-TiO{sub 2} nanocomposite may be attributed to the excellent catalytic activity of the nanocomposite on the dye degradation. A mechanism of the catalytic activity is also proposed. Redox behavior and quantized charging of the nanocomposite were confirmed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), respectively. The proposed protocol can be effectively utilized in wastewater treatment applications.

  15. La modified TiO{sub 2} photoanode and its effect on DSSC performance: A comparative study of doping and surface treatment on deep and surface charge trapping

    Energy Technology Data Exchange (ETDEWEB)

    Ako, Rajour Tanyi [Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, BE1410, Negara Brunei Darussalam (Brunei Darussalam); Ekanayake, Piyasiri, E-mail: piyasiri.ekanayake@ubd.edu.bn [Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, BE1410, Negara Brunei Darussalam (Brunei Darussalam); Centre for Advanced Material and Energy Sciences (CAMES), Universiti Brunei Darussalam, Jalan Tungku Link, BE1410, Negara Brunei Darussalam (Brunei Darussalam); Tan, Ai Ling [Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, BE1410, Negara Brunei Darussalam (Brunei Darussalam); Young, David James [Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, BE1410, Negara Brunei Darussalam (Brunei Darussalam); Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast, Maroochydore DC, Queensland, 4558 (Australia); Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research - A*STAR, #08-03, 2 Fusionopolis Way, Innovis, 138634 (Singapore)

    2016-04-01

    The effect of Lanthanum ions (La{sup 3+}) on charge trapping in dye-sensitized solar cell (DSSC) photoanodes has been investigated with doped and surface-treated TiO{sub 2} nanoparticles. Doped nanoparticles consisting of 0.5 mol.% Mg and La co-doped TiO{sub 2}, 0.5 mol.% Mg doped TiO{sub 2} and pure TiO{sub 2} were synthesized by the sol gel method. Surface-treated nanoparticles of Mg doped TiO{sub 2} and pure TiO{sub 2} were prepared by ball milling in 0.05 M aqueous La{sup 3+} solution. All materials were analyzed by XRD, XPS and UV–Vis DRS. Cell performance, surface free energy state changes and electron injection efficiency of DSSCs based on these nanoparticles were evaluated using current –voltage measurements, EIS and Incident photon to current conversion efficiency. Doped materials had La and Mg ions incorporated into the TiO{sub 2} lattice, while no lattice changes were observed for the surface-treated materials. Less visible light was absorbed by treated oxides compared with doped oxide samples. The overall power conversion efficiencies (PCE) of DSSC photoanodes based on doped materials were twice those of photoanodes fabricated from treated nanoparticles. Doping establishes deep traps that reduce the recombination of electron–hole (e–h) pairs. Conversely, the presence of absorbed oxygen in treated materials enhances e–h recombination with electrolyte at surface trap sites. - Highlights: • DSSC performance is investigated using photoanodes of doped and La{sup 3+} surface treated TiO{sub 2}. • TiO{sub 2} and Mg–TiO{sub 2} treated with La{sup 3+} absorbed less visible light. • A high concentration of absorbed oxygen on surface treated oxides reduced band bending. • Increased surface free energy in the modified DSSC anodes is caused more by Mg{sup 2+} at Ti{sup 4+} than by La{sup 3+} at the surfaces. • Near surface charge traps due to La{sup 3+} treatment promotes e–h recombination.

  16. Charge Transfer Effects in Naturally Occurring van der Waals Heterostructures (PbSe )1.16(TiSe2 )m (m =1 , 2)

    Science.gov (United States)

    Yao, Q.; Shen, D. W.; Wen, C. H. P.; Hua, C. Q.; Zhang, L. Q.; Wang, N. Z.; Niu, X. H.; Chen, Q. Y.; Dudin, P.; Lu, Y. H.; Zheng, Y.; Chen, X. H.; Wan, X. G.; Feng, D. L.

    2018-03-01

    van der Waals heterostructures (VDWHs) exhibit rich properties and thus has potential for applications, and charge transfer between different layers in a heterostructure often dominates its properties and device performance. It is thus critical to reveal and understand the charge transfer effects in VDWHs, for which electronic structure measurements have proven to be effective. Using angle-resolved photoemission spectroscopy, we studied the electronic structures of (PbSe )1.16(TiSe2 )m (m =1 , 2), which are naturally occurring VDWHs, and discovered several striking charge transfer effects. When the thickness of the TiSe2 layers is halved from m =2 to m =1 , the amount of charge transferred increases unexpectedly by more than 250%. This is accompanied by a dramatic drop in the electron-phonon interaction strength far beyond the prediction by first-principles calculations and, consequently, superconductivity only exists in the m =2 compound with strong electron-phonon interaction, albeit with lower carrier density. Furthermore, we found that the amount of charge transferred in both compounds is nearly halved when warmed from below 10 K to room temperature, due to the different thermal expansion coefficients of the constituent layers of these misfit compounds. These unprecedentedly large charge transfer effects might widely exist in VDWHs composed of metal-semiconductor contacts; thus, our results provide important insights for further understanding and applications of VDWHs.

  17. Charge separation in branched TiO{sub 2} nanorod array homojunction aroused by quantum effect for enhanced photocatalytic decomposition of gaseous benzene

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaoxia [State Key Laboratory of Materials and Processing Die & Mould Technology, Nanomaterials and Smart Sensors Research Laboratory, Department of Materials Science and Engineering, Huazhong University of Science and Technology, No. 1037, Luoyu Road, Wuhan 430074 (China); Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Wuhan 430062 (China); Ni, Qian [State Key Laboratory of Materials and Processing Die & Mould Technology, Nanomaterials and Smart Sensors Research Laboratory, Department of Materials Science and Engineering, Huazhong University of Science and Technology, No. 1037, Luoyu Road, Wuhan 430074 (China); Zeng, Dawen, E-mail: dwzeng@mail.hust.edu.cn [State Key Laboratory of Materials and Processing Die & Mould Technology, Nanomaterials and Smart Sensors Research Laboratory, Department of Materials Science and Engineering, Huazhong University of Science and Technology, No. 1037, Luoyu Road, Wuhan 430074 (China); Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Wuhan 430062 (China); Liao, Guanglan [State Key Laboratory of Digital Manufacturing Equipment and Technology, Huazhong University of Science and Technology, No. 1037, Luoyu Road, Wuhan 430074 (China); Xie, Changsheng [State Key Laboratory of Materials and Processing Die & Mould Technology, Nanomaterials and Smart Sensors Research Laboratory, Department of Materials Science and Engineering, Huazhong University of Science and Technology, No. 1037, Luoyu Road, Wuhan 430074 (China)

    2016-12-15

    Highlights: • Charge separation in homojunction based on the broadened band gap by quantum effect. • Absolute charge separation by the passivation effect of TiO{sub 2} nanorod. • Long-distance electron transfer behavior in photocatalysis. • Roughed surface for enhanced light harvesting by light trapping effect. - Abstract: As known, the electron transfer behavior in photocatalysis is short-distance transportation, which leads the photo-induced electrons and holes to be localized. The temporarily separated electrons and holes will recombine with each other in the localized region. In this paper, we successfully achieved electron transfer in a homojunction of branched rutile TiO{sub 2} nanorod @nanoparticle core-shell architecture by quantum confinement effect aroused by the nanoparticle, which is proved by the blue-shifting in UV–vis absorption spectrum of the homojunction. Meanwhile, an absolute charge separation is also achieved by the long-distance electron transfer along the single-crystalline rutile TiO{sub 2} nanorod as uninterrupted high-speed electron transfer channel to FTO substrates. Based on the effective charge separation, the photocatalytic decomposition of gaseous benzene by the homojunction is significantly enhanced, yielding 10 times CO{sub 2} than that of the nanorod array. This homojunction interfacial charge separation, aroused by quantum effect, through long-distance transfer along the single-crystalline nanorod gives us inspiration to achieve efficient charge separation with defect-less interfaces, which might can be utilized for real-time environmental abatement and energy generation simultaneously.

  18. An insight into the mechanism of charge transfer properties of hybrid organic (MEH-PPV): Inorganic (TiO2) nanocomposites

    International Nuclear Information System (INIS)

    Mittal, Tanu; Tiwari, Sangeeta; Mehta, Aarti; Sharma, Shailesh N.

    2016-01-01

    Now a days, inorganic nanoparticles are gaining importance and are potential candidate in different organic electronic device application like (LEDs, PVs) due to their novel properties and confinement in Nano-dimensions. [1, 2] In the present work, we have compared the properties of titanium di oxide (TiO 2 ) nanoparticles (NPs) synthesized by using two different chemical routes aqueous and ethanol respectively. These synthesized TiO 2 nanoparticles have been characterized by X-ray diffraction spectroscopy (XRD) for phase confirmation. It was observed that synthesized nanoparticles are in anatase phase for both preparation routes. Morphological information was collected by scanning electron microscopy (SEM) which confirms that particles are almost spherical in shape and distributed uniformly which is further ensured by transmission electron microscopy (TEM). Dynamic light scattering (DLS) technique was also used for further confirmation of size distribution of as-synthesized nanoparticles. Optical properties were also investigated by photoluminescence and UV-Vis spectroscopy and calculated bandgap was found to be in the range of 3.3-3.5eV for TiO 2 (aq/eth) nanoparticles. The increase in bandgap values with respect to bulk (3.2 eV) confirms that as- synthesized nanoparticles are confined in nanodimensions. As synthesized nanoparticles were interacted with MEHPPV polymer (donor) matrix to make their respective MEHPPV: TiO 2 nanocomposites and to confirm the charge transfer mechanism from polymer to nanoparticles. It can be observed from photoluminescence (PL) quenching experiments that continuous quenching obtained for respective nanocomposites confirms better charge transfer from polymer to inorganic TiO 2 nanoparticles respectively. Because of, better quenching and simultaneously enhanced charge transfer of respective nanocomposites, ensures that these nanocomposites are greatly applicable for photovoltaics (PVs) especially in Hybrid Solar cells (HSCs).

  19. The preparation, surface structure, zeta potential, surface charge density and photocatalytic activity of TiO2 nanostructures of different shapes

    International Nuclear Information System (INIS)

    Grover, Inderpreet Singh; Singh, Satnam; Pal, Bonamali

    2013-01-01

    Titania based nanocatalysts such as sodium titanates of different morphology having superior surface properties are getting wide importance in photocatalysis research. Despite having sodium (Na) contents and its high temperature synthesis (that generally deteriorate the photoreactivity), these Na-titanates often exhibit better photoactivity than P25-TiO 2 catalyst. Hence, this work demonstrated the influence of crystal structure, BET surface area, surface charge, zeta potential (ζ) and metal loading on the photocatalytic activity of as-prepared sodium titanate nanotube (TNT) and titania nanorod (TNR). Straw like hollow orthorhombic-TNT (Na 2 Ti 2 O 5 ·H 2 O) particles (W = 9–12 nm and L = 82–115 nm) and rice like pure anatase-TNR particles (W = 8–13 nm and L = 81–134 nm) are obtained by the hydrothermal treatment of P25-TiO 2 with NaOH, which in fact, altered the net surface charge of TNT and TNR particles. The observed ζ = −2.82 (P25-TiO 2 ), −13.5 (TNT) and −22.5 mV (TNR) are significantly altered by the Ag and Cu deposition. It has been found here that TNT displayed best photocatalytic activity for the imidacloprid insecticide (C 9 H 10 ClN 5 O 2 ) degradation to CO 2 formation under UV irradiation because of its largest surface area 176 m 2 g −1 among the catalysts studied.

  20. The preparation, surface structure, zeta potential, surface charge density and photocatalytic activity of TiO2 nanostructures of different shapes

    Science.gov (United States)

    Grover, Inderpreet Singh; Singh, Satnam; Pal, Bonamali

    2013-09-01

    Titania based nanocatalysts such as sodium titanates of different morphology having superior surface properties are getting wide importance in photocatalysis research. Despite having sodium (Na) contents and its high temperature synthesis (that generally deteriorate the photoreactivity), these Na-titanates often exhibit better photoactivity than P25-TiO2 catalyst. Hence, this work demonstrated the influence of crystal structure, BET surface area, surface charge, zeta potential (ζ) and metal loading on the photocatalytic activity of as-prepared sodium titanate nanotube (TNT) and titania nanorod (TNR). Straw like hollow orthorhombic-TNT (Na2Ti2O5·H2O) particles (W = 9-12 nm and L = 82-115 nm) and rice like pure anatase-TNR particles (W = 8-13 nm and L = 81-134 nm) are obtained by the hydrothermal treatment of P25-TiO2 with NaOH, which in fact, altered the net surface charge of TNT and TNR particles. The observed ζ = -2.82 (P25-TiO2), -13.5 (TNT) and -22.5 mV (TNR) are significantly altered by the Ag and Cu deposition. It has been found here that TNT displayed best photocatalytic activity for the imidacloprid insecticide (C9H10ClN5O2) degradation to CO2 formation under UV irradiation because of its largest surface area 176 m2 g-1 among the catalysts studied.

  1. Li insertion into Li4Ti5O12 spinel prepared by low temperature solid state route: Charge capability vs surface area

    Czech Academy of Sciences Publication Activity Database

    Zukalová, Markéta; Fabián, M.; Klusáčková, Monika; Klementová, Mariana; Pitňa Lásková, Barbora; Danková, Z.; Senna, M.; Kavan, Ladislav

    2018-01-01

    Roč. 265 (2018), s. 480-487 ISSN 0013-4686 R&D Projects: GA ČR GA15-06511S; GA MŠk LM2015087; GA MŠk 8F15003 Institutional support: RVO:61388955 ; RVO:68378271 Keywords : Li4Ti5O12 * Charge capacity * Solid state * Li insertion * Surface area Subject RIV: CG - Electrochemistry OBOR OECD: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) Impact factor: 4.798, year: 2016

  2. Charge transport in TiO.sub.2./sub. films with complex percolation pathways investigated by time-resolved terahertz spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Němec, Hynek; Zajac, Vít; Rychetský, Ivan; Fattakhova-Rohlfing, D.; Mandlmeier, B.; Bein, T.; Mics, Zoltan; Kužel, Petr

    2013-01-01

    Roč. 3, č. 3 (2013), s. 302-313 ISSN 2156-342X R&D Projects: GA ČR GAP204/12/0232; GA ČR GA13-12386S Grant - others:AVČR(CZ) M100101218 Institutional support: RVO:68378271 Keywords : terahertz spectroscopy * charge transport * TiO 2 nanoparticles Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.342, year: 2013

  3. Effect of B-site cation stoichiometry on electrical fatigue of RuO2//Pb(ZrxTi1-x)O3//RuO2 capacitors

    International Nuclear Information System (INIS)

    Al-Shareef, H.N.; Tuttle, B.A.; Warren, W.L.; Headley, T.J.; Dimos, D.; Voigt, J.A.; Nasby, R.D.

    1996-01-01

    There have been numerous reports that Pb(Zr x Ti 1-x )O 3 (PZT) thin-film capacitors with RuO 2 electrodes and compositions near the morphotropic phase boundary exhibit minimal decrease in switched polarization with electric-field cycling. We show that the fatigue performance of RuO 2 //PZT//RuO 2 capacitors strongly depends on PZT film composition. Specifically, we demonstrate that the rate of polarization fatigue increases with increasing Ti content for PZT thin films of tetragonal crystal symmetry deposited on RuO 2 electrodes. As the Ti content of the PZT films increased, the film gain morphology changed from columnar to granular and the volume percent of a fluorite-type second phase decreased. These microstructural trends and the possibility that the electrode material acts as a sink for oxygen vacancies are discussed to explain the fatigue dependence on B-site cation ratio for PZT films with RuO 2 electrodes. copyright 1996 American Institute of Physics

  4. The electronic structure of RbTiOPO4 and the effects of the A-site cation substitution in KTiOPO4-family crystals

    Science.gov (United States)

    Atuchin, V. V.; Kesler, V. G.; Meng, Guangsi; Lin, Z. S.

    2012-10-01

    The electronic structure of RbTiOPO4 has been investigated with x-ray photoemission spectroscopy. Detailed photoemission spectra of the element core levels have been recorded under excitation by nonmonochromatic Al Kα radiation (1486.6 eV). The chemical bonding parameters are compared to those reported for complex titanates and phosphates. The band structures of KTiOPO4, RbTiOPO4, K0.535R0.465TiOPO4 and TlTiOPO4 have been calculated by ab initio methods and compared to available experimental results. It is found that the band structure of KTP-type phosphate crystals is weakly dependent on the nature of the A-site (A=K, Rb, Tl) element.

  5. The electronic structure of RbTiOPO4 and the effects of the A-site cation substitution in KTiOPO4-family crystals

    International Nuclear Information System (INIS)

    Atuchin, V V; Kesler, V G; Meng, Guangsi; Lin, Z S

    2012-01-01

    The electronic structure of RbTiOPO 4 has been investigated with x-ray photoemission spectroscopy. Detailed photoemission spectra of the element core levels have been recorded under excitation by nonmonochromatic Al Kα radiation (1486.6 eV). The chemical bonding parameters are compared to those reported for complex titanates and phosphates. The band structures of KTiOPO 4 , RbTiOPO 4 , K 0.535 R 0.465 TiOPO 4 and TlTiOPO 4 have been calculated by ab initio methods and compared to available experimental results. It is found that the band structure of KTP-type phosphate crystals is weakly dependent on the nature of the A-site (A=K, Rb, Tl) element.

  6. Anionic or Cationic S-Doping in Bulk Anatase TiO 2 : Insights on Optical Absorption from First Principles Calculations

    KAUST Repository

    Harb, Moussab; Sautet, P.; Raybaud, P.

    2013-01-01

    as a function of the chemical potential of oxygen and considering three relevant sulfur chemical doping agents (S 2, H2S, and thiourea). It highlights that cationic configurations (S4+ and S6+) are strongly stabilized in a wide range of oxygen chemical

  7. Dye-sensitized solar cells employing doubly or singly open-ended TiO2 nanotube arrays: structural geometry and charge transport.

    Science.gov (United States)

    Choi, Jongmin; Song, Seulki; Kang, Gyeongho; Park, Taiho

    2014-09-10

    We systematically investigated the charge transport properties of doubly or singly open-ended TiO2 nanotube arrays (DNT and SNT, respectively) for their utility as electrodes in dye-sensitized solar cells (DSCs). The SNT or DNT arrays were transferred in a bottom-up (B-up) or top-up (T-up) configuration onto a fluorine-doped tin oxide (FTO) substrate onto which had been deposited a 2 μm thick TiO2 nanoparticle (NP) interlayer. This process yielded four types of DSCs prepared with SNTs (B-up or T-up) or DNT (B-up or T-up). The photovoltaic performances of these DSCs were analyzed by measuring the dependence of the charge transport on the DSC geometry. High resolution scanning electron microscopy techniques were used to characterize the electrode cross sections, and electrochemical impedance spectroscopy was used to characterize the electrical connection at the interface between the NT array and the TiO2 NP interlayer. We examined the effects of decorating the DNT or SNT arrays with small NPs (sNP@DNT and sNP@SNT, respectively) in an effort to increase the extent of dye loading. The DNT arrays decorated with small NPs performed better than the decorated SNT arrays, most likely because the Ti(OH)4 precursor solution flowed freely into the array through the open ends of the NTs in the DNT case but not in the SNT case. The sNP@DNT-based DSC exhibited a better PCE (10%) compared to the sNP@SNT-based DSCs (6.8%) because the electrolyte solution flow was not restricted, direct electron transport though the NT arrays was possible, the electrical connection at the interface between the NT array and the TiO2 NP interlayer was good, and the array provided efficient light harvesting.

  8. Study of the Bulk Charge Carrier Dynamics in Anatase and Rutile TiO2 Single Crystals by Femtosecond Time Resolved Spectroscopy

    KAUST Repository

    Maity, Partha

    2018-04-02

    Understanding of the fundamentals behind charge carriers of photo-catalytic materials are still illusive hindering progress in our quest for renewable energy. TiO2 anatase and rutile are the most understood phases in photo-catalysis and serve as the best model for fundamental studies. Their ultrafast charge carrier dynamics especially on TiO2 anatase single crystal (the most active phase) are unresolved. Here femtosecond time resolved spectroscopy (TRS) was carried out to explore the dynamics of photo-excited charge carriers’ recombination in anatase single crystal, for the first time using pump fluence effects, and compares it to that of the rutile single crystal. A significant difference in charge carrier recombination rates between both crystals is observed. We found that the time constants for carrier recombination are two orders of magnitude slower for anatase (101) when compared to those of rutile (110). Moreover, bulk defects introduced by reduction of the samples via annealing in ultra-high vacuum resulted in faster recombination rates for both polymorphs. Both states (fresh and reduced) probed by pump fluence dependence measurements revealed that the major recombination channel in fresh and reduced anatase and reduced rutile is the first-order Shockley–Reed mediated. However, for fresh rutile, third-body Auger recombination was observed, attributed to the presence of higher density of intrinsic charge carriers. At all excitation wavelengths and fluence investigated, anatase (101) single crystal show longer charge carrier lifetime when compared to rutile (110) single. This may explain the superiority of the anatase phase for the electron transfer H+ reduction to molecular hydrogen.

  9. Impact of cation stoichiometry on the early stage of growth of SrTiO{sub 3} deposited by pulsed laser deposition

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Chencheng, E-mail: c.xu@fz-juelich.de; Moors, Marco; Dittmann, Regina

    2015-12-30

    Highlights: • Stoichiometry dependence of SrTiO{sub 3} sub-monolayer growth monitored by RHEED/AFM. • Reduced surface diffusion of non-stoichiometric SrTiO{sub 3} was detected. • A modified step density model correlates surface diffusion and RHEED minimum. - Abstract: By performing in situ growth studies during pulsed laser deposition, we observed a strong reduction of the surface diffusion coefficients for slightly non-stoichiometric SrTiO{sub 3}. Both, stoichiometric and non-stoichiometric thin films exhibit 2D layer by layer growth. However, in the non-stoichiometric case the 2D island coalescence is significantly delayed, which goes along with a shift of the reflection high electron energy diffraction (RHEED) minimum. We could explain this shift of the RHEED minimum by developing a model for the step density evolution taking into account finite surface diffusion.

  10. Adjacent effect on positive charge transfer from radical cation of n-dodecane to scavenger studied by supbicosecond pulse radiolysis, statistical and Monte Carlo approach

    International Nuclear Information System (INIS)

    Saeki, A.; Tagawa, S.; Kozawa, T.; Yoshida, Y.

    2003-01-01

    Time-dependent behaviors of radical cation in n-dodecane in the presence of high-concentrated cation scavenger triethylamine were measured by subpicosecond pulse radiolysis system. The significant reduction of the initial yield in the optical density was observed. This reduction were not able to be explained by the first order rate constant. Therefore, we assumed that this phenomena occur due to the adjacent effect of the solute molecules. We approached this effect by the statistical model and configurational-bias Monte Carlo method. In both methods, we supposed a condition that the cation site in the radical cation is delocalized and will be scavenged rapidly within the time resolution if the solute molecules is adjacent to any sites of the solvent. In addition to the adjacent effect, the fact that a large part of the solvent molecules is excluded by the solute molecules especially at high concentration was taken into consideration. First, we formulated this effect by a statistical model. In addition to the above assumption, this model is based on the following assumption; the effects of molecule's shape, conformation and interaction among molecules were ignored and the aggregation of the solute molecules were treated randomly. As a result, the formula indicated good agreement with the experimental data. Second, as another approach, we adopted the configurational-bias Monte Carlo simulation to reproduce the liquid system. The OLPS model was used to describe the intermolecular and intramolecular potentials. The adjacent effect estimated by this method corresponded to the experimental data with a threshold of 0.5 nm. This value are close to a typical reaction radius. The average number of adjacent solvent molecules and the distribution of aggregated solute's number were also collected from the position data

  11. Electro-spray deposition of a mesoporous TiO2 charge collection layer: toward large scale and continuous production of high efficiency perovskite solar cells.

    Science.gov (United States)

    Kim, Min-cheol; Kim, Byeong Jo; Yoon, Jungjin; Lee, Jin-wook; Suh, Dongchul; Park, Nam-gyu; Choi, Mansoo; Jung, Hyun Suk

    2015-12-28

    The spin-coating method, which is widely used for thin film device fabrication, is incapable of large-area deposition or being performed continuously. In perovskite hybrid solar cells using CH(3)NH(3)PbI(3) (MAPbI(3)), large-area deposition is essential for their potential use in mass production. Prior to replacing all the spin-coating process for fabrication of perovskite solar cells, herein, a mesoporous TiO(2) electron-collection layer is fabricated by using the electro-spray deposition (ESD) system. Moreover, impedance spectroscopy and transient photocurrent and photovoltage measurements reveal that the electro-sprayed mesoscopic TiO(2) film facilitates charge collection from the perovskite. The series resistance of the perovskite solar cell is also reduced owing to the highly porous nature of, and the low density of point defects in, the film. An optimized power conversion efficiency of 15.11% is achieved under an illumination of 1 sun; this efficiency is higher than that (13.67%) of the perovskite solar cell with the conventional spin-coated TiO(2) films. Furthermore, the large-area coating capability of the ESD process is verified through the coating of uniform 10 × 10 cm(2) TiO(2) films. This study clearly shows that ESD constitutes therefore a viable alternative for the fabrication of high-throughput, large-area perovskite solar cells.

  12. Titanium embedded cage structure formation in AlnTi+ clusters and their interaction with Ar

    International Nuclear Information System (INIS)

    Torres, M. B.; Vega, A.; Balbás, L. C.; Aguilera-Granja, F.

    2014-01-01

    Recently, Ar physisorption was used as a structural probe for the location of the Ti dopant atom in aluminium cluster cations, Al n Ti + [Lang et al., J. Am. Soc. Mass Spectrom. 22, 1508 (2011)]. As an experiment result, the lack of Ar complexes for n > n c determines the cluster size for which the Ti atom is located inside of an Al cage. To elucidate the decisive factors for the formation of endohedrally Al n Ti + , experimentalists proposed detailed computational studies as indispensable. In this work, we investigated, using the density functional theory, the structural and electronic properties of singly titanium doped cationic clusters, Al n Ti + (n = 16–21) as well as the adsorption of an Ar atom on them. The first endohedral doped cluster, with Ti encapsulated in a fcc-like cage skeleton, appears at n c = 21, which is the critical number consistent with the exohedral-endohedral transition experimentally observed. At this critical size the non-crystalline icosahedral growth pattern, related to the pure aluminium clusters, with the Ti atom in the surface, changes into a endohedral fcc-like pattern. The map of structural isomers, relative energy differences, second energy differences, and structural parameters were determined and analyzed. Moreover, we show the critical size depends on the net charge of the cluster, being different for the cationic clusters (n c = 21) and their neutral counterparts (n c = 20). For the Al n Ti + · Ar complexes, and for n n Ti + clusters keeps unaltered in the Ar-cluster complexes. This fact indicates that Ar adsorption does not influence the cluster structure, providing support to the experimental technique used. For n c = 21, the smallest size of endohedral Ti doped cationic clusters, the Ar binding energy decreases drastically, whereas the Ar-cluster distance increases substantially, point to Ar physisorption, as assumed by the experimentalists. Calculated Ar adsorption energies agree well with available experimental binding

  13. Screened coulomb hybrid DFT study on electronic structure and optical properties of anionic and cationic Te-doped anatase TiO2

    KAUST Repository

    Harb, Moussab

    2013-01-01

    The origin of the enhanced visible-light optical absorption in Te-doped bulk anatase TiO2 is investigated in the framework of DFT and DFPT within HSE06 in order to ensure accurate electronic structure and optical transition predictions. Various

  14. Modelling of cation displacements in SrTiO.sub.3./sub. by means of multi-energy anomalous X-ray diffuse scattering

    Czech Academy of Sciences Publication Activity Database

    Kopecký, Miloš; Fábry, Jan; Kub, Jiří

    2016-01-01

    Roč. 49, Jun (2016), 1016-1020 ISSN 1600-5767 R&D Projects: GA ČR GA15-04121S Institutional support: RVO:68378271 Keywords : X-ray diffuse scattering * atomic displacements * anomalous X-ray scattering * SrTiO 3 Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.495, year: 2016

  15. Insulator-semiconductor interface fixed charges in AlGaN/GaN metal-insulator-semiconductor devices with Al2O3 or AlTiO gate dielectrics

    Science.gov (United States)

    Le, Son Phuong; Nguyen, Duong Dai; Suzuki, Toshi-kazu

    2018-01-01

    We have investigated insulator-semiconductor interface fixed charges in AlGaN/GaN metal-insulator-semiconductor (MIS) devices with Al2O3 or AlTiO (an alloy of Al2O3 and TiO2) gate dielectrics obtained by atomic layer deposition on AlGaN. Analyzing insulator-thickness dependences of threshold voltages for the MIS devices, we evaluated positive interface fixed charges, whose density at the AlTiO/AlGaN interface is significantly lower than that at the Al2O3/AlGaN interface. This and a higher dielectric constant of AlTiO lead to rather shallower threshold voltages for the AlTiO gate dielectric than for Al2O3. The lower interface fixed charge density also leads to the fact that the two-dimensional electron concentration is a decreasing function of the insulator thickness for AlTiO, whereas being an increasing function for Al2O3. Moreover, we discuss the relationship between the interface fixed charges and interface states. From the conductance method, it is shown that the interface state densities are very similar at the Al2O3/AlGaN and AlTiO/AlGaN interfaces. Therefore, we consider that the lower AlTiO/AlGaN interface fixed charge density is not owing to electrons trapped at deep interface states compensating the positive fixed charges and can be attributed to a lower density of oxygen-related interface donors.

  16. Charge transfer and band bending at Au/Pb(Zr0.2Ti0.8)O3 interfaces investigated by photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Apostol, Nicoleta G.; Stoflea, Laura E.; Lungu, George A.; Chirila, Cristina; Trupina, Lucian; Negrea, Raluca F.; Ghica, Corneliu; Pintilie, Lucian; Teodorescu, Cristian M.

    2013-01-01

    The growth of gold layers on Pb(Zr,Ti)O 3 (PZT) deposited on SrTiO 3 is investigated by X-ray photoelectron spectroscopy in the Au thickness range 2–100 Å. Two phases are identified, with compositions close to nominal PZT. The ‘standard’ phase is represented by all binding energies (Pb 4f, Ti 2p, Zr 3d, O 1s) sensibly equal to the nominal values for PZT, whereas the ‘charged’ phase exhibits all core levels are shifted by ∼1 eV toward higher binding energies. By taking into account also scanning probe microscopy images together with recent photoemission results, the ‘charged’ phase belongs to P (+) regions of PZT, whereas the ‘normal’ phase corresponds to regions with no net ferroelectric polarization perpendicular to the surface. Au deposition proceeds in a band bending of Φ PZT − Φ Au ∼ 0.4–0.5 eV for both phases, identified as similar shifts toward higher binding energies of all Pb, Ti, Zr, O core levels with Au deposition. The Au 4f core level exhibits also an unusually low binding energy component 1 eV below the ‘nominal’ Au 4f binding energy position (metal Au). This implies the existence of negatively charged gold, or electron transfer from PZT to Au, although the ‘normal’ PZT phase have a higher work function, as it is derived from the band bending. Most probably this charge transfer occurs toward Au nanoparticles, which have even higher ionization energies. High resolution transmission electron microscopy evidenced the formation of such isolated nanoparticles.

  17. The preparation, surface structure, zeta potential, surface charge density and photocatalytic activity of TiO{sub 2} nanostructures of different shapes

    Energy Technology Data Exchange (ETDEWEB)

    Grover, Inderpreet Singh; Singh, Satnam; Pal, Bonamali, E-mail: bpal@thapar.edu

    2013-09-01

    Titania based nanocatalysts such as sodium titanates of different morphology having superior surface properties are getting wide importance in photocatalysis research. Despite having sodium (Na) contents and its high temperature synthesis (that generally deteriorate the photoreactivity), these Na-titanates often exhibit better photoactivity than P25-TiO{sub 2} catalyst. Hence, this work demonstrated the influence of crystal structure, BET surface area, surface charge, zeta potential (ζ) and metal loading on the photocatalytic activity of as-prepared sodium titanate nanotube (TNT) and titania nanorod (TNR). Straw like hollow orthorhombic-TNT (Na{sub 2}Ti{sub 2}O{sub 5}·H{sub 2}O) particles (W = 9–12 nm and L = 82–115 nm) and rice like pure anatase-TNR particles (W = 8–13 nm and L = 81–134 nm) are obtained by the hydrothermal treatment of P25-TiO{sub 2} with NaOH, which in fact, altered the net surface charge of TNT and TNR particles. The observed ζ = −2.82 (P25-TiO{sub 2}), −13.5 (TNT) and −22.5 mV (TNR) are significantly altered by the Ag and Cu deposition. It has been found here that TNT displayed best photocatalytic activity for the imidacloprid insecticide (C{sub 9}H{sub 10}ClN{sub 5}O{sub 2}) degradation to CO{sub 2} formation under UV irradiation because of its largest surface area 176 m{sup 2} g{sup −1} among the catalysts studied.

  18. Anion and cation diffusion in barium titanate and strontium titanate

    International Nuclear Information System (INIS)

    Kessel, Markus Franz

    2012-01-01

    Perovskite oxides show various interesting properties providing several technical applications. In many cases the defect chemistry is the key to understand and influence the material's properties. In this work the defect chemistry of barium titanate and strontium titanate is analysed by anion and cation diffusion experiments and subsequent time-of-flight secondary ion mass spectrometry (ToF-SIMS). The reoxidation equation for barium titanate used in multi-layer ceramic capacitors (MLCCs) is found out by a combination of different isotope exchange experiments and the analysis of the resulting tracer diffusion profiles. It is shown that the incorporation of oxygen from water vapour is faster by orders of magnitude than from molecular oxygen. Chemical analysis shows the samples contain various dopants leading to a complex defect chemistry. Dysprosium is the most important dopant, acting partially as a donor and partially as an acceptor in this effectively acceptor-doped material. TEM and EELS analysis show the inhomogeneous distribution of Dy in a core-shell microstructure. The oxygen partial pressure and temperature dependence of the oxygen tracer diffusion coefficients is analysed and explained by the complex defect chemistry of Dy-doped barium titanate. Additional fast diffusion profiles are attributed to fast diffusion along grain boundaries. In addition to the barium titanate ceramics from an important technical application, oxygen diffusion in cubic, nominally undoped BaTiO 3 single crystals has been studied by means of 18 O 2 / 16 O 2 isotope exchange annealing and subsequent determination of the isotope profiles in the solid by ToF-SIMS. It is shown that a correct description of the diffusion profiles requires the analysis of the diffusion through the surface space-charge into the material's bulk. Surface exchange coefficients, space-charge potentials and bulk diffusion coefficients are analysed as a function of oxygen partial pressure and temperature. The

  19. Electric field changes on Au nanoparticles on semiconductor supports--the molecular voltmeter and other methods to observe adsorbate-induced charge-transfer effects in Au/TiO2 nanocatalysts.

    Science.gov (United States)

    McEntee, Monica; Stevanovic, Ana; Tang, Wenjie; Neurock, Matthew; Yates, John T

    2015-02-11

    Infrared (IR) studies of Au/TiO2 catalyst particles indicate that charge transfer from van der Waals-bound donor or acceptor molecules on TiO2 to or from Au occurs via transport of charge carriers in the semiconductor TiO2 support. The ΔνCO on Au is shown to be proportional to the polarizability of the TiO2 support fully covered with donor or acceptor molecules, producing a proportional frequency shift in νCO. Charge transfer through TiO2 is associated with the population of electron trap sites in the bandgap of TiO2 and can be independently followed by changes in photoluminescence intensity and by shifts in the broad IR absorbance region for electron trap sites, which is also proportional to the polarizability of donors by IR excitation. Density functional theory calculations show that electron transfer from the donor molecules to TiO2 and to supported Au particles produces a negative charge on the Au, whereas the transfer from the Au particles to the TiO2 support into acceptor molecules results in a positive charge on the Au. These changes along with the magnitudes of the shifts are consistent with the Stark effect. A number of experiments show that the ∼3 nm Au particles act as "molecular voltmeters" in influencing ΔνCO. Insulator particles, such as SiO2, do not display electron-transfer effects to Au particles on their surface. These studies are preliminary to doping studies of semiconductor-oxide particles by metal ions which modify Lewis acid/base oxide properties and possibly strongly modify the electron-transfer and catalytic activity of supported metal catalyst particles.

  20. Interfacial charge recombination via the triplet state? Mimicry of photoprotection in the photosynthetic process with a dye-sensitized TiO 2 solar cell reaction

    Science.gov (United States)

    Weng, Yu-Xiang; Li, Long; Liu, Yin; Wang, Li; Yang, Guo-Zhen; Sheng, Jian-Qun

    2002-04-01

    Evidence for the photoinduced charge recombination to the excited-triplet state has been observed in chemical solar cell reaction consisting of dye-sensitized TiO 2 colloidal ethanol solution, which mimicks the photoprotection function in the photosynthetic units. The dye is all -trans-retinoic acid, a structural analog of β-carotenoid. Two channels of charge recombination, i.e., through triplet and ground states were observed by nano-second flash photolysis. The possibility of applying the function of photoprotection to the synthetic solar cell is discussed, which provides a potential entry of molecular engineering of the dye to improve the long term stability of the synthetic solar cell.

  1. Cyclic voltammetry modeling of proton transport effects on redox charge storage in conductive materials: application to a TiO2 mesoporous film.

    Science.gov (United States)

    Kim, Y S; Balland, V; Limoges, B; Costentin, C

    2017-07-21

    Cyclic voltammetry is a particularly useful tool for characterizing charge accumulation in conductive materials. A simple model is presented to evaluate proton transport effects on charge storage in conductive materials associated with a redox process coupled with proton insertion in the bulk material from an aqueous buffered solution, a situation frequently encountered in metal oxide materials. The interplay between proton transport inside and outside the materials is described using a formulation of the problem through introduction of dimensionless variables that allows defining the minimum number of parameters governing the cyclic voltammetry response with consideration of a simple description of the system geometry. This approach is illustrated by analysis of proton insertion in a mesoporous TiO 2 film.

  2. Oxidation states of Fe and Ti in blue sapphire

    International Nuclear Information System (INIS)

    Wongrawang, P; Wongkokua, W; Monarumit, N; Thammajak, N; Wathanakul, P

    2016-01-01

    X-ray absorption near-edge spectroscopy (XANES) can be used to study the oxidation state of a dilute system such as transition metal defects in solid-state samples. In blue sapphire, Fe and Ti are defects that cause the blue color. Inter-valence charge transfer (IVCT) between Fe 2+ and Ti 4+ has been proposed to describe the optical color’s origin. However, the existence of divalent iron cations has not been thoroughly investigated. Fluorescent XANES is therefore employed to study K-edge absorptions of Fe and Ti cations in various blue sapphire samples including natural, synthetic, diffused and heat-treated sapphires. All the samples showed an Fe absorption edge at 7124 eV, corresponding to the Fe 3+ state; and Ti at 4984 eV, corresponding to Ti 4+ . From these results, we propose Fe 3+ -Ti 4+ mixed acceptor states located at 1.75 eV and 2.14 eV above the valence band of corundum, that correspond to 710 nm and 580 nm bands of UV–vis absorption spectra, to describe the cause of the color of blue sapphire. (paper)

  3. Localized vs. delocalized character of charge carriers in LaAlO3/SrTiO3 heterostructure

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Kejin; Schlappa, Justine; Strocov, Vladimir; Frison, Ruggero; Patthey, Luc; Schmitt, Thorsten [Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Radovic, Milan [Laboratory for Synchrotron and Neutron Spectroscopy, Ecole Polytechnique Federale de Lausanne, CH-1015 Lausanne (Switzerland); Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Mesot, Joel [Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Laboratory for Synchrotron and Neutron Spectroscopy, Ecole Polytechnique Federale de Lausanne, CH-1015 Lausanne (Switzerland)

    2011-07-01

    Oxide heterostructures have been attracting great attention due to extraordinary phenomena occurring at the interface and their potential application for device design. A particularly fascinating system is the two-dimensional conductive interface between the band insulators LaAlO{sub 3} (LAO) and SrTiO{sub 3} (STO), which can be even driven to magnetic and superconducting phases at low temperatures. Resonant inelastic X-ray scattering at Ti L-edges is particularly suitable to address the electronic structure of its interface since the Ti{sup 3+} states clearly display strong dd excitations while Ti{sup 4+} states exhibit only elastic emission in the low energy loss regime. Our studies on LAO/STO superlattices prepared by pulsed laser deposition unambiguously reveal the presence of both localized and delocalized Ti 3d carriers generated during the building of the LAO/STO interfaces. Systematic studies on samples before and after annealing under O{sub 2} atmosphere and high temperature show that the dual character carriers can be either induced by electron transfer due to the polar-discontinuity or by oxygen vacancies defects. Oxygen vacancies and electronic reconstruction are equivalent in balancing the built-up electric potential.

  4. Intramolecular, Exciplex-Mediated, Proton-Coupled, Charge-Transfer Processes in N,N-Dimethyl-3-(1-pyrenyl)propan-1-ammonium Cations: Influence of Anion, Solvent Polarity, and Temperature.

    Science.gov (United States)

    Safko, Trevor M; Faleiros, Marcelo M; Atvars, Teresa D Z; Weiss, Richard G

    2016-06-16

    An intramolecular exciplex-mediated, proton-coupled, charge-transfer (PCCT) process has been investigated for a series of N,N-dimethyl-3-(1-pyrenyl)propan-1-ammonium cations with different anions (PyS) in solvents of low to intermediate polarity over a wide temperature range. Solvent mediates both the equilibrium between conformations of the cation that place the pyrenyl and ammonium groups in proximity (conformation C) or far from each other (conformation O) and the ability of the ammonium group to transfer a proton adiabatically in the PyS excited singlet state. Thus, exciplex emission, concurrent with the PCCT process, was observed only in hydrogen-bond accepting solvents of relatively low polarity (tetrahydrofuran, ethyl acetate, and 1,4-dioxane) and not in dichloromethane. From the exciplex emission and other spectroscopic and thermodynamic data, the acidity of the ammonium group in conformation C of the excited singlet state of PyS (pKa*) has been estimated to be ca. -3.4 in tetrahydrofuran. The ratios between the intensities of emission from the exciplex and the locally excited state (IEx/ILE) appear to be much more dependent on the nature of the anion than are the rates of exciplex formation and decay, although the excited state data do not provide a quantitative measure of the anion effect on the C-O equilibrium. The activation energies associated with exciplex formation in THF are calculated to be 0.08 to 0.15 eV lower than for the neutral amine, N,N-dimethyl-3-(1-pyrenyl)propan-1-amine. Decay of the exciplexes formed from the deprotonation of PyS is hypothesized to occur through charge-recombination processes. To our knowledge, this is the first example in which photoacidity and intramolecular exciplex formation (i.e., a PCCT reaction) are coupled.

  5. Comparison of modification strategies towards enhanced charge carrier separation and photocatalytic degradation activity of metal oxide semiconductors (TiO2, WO3 and ZnO)

    Science.gov (United States)

    Kumar, S. Girish; Rao, K. S. R. Koteswara

    2017-01-01

    Metal oxide semiconductors (TiO2, WO3 and ZnO) finds unparalleled opportunity in wastewater purification under UV/visible light, largely encouraged by their divergent admirable features like stability, non-toxicity, ease of preparation, suitable band edge positions and facile generation of active oxygen species in the aqueous medium. However, the perennial failings of these photocatalysts emanates from the stumbling blocks like rapid charge carrier recombination and meager visible light response. In this review, tailoring the surface-bulk electronic structure through the calibrated and veritable approaches such as impurity doping, deposition with noble metals, sensitizing with other compounds (dyes, polymers, inorganic complexes and simple chelating ligands), hydrogenation process (annealing under hydrogen atmosphere), electronic integration with other semiconductors, modifying with carbon nanostructures, designing with exposed facets and tailoring with hierarchical morphologies to overcome their critical drawbacks are summarized. Taking into account the materials intrinsic properties, the pros and cons together with similarities and striking differences for each strategy in specific to TiO2, WO3 & ZnO are highlighted. These subtlety enunciates the primacy for improving the structure-electronic properties of metal oxides and credence to its fore in the practical applications. Future research must focus on comparing the performances of ZnO, TiO2 and WO3 in parallel to get insight into their photocatalytic behaviors. Such comparisons not only reveal the changed surface-electronic structure upon various modifications, but also shed light on charge carrier dynamics, free radical generation, structural stability and compatibility for photocatalytic reactions. It is envisioned that these cardinal tactics have profound implications and can be replicated to other semiconductor photocatalysts like CeO2, In2O3, Bi2O3, Fe2O3, BiVO4, AgX, BiOX (X = Cl, Br & I), Bi2WO6, Bi2MoO6

  6. Charge retention characteristics of (Bi,La)4Ti3O12 capacitors : comparison with Pb(Zr,Ti)O3 capacitors

    International Nuclear Information System (INIS)

    Yoon, J. G.; Kim, D. J.; So, Y. W.

    2005-01-01

    We investigated the retention characteristics of (Bi,La) 4 Ti 3 O 12 (BLT) capacitors with Pt electrodes and compared them with Pb(Zr,Ti)O 3 (PZT) capacitors in the same- and opposite-state retentions. Polarization relaxations in short-time regime (t < 100 s) were well described by a power-law decay function, but the polarization relaxation of BLT was more significant than that of PZT. We discuss the difference in the relaxation process of polarization in conjunction with film microstructures and magnitudes of polarization for BLT and PZT. In long-time opposite-state retention, BLT capacitors showed much better characteristics than PZT. For both BLT and PZT, the opposite-state retention loss was governed by the development of an internal field during retention. For BLT capacitors, internal field development was much weaker than for PZT after retention, resulting in a good opposite-state retention. Structural and electrical properties are discussed in conjunction with the retention characteristics of the materials.

  7. Parallel charge sheets of electron liquid and gas in La0.5Sr0.5TiO3/SrTiO3 heterostructures

    Science.gov (United States)

    Renshaw Wang, X.; Sun, L.; Huang, Z.; Lü, W. M.; Motapothula, M.; Annadi, A.; Liu, Z. Q.; Zeng, S. W.; Venkatesan, T.; Ariando

    2015-12-01

    We show here a new phenomenon in La0.5Sr0.5TiO3/SrTiO3 (LSTO/STO) heterostructures; that is a coexistence of three-dimensional electron liquid (3DEL) and 2D electron gas (2DEG), separated by an intervening insulating LSTO layer. The two types of carriers were revealed through multi-channel analysis of the evolution of nonlinear Hall effect as a function of film thickness, temperature and back gate voltage. We demonstrate that the 3D electron originates from La doping in LSTO film and the 2D electron at the surface of STO is due to the polar field in the intervening insulating layer. As the film thickness is reduced below a critical thickness of 6 unit cells (uc), an abrupt metal-to-insulator transition (MIT) occurs without an intermediate semiconducting state. The properties of the LSTO layer grown on different substrates suggest that the insulating phase of the intervening layer is a result of interface strain induced by the lattice mismatch between the film and substrate. Further, by fitting the magnetoresistance (MR) curves, the 6 unit cell thick LSTO is shown to exhibit spin-orbital coupling. These observations point to new functionalities, in addition to magnetism and superconductivity in STO-based systems, which could be exploited in a multifunctional context.

  8. High charge carrier density at the NaTaO3/SrTiO3 hetero-interface

    KAUST Repository

    Nazir, Safdar; Schwingenschlö gl, Udo

    2011-01-01

    The formation of a (quasi) two-dimensional electron gas between the band insulators NaTaO3 and SrTiO3 is studied by means of the full-potential linearized augmented plane-wave method of density functional theory. Optimization of the atomic positions

  9. The structural defects and UV-VIS spectral characterization of TiO2 particles doped in the lattice with Cr3+ cations

    International Nuclear Information System (INIS)

    Liu, Z.L.; Cui, Z.L.; Zhang, Z.K.

    2005-01-01

    Titania nanoparticles doped with Cr 3+ (2% relative to molar quantity of titania) were prepared and examined by EDS, HRTEM, XRD, and UV-VIS analysis. HRTEM images showed the detailed atomic arrays and vacancy defects of the doped Titania nanocrystals and revealed that the implanted Cr element existed in titania mainly as Cr 3+ ions which located at the lattice positions of Ti 4+ ions. Compared with pure titania, the UV-VIS spectra of the Cr 3+ doped titania show significantly increased absorbance in visible light region. This indicated that the presence of the Cr 3+ ions affected the lattice structure of titania nanocrystals and plays an reformative role in spectral feature of titania

  10. Adsorption and Photodesorption of CO from Charged Point Defects on TiO 2 (110)

    Energy Technology Data Exchange (ETDEWEB)

    Mu, Rentao; Dahal, Arjun P.; Wang, Zhitao; Dohnalek, Zdenek; Kimmel, Gregory A.; Petrik, Nikolay G.; Lyubinetsky, Igor V.

    2017-09-12

    Adsorption and photodesorption of weakly-bound carbon monoxide, CO, from reduced and hydroxylated rutile TiO2(110) (r- and h- TiO2(110)) at sub-monolayer coverages is studied with atomically-resolved scanning tunneling microscopy (STM) along with ensemble-averaged temperature-programmed desorption (TPD) and angle-resolved photon-stimulated desorption (PSD) at low temperatures ( 50 K). STM data weighted by the concentration of each kind of adsorption sites on r-TiO2(110) give an adsorption probability which is the highest for the bridging oxygen vacancies (VO) and very low for the Ti5c sites closest to VO. Occupancy of the remaining Ti5c sites with CO is significant, but smaller than for VO. The probability distribution for the different adsorption sites corresponds to a very small difference in CO adsorption energies: < 0.02 eV. We also find that UV irradiation stimulates both diffusion and desorption of CO at low temperature. CO photodesorbs primarily from the vacancies with a bi-modal angular distribution. In addition to a major, normal to the surface component, there is a broader cosine component indicating scattering from the surface which likely also leads to photo-stimulated diffusion. Hydroxylation of VO’s does not significantly change the CO PSD yield and angular distribution, indicating that not atomic but rather electronic surface defects are involved in the site-specific PSD process. We suggest that photodesorption can be initiated by recombination of photo-generated holes with excess unpaired electrons localized near the surface point-defect (either VO or bridging hydroxyl), leading to the surface atoms rearrangement and ejection of the weakly-bound CO molecules.

  11. Atomic scale simulations of pyrochlore oxides with a tight-binding variable-charge model: implications for radiation tolerance

    International Nuclear Information System (INIS)

    Sattonnay, G; Tétot, R

    2014-01-01

    Atomistic simulations with new interatomic potentials derived from a tight-binding variable-charge model were performed in order to investigate the lattice properties and the defect formation energies in Gd 2 Ti 2 O 7 and Gd 2 Zr 2 O 7 pyrochlores. The main objective was to determine the role played by the defect stability on the radiation tolerance of these compounds. Calculations show that the titanate has a more covalent character than the zirconate. Moreover, the properties of oxygen Frenkel pairs, cation antisite defects and cation Frenkel pairs were studied. In Gd 2 Ti 2 O 7 the cation antisite defect and the Ti-Frenkel pair are not stable: they evolve towards more stable defect configurations during the atomic relaxation process. This phenomenon is driven by a decrease of the Ti coordination number down to five which leads to a local atomic reorganization and strong structural distortions around the defects. These kinds of atomic rearrangements are not observed around defects in Gd 2 Zr 2 O 7 . Therefore, the defect stability in A 2 B 2 O 7 depends on the ability of B atoms to accommodate high coordination number (higher than six seems impossible for Ti). The accumulation of structural distortions around Ti-defects due to this phenomenon could drive the Gd 2 Ti 2 O 7 amorphization induced by irradiation. (paper)

  12. Synthesis of Cr3+-doped TiO2 nanoparticles: characterization and evaluation of their visible photocatalytic performance and stability.

    Science.gov (United States)

    Mendiola-Alvarez, Sandra Yadira; Guzmán-Mar, Jorge Luis; Turnes-Palomino, Gemma; Maya-Alejandro, Fernando; Caballero-Quintero, Adolfo; Hernández-Ramírez, Aracely; Hinojosa-Reyes, Laura

    2017-09-28

    Cr 3+ -doped TiO 2 nanoparticles (Ti-Cr) were synthesized by microwave-assisted sol-gel method. The Ti-Cr catalyst was characterized by X-ray diffraction, ultraviolet-visible diffuse reflectance spectroscopy, N 2 adsorption-desorption analysis, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy (XPS) and zetametry. The anatase mesoporous Ti-Cr material exhibited a specific surface area of 54.5 m 2 /g. XPS analysis confirmed the proper substitution of Ti 4+ cations by Cr 3+ cations in the TiO 2 matrix. The particle size was of average size of 17 nm for the undoped TiO 2 but only 9.5 nm for Ti-Cr. The Cr atoms promoted the formation of hydroxyl radicals and modified the surface adsorptive properties of TiO 2 due to the increase in surface acidity of the material. The photocatalytic evaluation demonstrated that the Ti-Cr catalyst completely degraded (4-chloro-2-methylphenoxy) acetic acid under visible light irradiation, while undoped TiO 2 and P25 allowed 45.7% and 31.1%, respectively. The rate of degradation remained 52% after three cycles of catalyst reuse. The higher visible light photocatalytic activity of Ti-Cr was attributed to the beneficial effect of Cr 3+ ions on the TiO 2 surface creating defects within the TiO 2 crystal lattice, which can act as charge-trapping sites, reducing the electron-hole recombination process.

  13. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.

    2003-01-01

    and the expulsion of anions; a broad anodic peak centered at ca. - 0.5 V representing the expulsion of cations; and a second broad peak at +0.2 to +0.5 V corresponding to anions being inserted. Although the motion of cations is the most important, as expected, there is a significant anion contribution, thereby...... complicating reproducibility when employing PPy(DBS) polymers as actuators. When the cation is doubly charged, it enters the film less readily, and anions dominate the mobility. Using a large and bulky cation switches the mechanism to apparently total anion motion. The changes in area of the three peaks...

  14. Copper diffusion in In2S3 and charge separation at In2S3/CuSCN and TiO2/In2S3 interfaces

    International Nuclear Information System (INIS)

    Juma, Albert Owino

    2013-01-01

    The concept of inorganic nanostructured solar cells consists of a very thin absorber layer sandwiched between highly structured electron and hole conductors. When a TiO 2 /In 2 S 3 /CuSCN nanocomposite heterostructure is illuminated with light, photo-generated electrons in In 2 S 3 can be injected into the conduction band of TiO 2 and holes into the valence band of CuSCN. Charge transfer at the interfaces is limited by the deposition parameters, band alignment and diffusion of Cu from CuSCN into In 2 S 3 , which was the focus of this work. TiO 2 nanoparticles were screen printed onto SnO 2 :F (FTO)-coated glass substrates to give a layer of nanoporous (np) TiO 2 . In 2 S 3 layers were deposited by thermal evaporation or ion layer gas reaction (ILGAR) methods producing Cl-free (In(acac) 3 precursor) and Cl-containing (InCl 3 precursor) layers. A spray-spin method was developed for deposition of CuSCN onto In 2 S 3 . Diffusion of Cu into In 2 S 3 layers was investigated by Rutherford backscattering spectrometry (RBS) while charge transport mechanisms were studied with surface photovoltage (SPV) technique in the fixed capacitor configuration. The activation energy (Ea) for Cu diffusion in thermally evaporated and Cl-free ILGAR In 2 S 3 layers was 0.30 and 0.24 eV, respectively but increased to between 0.72 and 0.78 eV for Cl-containing In 2 S 3 with residual Cl concentrations of 7.8 - 13.8 at.%. The diffusion prefactor (D 0 ) was six orders of magnitude higher for Cl-containing compared to Cl-free layers. The relationship between E a and D 0 was described by the Meyer-Neldel rule with a Meyer-Neldel energy of 40 meV. The presence of Cl has no significant influence on the structural properties of In 2 S 3 but resulted in a modified diffusion mechanism for Cu diffusion. The photovoltage of In 2 S 3 /CuSCN samples decreased after annealing for longer than 2 min at 200 C. A defect band was formed near the interface where holes accumulated and electrons tunneled through

  15. Stability and charge separation of different CH3NH3SnI3/TiO2 interface: A first-principles study

    Science.gov (United States)

    Yang, Zhenzhen; Wang, Yuanxu; Liu, Yunyan

    2018-05-01

    Interface has an important effect on charge separation of perovskite solar cells. Using first-principles calculations, we studied several different interfaces between CH3NH3SnI3 and TiO2. The interfacial structure and electronic structure of these interfaces are thoroughly explored. We found that the SnI2/anatase (SnI2/A) system is more stable than the other three systems, because an anatase surface can make Snsbnd I bond faster restore to the pristine value than a rutile surface, and SnI2/A system has a smaller standard deviation. The calculated plane-averaged electrostatic potential and the density of states suggest that SnI2/anatase interface has a better separation of photo-generated electron-hole pairs.

  16. Defects or charge transfer: Different possibilities to explain the photoluminescence in crystalline Ba(Zr{sub x}Ti{sub 1−x})O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Agda E., E-mail: agda@fct.unesp.br [Universidade Estadual Paulista, Faculdade de Ciências e Tecnologia, Presidente Prudente, SP (Brazil); Sasaki, Guilherme S.; Camacho, Sabrina A.; Teixeira, Silvio R. [Universidade Estadual Paulista, Faculdade de Ciências e Tecnologia, Presidente Prudente, SP (Brazil); Li, Maximo S. [Universidade de São Paulo, Instituto de Física, São Carlos, SP (Brazil); Longo, Elson [Universidade estadual Paulista, Instituto de Química, Araraquara, SP (Brazil)

    2016-11-15

    In this work, BZT (Ba (Zr{sub x}Ti{sub 1−x})O{sub 3}), composite ceramic powder with x=0, 0.25, 0.50, 0.75 and 1 (mol) was prepared by the microwave-assisted hydrothermal method. The structural, morphological and optical properties of the compounds were determined by XRD, SEM, Raman, UV–vis and photoluminescence analysis. The results showed that the stability of the BZ phase was strongly influenced by the isomorphic Zr/Ti substitution, and that the BZ sample had the greatest structural order for short and long distances compared to the other. The BZT ceramic composite showed optical behavior also influenced by the concentration of Zr, resulting in a growing photoluminescence emission with increasing Zr ion in the network. The BZ sample showed higher photoluminescent intensity in a region including the entire visible spectrum. Although the effect of photoluminescence in these materials is dependent on the presence of defects, which produce excitons for radiative recombination, in the BZ compound, there might have been other effects causing the intense photoluminescence. In this case, high emission is associated with the a charge transfer between neighboring clusters [ZrO{sub 6}] in a nanoparticle surface interface, which in turn are joined to form BZ mesocrystals on a micrometer scale. The photoluminescence observed in the BZT compound had a predominantly white color, a feature that gives it high potential for applications in white light-emitting devices.

  17. Comparison of Nonlinear Filtering Methods for Estimating the State of Charge of Li4Ti5O12 Lithium-Ion Battery

    Directory of Open Access Journals (Sweden)

    Jianping Gao

    2015-01-01

    Full Text Available Accurate state of charge (SoC estimation is of great significance for the lithium-ion battery to ensure its safety operation and to prevent it from overcharging or overdischarging. To achieve reliable SoC estimation for Li4Ti5O12 lithium-ion battery cell, three filtering methods have been compared and evaluated. A main contribution of this study is that a general three-step model-based battery SoC estimation scheme has been proposed. It includes the processes of battery data measurement, parametric modeling, and model-based SoC estimation. With the proposed general scheme, multiple types of model-based SoC estimators have been developed and evaluated for battery management system application. The detailed comparisons on three advanced adaptive filter techniques, which include extend Kalman filter, unscented Kalman filter, and adaptive extend Kalman filter (AEKF, have been implemented with a Li4Ti5O12 lithium-ion battery. The experimental results indicate that the proposed model-based SoC estimation approach with AEKF algorithm, which uses the covariance matching technique, performs well with good accuracy and robustness; the mean absolute error of the SoC estimation is within 1% especially with big SoC initial error.

  18. MoS2 quantum dots@TiO2 nanotube composites with enhanced photoexcited charge separation and high-efficiency visible-light driven photocatalysis

    Science.gov (United States)

    Zhao, Fenfen; Rong, Yuefei; Wan, Junmin; Hu, Zhiwen; Peng, Zhiqin; Wang, Bing

    2018-03-01

    MoS2 quantum dots (QDs) that are 5 nm in size were deposited on the surface of ultrathin TiO2 nanotubes (TNTs) with 5 nm wall thickness by using an improved hydrothermal method to form a MoS2 QDs@TNT visible-light photocatalyst. The ultrathin TNTs with high percentage of photocatalytic reactive facets were fabricated by the commercially available TiO2 nanoparticles (P25) through an improved hydrothermal method, and the MoS2 QDs were acquired by using a surfactant-assisted technique. The novel MoS2 QDs@TNT photocatalysts showed excellent photocatalytic activity with a decolorization rate of 92% or approximately 3.5 times more than that of pure TNTs for the high initial concentration of methylene blue solution (20 mg l-1) within 40 min under visible-light irradiation. MoS2 as the co-catalysts favored the broadening of TNTs into the visible-light absorption scope. The quantum confinement and edge effects of the MoS2 QDs and the heterojunction formed between the MoS2 QDs and TNTs efficiently extended the lifetime of photoinduced charges, impeded the recombination of photoexcited electron-hole pairs, and improved the visible-light-driven high-efficiency photocatalysis.

  19. Nanoclay gelation approach toward improved dye-sensitized solar cell efficiencies: an investigation of charge transport and shift in the TiO2 conduction band.

    Science.gov (United States)

    Wang, Xiu; Kulkarni, Sneha A; Ito, Bruno Ieiri; Batabyal, Sudip K; Nonomura, Kazuteru; Wong, Chee Cheong; Grätzel, Michael; Mhaisalkar, Subodh G; Uchida, Satoshi

    2013-01-23

    Nanoclay minerals play a promising role as additives in the liquid electrolyte to form a gel electrolyte for quasi-solid-state dye-sensitized solar cells, because of the high chemical stability, unique swelling capability, ion exchange capacity, and rheological properties of nanoclays. Here, we report the improved performance of a quasi-solid-state gel electrolyte that is made from a liquid electrolyte and synthetic nitrate-hydrotalcite nanoclay. Charge transport mechanisms in the gel electrolyte and nanoclay interactions with TiO(2)/electrolyte interface are discussed in detail. The electrochemical analysis reveals that the charge transport is solely based on physical diffusion at the ratio of [PMII]:[I(2)] = 10:1 (where PMII is 1-propyl-3-methylimidazolium iodide). The calculated physical diffusion coefficient shows that the diffusion of redox ions is not affected much by the viscosity of nanoclay gel. The addition of nitrate-hydrotalcite clay in the electrolyte has the effect of buffering the protonation process at the TiO(2)/electrolyte interface, resulting in an upward shift in the conduction band and a boost in open-circuit voltage (V(OC)). Higher V(OC) values with undiminished photocurrent is achieved with nitrate-hydrotalcite nanoclay gel electrolyte for organic as well as for inorganic dye (D35 and N719) systems. The efficiency for hydrotalcite clay gel electrolyte solar cells is increased by 10%, compared to that of the liquid electrolyte. The power conversion efficiency can reach 10.1% under 0.25 sun and 9.6% under full sun. This study demonstrates that nitrate-hydrotalcite nanoclay in the electrolyte not only solidifies the liquid electrolyte to prevent solvent leakage, but also facilitates the improvement in cell efficiency.

  20. The cation-π interaction.

    Science.gov (United States)

    Dougherty, Dennis A

    2013-04-16

    The chemistry community now recognizes the cation-π interaction as a major force for molecular recognition, joining the hydrophobic effect, the hydrogen bond, and the ion pair in determining macromolecular structure and drug-receptor interactions. This Account provides the author's perspective on the intellectual origins and fundamental nature of the cation-π interaction. Early studies on cyclophanes established that water-soluble, cationic molecules would forego aqueous solvation to enter a hydrophobic cavity if that cavity was lined with π systems. Important gas phase studies established the fundamental nature of the cation-π interaction. The strength of the cation-π interaction (Li(+) binds to benzene with 38 kcal/mol of binding energy; NH4(+) with 19 kcal/mol) distinguishes it from the weaker polar-π interactions observed in the benzene dimer or water-benzene complexes. In addition to the substantial intrinsic strength of the cation-π interaction in gas phase studies, the cation-π interaction remains energetically significant in aqueous media and under biological conditions. Many studies have shown that cation-π interactions can enhance binding energies by 2-5 kcal/mol, making them competitive with hydrogen bonds and ion pairs in drug-receptor and protein-protein interactions. As with other noncovalent interactions involving aromatic systems, the cation-π interaction includes a substantial electrostatic component. The six (four) C(δ-)-H(δ+) bond dipoles of a molecule like benzene (ethylene) combine to produce a region of negative electrostatic potential on the face of the π system. Simple electrostatics facilitate a natural attraction of cations to the surface. The trend for (gas phase) binding energies is Li(+) > Na(+) > K(+) > Rb(+): as the ion gets larger the charge is dispersed over a larger sphere and binding interactions weaken, a classical electrostatic effect. On other hand, polarizability does not define these interactions. Cyclohexane is

  1. Zirconolite glass-ceramics for plutonium immobilization: The effects of processing redox conditions on charge compensation and durability

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yingjie, E-mail: yzx@ansto.gov.au; Gregg, Daniel J.; Kong, Linggen; Jovanovich, Miodrag; Triani, Gerry

    2017-07-15

    Zirconolite glass-ceramic samples doped with plutonium have been prepared via hot isostatic pressing. The effects of processing redox and plutonium loadings on plutonium valences, the presence of cation vacancies, zirconolite phase compositions, microstructures and durability have been investigated. Either tetravalent or trivalent plutonium ions may be incorporated on the Ca-site of CaZrTi{sub 2}O{sub 7} zirconolite with the Ca-site cation vacancies and the incorporation of Al{sup 3+} ions on the Ti-site for charge compensation. Plutonium and gadolinium (as a neutron absorber) are predominantly partitioned in zirconolite phases leading to the formation of chemically durable glass-ceramics suitable for the immobilization of impure plutonium wastes arising from the nuclear fuel cycle. - Highlights: •Plutonium validations of zirconolite glass-ceramics. •Effects of processing redox and plutonium loading. •Zirconolite phase compositions and plutonium valences. •Cation vacancies and chemical durability.

  2. Probing charge transfer during metal-insulator transitions in graphene-LaAlO3/SrTiO3 systems

    Science.gov (United States)

    Aliaj, I.; Sambri, A.; Miseikis, V.; Stornaiuolo, D.; di Gennaro, E.; Coletti, C.; Pellegrini, V.; Miletto Granozio, F.; Roddaro, S.

    2018-06-01

    Two-dimensional electron systems (2DESs) at the interface between LaAlO3 (LAO) and SrTiO3 (STO) perovskite oxides display a wide class of tunable phenomena ranging from superconductivity to metal-insulator transitions. Most of these effects are strongly sensitive to surface physics and often involve charge transfer mechanisms, which are, however, hard to detect. In this work, we realize hybrid field-effect devices where graphene is used to modulate the transport properties of the LAO/STO 2DES. Different from a conventional gate, graphene is semimetallic and allows us to probe charge transfer with the oxide structure underneath the field-effect electrode. In LAO/STO samples with a low initial carrier density, graphene-covered regions turn insulating when the temperature is lowered to 3 K, but conduction can be restored in the oxide structure by increasing the temperature or by field effect. The evolution of graphene's electron density is found to be inconsistent with a depletion of LAO/STO, but it rather points to a localization of interfacial carriers in the oxide structure.

  3. Enhanced separation efficiency of photoinduced charges for antimony-doped tin oxide (Sb-SnO{sub 2})/TiO{sub 2} heterojunction semiconductors with varied Sb doping concentration

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhen-Long [School of Physics and Electronics, Henan University, Kaifeng 475004 (China); Ma, Wen-Hai [School of Physical Education, Henan University, Kaifeng 475004 (China); Mao, Yan-Li, E-mail: ylmao1@163.com [School of Physics and Electronics, Henan University, Kaifeng 475004 (China); Institute for Computational Materials Science, Henan University, Kaifeng 475004 (China)

    2014-09-07

    In this paper, antimony-doped tin oxide (Sb-SnO{sub 2}) nanoparticles were synthesized with varied Sb doping concentration, and the Sb-SnO{sub 2}/TiO{sub 2} heterojunction semiconductors were prepared with Sb-SnO{sub 2} and TiO{sub 2}. The separation efficiency of photoinduced charges was characterized with surface photovoltage (SPV) technique. Compared with Sb-SnO{sub 2} and TiO{sub 2}, Sb-SnO{sub 2}/TiO{sub 2} presents an enhanced separation efficiency of photoinduced charges, and the SPV enhancements were estimated to be 1.40, 1.43, and 1.99 for Sb-SnO{sub 2}/TiO{sub 2} composed of Sb-SnO{sub 2} with the Sb doping concentration of 5%, 10%, and 15%, respectively. To understand the enhancement, the band structure of Sb-SnO{sub 2} and TiO{sub 2} in the heterojunction semiconductor was determined, and the conduction band offsets (CBO) between Sb-SnO{sub 2} and TiO{sub 2} were estimated to be 0.56, 0.64, and 0.98 eV for Sb-SnO{sub 2}/TiO{sub 2} composed of Sb-SnO{sub 2} with the Sb doping concentration of 5%, 10%, and 15%, respectively. These results indicate that the separation efficiency enhancement is resulting from the energy level matching, and the increase of enhancement is due to the rising of CBO.

  4. Internal reflection flash photolysis study of the photochemistry of eosin at TiO sub 2 semiconductor electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, M.A.; Fitzgerald, E.C.; Spitler, M.T. (Polaroid Corp., Cambridge, MA (USA))

    1989-08-10

    It is shown that the photoelectrochemical data on eosin Y sensitized TiO{sub 2} single-crystal electrodes cannot be interpreted unambiguously without concomitant data from flash photolysis measurements on this system. By use of a combination of internal reflection spectroscopy and laser flash photolysis, electron exchange with TiO{sub 2} was observed for the excited singlet state, the triplet state, and the cation radical of the dye. With a temporal resolution of 100 ns, the kinetics of the charge transfer are compared with those of the dye in solution and used to interpret the photoelectrochemistry of the dye at the electrode. Spectroscopic evidence revealed photocurrent production by the triplet state and a reduction of the eosin cation radical by electrons from the TiO{sub 2} conduction band and by hydroquinone.

  5. Structural and energetic study of cation-π-cation interactions in proteins.

    Science.gov (United States)

    Pinheiro, Silvana; Soteras, Ignacio; Gelpí, Josep Lluis; Dehez, François; Chipot, Christophe; Luque, F Javier; Curutchet, Carles

    2017-04-12

    Cation-π interactions of aromatic rings and positively charged groups are among the most important interactions in structural biology. The role and energetic characteristics of these interactions are well established. However, the occurrence of cation-π-cation interactions is an unexpected motif, which raises intriguing questions about its functional role in proteins. We present a statistical analysis of the occurrence, composition and geometrical preferences of cation-π-cation interactions identified in a set of non-redundant protein structures taken from the Protein Data Bank. Our results demonstrate that this structural motif is observed at a small, albeit non-negligible frequency in proteins, and suggest a preference to establish cation-π-cation motifs with Trp, followed by Tyr and Phe. Furthermore, we have found that cation-π-cation interactions tend to be highly conserved, which supports their structural or functional role. Finally, we have performed an energetic analysis of a representative subset of cation-π-cation complexes combining quantum-chemical and continuum solvation calculations. Our results point out that the protein environment can strongly screen the cation-cation repulsion, leading to an attractive interaction in 64% of the complexes analyzed. Together with the high degree of conservation observed, these results suggest a potential stabilizing role in the protein fold, as demonstrated recently for a miniature protein (Craven et al., J. Am. Chem. Soc. 2016, 138, 1543). From a computational point of view, the significant contribution of non-additive three-body terms challenges the suitability of standard additive force fields for describing cation-π-cation motifs in molecular simulations.

  6. 高钛渣中TiC表面电荷的形成与破坏%The Formation and the Destruction of Surface Charge of TiC in the Titania Slag

    Institute of Scientific and Technical Information of China (English)

    王淑兰; 钟和香; 张丽君

    2004-01-01

    研究了高钛渣电导率与TiC含量、粒度的关系.TiC含量增加,炉渣电导率先减小后增加;TiC粒度增加,炉渣电导率增加.TiC对炉渣电导率的影响规律表明,TiC在渣中带有电荷,形成胶体颗粒,提高炉渣粘度;碱性电解质能够改变TiC带电状态,降低炉渣粘度.

  7. A novel research approach on the dynamic properties of photogenerated charge carriers at Ag{sub 2}S quantum-dots-sensitized TiO{sub 2} films by a frequency-modulated surface photovoltage technology

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yu; Zhang, Wei [Liaoning Key Laboratory for Green Synthesis and Preparative Chemistry of Advanced Materials, College of Chemistry, Liaoning University, Shenyang 110036 (China); Xie, Tengfeng; Wang, Dejun [College of Chemistry, Jilin University, Changchun 130012 (China); Song, Xi-Ming, E-mail: songlab@lnu.edu.cn [Liaoning Key Laboratory for Green Synthesis and Preparative Chemistry of Advanced Materials, College of Chemistry, Liaoning University, Shenyang 110036 (China)

    2013-09-01

    Graphical abstract: The changed SPV with chopping frequencies indicate the separation speeds of photogenerated charge carriers in different films. - Highlights: • Ag{sub 2}S-sensitized TiO{sub 2} films show good photoelectric responses in visible-light region. • Frequency-modulated SPV give dynamic information and evidence of Ag{sub 2}S QDSSCs’ performance. • Frequency-modulated SPV can supply complementary information in the study of Ag{sub 2}S ODSSCs. - Abstract: Ag{sub 2}S quantum-dots-sensitized TiO{sub 2} films with different amount of Ag{sub 2}S were fabricated by a successive ionic layer adsorption and reaction (SILAR) method. The separation and transport of photogenerated charge carriers at different spectral regions were studied by the frequency-modulated surface photovoltage technology. Some novel dynamic information of photogenerated charge carriers in a wide spectral range is found. The results indicate that the rate and direction of separation (diffusion) for photogenerated charge carriers are closely related to the performance of quantum-dots-sensitized solar cells (QDSSCs) based on the Ag{sub 2}S/TiO{sub 2} nano-structure.

  8. Kinetic Modeling of the Lif:Mg,Ti TL System including Defect Creation: Implications to, and Development of Track Structure Theory Calculations of Heavy Charged Particle Radiation Effects

    International Nuclear Information System (INIS)

    Eliyahu, Ian

    2015-01-01

    In this research, various kinetic models were developed for LiF:Mg,Ti crystals, both in the irradiation and recombination stages. The models were later used to improve on track structure theory, which attempts to describe radiation effects of Heavy charged particle. To achieve this goal, the research focused on three main areas of endeavor. 1. In the first experimental measurements of optical absorption on LiF:Mg,Ti following low ionization density radiation (photons) and high ionization density protons and He ions were carried out in order to investigate the degree of applicability of track structure theory to the prediction of heavy charged particle induced effects of radiation. These measurements are described below. a) Photon induced optical absorption (OA) dose response was measured over an extended dose-range from 10 Gy to 105 Gy for the main OA bands in LiF:Mg,Ti, i.e., the 4.0 eV band (trapping center associated with glow peak 5 in the thermoluminescence glow curve), 4.77 eV band , 5.08 eV (F band) and 5.45 eV band. The extended dose-range allowed the unambiguous determination of linear/exponentially saturation behavior for all the OA bands. For the two main OA bands of interest at 4.0 eV and 5.08 eV, the dose filling factor was determined to be 5 ± 0.6.10-4 Gy-1 and 6.1 ± 0.4 × 10-5 Gy-1 respectively. The surprising, previously unexplained, linear/exponentially saturating dose response of the F band even though vacancies/F centers are being created by the radiation was explained in a kinetic analysis also described in the following. b) Heavy charged particle (HCP) optical absorption was carried out for 1.4 MeV protons and 4 MeV He ions at the SARAF, RARAF and BINA accelerators. Fluence response was measured over the extended range from 1010 cm-2 to 2.1014 cm-2. The low fluence region from 1010 cm-2 to 1011 cm-2 in the no-track-overlap regime allows a comparison of the experimental measurements and the track structure theory (TST) evaluations of the

  9. First principles analysis of the CDW instability of single-layer 1T-TiSe2 and its evolution with charge carrier density

    Science.gov (United States)

    Guster, Bogdan; Canadell, Enric; Pruneda, Miguel; Ordejón, Pablo

    2018-04-01

    We present a density functional theory study of the electronic structure of single-layer TiSe2, and focus on the charge density wave (CDW) instability present on this 2D material. We explain the 2× 2 periodicity of the CDW from the phonon band structure of the undistorted crystal, which is unstable under one of the phonon modes at the M point. This can be understood in terms of a partial band gap opening at the Fermi level, which we describe on the basis of the symmetry of the involved crystal orbitals, leading to an energy gain upon the displacement of the atoms following the phonon mode in a 2  ×  1 structure. Furthermore, the combination of the corresponding phonons for the three inequivalent M points of the Brillouin zone leads to the 2  ×  2 distortion characteristic of the CDW state. This leads to a further opening of a full gap, which reduces the energy of the 2  ×  2 structure compared to the 2  ×  1 one of a single M point phonon, and makes the CDW structure the most stable one. We also analyze the effect of charge injection into the layer on the structural instability. We predict that the 2  ×  2 structure only survives for a certain range of doping levels, both for electrons and for holes, as doping reduces the energy gain due to the gap opening. We predict the transition from the commensurate 2  ×  2 distortion to an incommensurate one with increasing wavelength upon increasing the doping level, followed by the appearance of the undistorted 1  ×  1 structure for larger carrier concentrations.

  10. Interfacial charge-induced polarization switching in Al{sub 2}O{sub 3}/Pb(Zr,Ti)O{sub 3} bi-layer

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yu Jin; Park, Min Hyuk; Jeon, Woojin; Kim, Han Joon; Moon, Taehwan; Lee, Young Hwan; Kim, Keum Do; Hyun, Seung Dam; Hwang, Cheol Seong, E-mail: cheolsh@snu.ac.kr [Department of Materials Science & Engineering and Inter-University Semiconductor Research Center, College of Engineering, Seoul National University, Seoul 151-744 (Korea, Republic of)

    2015-12-14

    Detailed polarization switching behavior of an Al{sub 2}O{sub 3}/Pb(Zr,Ti)O{sub 3} (AO/PZT) structure is examined by comparing the phenomenological thermodynamic model to the experimental polarization–voltage (P-V) results. Amorphous AO films with various thicknesses (2–10 nm) were deposited on the polycrystalline 150-nm-thick PZT film. The thermodynamic calculation showed that the transition from the ferroelectric-like state to the paraelectric-like state with increasing AO thickness occurs at ∼3 nm thickness. This paraelectric-like state should have exhibited a negative capacitance effect without permanent polarization switching if no other adverse effects are involved. However, experiments showed typical ferroelectric-like hysteresis loops where the coercive voltage increased with the increasing AO thickness, which could be explained by the carrier injection through the thin AO layer and trapping of the carriers at the AO/PZT interface. The fitting of the experimental P-V loops using the thermodynamic model considering the depolarization energy effect showed that trapped charge density was ∼±0.1 Cm{sup −2} and critical electric field at the Pt electrode/AO interface, at which the carrier transport occurs, was ∼±10 MV/cm irrespective of the AO thickness. Energy band model at each electrostatic state along the P-V loop was provided to elucidate correlation between macroscopic polarization and internal charge state of the stacked films.

  11. Cation interdiffusion in polycrystalline calcium and strontium titanate

    International Nuclear Information System (INIS)

    Butler, E.P.; Jain, H.; Smyth, D.M.

    1991-01-01

    This paper discusses a method that has been developed to study bulk lattice interdiffusion between calcium and strontium titanate by fabrication of a diffusion couple using cosintering. The measured interdiffusion coefficients, D(C), indicate that strontium impurity diffusion in calcium titanate occurs at a faster rate than calcium impurity diffusion in strontium titanate. These interdiffusion coefficients are composition independent when the concentration of the calcium cation exceeds that of the strontium cation; otherwise D(C) is strongly composition dependent. Investigations into the effect of cation nonstoichiometry give results that are consistent with a defect incorporation reaction in which excess TiO 2 , within the solid solubility limit, produces A-site cation vacancies as compensating defects. The interdiffusion coefficients increase with increasing concentrations of TiO 2 , so it is concluded that interdiffusion of these alkaline-earth cations in their titanates occurs via a vacancy mechanism

  12. Theoretical study of disorder in Ti-substituted La2Zr2O7

    International Nuclear Information System (INIS)

    Chartier, Alain; Meis, Constantin; Weber, William J.; Corrales, L. Rene

    2002-01-01

    Pyrochlores have the striking feature that their radiation resistance is highly dependent on their composition. In this work, the propensity of a pyrochlore to transform to a cation-disordered structure and the influence of titanium ions is ascertained from the mechanisms of defect formation. A detailed study of defect formation and migration activation energies in Ti-substituted La 2 Zr 2 O 7 is carried out by modern theoretical computational methods that include the use of a classical interatomic potential with a modified shell model to capture the effects of local charge transfer. The results show that La 2 Zr 2 O 7 has a tendency towards cation disorder, whereas, substitution of Zr with Ti makes this tendency energetically less favorable

  13. [Noncovalent cation-π interactions--their role in nature].

    Science.gov (United States)

    Fink, Krzysztof; Boratyński, Janusz

    2014-11-07

    Non-covalent interactions play an extremely important role in organisms. The main non-covalent interactions in nature are: ion-ion interactions, dipole-dipole interactions, hydrogen bonds, and van der Waals interactions. A new kind of intermolecular interactions--cation-π interactions--is gaining increasing attention. These interactions occur between a cation and a π system. The main contributors to cation-π interactions are electrostatic, polarization and, to a lesser extent, dispersion interactions. At first, cation-π interactions were studied in a gas phase, with metal cation-aromatic system complexes. The characteristics of these complexes are as follows: an increase of cation atomic number leads to a decrease of interaction energy, and an increase of cation charge leads to an increase of interaction energy. Aromatic amino acids bind with metal cations mainly through interactions with their main chain. Nevertheless, cation-π interaction with a hydrophobic side chain significantly enhances binding energy. In water solutions most cations preferentially interact with water molecules rather than aromatic systems. Cation-π interactions occur in environments with lower accessibility to a polar solvent. Cation-π interactions can have a stabilizing role on the secondary, tertiary and quaternary structure of proteins. These interactions play an important role in substrate or ligand binding sites in many proteins, which should be taken into consideration when the screening of effective inhibitors for these proteins is carried out. Cation-π interactions are abundant and play an important role in many biological processes.

  14. Computational study of ethanol adsorption and reaction over rutile TiO2 (110) surfaces

    KAUST Repository

    Muir, J. N.

    2012-01-01

    Studies of the modes of adsorption and the associated changes in electronic structures of renewable organic compounds are needed in order to understand the fundamentals behind surface reactions of catalysts for future energies. Using planewave density functional theory (DFT) calculations, the adsorption of ethanol on perfect and O-defected TiO 2 rutile (110) surfaces was examined. On both surfaces the dissociative adsorption mode on five-fold coordinated Ti cations (Ti 4+ 5c) was found to be more favourable than the molecular adsorption mode. On the stoichiometric surface E ads was found to be equal to 0.85 eV for the ethoxide mode and equal to 0.76 eV for the molecular mode. These energies slightly increased when adsorption occurred on the Ti 4+ 5c closest to the O-defected site. However, both considerably increased when adsorption occurred at the removed bridging surface O; interacting with Ti 3+ cations. In this case the dissociative adsorption becomes strongly favoured (E ads = 1.28 eV for molecular adsorption and 2.27 eV for dissociative adsorption). Geometry and electronic structures of adsorbed ethanol were analysed in detail on the stoichiometric surface. Ethanol does not undergo major changes in its structure upon adsorption with its C-O bond rotating nearly freely on the surface. Bonding to surface Ti atoms is a σ type transfer from the O2p of the ethanol-ethoxide species. Both ethanol and ethoxide present potential hole traps on O lone pairs. Charge density and work function analyses also suggest charge transfer from the adsorbate to the surface, in which the dissociative adsorptions show a larger charge transfer than the molecular adsorption mode. This journal is © 2012 the Owner Societies.

  15. Divalent cation shrinks DNA but inhibits its compaction with trivalent cation.

    Science.gov (United States)

    Tongu, Chika; Kenmotsu, Takahiro; Yoshikawa, Yuko; Zinchenko, Anatoly; Chen, Ning; Yoshikawa, Kenichi

    2016-05-28

    Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions.

  16. Cooperative effect of adsorbed cations on electron transport and recombination behavior in dye-sensitized solar cells

    International Nuclear Information System (INIS)

    Kou, Dongxing; Liu, Weiqing; Hu, Linhua; Dai, Songyuan

    2013-01-01

    Highlights: • Disclose the mechanism of cooperative effects of adsorbed cations in DSCs. • Characterize the influence of adsorption of Im + s on photoinduced electron density. • The effect of Li + is orderly enhanced in DSCs with increasing alkyl chain length. • The DSCs efficiencies are relatively depended on the trade-off between J sc and FF. -- Abstract: Lithium ion (Li + ) and imidazolium cations (Im + s) had been reported to have competitive effects on the photoinduced electrons in TiO 2 -electrolyte systems. Herein, a further investigation about their cooperative effect in dye-sensitized solar cells (DSCs) using organic liquid electrolyte is developed by altering alkyl chain length. Imidazolium iodides (Im + I − s) with different alkyl chain length (3, 6, and 12) were synthesized and used as iodide sources. The adsorption amount of Im + s onto TiO 2 , band edge shifts, trap states distribution, electron recombination/transport processes and ion transport within the electrolyte for DSCs were detected. It is found that the multilayered adsorption of Im + s can induce a lower photoinduced electron density. In-depth characterizations indicate that this negative effect can be reduced as the adsorption amount decreased with increasing alkyl chain length and the effect of Li + is consequently strengthened in varying degrees. The decisive role of Li + in cation-controlled interfacial charge injection process finally contributes an ordinal increase of short-circuit photocurrent density J sc for DSCs with increasing alkyl chain length because of the increasing charge injection efficiency η inj . Additionally, a large power dissipation in ions transport process is induced by the long alkyl chain of Im + s. Overall, the cell efficiencies are relatively dependent of the trade-off between J sc and FF, which is essentially related to the cooperative effect of adsorbed cations

  17. Restructuring of a peat in interaction with multivalent cations: effect of cation type and aging time.

    Science.gov (United States)

    Kunhi Mouvenchery, Yamuna; Jaeger, Alexander; Aquino, Adelia J A; Tunega, Daniel; Diehl, Dörte; Bertmer, Marko; Schaumann, Gabriele Ellen

    2013-01-01

    It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM) molecules via cation bridges (CaB). The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al(3+), Ca(2+) or Na(+), respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>2 h) than deprotonation of functional groups (cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB) and molecular mobility of water (NMR analysis) suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat) cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is decisive for CaB and aging-induced structural reorganisation can enhance cross-link formation.

  18. Stable polyfluorinated cycloalkenyl cations and their NMR spectra

    International Nuclear Information System (INIS)

    Snegirev, V.F.; Galakhov, M.V.; Makarov, K.N.; Bakhmutov, V.I.

    1986-01-01

    New stable 1-methoxyperfluoro-2-ethylcyclobutenyl, 1-methoxyperfluoro-2-methylcyclo-pentenyl, and 1-methoxyperfluoro-2-ethylcyclohexenyl cations were obtained by the action of antimony pentafluoride on the corresponding olefins. The distribution of the charges in the investigated polyfluorinated cycloalkenyl cations was investigated by 13 C NMR method

  19. Titanium embedded cage structure formation in Al{sub n}Ti{sup +} clusters and their interaction with Ar

    Energy Technology Data Exchange (ETDEWEB)

    Torres, M. B., E-mail: begonia@ubu.es [Departamento de Matemáticas y Computación, Universidad de Burgos, 09006 Burgos (Spain); Vega, A.; Balbás, L. C. [Departamento de Física Teórica, Universidad de Valladolid, 47011 Valladolid (Spain); Aguilera-Granja, F. [Instituto de Física, Universidad de San Luis Potosí, 78000 San Luis de Potosí (Mexico)

    2014-05-07

    Recently, Ar physisorption was used as a structural probe for the location of the Ti dopant atom in aluminium cluster cations, Al{sub n}Ti{sup +} [Lang et al., J. Am. Soc. Mass Spectrom. 22, 1508 (2011)]. As an experiment result, the lack of Ar complexes for n > n{sub c} determines the cluster size for which the Ti atom is located inside of an Al cage. To elucidate the decisive factors for the formation of endohedrally Al{sub n}Ti{sup +}, experimentalists proposed detailed computational studies as indispensable. In this work, we investigated, using the density functional theory, the structural and electronic properties of singly titanium doped cationic clusters, Al{sub n}Ti{sup +} (n = 16–21) as well as the adsorption of an Ar atom on them. The first endohedral doped cluster, with Ti encapsulated in a fcc-like cage skeleton, appears at n{sub c} = 21, which is the critical number consistent with the exohedral-endohedral transition experimentally observed. At this critical size the non-crystalline icosahedral growth pattern, related to the pure aluminium clusters, with the Ti atom in the surface, changes into a endohedral fcc-like pattern. The map of structural isomers, relative energy differences, second energy differences, and structural parameters were determined and analyzed. Moreover, we show the critical size depends on the net charge of the cluster, being different for the cationic clusters (n{sub c} = 21) and their neutral counterparts (n{sub c} = 20). For the Al {sub n} Ti {sup +} · Ar complexes, and for n < 21, the preferred Ar adsorption site is on top of the exohedral Ti atom, with adsorption energy in very good agreement with the experimental value. Instead, for n = 21, the Ar adsorption occurs on the top an Al atom with very low absorption energy. For all sizes the geometry of the Al{sub n}Ti{sup +} clusters keeps unaltered in the Ar-cluster complexes. This fact indicates that Ar adsorption does not influence the cluster structure, providing support

  20. Electrical transport through Pb(Zr,Ti)O3 p-n and p-p heterostructures modulated by bound charges at a ferroelectric surface: Ferroelectric p-n diode

    Science.gov (United States)

    Watanabe, Yukio

    1999-05-01

    Current through (Pb,La)(Zr,Ti)O3 ferroelectrics on perovskite semiconductors is found to exhibit diode characteristics of which polarity is universally determined by the carrier conduction-type semiconductors. A persisting highly reproducible resistance modulation by a dc voltage, which has a short retention, is observed and is ascribed to a band bending of the ferroelectric by the formation of charged traps. This interpretation is consistent with a large relaxation current observed at a low voltage. On the other hand, a reproducible resistance modulation by a pulse voltage, which has a long retention, is observed in metal/(Pb,La)(Zr,Ti)O3/SrTiO3:Nb but not in metal/(Pb,La)(Zr,Ti)O3/(La,Sr)2CuO4 and is attributed to a possible band bending due to the spontaneous polarization (P) switching. The observed current voltage (IV) characteristics, the polarity dependence, the relaxation, and the modulation are explicable, if we assume a p-n or a p-p junction at the ferroelectric semiconductor interface (p: hole conduction type, n: electron conduction type). The analysis suggests that an intrinsically inhomogeneous P (∇P) near the ferroelectric/metal interface is likely very weak or existing in a very thin layer, when a reaction of the metal with the ferroelectric is eliminated. Additionally, the various aspects of transport through ferroelectrics are explained as a transport in the carrier depleted region.

  1. Effect of Titanium Dioxide Dopping on Charge Trapping in ...

    African Journals Online (AJOL)

    The charge storage properties of corona charged pure and TiO2 doped polystyrene (PS) films have been studied. Thermally stimulated charge decay and open circuit thermally stimulated charges were measured. A half-value charge decay temperature T1/2 ∼ 140oC is optimum at 3 wt % TiO2 doping. This implies that ...

  2. Fabrication and photovoltaic performance of niobium doped TiO{sub 2} hierarchical microspheres with exposed {001} facets and high specific surface area

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yongqiang; Ran, Huili [School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001 (China); State Centre for International Cooperation on Designer Low-Carbon and Environmental Materials, Zhengzhou University, Zhengzhou 450001 (China); Fan, Jiajie, E-mail: fanjiajie@zzu.edu.cn [School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001 (China); State Centre for International Cooperation on Designer Low-Carbon and Environmental Materials, Zhengzhou University, Zhengzhou 450001 (China); Zhang, Xiaoli; Mao, Jing [School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001 (China); State Centre for International Cooperation on Designer Low-Carbon and Environmental Materials, Zhengzhou University, Zhengzhou 450001 (China); Shao, Guosheng [School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001 (China); State Centre for International Cooperation on Designer Low-Carbon and Environmental Materials, Zhengzhou University, Zhengzhou 450001 (China); Institute for Renewable Energy and Environmental Technologies, University of Bolton, Bolton BL3 5AB (United Kingdom)

    2017-07-15

    Highlights: • Nb-doped hierarchical TiO{sub 2} microsphere DSSCs show enhanced performance. • Nb{sup 5+} dopant replaces Ti{sup 4+} cation in TiO{sub 2} lattice. • Electrons transport was enhanced due to the down-shifted conduction band minimum. • Exposed (001) facets and high specific surface area allows high dye-loading. - Abstract: The niobium doped hierarchical anatase TiO{sub 2} microspheres, which are consist of a serried nano-thorns and plicate nano-ribbons with exposed {001} facets, were synthesized using hydrothermal method followed by heat treatment. The effects of niobium on the microstructures and photovoltaic performances of the dye-sensitized solar cells (DSSCs) were studied. The results revealed that Nb{sup 5+} doping replaces Ti{sup 4+} cations in TiO{sub 2} lattice, and the bandgap of the films varies with increasing Nb doping concentration because of the downshift of the conduction band minimum (CBM). The niobium-doped TiO{sub 2} DSSCs with moderate loadings show enhanced performance comparing with their pure TiO{sub 2} counterparts. Optimally, the conversion efficiency of the Nb-3.5 (Nb 3.5 mol%) DSSC is 4.99%. This is higher than that (4.39%) of pure TiO{sub 2} cells by 13.7%. This is due to the fact that the Nb-doped solar cells have increased the number of the photo-induced electrons because of their exposed (001) facets and higher specific surface area; and enhanced electrons collection and transport because of the downshifted CBM of the Nb-doped TiO{sub 2}. However, heavy Nb doping results in the decrease of the performance of the niobium-doped cells due to the excessive defects within the Nb-TiO{sub 2} samples resulting in enhanced charge recombination at defects.

  3. Ordered Fe(II)Ti(IV)O3 Mixed Monolayer Oxide on Rutile TiO2(011).

    Science.gov (United States)

    Halpegamage, Sandamali; Ding, Pan; Gong, Xue-Qing; Batzill, Matthias

    2015-08-25

    Oxide monolayers supported or intermixed with an oxide support are potential nanocatalysts whose properties are determined by the interplay with the support. For fundamental studies of monolayer oxides on metal oxide supports, well-defined systems are needed, but so far, the synthesis of monolayer oxides with long-range order on single-crystal oxide surfaces is rare. Here, we show by a combination of scanning tunneling microscopy, photoemission spectroscopy, and density functional theory (DFT)-based computational analysis that the rutile TiO2(011) surface supports the formation of an ordered mixed FeTiO3 monolayer. Deposition of iron in a slightly oxidizing atmosphere (10(-8) Torr O2) and annealing to 300 °C results in a well-ordered surface structure with Fe in a 2+ charge state and Ti in a 4+ charge states. Low-energy ion scattering suggests that the cation surface composition is close to half Fe and half Ti. This surface is stable in ultrahigh vacuum to annealing temperatures of 300 °C before the iron is reduced. DFT simulations confirm that a surface structure with coverage of 50% FeO units is stable and forms an ordered structure. Although distinct from known bulk phases of the iron-titanium oxide systems, the FeTiO3 monolayer exhibits some resemblance to the ilmenite structure, which may suggest that a variety of different mixed oxide phases (of systems that exist in a bulk ilmenite phase) may be synthesized in this way on the rutile TiO2(011) substrate.

  4. K{sub 2}MnF{sub 5}·H{sub 2}O as reactant for synthesizing highly efficient red emitting K{sub 2}TiF{sub 6}:Mn{sup 4+} phosphors by a modified cation exchange approach

    Energy Technology Data Exchange (ETDEWEB)

    Han, Tao, E-mail: danbaiht@126.com; Wang, Jun; Lang, Tianchun; Tu, Mingjing; Peng, Lingling

    2016-11-01

    As reactant for synthesizing K{sub 2}TiF{sub 6}:Mn{sup 4+} phosphors, the cross-shaped and cuboid-shaped K{sub 2}MnF{sub 5}·H{sub 2}O powders were prepared by the simple chemical method. Based on the reaction mechanism, oxidizing K{sub 2}MnF{sub 5}·H{sub 2}O (Mn{sup 3+}) to Mn{sup 4+} by KMnO{sub 4} (Mn{sup 7+}), a modified cation exchange approach for synthesizing highly efficient red emitting K{sub 2}TiF{sub 6}:Mn{sup 4+} phosphor was proposed. The obtained K{sub 2}TiF{sub 6}:Mn{sup 4+} (2.7–5.3 at.%) phosphors have the size of 30–80 μm with a rough surface, their emission spectra consist of five narrow bands extending from 580 to 660 nm with the strongest peak at 634.8 nm, whose relative emitting intensity depends on the molar ratio of KMnO{sub 4} to K{sub 2}MnF{sub 5}·H{sub 2}O (the platform value = 3.2), and two broad excitation bands are peaking at ∼365 nm and ∼460 nm. The internal quantum yield of our synthesized K{sub 2}TiF{sub 6}:Mn{sup 4+} phosphors is up to 82.5%, which is higher than the commercial CaAlSiN{sub 3}:Eu{sup 2+} value, their excitation bands peak at ∼460 and ∼365 nm are consistent with those of Y{sub 3}A{sub 5}O{sub 12}:Ce{sup 3+} phosphors and their emission bands are more suitable for the sensitivity curve of photopic human vision. In addition, our synthesized phosphors show better thermal quenching properties. These findings show a large potential of the synthesized K{sub 2}TiF{sub 6}:Mn{sup 4+} phosphors for commercialization. - Highlights: • We synthesize the cross-shaped and cuboid-shaped K{sub 2}MnF{sub 5}·H{sub 2}O. • K{sub 2}MnF{sub 5}·H{sub 2}O is as a reactant for synthesizing K{sub 2}TiF{sub 6}:Mn{sup 4+} phosphors. • K{sub 2}TiF{sub 6}:Mn{sup 4+} will improve the current white LED with high CRI for indoor lighting.

  5. Coupling of electric charge and magnetic field via electronic phase separation in (La,Pr,Ca)MnO3/Pb(Mg1/3Nb2/3)O3-PbTiO3 multiferroic heterostructures

    Science.gov (United States)

    Zheng, Ming; Wang, Wei

    2016-04-01

    The electric-field-tunable non-volatile resistivity and ferromagnetism switching in the (La0.5Pr0.5)0.67Ca0.33MnO3 films grown on (111)-oriented 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 ferroelectric single-crystal substrates have been investigated. By combining the 180° ferroelectric domain switching and in situ X-ray diffraction and resistivity measurements, we identify that this voltage control of order parameters stems from the domain switching-induced accumulation/depletion of charge carriers at the interface rather than induced lattice strain effect. In particular, the polarization-induced charge effect (i.e., ferroelectric field effect) is strongly dependent on the magnetic field. This, together with the charge-modulated magnetoresistance and magnetization, reveals the strong correlation between the electric charge and the magnetic field. Further, we found that this coupling is essentially driven by the electronic phase separation, the relative strength of which could be determined by recording charge-tunability of resistivity [ (Δρ/ρ)c h arg e ] under various magnetic fields. These findings present a potential strategy for elucidating essential physics of perovskite manganites and delivering prototype electronic devices for non-volatile information storage.

  6. Cationic niosomes an effective gene carrier composed of novel spermine-derivative cationic lipids: effect of central core structures.

    Science.gov (United States)

    Opanasopit, Praneet; Leksantikul, Lalita; Niyomtham, Nattisa; Rojanarata, Theerasak; Ngawhirunpat, Tanasait; Yingyongnarongkul, Boon-Ek

    2017-05-01

    Cationic niosomes formulated from Span 20, cholesterol (Chol) and novel spermine-based cationic lipids of multiple central core structures (di(oxyethyl)amino, di(oxyethyl)amino carboxy, 3-amino-1,2-dioxypropyl and 2-amino-1,3-dioxypropyl) were successfully prepared for improving transfection efficiency in vitro. The niosomes composed of spermine cationic lipid with central core structure of di(oxyethyl)amino revealed the highest gene transfection efficiency. To investigate the factors affecting gene transfection and cell viability including differences in the central core structures of cationic lipids, the composition of vesicles, molar ratio of cationic lipids in formulations and the weight ratio of niosomes to DNA. Cationic niosomes composed of nonionic surfactants (Span20), cholesterol and spermine-based cationic lipids of multiple central core structures were formulated. Gene transfection and cell viability were evaluated on a human cervical carcinoma cell line (HeLa cells) using pDNA encoding green fluorescent protein (pEGFP-C2). The morphology, size and charge were also characterized. High transfection efficiency was obtained from cationic niosomes composed of Span20:Chol:cationic lipid at the molar ratio of 2.5:2.5:0.5 mM. Cationic lipids with di(oxyethyl)amino as a central core structure exhibited highest transfection efficiency. In addition, there was also no serum effect on transfection efficiency. These novel cationic niosomes may constitute a good alternative carrier for gene transfection.

  7. Resolving the radical cation formation from the lowest-excited singlet (S-1) state of terthiophene in a TiO2-SiO2 hybrid polymer matrix

    DEFF Research Database (Denmark)

    Helbig, M.; Ruseckas, A.; Grage, M.M.-L.

    1999-01-01

    and simultaneous rise of 3T(-)(+.) radical cation absorption. The observed kinetics of electron transfer are independent of excess vibrational energy in the S-1 state, and can be described by a biexponential function with time constants of similar to 1 ps (for similar to 62% of the excited 3T molecules...

  8. Comparison of modification strategies towards enhanced charge carrier separation and photocatalytic degradation activity of metal oxide semiconductors (TiO{sub 2}, WO{sub 3} and ZnO)

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, S. Girish [Department of Physics, Indian Institute of Science, Bengaluru, 560012 Karnataka (India); Department of Chemistry, School of Engineering and Technology, CMR University, Bengaluru, 562149, Karnataka (India); Rao, K.S.R. Koteswara, E-mail: raoksrk@gmail.com [Department of Physics, Indian Institute of Science, Bengaluru, 560012 Karnataka (India)

    2017-01-01

    Graphical abstract: Semiconductor metal oxides: Modifications, charge carrier dynamics and photocatalysis. - Highlights: • TiO{sub 2}, WO{sub 3} and ZnO based photocatalysis is reviewed. • Advances to improve the efficiency are emphasized. • Differences and similarities in the modifications are highlighted. • Charge carrier dynamics for each strategy are discussed. - Abstract: Metal oxide semiconductors (TiO{sub 2}, WO{sub 3} and ZnO) finds unparalleled opportunity in wastewater purification under UV/visible light, largely encouraged by their divergent admirable features like stability, non-toxicity, ease of preparation, suitable band edge positions and facile generation of active oxygen species in the aqueous medium. However, the perennial failings of these photocatalysts emanates from the stumbling blocks like rapid charge carrier recombination and meager visible light response. In this review, tailoring the surface-bulk electronic structure through the calibrated and veritable approaches such as impurity doping, deposition with noble metals, sensitizing with other compounds (dyes, polymers, inorganic complexes and simple chelating ligands), hydrogenation process (annealing under hydrogen atmosphere), electronic integration with other semiconductors, modifying with carbon nanostructures, designing with exposed facets and tailoring with hierarchical morphologies to overcome their critical drawbacks are summarized. Taking into account the materials intrinsic properties, the pros and cons together with similarities and striking differences for each strategy in specific to TiO{sub 2}, WO{sub 3} & ZnO are highlighted. These subtlety enunciates the primacy for improving the structure-electronic properties of metal oxides and credence to its fore in the practical applications. Future research must focus on comparing the performances of ZnO, TiO{sub 2} and WO{sub 3} in parallel to get insight into their photocatalytic behaviors. Such comparisons not only reveal

  9. Isomerization of propargyl cation to cyclopropenyl cation ...

    Indian Academy of Sciences (India)

    step) for isomeri- zation of the linear propargyl cation to ..... C3, C4 and C5. The ZPE corrections in each case are derived from the. B3LYP calculations. ..... the converse of which gives the relative capacity of the. LPD's to stabilize TS6 with respect ...

  10. Synthesis of reduced graphene oxide-anatase TiO2 nanocomposite and its improved photo-induced charge transfer properties.

    Science.gov (United States)

    Wang, Ping; Zhai, Yueming; Wang, Dejun; Dong, Shaojun

    2011-04-01

    The construction of reduced graphene oxide or graphene oxide with semiconductor has gained more and more attention due to its unexpected optoelectronic and electronic properties. The synthesis of reduced graphene oxide (RGO) or graphene oxide-semiconductor nanocomposite with well-dispersed decorated particles is still a challenge now. Herein, we demonstrate a facile method for the synthesis of graphene oxide-amorphous TiO(2) and reduced graphene oxide-anatase TiO(2) nanocomposites with well-dispersed particles. The as-synthesized samples were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-Vis absorption spectroscopy, Fourier transform infrared spectrometry, and thermogravimetric analysis. The photovoltaic properties of RGO-anatase TiO(2) were also compared with that of similar sized anatase TiO(2) by transient photovoltage technique, and it was interesting to find that the combination of reduced graphene oxide with anatase TiO(2) will significantly increase the photovoltaic response and retard the recombination of electron-hole pairs in the excited anatase TiO(2).

  11. Charge states of ions, and mechanisms of charge ordering transitions

    Science.gov (United States)

    Pickett, Warren E.; Quan, Yundi; Pardo, Victor

    2014-07-01

    To gain insight into the mechanism of charge ordering transitions, which conventionally are pictured as a disproportionation of an ion M as 2Mn+→M(n+1)+ + M(n-1)+, we (1) review and reconsider the charge state (or oxidation number) picture itself, (2) introduce new results for the putative charge ordering compound AgNiO2 and the dual charge state insulator AgO, and (3) analyze the cationic occupations of the actual (not formal) charge, and work to reconcile the conundrums that arise. We establish that several of the clearest cases of charge ordering transitions involve no disproportion (no charge transfer between the cations, and hence no charge ordering), and that the experimental data used to support charge ordering can be accounted for within density functional-based calculations that contain no charge transfer between cations. We propose that the charge state picture retains meaning and importance, at least in many cases, if one focuses on Wannier functions rather than atomic orbitals. The challenge of modeling charge ordering transitions with model Hamiltonians isdiscussed.

  12. Anion and cation diffusion in barium titanate and strontium titanate; Anionen- und Kationendiffusion in Barium- und Strontiumtitanat

    Energy Technology Data Exchange (ETDEWEB)

    Kessel, Markus Franz

    2012-12-19

    Perovskite oxides show various interesting properties providing several technical applications. In many cases the defect chemistry is the key to understand and influence the material's properties. In this work the defect chemistry of barium titanate and strontium titanate is analysed by anion and cation diffusion experiments and subsequent time-of-flight secondary ion mass spectrometry (ToF-SIMS). The reoxidation equation for barium titanate used in multi-layer ceramic capacitors (MLCCs) is found out by a combination of different isotope exchange experiments and the analysis of the resulting tracer diffusion profiles. It is shown that the incorporation of oxygen from water vapour is faster by orders of magnitude than from molecular oxygen. Chemical analysis shows the samples contain various dopants leading to a complex defect chemistry. Dysprosium is the most important dopant, acting partially as a donor and partially as an acceptor in this effectively acceptor-doped material. TEM and EELS analysis show the inhomogeneous distribution of Dy in a core-shell microstructure. The oxygen partial pressure and temperature dependence of the oxygen tracer diffusion coefficients is analysed and explained by the complex defect chemistry of Dy-doped barium titanate. Additional fast diffusion profiles are attributed to fast diffusion along grain boundaries. In addition to the barium titanate ceramics from an important technical application, oxygen diffusion in cubic, nominally undoped BaTiO{sub 3} single crystals has been studied by means of {sup 18}O{sub 2}/{sup 16}O{sub 2} isotope exchange annealing and subsequent determination of the isotope profiles in the solid by ToF-SIMS. It is shown that a correct description of the diffusion profiles requires the analysis of the diffusion through the surface space-charge into the material's bulk. Surface exchange coefficients, space-charge potentials and bulk diffusion coefficients are analysed as a function of oxygen partial

  13. Soudage par explosion thermique sous charge de cermets poreux à base de TiC-Ni sur substrat en acier-comportement tribologique Welding of porous TiC–Ni based cermets on substrate steel by thermal explosion under load-tribological behaviour

    Directory of Open Access Journals (Sweden)

    Lemboub Samia

    2013-11-01

    Full Text Available Dans ce travail, nous nous intéressons à l'élaboration de cermets à base de TiC-Ni par dispersion de particules de carbures, oxydes ou borures dans une matrice de nickel, grâce à la technique de l'explosion thermique sous une charge de 20 MPa. La combustion de mélanges actifs (Ti-C-Ni-An où An = Al2O3, MgO, SiC, TiB2, WC, basée sur la réaction de synthèse de TiC (ΔHf298K = −184 kJ/mole, génère des cermets complexes. Un court maintien sous charge du cermet à 1373 K, après l'explosion thermique, permet son soudage sur un substrat en acier XC55. Les cermets obtenus dans ces conditions demeurent poreux et conservent une porosité de l'ordre de 25–35 %. La densité relative du cermet, sa dureté et son comportement tribologique, dépendront de la nature de l'addition dans les mélanges de départ. Porous TiC-Ni based cermets were obtained by dispersion of carbides, oxides or borides particles in a nickel matrix thanks to the thermal explosion technique realized under a load of 20 MPa. The combustion of active mixtures (Ti-C-Ni-An where An = Al2O3, MgO, SiC, TiB2 or WC based on the titanium carbide reaction synthesis (ΔHf = −184 kJ/mol, generates porous complex cermets. After the thermal explosion, a short maintenance under load at 1373 K of the combustion product, allows at the same time the cermets welding on a carbon steel substrate. The obtained cermets under these conditions preserve a porosity of about 25–35%. The relative density, hardness and tribological behaviour of the complex cermets depend on the additions nature (An in the starting mixtures.

  14. Enhanced charge collection and photocatalysis performance of CdS and PbS nanoclusters co-sensitized TiO{sub 2} porous film

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Miao; Xu, Yanyan; Gong, Zezhou; Tao, Jiajia [School of Physics & Material Science, Anhui University, Hefei 230601 (China); Sun, Zhaoqi, E-mail: szq@ahu.edu.cn [School of Physics & Material Science, Anhui University, Hefei 230601 (China); Lv, Jianguo [School of Electronic & Information Engineering, Hefei Normal University, Hefei, 230601 (China); National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Sciences, Shanghai 200083 (China); Chen, Xiaoshuang [National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Sciences, Shanghai 200083 (China); Jiang, Xishun [School of Physics & Material Science, Anhui University, Hefei 230601 (China); School of Mechanical & Electronic Engineering, Chuzhou University, Chuzhou, 239000 (China); He, Gang; Wang, Peihong; Meng, Fanming [School of Physics & Material Science, Anhui University, Hefei 230601 (China)

    2015-11-15

    A novel translucent TiO{sub 2} porous film was prepared through etched method. The CdS, PbS and CdS/PbS nanoclusters were imbedded on TiO{sub 2} porous film by successive ionic layer adsorption and reaction method. Microstructure, morphology, optical and photoelectron-chemical properties of the as-synthesized thin films were investigated systematically. XRD and morphology analysis showed that PbS or CdS nanoclusters have been attached to the TiO{sub 2} porous films. It was found that the energy band gap of TiO{sub 2} porous film decreased from 3.46 to 3.2 eV after sensitized with nanoclusters. The photocurrent density of ITO/TiO{sub 2} photoelectrode increased from 0.017 to 0.28 mA/cm{sup 2} after co-sensitized with CdS and PbS nanoclusters. Besides, the photoelectrode sensitized with two sorts of nanoclusters showed evident higher photocurrent density than which sensitized just one sort of nanoclusters. The photocurrent density of ITO/TiO{sub 2}/PbS and TO/TiO{sub 2}/CdS photoelectrode was 0.11 mA/cm{sup 2} and 0.22 mA/cm{sup 2} respectively. 0.28 mA/cm{sup 2} can be obtained by ITO/TiO{sub 2}/CdS/PbS photoelectrode. The results showed that the optical and photoelectrochemistry properties and phtotcatalysis performance of TiO{sub 2} porous film were greatly improved by co-sensitized with CdS and PbS nanoclusters. - Graphical abstract: When CdS and PbS were brought in the cascade structure, such a Fermi level alignment causes upward and downward shifts of the band edges for PbS and CdS, respectively. Therefore the resulting band edges for the ITO/TiO{sub 2}/CdS/PbS devices are inferred to have a stepwise structure. The elevated conduction band edge of PbS provides a higher driving force for the injection of photogenerated electrons from PbS to CdS as well as the injection of excited holes from CdS to PbS. Such a structure offers efficient separation and transport of the excited electrons and holes. - Highlights: • Ti films were obtained from direct current

  15. Photoionization study of Ne-like K9+, Ca10+, Sc11+, Ti12+, V13+, Cr14+, Mn15+, and Fe16+ ions using the screening constant by unit nuclear charge method

    International Nuclear Information System (INIS)

    Goyal, Arun; Khatri, Indu; Sow, Malick; Sakho, Ibrahima; Aggarwal, Sunny; Singh, A.K.; Mohan, Man

    2016-01-01

    Photoionization of the 2s 2 2p 6 ( 1 S 0 ) ground state of the Ne-like (Z=19–29) ions is presented in this paper. Resonance energies and total natural width of the 2s2p 6 np 1 P series of the Ne-like K 9+ , Ca 10+ , Sc 11+ , Ti 12+ , V 13+ , Cr 14+ , Mn 15+ , and Fe 16+ are reported. All the calculations are made using the Screening constant by unit nuclear charge (SCUNC) formalism. New data for Ne-like K 9+ , Sc 11+ , Ti 12+ , V 13+ , Cr 14+ , and Mn 15+ ions are tabulated. Good agreements are found with available literature data. - Highlights: • Photoionization of ground state of the Ne-like (Z=19–29) presented. • good agreements with scarce literature data. • New data for Ne-like K 9+ , Sc 11+ , Ti 12+ , V 13+ , Cr 14+ , and Mn 15+ ions. • Useful guidelines for application in laboratory, astrophysics, and plasma physics.

  16. Effect of doping of trivalent cations Ga{sup 3+}, Sc{sup 3+}, Y{sup 3+} in Li{sub 1.3}Al{sub 0.3}Ti{sub 1.7} (PO{sub 4}){sub 3} (LATP) system on Li{sup +} ion conductivity

    Energy Technology Data Exchange (ETDEWEB)

    Kothari, Dharmesh H.; Kanchan, D.K., E-mail: dkkanchan.ssi@gmail.com

    2016-11-15

    We report the effect of trivalent cations dopants in the Li{sub 1.3}Al{sub 0.3−x}R{sub x}Ti{sub 1.7}(PO{sub 4}){sub 3} (R=Ga{sup 3+}, Sc{sup 3+}, Y{sup 3+}) NASICON ceramic system in the concentration range x=0.01,0.03,0.05,0.07, on the Li{sup +} ion conducting properties using impedance spectroscopy. The samples were prepared by solid state reaction method and characterized by X-Ray Diffraction and density measurements. The electrical properties were studied using impedance spectroscopy in frequency range 10 Hz to 20 MHz and temperature range 303 K to 423 K. Although the porosity of the material decreased with doping, the overall Li{sup +} ion conductivity of the system did not improve with doping. Ionic radii of the dopant cations was found to be an important factor in formation of impurity phases and low Li{sup +} ion conductivity. Gallium doped samples exhibited a higher Li{sup +} ion conductivity compared to its scandium and yttrium doped counterparts.

  17. The A-cation deficient perovskite series La2-xCoTiO6-δ (0 ≤ x ≤ 0.20): new components for potential SOFC composite cathodes

    DEFF Research Database (Denmark)

    Gomez-Perez, Alejandro; Teresa Azcondo, M.; Yuste, Mercedes

    2016-01-01

    La2-xCoTiO6-delta/Ce0.9Gd0.1O2-delta composites are presented as promising new cathodes for solid oxide fuel cells. The B-site ordering characteristic of double perovskites is present in the whole series. Additionally, increasing amounts of La-vacancies give rise to ordering of alternating La...

  18. Selective adsorption of ions in charged slit-systems

    Directory of Open Access Journals (Sweden)

    M.Valiskó

    2013-01-01

    Full Text Available We study the selective adsorption of various cations into a layered slit system using grand canonical Monte Carlo simulations. The slit system is formed by a series of negatively charged membranes. The electrolyte contains two kinds of cations with different sizes and valences modeled by charged hard spheres immersed in a continuum dielectric solvent. We present results for various cases depending on the combinations of the properties of the competing cations. We concentrate to the case when the divalent cations are larger than the monovalent cations. In this case, size and charge have counterbalancing effects, which results in interesting selectivity phenomena.

  19. Cation Exchange Water Softeners

    Science.gov (United States)

    WaterSense released a notice of intent to develop a specification for cation exchange water softeners. The program has made the decision not to move forward with a spec at this time, but is making this information available.

  20. Short-length and high-density TiO{sub 2} nanorod arrays for the efficient charge separation interface in perovskite solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Guannan; Shi, Chengwu, E-mail: shicw506@foxmail.com; Zhang, Zhengguo; Li, Nannan; Li, Long

    2017-05-15

    The TiO{sub 2} nanorod arrays with the length of 70 nm, the diameter of 20 nm, and the areal density of 1000 µm{sup −2} were firstly prepared by the hydrothermal method using the aqueous grown solution of 38 mM titanium isopropoxide and 6 M hydrochloric acid at 170 °C for 60 min. Over-500 nm-thickness CH{sub 3}NH{sub 3}PbI{sub 3−x}Br{sub x} absorber layers were successfully obtained by sequential deposition routes using 1.7 M PbI{sub 2}·DMSO complex precursor solution and 0.465 M isopropanol solution of the methylammonium halide mixture with the molar ratio of CH{sub 3}NH{sub 3}I/CH{sub 3}NH{sub 3}Br=85/15. The perovskite solar cells based on the TiO{sub 2} nanorod array and 560 nm-thickness CH{sub 3}NH{sub 3}PbI{sub 3−x}Br{sub x} absorber layer exhibited the best photoelectric conversion efficiency (PCE) of 15.93%, while the corresponding planar perovskite solar cells without the TiO{sub 2} nanorod array and with 530 nm-thickness CH{sub 3}NH{sub 3}PbI{sub 3−x}Br{sub x} absorber layer gave the best PCE of 12.82% at the relative humidity of 50–54%. - Graphical abstract: The TiO{sub 2} nanorod arrays with the length of 70 nm, the diameter of 20 nm, and the areal density of 1000 µm{sup −2} were prepared by the hydrothermal method using the aqueous grown solution of 38 mM titanium isopropoxide and 6 M hydrochloric acid at 170 °C for 60 min. The optimal annealing temperature of TiO{sub 2} nanorod arrays was 450 °C. The perovskite solar cells based on the TiO{sub 2} nanorod array and 560 nm-thickness CH{sub 3}NH{sub 3}PbI{sub 3−x}Br{sub x} absorber layer exhibited the best photoelectric conversion efficiency (PCE) of 15.93% and the average PCE of 13.41±2.52%, while the corresponding planar perovskite solar cells without the TiO{sub 2} nanorod array and with 530 nm-thickness CH{sub 3}NH{sub 3}PbI{sub 3−x}Br{sub x} absorber layer gave the best PCE of 12.82% and the average PCE of 10.54±2.28% at the relative humidity of 50–54%. - Highlights:

  1. Short-length and high-density TiO2 nanorod arrays for the efficient charge separation interface in perovskite solar cells

    International Nuclear Information System (INIS)

    Xiao, Guannan; Shi, Chengwu; Zhang, Zhengguo; Li, Nannan; Li, Long

    2017-01-01

    The TiO 2 nanorod arrays with the length of 70 nm, the diameter of 20 nm, and the areal density of 1000 µm −2 were firstly prepared by the hydrothermal method using the aqueous grown solution of 38 mM titanium isopropoxide and 6 M hydrochloric acid at 170 °C for 60 min. Over-500 nm-thickness CH 3 NH 3 PbI 3−x Br x absorber layers were successfully obtained by sequential deposition routes using 1.7 M PbI 2 ·DMSO complex precursor solution and 0.465 M isopropanol solution of the methylammonium halide mixture with the molar ratio of CH 3 NH 3 I/CH 3 NH 3 Br=85/15. The perovskite solar cells based on the TiO 2 nanorod array and 560 nm-thickness CH 3 NH 3 PbI 3−x Br x absorber layer exhibited the best photoelectric conversion efficiency (PCE) of 15.93%, while the corresponding planar perovskite solar cells without the TiO 2 nanorod array and with 530 nm-thickness CH 3 NH 3 PbI 3−x Br x absorber layer gave the best PCE of 12.82% at the relative humidity of 50–54%. - Graphical abstract: The TiO 2 nanorod arrays with the length of 70 nm, the diameter of 20 nm, and the areal density of 1000 µm −2 were prepared by the hydrothermal method using the aqueous grown solution of 38 mM titanium isopropoxide and 6 M hydrochloric acid at 170 °C for 60 min. The optimal annealing temperature of TiO 2 nanorod arrays was 450 °C. The perovskite solar cells based on the TiO 2 nanorod array and 560 nm-thickness CH 3 NH 3 PbI 3−x Br x absorber layer exhibited the best photoelectric conversion efficiency (PCE) of 15.93% and the average PCE of 13.41±2.52%, while the corresponding planar perovskite solar cells without the TiO 2 nanorod array and with 530 nm-thickness CH 3 NH 3 PbI 3−x Br x absorber layer gave the best PCE of 12.82% and the average PCE of 10.54±2.28% at the relative humidity of 50–54%. - Highlights: • Preparation of TiO 2 nanorod array with length of 70 nm and density of 1000 µm −2 . • Influence of annealing temperatures on the -OH content of Ti

  2. Cationic antimicrobial peptides inactivate Shiga toxin-encoding bacteriophages

    Science.gov (United States)

    Del Cogliano, Manuel E.; Hollmann, Axel; Martinez, Melina; Semorile, Liliana; Ghiringhelli, Pablo D.; Maffía, Paulo C.; Bentancor, Leticia V.

    2017-12-01

    Shiga toxin (Stx) is the principal virulence factor during Shiga toxin-producing Escherichia coli (STEC) infections. We have previously reported the inactivation of bacteriophage encoding Stx after treatment with chitosan, a linear polysaccharide polymer with cationic properties. Cationic antimicrobial peptides (cAMPs) are short linear aminoacidic sequences, with a positive net charge, which display bactericidal or bacteriostatic activity against a wide range of bacterial species. They are promising novel antibiotics since they have shown bactericidal effects against multiresistant bacteria. To evaluate whether cationic properties are responsible for bacteriophage inactivation, we tested seven cationic peptides with proven antimicrobial activity as anti-bacteriophage agents, and one random sequence cationic peptide with no antimicrobial activity as a control. We observed bacteriophage inactivation after incubation with five cAMPs, but no inactivating activity was observed with the random sequence cationic peptide or with the non alpha helical cAMP Omiganan. Finally, to confirm peptide-bacteriophage interaction, zeta potential was analyzed by following changes on bacteriophage surface charges after peptide incubation. According to our results we could propose that: 1) direct interaction of peptides with phage is a necessary step for bacteriophage inactivation, 2) cationic properties are necessary but not sufficient for bacteriophage inactivation, and 3) inactivation by cationic peptides could be sequence (or structure) specific. Overall our data suggest that these peptides could be considered a new family of molecules potentially useful to decrease bacteriophage replication and Stx expression.

  3. Cationic Antimicrobial Peptides Inactivate Shiga Toxin-Encoding Bacteriophages

    Directory of Open Access Journals (Sweden)

    Manuel E. Del Cogliano

    2017-12-01

    Full Text Available Shiga toxin (Stx is the principal virulence factor during Shiga toxin-producing Escherichia coli (STEC infections. We have previously reported the inactivation of bacteriophage encoding Stx after treatment with chitosan, a linear polysaccharide polymer with cationic properties. Cationic antimicrobial peptides (cAMPs are short linear aminoacidic sequences, with a positive net charge, which display bactericidal or bacteriostatic activity against a wide range of bacterial species. They are promising novel antibiotics since they have shown bactericidal effects against multiresistant bacteria. To evaluate whether cationic properties are responsible for bacteriophage inactivation, we tested seven cationic peptides with proven antimicrobial activity as anti-bacteriophage agents, and one random sequence cationic peptide with no antimicrobial activity as a control. We observed bacteriophage inactivation after incubation with five cAMPs, but no inactivating activity was observed with the random sequence cationic peptide or with the non-alpha helical cAMP Omiganan. Finally, to confirm peptide-bacteriophage interaction, zeta potential was analyzed by following changes on bacteriophage surface charges after peptide incubation. According to our results we could propose that: (1 direct interaction of peptides with phage is a necessary step for bacteriophage inactivation, (2 cationic properties are necessary but not sufficient for bacteriophage inactivation, and (3 inactivation by cationic peptides could be sequence (or structure specific. Overall our data suggest that these peptides could be considered a new family of molecules potentially useful to decrease bacteriophage replication and Stx expression.

  4. Radiation chemistry of aromatic dimer radical cations

    International Nuclear Information System (INIS)

    Okamoto, Kazumasa; Tagawa, Seiichi

    2009-01-01

    π-π Interactions of aromatic molecules are paid attention much in many fields, especially biology, chemistry, and applied physics, represented as protein, DNA, electron donor-accepter complexes, charge transfers, and self assembly molecules. Aromatic molecules including benzene rings are the simplest case to study the π-π interactions. To interpret the charge resonance (CR) structure in the dimer radical cations, spectroscopic and ESR methods have been carried out. The spectroscopic study on the dimer radical ion of molecules with two chromophores would be profitable to identify the electronic and configurational properties. In this article, dynamics of the dimer radical cation of benzenes, polystyrenes, and resist polymers is described on the basis of direct observation of CR band by the nanosecond pulse radiolysis and low temperature γ-radiolysis methods. (author)

  5. Charge transfer mechanism for the formation of metallic states at the KTaO3/SrTiO3 interface

    KAUST Repository

    Nazir, Safdar; Schwingenschlö gl, Udo; Singh, Nirpendra

    2011-01-01

    The electronic and optical properties of the KTaO3/SrTiO3 heterointerface are analyzed by the full-potential linearized augmented plane-wave approach of density functional theory. Optimization of the atomic positions points at subordinate changes

  6. 3D Bi2S3/TiO2 cross-linked heterostructure: An efficient strategy to improve charge transport and separation for high photoelectrochemical performance

    Science.gov (United States)

    Han, Minmin; Jia, Junhong

    2016-10-01

    A novel 3D cross-linked heterostructure of TiO2 nanorods connecting with each other via ultrathin Bi2S3 nanosheets is constructed by a facile and effective strategy. The growth mechanism has been investigated and proposed based on the evolution of microstructure by changing the reaction parameters. Benefiting from the unique cross-linked heterostructure, the as-prepared Bi2S3 nanosheets modified TiO2 nanorods arrays could achieve a high energy conversion efficiency of 3.29% which is the highest value to date for Bi2S3-only sensitized solar cells as the reported highest value is 2.23% and other reported values are less than 1%. Furthermore, the photoelectrochemical studies clearly reveal that the novel cross-linked heterostructure exhibits much better activity than 0D nanoparticles decorated TiO2 nanorods under visible light irradiation, which may be primarily ascribed to the efficient electron transfer from 2D ultrathin Bi2S3 nanosheets to 1D TiO2 nanorod arrays. The promising results in this work confirm the advantages of cross-linked heterostructure and also undoubtedly offer an attractive synthesis strategy to fabricate other nanorod-based hierarchical architecture as well as nano-devices for solar energy conversion.

  7. Enhanced photoelectrochemical and photocatalytic behaviors of MFe2O4 (M = Ni, Co, Zn and Sr) modified TiO2 nanorod arrays

    Science.gov (United States)

    Gao, Xin; Liu, Xiangxuan; Zhu, Zuoming; Wang, Xuanjun; Xie, Zheng

    2016-07-01

    Modified TiO2 nanomaterials are considered to be promising in energy conversion and ferrites modification may be one of the most efficient modifications. In this research, various ferrites, incorporated with various cations (MFe2O4, M = Ni, Co, Zn, and Sr), are utilized to modify the well aligned TiO2 nanorod arrays (NRAs), which is synthesized by hydrothermal method. It is found that all MFe2O4/TiO2 NRAs show obvious red shift into the visible light region compared with the TiO2 NRAs. In particular, NiFe2O4 modification is demonstrated to be the best way to enhance the photoelectrochemical and photocatalytic activity of TiO2 NRAs. Furthermore, the separation and transfer of charge carriers after MFe2O4 modification are clarified by electrochemical impedance spectroscopy measurements. Finally, the underlying mechanism accounting for the enhanced photocatalytic activity of MFe2O4/TiO2 NRAs is proposed. Through comparison among different transition metals modified TiO2 with the same synthesis process and under the same evaluating condition, this work may provide new insight in designing modified TiO2 nanomaterials as visible light active photocatalysts.

  8. Structure relationship of cationic lipids on gene transfection mediated by cationic liposomes.

    Science.gov (United States)

    Paecharoenchai, Orapan; Niyomtham, Nattisa; Apirakaramwong, Auayporn; Ngawhirunpat, Tanasait; Rojanarata, Theerasak; Yingyongnarongkul, Boon-ek; Opanasopit, Praneet

    2012-12-01

    The aim of this study was to investigate the transfection efficiency of cationic liposomes formulated with phosphatidylcholine (PC) and novel synthesized diethanolamine-based cationic lipids at a molar ratio of 5:1 in comparison with Lipofectamine™ 2000. Factors affecting transfection efficiency and cell viability, including the chemical structure of the cationic lipids, such as different amine head group (diamine and polyamine; and non-spermine and spermine) and acyl chain lengths (C14, C16, and C18) and the weight ratio of liposomes to DNA were evaluated on a human cervical carcinoma cell line (HeLa cells) using the pDNA encoding green fluorescent protein (pEGFP-C2). Characterizations of these lipoplexes in terms of size and charge measurement and agarose gel electrophoresis were performed. The results from this study revealed that almost no transfection was observed in the liposome formulations composed of cationic lipids with a non-spermine head group. In addition, the transfection efficiency of these cationic liposomes was in the following order: spermine-C14 > spermine-C16 > spermine-C18. The highest transfection efficiency was observed in the formulation of spermine-C14 liposomes at a weight ratio of 25; furthermore, this formulation was safe for use in vitro. In conclusion, cationic liposomes containing spermine head groups demonstrated promising potential as gene carriers.

  9. Restructuring of a peat in interaction with multivalent cations: effect of cation type and aging time.

    Directory of Open Access Journals (Sweden)

    Yamuna Kunhi Mouvenchery

    Full Text Available It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM molecules via cation bridges (CaB. The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al(3+, Ca(2+ or Na(+, respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>>2 h than deprotonation of functional groups (<2 h and was described by a Langmuir model. The maximum uptake increased with pH of cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB and molecular mobility of water (NMR analysis suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is

  10. Significant role of cationic polymers in drug delivery systems.

    Science.gov (United States)

    Farshbaf, Masoud; Davaran, Soodabeh; Zarebkohan, Amir; Annabi, Nasim; Akbarzadeh, Abolfazl; Salehi, Roya

    2017-11-06

    Cationic polymers are characterized as the macromolecules that possess positive charges, which can be either inherently in the polymer side chains and/or its backbone. Based on their origins, cationic polymers are divided in two category including natural and synthetic, in which the possessed positive charges are as result of primary, secondary or tertiary amine functional groups that could be protonated in particular situations. Cationic polymers have been employed commonly as drug delivery agents due to their superior encapsulation efficacy, enhanced bioavailability, low toxicity and improved release profile. In this paper, we focus on the most prominent examples of cationic polymers which have been revealed to be applicable in drug delivery systems and we also discuss their general synthesis and surface modification methods as well as their controlled release profile in drug delivery.

  11. Chemical bonding and structural ordering of cations in silicate glasses

    International Nuclear Information System (INIS)

    Calas, G.; Cormier, L.; Galoisy, L.; Ramos, A.; Rossano, St.

    1997-01-01

    The specific surrounding of cations in multicomponent silicate glasses is briefly presented. Information about interatomic distances and site geometry may be gained by using spectroscopic methods among which x-ray absorption spectroscopy may be used for the largest number of glass components. Scattering of x-rays and neutrons may also be used to determine the importance of medium range order around specific cations. All the existing data show that cations occur in sites with a well-defined geometry, which are in most cases connected to the silicate polymeric network. Medium range order has been detected around cations such as Ti, Ca and Ni, indicating that these elements have an heterogeneous distribution within the glassy matrix. (authors)

  12. Does the cation really matter? The effect of modifying an ionic liquid cation on an SN2 process.

    Science.gov (United States)

    Tanner, Eden E L; Yau, Hon Man; Hawker, Rebecca R; Croft, Anna K; Harper, Jason B

    2013-09-28

    The rate of reaction of a Menschutkin process in a range of ionic liquids with different cations was investigated, with temperature-dependent kinetic data giving access to activation parameters for the process in each solvent. These data, along with molecular dynamics simulations, demonstrate the importance of accessibility of the charged centre on the cation and that the key interactions are of a generalised electrostatic nature.

  13. XPS study on Mg0.9-xTi0.1PdxNi (x = 0.04, 0.06, 0.08, 0.1) hydrogen storage electrode alloys after charge-discharge cycles

    International Nuclear Information System (INIS)

    Tian Qifeng; Zhang Yao; Wu Yuanxin

    2009-01-01

    The passive film composition of Mg 0.9-x Ti 0.1 Pd x Ni (x = 0.04, 0.06, 0.08, 0.1) hydrogen storage alloys after 40 charge-discharge cycles has been investigated by means of X-ray photoelectron spectroscopy (XPS) in combination with Ar + sputtering technology. With the XPSPEAK software, high resolution spectra of alloy elements and oxygen were deconvolved into individual peaks. Composites formed by metal elements and their relative contents were also deduced. It was found that the composites originated from Mg and Ni were mainly in the form of their oxides and hydroxides, which existed at the top surface of alloys. With the increase of sputtering depth, the hydroxides of Mg and Ni gradually disappeared while corresponding oxides dominated their passive products. According to the analysis results of oxygen spectra, the elemental segregation of Mg and Ni was influenced by the substitution of Pd because the addition of Pd slightly enhanced the surface energy of the alloys and suppressed the formation of Mg hydroxide and oxide. Ti and Pd presented multiple-oxides from the surface to the inner alloys and metallic Pd appeared in the sub-layers of the alloys' surface. The possible mechanisms of the formation of passive products were suggested on the basis of the discussion in the paper.

  14. Seasonal variations in Na, K, Mg and Ca charge balance in marine brown algae from Saurashtra Coast (NW coast of India)

    Digital Repository Service at National Institute of Oceanography (India)

    Rao, Ch.K.; Singbal, S.Y.S.

    ) strongly correlated with Cl content suggesting that these cations were balanced by chloride ions. Divalent cations (Ca + Mg) seem to be balanced by the anion sulphate. Ash content of the algae was accounted by these major cations and anions. Charge...

  15. Cation radicals of xanthophylls.

    Science.gov (United States)

    Galinato, Mary Grace I; Niedzwiedzki, Dariusz; Deal, Cailin; Birge, Robert R; Frank, Harry A

    2007-10-01

    Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, beta-cryptoxanthin, beta-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing pi-chain length. However, zeaxanthin and beta-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of beta-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

  16. Identifi cation of Sectarianism

    Directory of Open Access Journals (Sweden)

    Martinovich Vladimir

    2016-03-01

    Full Text Available «New religious movements and society» is traditionally one of the most sophisticated topics in the area of new religions studies. Its problem field is so huge that up to now by far not all important research themes where even touched by scientists from all over the world. The problem of the process of the identification of sectarianism by diff erent societal institutions is one of such untouched themes that is taken as the main subject of this article. This process by itself is an inseparable part of the every societal deliberate reaction to the very existence of unconventional religiosity, its unstructured and mainly structured types. The focal point of the article is step-by-step analysis of the general structure elements of the process of the identification of sectarianism without any reference to the specific time and place of its flow. Special attention is paid to the analysis of the subjects of the identification of sectarianism, to the criteria for religious groups to be qualified as new religious movements, and to the specific features of the process of documents filtration. The causes of selective perception of sectarianism are disclosed. Some main consequences and unpredictable outcomes of the process of the identification of sectarianism are described.

  17. Electrospray ionization tandem mass spectrometry of ammonium cationized polyethers.

    Science.gov (United States)

    Nasioudis, Andreas; Heeren, Ron M A; van Doormalen, Irene; de Wijs-Rot, Nicolette; van den Brink, Oscar F

    2011-05-01

    Quaternary ammonium salts (Quats) and amines are known to facilitate the MS analysis of high molar mass polyethers by forming low charge state adduct ions. The formation, stability, and behavior upon collision-induced dissociation (CID) of adduct ions of polyethers with a variety of Quats and amines were studied by electrospray ionization quadrupole time-of-flight, quadrupole ion trap, and linear ion trap tandem mass spectrometry (MS/MS). The linear ion trap instrument was part of an Orbitrap hybrid mass spectrometer that allowed accurate mass MS/MS measurements. The Quats and amines studied were of different degree of substitution, structure, and size. The stability of the adduct ions was related to the structure of the cation, especially the amine's degree of substitution. CID of singly/doubly charged primary and tertiary ammonium cationized polymers resulted in the neutral loss of the amine followed by fragmentation of the protonated product ions. The latter reveals information about the monomer unit, polymer sequence, and endgroup structure. In addition, the detection of product ions retaining the ammonium ion was observed. The predominant process in the CID of singly charged quaternary ammonium cationized polymers was cation detachment, whereas their doubly charged adduct ions provided the same information as the primary and tertiary ammonium cationized adduct ions. This study shows the potential of specific amines as tools for the structural elucidation of high molar mass polyethers. © American Society for Mass Spectrometry, 2011

  18. Remarkable fluorescence enhancement versus complex formation of cationic porphyrins on the surface of ZnO nanoparticles

    KAUST Repository

    Aly, Shawkat Mohammede; Eita, Mohamed Samir; Khan, Jafar Iqbal; Alarousu, Erkki; Mohammed, Omar F.

    2014-01-01

    the first experimental measurements demonstrating a clear transition from pronounced fluorescence enhancement to charge transfer (CT) complex formation by simply changing the nature and location of the positive charge of the meso substituent of the cationic

  19. Effect of cations on the hydrated proton.

    Science.gov (United States)

    Ottosson, Niklas; Hunger, Johannes; Bakker, Huib J

    2014-09-17

    We report on a strong nonadditive effect of protons and other cations on the structural dynamics of liquid water, which is revealed using dielectric relaxation spectroscopy in the frequency range of 1-50 GHz. For pure acid solutions, protons are known to have a strong structuring effect on water, leading to a pronounced decrease of the dielectric response. We observe that this structuring is reduced when protons are cosolvated with salts. This reduction is exclusively observed for combinations of protons with other ions; for all studied solutions of cosolvated salts, the effect on the structural dynamics of water is observed to be purely additive, even up to high concentrations. We derive an empirical model that quantitatively describes the nonadditive effect of cosolvated protons and cations. We argue that the effect can be explained from the special character of the proton in water and that Coulomb fields exerted by other cations, in particular doubly charged cations like Mg(2+)aq and Ca(2+)aq, induce a localization of the H(+)aq hydration structures.

  20. Discovery of S···C≡N Intramolecular Bonding in a Thiophenylcyanoacrylate-Based Dye: Realizing Charge Transfer Pathways and Dye···TiO 2 Anchoring Characteristics for Dye-Sensitized Solar Cells

    Energy Technology Data Exchange (ETDEWEB)

    Cole, Jacqueline M. [Cavendish; ISIS; Argonne National Laboratory, 9700 S. Cass Avenue, Argonne, Illinois 60439, United States; Department; Blood-Forsythe, Martin A. [Cavendish; Lin, Tze-Chia [Cavendish; Pattison, Philip [Swiss; Gong, Yun [Cavendish; Vázquez-Mayagoitia, Álvaro [Argonne National Laboratory, 9700 S. Cass Avenue, Argonne, Illinois 60439, United States; Waddell, Paul G. [Cavendish; Australian Centre for Neutron Scattering, Australian Nuclear Science; Zhang, Lei [Cavendish; Koumura, Nagatoshi [National Institute of Advanced Industrial Science and Technology, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan; Mori, Shogo [Division

    2017-07-25

    Donor-pi-acceptor dyes containing thiophenyl pi-conjugated units and cyanoacrylate acceptor groups are among the best-performing organic chromophores used in dye-sensitized solar cell (DSC) applications. Yet, the molecular origins of their high photovoltaic output have remained unclear until now. This synchrotron-based X-ray diffraction study elucidates these origins for the high-performance thiophenylcyanoacrylate-based dye MK-2 (7.7% DSC device efficiency) and its molecular building block, MK-44. The crystal structures of MK-2 and MK-44 are both determined, while a high-resolution charge-density mapping of the smaller molecule was also possible, enabling the nature of its bonding to be detailed. A strong S center dot center dot center dot C equivalent to N intramolecular interaction is discovered, which bears a bond critical point, thus proving that this interaction should be formally classified as a chemical bond. A topological analysis of the pi-conjugated portion of MK-44 shows that this S center dot center dot center dot C equivalent to N bonding underpins the highly efficient intramolecular charge transfer(ICT) in thiophenylcyanoacrylate dyes. This manifests as two bipartite ICT pathways bearing carboxylate and nitrile end points. In turn, these pathways dictate a preferred COO/CN anchoring mode for the dye as it adsorbs onto TiO2 surfaces, to form the dye TiO2 interface that constitutes the DSC working electrode. These results corroborate a recent proposal that all cyanoacrylate groups anchor onto TiO2 in this COO/CN binding configuration. Conformational analysis of the MK-44 and MK-2 crystal structures reveals that this S center dot center dot center dot C equivalent to N bonding will persist in MK-2. Accordingly, this newly discovered bond affords a rational explanation for the attractive photovoltaic properties of,MK-2. More generally, this study provides the first unequivocal evidence for an S center dot center dot center dot C equivalent to N

  1. A study of charge transfer kinetics in dye-sensitized surface conductivity solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Friedrich, Dennis

    2011-05-15

    concentration of the redox species in the electrolyte film, having the fastest decay at the lowest concentration of the redox couple. This was due to the regeneration of the oxidized dye by iodide, screening the positive charge from recombination with injected electrons. The adsorption of cations such as Li{sup +} led to a relatively weak increase of the electron lifetime, although in combination with a redox couple these effects were less clear. The replacement of the iodide/iodine redox couple by the kinetically fast ferrocene/ ferrocenium system caused a dramatic increase of the decay rates of photogenerated charge carriers in subset devices. Thus, showing the importance of the kinetically slow reduction rates of the oxidized redox couple iodide/iodine, leading to an increase of the electron lifetime by the reduction of the dye cation. The analysis of charge carrier kinetics in TiO{sub 2} powders and films displayed a decrease of the decay rate upon dye-sensitization after band-to-band excitation with laser pulses at 355 nm. In the case of ZnO films, the presence of the dye induced a significantly accelerated decay after excitation at 355 nm. In contrast to the ZnO films, ZnO nanorods displayed no such destructive influence of the dye adsorption. Furthermore, after exciting the sample at 355 nm, the decay was found to be independent of the dye and mainly depending on the recombination of electron-hole pairs and electrons with the dye cation at 355 nm and 532 nm, respectively. (orig.)

  2. Predicting Organic Cation Sorption Coefficients: Accounting for Competition from Sorbed Inorganic Cations Using a Simple Probe Molecule.

    Science.gov (United States)

    Jolin, William C; Goyetche, Reaha; Carter, Katherine; Medina, John; Vasudevan, Dharni; MacKay, Allison A

    2017-06-06

    With the increasing number of emerging contaminants that are cationic at environmentally relevant pH values, there is a need for robust predictive models of organic cation sorption coefficients (K d ). Current predictive models fail to account for the differences in the identity, abundance, and affinity of surface-associated inorganic exchange ions naturally present at negatively charged receptor sites on environmental solids. To better understand how organic cation sorption is influenced by surface-associated inorganic exchange ions, sorption coefficients of 10 organic cations (including eight pharmaceuticals and two simple probe organic amines) were determined for six homoionic forms of the aluminosilicate mineral, montmorillonite. Organic cation sorption coefficients exhibited consistent trends for all compounds across the various homoionic clays with sorption coefficients (K d ) decreasing as follows: K d Na + > K d NH 4 + ≥ K d K + > K d Ca 2+ ≥ K d Mg 2+ > K d Al 3+ . This trend for competition between organic cations and exchangeable inorganic cations is consistent with the inorganic cation selectivity sequence, determined for exchange between inorganic ions. Such consistent trends in competition between organic and inorganic cations suggested that a simple probe cation, such as phenyltrimethylammonium or benzylamine, could capture soil-to-soil variations in native inorganic cation identity and abundance for the prediction of organic cation sorption to soils and soil minerals. Indeed, sorption of two pharmaceutical compounds to 30 soils was better described by phenyltrimethylammonium sorption than by measures of benzylamine sorption, effective cation exchange capacity alone, or a model from the literature (Droge, S., and Goss, K. Environ. Sci. Technol. 2013, 47, 14224). A hybrid approach integrating structural scaling factors derived from this literature model of organic cation sorption, along with phenyltrimethylammonium K d values, allowed for

  3. Nonstoichiometry of Epitaxial FeTiO(3+delta) Films

    Science.gov (United States)

    2003-01-01

    nonstoichiometry of the FeTiO3 +8 films was probably produced by cation vacancies and disarrangement of Fe3+ and Ti4 ions, which randomly occupied both interstitial...and substitutional sites of the FeTiO 3 related structure. INTRODUCTION Solid solutions of ot-Fe20 3- FeTiO3 (hematite-ilmenite) series are known to...tried to confirm preparation conditions of stoichiometric FeTiO 3 films. According to a literature on bulk crystal growth of FeTiO3 [5], very low oxygen

  4. Synthesis and Molecular Structure of a Novel Compound Containing a Carbonate-Bridged Hexacalcium Cluster Cation Assembled on a Trimeric Trititanium(IV)-Substituted Wells-Dawson Polyoxometalate.

    Science.gov (United States)

    Hoshino, Takahiro; Isobe, Rina; Kaneko, Takuya; Matsuki, Yusuke; Nomiya, Kenji

    2017-08-21

    A novel compound containing a hexacalcium cluster cation, one carbonate anion, and one calcium cation assembled on a trimeric trititanium(IV)-substituted Wells-Dawson polyoxometalate (POM), [{Ca 6 (CO 3 )(μ 3 -OH)(OH 2 ) 18 }(P 2 W 15 Ti 3 O 61 ) 3 Ca(OH 2 ) 3 ] 19- (Ca 7 Ti 9 Trimer), was obtained as the Na 7 Ca 6 salt (NaCa-Ca 7 Ti 9 Trimer) by the reaction of calcium chloride with the monomeric trititanium(IV)-substituted Wells-Dawson POM species "[P 2 W 15 Ti 3 O 59 (OH) 3 ] 9- " (Ti 3 Monomer). Ti 3 Monomer was generated in situ under basic conditions from the separately prepared tetrameric species with bridging Ti(OH 2 ) 3 groups and an encapsulated Cl - ion, [{P 2 W 15 Ti 3 O 59 (OH) 3 } 4 {μ 3 -Ti(H 2 O) 3 } 4 Cl] 21- (Ti 16 Tetramer). The Na 7 Ca 6 salt of Ca 7 Ti 9 Trimer was characterized by complete elemental analysis, thermogravimetric (TG) and differential thermal analyses (DTA), FTIR, single-crystal X-ray structure analysis, and solution 183 W and 31 P NMR spectroscopy. X-ray crystallography revealed that the [Ca 6 (CO 3 )(μ 3 -OH)(OH 2 ) 18 ] 9+ cluster cation was composed of six calcium cations linked by one μ 6 -carbonato anion and one μ 3 -OH - anion. The cluster cation was assembled, together with one calcium ion, on a trimeric species composed of three tri-Ti(IV)-substituted Wells-Dawson subunits linked by Ti-O-Ti bonds. Ca 7 Ti 9 Trimer is an unprecedented POM species containing an alkaline-earth-metal cluster cation and is the first example of alkaline-earth-metal ions clustered around a titanium(IV)-substituted POM.

  5. Sorption of the organic cation metoprolol on silica gel from its aqueous solution considering the competition of inorganic cations.

    Science.gov (United States)

    Kutzner, Susann; Schaffer, Mario; Börnick, Hilmar; Licha, Tobias; Worch, Eckhard

    2014-05-01

    Systematic batch experiments with the organic monovalent cation metoprolol as sorbate and the synthetic material silica gel as sorbent were conducted with the aim of characterizing the sorption of organic cations onto charged surfaces. Sorption isotherms for metoprolol (>99% protonated in the tested pH of around 6) in competition with mono- and divalent inorganic cations (Na(+), NH4(+), Ca(2+), and Mg(2+)) were determined in order to assess their influence on cation exchange processes and to identify the role of further sorptive interactions. The obtained sorption isotherms could be described well by an exponential function (Freundlich isotherm model) with consistent exponents (about 0.8). In general, a decreasing sorption of metoprolol with increasing concentrations in inorganic cations was observed. Competing ions of the same valence showed similar effects. A significant sorption affinity of metoprolol with ion type dependent Freundlich coefficients KF,0.77 between 234.42 and 426.58 (L/kg)(0.77) could still be observed even at very high concentrations of competing inorganic cations. Additional column experiments confirm this behavior, which suggests the existence of further relevant interactions beside cation exchange. In subsequent batch experiments, the influence of mixtures with more than one competing ion and the effect of a reduced negative surface charge at a pH below the point of zero charge (pHPZC ≈ 2.5) were also investigated. Finally, the study demonstrates that cation exchange is the most relevant but not the sole mechanism for the sorption of metoprolol on silica gel. Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. Charge recombination reduction in dye-sensitized solar cells by means of an electron beam-deposited TiO2 buffer layer between conductive glass and photoelectrode

    International Nuclear Information System (INIS)

    Manca, Michele; Malara, Francesco; Martiradonna, Luigi; De Marco, Luisa; Giannuzzi, Roberto; Cingolani, Roberto; Gigli, Giuseppe

    2010-01-01

    A thin anatase titanium dioxide compact film was deposited by electron beam evaporation as buffer layer between the conductive transparent electrode and the porous TiO 2 -based photoelectrode in dye-sensitized solar cells. The effect of such a buffer layer on the back transfer reaction of electrons to tri-iodide ions in liquid electrolyte-based cells has been studied by means of both electrochemical impedance spectroscopy and open circuit photovoltage decay analysis. The influence of the thickness has been also investigated and an increment in overall quantum conversion efficiency η as high as + 31% with respect to the standard cell - fabricated onto an uncoated conductive glass - has been revealed in the case of a 120 nm thick buffer layer.

  7. Topotactic oxidation of TiGaPO-1, a pyridine-templated titanium gallophosphate with a new octahedral-tetrahedral 3-D framework structure containing Ti(III)/Ti(IV).

    Science.gov (United States)

    Chippindale, Ann M; Grimshaw, Mark R; Powell, Anthony V; Cowley, Andrew R

    2005-06-13

    The first 3-D open-framework TiGaPO complex, constructed from Ti(III)O(6), Ti(IV)O(6), GaO(4), and PO(4) polyhedra, contains pyridinium cations in a 1-D pore network and can be oxidized in air at 543 K with retention of the original framework structure.

  8. Repulsion between oppositely charged planar macroions.

    Directory of Open Access Journals (Sweden)

    YongSeok Jho

    Full Text Available The repulsive interaction between oppositely charged macroions is investigated using Grand Canonical Monte Carlo simulations of an unrestricted primitive model, including the effect of inhomogeneous surface charge and its density, the depth of surface charge, the cation size, and the dielectric permittivity of solvent and macroions, and their contrast. The origin of the repulsion is a combination of osmotic pressure and ionic screening resulting from excess salt between the macroions. The excess charge over-reduces the electrostatic attraction between macroions and raises the entropic repulsion. The magnitude of the repulsion increases when the dielectric constant of the solvent is lowered (below that of water and/or the surface charge density is increased, in good agreement with experiment. Smaller size of surface charge and the cation, their discreteness and mobility are other factors that enhance the repulsion and charge inversion phenomenons.

  9. Anaerobic toxicity of cationic silver nanoparticles

    International Nuclear Information System (INIS)

    Gitipour, Alireza; Thiel, Stephen W.; Scheckel, Kirk G.; Tolaymat, Thabet

    2016-01-01

    The microbial toxicity of silver nanoparticles (AgNPs) stabilized with different capping agents was compared to that of Ag"+ under anaerobic conditions. Three AgNPs were investigated: (1) negatively charged citrate-coated AgNPs (citrate-AgNPs), (2) minimally charged polyvinylpyrrolidone coated AgNPs (PVP-AgNPs) and (3) positively charged branched polyethyleneimine coated AgNPs (BPEI-AgNPs). The AgNPs investigated in this experiment were similar in size (10–15 nm), spherical in shape, but varied in surface charge which ranged from highly negative to highly positive. While, at AgNPs concentrations lower than 5 mg L"−"1, the anaerobic decomposition process was not influenced by the presence of the nanoparticles, there was an observed impact on the diversity of the microbial community. At elevated concentrations (100 mg L"−"1 as silver), only the cationic BPEI-AgNPs demonstrated toxicity similar in magnitude to that of Ag"+. Both citrate and PVP-AgNPs did not exhibit toxicity at the 100 mg L"−"1 as measured by biogas evolution. These findings further indicate the varying modes of action for nanoparticle toxicity and represent one of the few studies that evaluate end-of-life management concerns with regards to the increasing use of nanomaterials in our everyday life. These findings also highlight some of the concerns with a one size fits all approach to the evaluation of environmental health and safety concerns associated with the use of nanoparticles. - Highlights: • At concentrations -1 the anaerobic decomposition process was not impacted. • An impact on the microbial community at concentrations -1 were observed. • At high concentrations (100 mg L"−"1), the cationic BPEI-AgNPs demonstrated toxicity. • Toxicity was demonstrated without the presence of oxidative dissolution of silver. • A one size fits all approach for the evaluation of NPs may not be accurate.

  10. Magnetoelectric properties of Pb free Bi2FeTiO6: A theoretical investigation

    Science.gov (United States)

    Patra, Lokanath; Ravindran, P.

    2018-05-01

    The structural, electronic, magnetic and ferroelectric properties of Pb free double perovskite multiferroic Bi2FeTiO6 are investigated using density functional theory within the general gradient approximation (GGA) method. Our structural optimization using total energy calculations for different potential structures show a minimum energy for a non-centrosymmetric rhombohedral structure with R3c space group. Bi2FeTiO6 is found to be an antiferromagnetic insulator with C-type magnetic ordering with bandgap value of 0.3 eV. The calculated magnetic moment of 3.52 μB at Fe site shows the high spin arrangement of 3d electrons which is also confirmed by our orbital projected density of states analysis. We have analyzed the characteristics of bonding present between the constituents of Bi2FeTiO6 with the help of calculated partial density of states and Born effective charges. The ground state of the nearest centrosymmetric structure is found to be a G-type antiferromagnet with half metallicity showing that by the application of external electric field we can not only get a polarized state but also change the magnetic ordering and electronic structure in the present compound indicating strong magnetoelectric coupling. The cation sites the coexistence of Bi 6s lone pair (bring disproportionate charge distribution) and Ti4+ d0 ions which brings covalency produces off-center displacement and favors a non-centrosymmetric ground state and thus ferroelectricity. Our Berry phase calculation gives a polarization of 48 µCcm-2 for Bi2FeTiO6.

  11. Synthesis and characterization of Fe3+ doped TiO2 nanoparticles and films and their performance for photocurrent response under UV illumination

    International Nuclear Information System (INIS)

    Elghniji, Kais; Atyaoui, Atef; Livraghi, Stefano; Bousselmi, Latifa; Giamello, Elio; Ksibi, Mohamed

    2012-01-01

    Graphical abstract: Schematic diagram illustrating the charge transfer from excited TiO 2 to the different states of Fe 3+ ions; C B and V B refer to the energy levels of the conduction and valence bands of TiO 2 , respectively. Highlights: ► In this study we examine the Iron as catalyst precursor to synthesize the Fe 3+ doped TiO 2 nanoparticles. ► The Fe 3+ doped TiO 2 catalysts show the presence of a mixed phase of anatase. ► The iron is completely absent in the XRD pattern of the doped iron TiO 2 powder. ► The analysis of EPR result further confirms that Fe 3+ ion are successfully doped in the TiO 2 lattice by substituting Ti 4+ . ► Fe 3+ doping can efficiently separate the photo-generated electrons and holes. - Abstract: Undoped TiO 2 and Fe 3+ doped (0.1, 0.3, 0.6 and 1 wt.%) TiO 2 nanoparticles have been synthesized by the acid-catalyzed sol–gel method. Iron cations are introduced in the initial solution, before gelification, what promotes their lattice localization. The Fe 3+ doped TiO 2 films have been fabricated using a dip-coating technique. The effect of iron content on the crystalline structure, phase transformation and grain growth were determined by X-ray diffraction (XRD), Raman spectroscopy, UV–visible diffused reflectance spectroscopy (DRS) and Electron paramagnetic resonance (EPR) spectroscopy. It has demonstrated that all catalysts are composed of mixed-phase crystals of anatase and brookite with anatase as dominant phase. The crystallinity of the brookite and anatase phases decreased with increasing the iron content. The analysis of EPR result further confirms that Fe 3+ ion are successfully doped in the TiO 2 lattice by substituting Ti 4+ . It was demonstrated that Fe 3+ ion in the TiO 2 films plays a role as the intermediate for the efficient separation of photogenerated hole–electron pairs and increases the photocurrent response of the film under UV light irradiation. The maximum photocurrent is obtained on the Fe 3+ doped Ti

  12. Synthesis and characterization of Fe{sup 3+} doped TiO{sub 2} nanoparticles and films and their performance for photocurrent response under UV illumination

    Energy Technology Data Exchange (ETDEWEB)

    Elghniji, Kais [University of Sfax, Laboratoire Eau, Energie et Environnement (LR3E), Ecole Nationale d' Ingenieurs de Sfax, B.P. 1173, 3038 Sfax (Tunisia); Atyaoui, Atef [Centre de Recherches et des Technologies des Eaux, Technopole de Borj Cedria B.P. 273, 8020 Soliman (Tunisia); Livraghi, Stefano [Dipartimento di Chimica I.F.M and NIS, Universita degli Studi di Torino, Via P. Giuria, 7 10125 Torino (Italy); Bousselmi, Latifa [Centre de Recherches et des Technologies des Eaux, Technopole de Borj Cedria B.P. 273, 8020 Soliman (Tunisia); Giamello, Elio [Dipartimento di Chimica I.F.M and NIS, Universita degli Studi di Torino, Via P. Giuria, 7 10125 Torino (Italy); Ksibi, Mohamed, E-mail: Mohamed.Ksibi@tunet.tn [University of Sfax, Laboratoire Eau, Energie et Environnement (LR3E), Ecole Nationale d' Ingenieurs de Sfax, B.P. 1173, 3038 Sfax (Tunisia)

    2012-11-15

    Graphical abstract: Schematic diagram illustrating the charge transfer from excited TiO{sub 2} to the different states of Fe{sup 3+} ions; C{sub B} and V{sub B} refer to the energy levels of the conduction and valence bands of TiO{sub 2}, respectively. Highlights: Black-Right-Pointing-Pointer In this study we examine the Iron as catalyst precursor to synthesize the Fe{sup 3+} doped TiO{sub 2} nanoparticles. Black-Right-Pointing-Pointer The Fe{sup 3+} doped TiO{sub 2} catalysts show the presence of a mixed phase of anatase. Black-Right-Pointing-Pointer The iron is completely absent in the XRD pattern of the doped iron TiO{sub 2} powder. Black-Right-Pointing-Pointer The analysis of EPR result further confirms that Fe{sup 3+} ion are successfully doped in the TiO{sub 2} lattice by substituting Ti{sup 4+}. Black-Right-Pointing-Pointer Fe{sup 3+} doping can efficiently separate the photo-generated electrons and holes. - Abstract: Undoped TiO{sub 2} and Fe{sup 3+} doped (0.1, 0.3, 0.6 and 1 wt.%) TiO{sub 2} nanoparticles have been synthesized by the acid-catalyzed sol-gel method. Iron cations are introduced in the initial solution, before gelification, what promotes their lattice localization. The Fe{sup 3+} doped TiO{sub 2} films have been fabricated using a dip-coating technique. The effect of iron content on the crystalline structure, phase transformation and grain growth were determined by X-ray diffraction (XRD), Raman spectroscopy, UV-visible diffused reflectance spectroscopy (DRS) and Electron paramagnetic resonance (EPR) spectroscopy. It has demonstrated that all catalysts are composed of mixed-phase crystals of anatase and brookite with anatase as dominant phase. The crystallinity of the brookite and anatase phases decreased with increasing the iron content. The analysis of EPR result further confirms that Fe{sup 3+} ion are successfully doped in the TiO{sub 2} lattice by substituting Ti{sup 4+}. It was demonstrated that Fe{sup 3+} ion in the TiO{sub 2} films

  13. Unusual photoelectric behaviors of Mo-doped TiO2 multilayer thin films prepared by RF magnetron co-sputtering: effect of barrier tunneling on internal charge transfer

    Science.gov (United States)

    Yan, B. X.; Luo, S. Y.; Mao, X. G.; Shen, J.; Zhou, Q. F.

    2013-01-01

    Mo-doped TiO2 multilayer thin films were prepared by RF magnetron co-sputtering. Microstructures, crystallite parameters and the absorption band were investigated with atomic force microscopy, X-ray diffraction and ultraviolet-visible spectroscopy. Internal carrier transport characteristics and the photoelectric property of different layer-assemble modes were examined on an electrochemical workstation under visible light. The result indicates that the double-layer structure with an undoped surface layer demonstrated a red-shifted absorption edge and a much stronger photocurrent compared to the uniformly doped sample, signifying that the electric field implanted at the interface between particles in different layers accelerated internal charge transfer effectively. However, a heavily doped layer implanted at the bottom of the three-layer film merely brought about negative effects on the photoelectric property, mainly because of the Schottky junction existing above the substrate. Nevertheless, this obstacle was successfully eliminated by raising the Mo concentration to 1020 cm-3, where the thickness of the depletion layer fell into the order of angstroms and the tunneling coefficient manifested a dramatic increase. Under this circumstance, the Schottky junction disappeared and the strongest photocurrent was observed in the three-layer film.

  14. Average and local atomic-scale structure in BaZrxTi(1-x)O3 (x = 0. 10, 0.20, 0.40) ceramics by high-energy x-ray diffraction and Raman spectroscopy.

    Science.gov (United States)

    Buscaglia, Vincenzo; Tripathi, Saurabh; Petkov, Valeri; Dapiaggi, Monica; Deluca, Marco; Gajović, Andreja; Ren, Yang

    2014-02-12

    High-resolution x-ray diffraction (XRD), Raman spectroscopy and total scattering XRD coupled to atomic pair distribution function (PDF) analysis studies of the atomic-scale structure of archetypal BaZrxTi(1-x)O3 (x = 0.10, 0.20, 0.40) ceramics are presented over a wide temperature range (100-450 K). For x = 0.1 and 0.2 the results reveal, well above the Curie temperature, the presence of Ti-rich polar clusters which are precursors of a long-range ferroelectric order observed below TC. Polar nanoregions (PNRs) and relaxor behaviour are observed over the whole temperature range for x = 0.4. Irrespective of ceramic composition, the polar clusters are due to locally correlated off-centre displacement of Zr/Ti cations compatible with local rhombohedral symmetry. Formation of Zr-rich clusters is indicated by Raman spectroscopy for all compositions. Considering the isovalent substitution of Ti with Zr in BaZrxTi1-xO3, the mechanism of formation and growth of the PNRs is not due to charge ordering and random fields, but rather to a reduction of the local strain promoted by the large difference in ion size between Zr(4+) and Ti(4+). As a result, non-polar or weakly polar Zr-rich clusters and polar Ti-rich clusters are randomly distributed in a paraelectric lattice and the long-range ferroelectric order is disrupted with increasing Zr concentration.

  15. [6]Helicene as a novel molecular tweezer for the univalent silver cation: Experimental and theoretical study

    Czech Academy of Sciences Publication Activity Database

    Klepetářová, B.; Makrlík, E.; Jaklová Dytrtová, Jana; Böhm, S.; Vaňura, P.; Storch, Jan

    2015-01-01

    Roč. 1097, Oct 5 (2015), s. 124-128 ISSN 0022-2860 R&D Projects: GA ČR GP13-21409P; GA ČR GAP207/10/1124; GA TA ČR TA01010646; GA MPO FR-TI3/628 Institutional support: RVO:61388963 ; RVO:67985858 Keywords : univalent silver cation * [6]helicene * cation-pi interaction * structures Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.780, year: 2015

  16. Effect of electrolyte valency, alginate concentration and pH on engineered TiO₂ nanoparticle stability in aqueous solution.

    Science.gov (United States)

    Loosli, Frédéric; Le Coustumer, Philippe; Stoll, Serge

    2015-12-01

    Agglomeration and disagglomeration processes are expected to play a key role on the fate of engineered nanoparticles in natural aquatic systems. These processes are investigated here in detail by studying first the stability of TiO2 nanoparticles in the presence of monovalent and divalent electrolytes at different pHs (below and above the point of zero charge of TiO2) and discussing the importance of specific divalent cation adsorption with the help of the DLVO theory as well as the importance of the nature of the counterions. Then the impact of one polysaccharide (alginate) on the stability of agglomerates formed under pH and water hardness representative of Lake Geneva environmental conditions is investigated. In these conditions the large TiO2 agglomerates (diameter>1μm) are positively charged due to Ca(2+) and Mg(2+) specific adsorption and alginate, which is negatively charged, adsorbs onto the agglomerate surface. Our results indicate that the presence of alginate at typical natural organic matter concentration (1-10 mg L(-1)) strongly modifies the TiO2 agglomerate (50 mg L(-1)) stability by inducing their partial and rapid disagglomeration. The importance of disagglomeration is found dependent on the alginate concentration with maximum of disagglomeration obtained for alginate concentration ≥8 mg L(-1) and leading to 400 nm fragments. From an environmental point of view partial restabilization of TiO2 agglomerates in the presence of alginate constitutes an important outcome. Disagglomeration will enhance their transport and residence time in aquatic systems which is an important step in the current knowledge on risk assessment associated to engineered nanoparticles. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Cationic Antimicrobial Polymers and Their Assemblies

    Science.gov (United States)

    Carmona-Ribeiro, Ana Maria; de Melo Carrasco, Letícia Dias

    2013-01-01

    Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs). The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications. PMID:23665898

  18. Cationic Antimicrobial Polymers and Their Assemblies

    Directory of Open Access Journals (Sweden)

    Ana Maria Carmona-Ribeiro

    2013-05-01

    Full Text Available Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs. The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications.

  19. Regulation of Cation Balance in Saccharomyces cerevisiae

    Science.gov (United States)

    Cyert, Martha S.; Philpott, Caroline C.

    2013-01-01

    All living organisms require nutrient minerals for growth and have developed mechanisms to acquire, utilize, and store nutrient minerals effectively. In the aqueous cellular environment, these elements exist as charged ions that, together with protons and hydroxide ions, facilitate biochemical reactions and establish the electrochemical gradients across membranes that drive cellular processes such as transport and ATP synthesis. Metal ions serve as essential enzyme cofactors and perform both structural and signaling roles within cells. However, because these ions can also be toxic, cells have developed sophisticated homeostatic mechanisms to regulate their levels and avoid toxicity. Studies in Saccharomyces cerevisiae have characterized many of the gene products and processes responsible for acquiring, utilizing, storing, and regulating levels of these ions. Findings in this model organism have often allowed the corresponding machinery in humans to be identified and have provided insights into diseases that result from defects in ion homeostasis. This review summarizes our current understanding of how cation balance is achieved and modulated in baker’s yeast. Control of intracellular pH is discussed, as well as uptake, storage, and efflux mechanisms for the alkali metal cations, Na+ and K+, the divalent cations, Ca2+ and Mg2+, and the trace metal ions, Fe2+, Zn2+, Cu2+, and Mn2+. Signal transduction pathways that are regulated by pH and Ca2+ are reviewed, as well as the mechanisms that allow cells to maintain appropriate intracellular cation concentrations when challenged by extreme conditions, i.e., either limited availability or toxic levels in the environment. PMID:23463800

  20. Sorption by cation exchange

    International Nuclear Information System (INIS)

    Bradbury, M.H.; Baeyens, B.

    1994-04-01

    A procedure for introducing exchange into geochemical/surface complexation codes is described. Beginning with selectivity coefficients, K c , defined in terms of equivalent fractional ion occupancies, a general expression for the molar based exchange code input parameters, K ex , is derived. In natural systems the uptake of nuclides onto complex sorbents often occurs by more than one mechanism. The incorporation of cation exchange and surface complexation into a geochemical code therefore enables sorption by both mechanisms to be calculated simultaneously. The code and model concepts are tested against sets of experimental data from widely different sorption studies. A proposal is made to set up a data base of selectivity coefficients. Such a data base would form part of a more general one consisting of sorption mechanism specific parameters to be used in conjunction with geochemical/sorption codes to model and predict sorption. (author) 6 figs., 6 tabs., 26 refs

  1. Inhomogeneity at the LaAlO3/SrTiO3 interface

    Science.gov (United States)

    Claeson, T.; Kalabukhov, A.; Gunnarsson, R.; Winkler, D.; Borjesson, J.; Ljustina, N.; Olsson, E.; Popok, V.; Boikov, Yu.; Serenkov, I.; Sakharov, V.

    2010-03-01

    High electrical conductivity has been reported for the interface between two wide-band gap insulators, LaAlO3 (LAO) and SrTiO3 (STO). It occurs above a critical thickness of LAO and can be tuned by an electric field. The conduction has been attributed to i) ``polar catastrophe'' , where the electrostatic charge at the interface is compensated by the transfer of half an electron per unit cell to the interface, ii) oxygen vacancies in the STO, and iii) cation intermixing, which may result in the formation of metallic La1-xSrxTiO3 layer. The relation between microstructure and electrical properties is crucial for understanding the origin of electrical conductivity. We have investigated the interface composition using medium-energy ion spectroscopy, high resolution electron microscopy, and Kelvin probe force microscopy. We find a correlation between cationic intermixing at the interface and electrical properties and inhomogeneities of the interface conductivity that may support a percolation model. Work supported by Swedish VR & KAW, Russian ISTC 3743, EC NANOXIDE

  2. Highly uniform bipolar resistive switching characteristics in TiO2/BaTiO3/TiO2 multilayer

    International Nuclear Information System (INIS)

    Ma, W. J.; Zhang, X. Y.; Wang, Ying; Zheng, Yue; Lin, S. P.; Luo, J. M.; Wang, B.; Li, Z. X.

    2013-01-01

    Nanoscale multilayer structure TiO 2 /BaTiO 3 /TiO 2 has been fabricated on Pt/Ti/SiO 2 /Si substrate by chemical solution deposition method. Highly uniform bipolar resistive switching (BRS) characteristics have been observed in Pt/TiO 2 /BaTiO 3 /TiO 2 /Pt cells. Analysis of the current-voltage relationship demonstrates that the space-charge-limited current conduction controlled by the localized oxygen vacancies should be important to the resistive switching behavior. X-ray photoelectron spectroscopy results indicated that oxygen vacancies in TiO 2 play a crucial role in the resistive switching phenomenon and the introduced TiO 2 /BaTiO 3 interfaces result in the high uniformity of bipolar resistive switching characteristics

  3. Anisotropic thermal expansion of La(n)(Ti,Fe)(n)O(3n + 2) (n = 5 and 6).

    Science.gov (United States)

    Wölfel, Alexander; Dorscht, Philipp; Lichtenberg, Frank; van Smaalen, Sander

    2013-04-01

    Crystal structures are reported for two perovskite-related compounds with nominal compositions La5(Ti(0.8)Fe(0.2))5O17 and La6(Ti(0.67)Fe(0.33))6O20 at seven different temperatures between 90 and 350 K. For both compounds no evidence of a structural phase transition in the investigated range of temperatures was found. The thermal expansions are found to be anisotropic, with the largest thermal expansion along a direction parallel to the slabs of these layered compounds. The origin of this anisotropy is proposed to be a temperature dependence of tilts of the octahedral (Ti,Fe)O6 groups. It is likely that the same mechanism will determine similar anisotropic thermal behaviour of other compounds A(n)B(n)O(3n + 2). The crystal structures have revealed partial chemical order of Ti/Fe over the B sites, with iron concentrated towards the centers of the slabs. Local charge compensation is proposed as the driving force for the chemical order, where the highest-valent cation moves to sites near the oxygen-rich borders of the slabs. A linear dependence on the site occupation fraction by Fe of the computed valences leads to extrapolated valence values close to the formal valence of Ti(4+) for sites fully occupied by Ti, and of Fe(3+) for sites fully occupied by Fe. These results demonstrate the power of the bond-valence method, and they show that refined oxygen positions are the weighted average of oxygen positions in TiO6 and FeO6 octahedral groups.

  4. From cation to oxide: hydroxylation and condensation of aqueous complexes

    International Nuclear Information System (INIS)

    Jolivet, J.P.

    1997-01-01

    Hydroxylation, condensation and precipitation of metal cations in aqueous solution are briefly reviewed. Hydroxylation of aqueous complexes essentially depends on the format charge (oxidation state), the size and the pH of the medium. It is the step allowing the condensation reaction. Depending on the nature of complexes (aqua-hydroxo, oxo-hydroxo), the. mechanism of condensation is different, olation or ox-olation respectively. The first one leads to poly-cations or hydroxides more or less stable against dehydration. The second one leads to poly-anions or oxides. Oligomeric species (poly-cations, poly-anions) are form from charged monomer complexes while the formation of solid phases requires non-charged precursors. Because of their high lability, charged oligomers are never the precursors of solids phases. The main routes for the formation of solid phases from solution are studied with two important and representative elements, Al and Si. For Al 3+ ions, different methods (base addition in solution, thermo-hydrolysis, hydrothermal synthesis) are discussed in relation to the crystal structure of the solid phase obtained. For silicic species condensing by ox-olation, the role of acid or base catalysis on the morphology of gels is studied. The influence of complexing ligands on the processes and on the characteristics of solids (morphology of particles, basic salts and polymetallic oxides formation) is studied. (author)

  5. Cationic polymers and porous materials

    KAUST Repository

    Han, Yu

    2017-04-27

    According to one or more embodiments, cationic polymers may be produced which include one or more monomers containing cations. Such cationic polymers may be utilized as structure directing agents to form mesoporous zeolites. The mesoporous zeolites may include micropores as well as mesopores, and may have a surface area of greater than 350 m2/g and a pore volume of greater than 0.3 cm3/g. Also described are core/shell zeolites, where at least the shell portion includes a mesoporous zeolite material.

  6. Cationic polymers and porous materials

    KAUST Repository

    Han, Yu; Tian, Qiwei; Dong, Xinglong; Liu, Zhaohui; Basset, Jean-Marie; Saih, Youssef; Sun, Miao; Xu, Wei; Shaikh, Sohel

    2017-01-01

    According to one or more embodiments, cationic polymers may be produced which include one or more monomers containing cations. Such cationic polymers may be utilized as structure directing agents to form mesoporous zeolites. The mesoporous zeolites may include micropores as well as mesopores, and may have a surface area of greater than 350 m2/g and a pore volume of greater than 0.3 cm3/g. Also described are core/shell zeolites, where at least the shell portion includes a mesoporous zeolite material.

  7. Synthetic cation-selective nanotube: permeant cations chaperoned by anions.

    Science.gov (United States)

    Hilder, Tamsyn A; Gordon, Dan; Chung, Shin-Ho

    2011-01-28

    The ability to design ion-selective, synthetic nanotubes which mimic biological ion channels may have significant implications for the future treatment of bacteria, diseases, and as ultrasensitive biosensors. We present the design of a synthetic nanotube made from carbon atoms that selectively allows monovalent cations to move across and rejects all anions. The cation-selective nanotube mimics some of the salient properties of biological ion channels. Before practical nanodevices are successfully fabricated it is vital that proof-of-concept computational studies are performed. With this in mind we use molecular and stochastic dynamics simulations to characterize the dynamics of ion permeation across a single-walled (10, 10), 36 Å long, carbon nanotube terminated with carboxylic acid with an effective radius of 5.08 Å. Although cations encounter a high energy barrier of 7 kT, its height is drastically reduced by a chloride ion in the nanotube. The presence of a chloride ion near the pore entrance thus enables a cation to enter the pore and, once in the pore, it is chaperoned by the resident counterion across the narrow pore. The moment the chaperoned cation transits the pore, the counterion moves back to the entrance to ferry another ion. The synthetic nanotube has a high sodium conductance of 124 pS and shows linear current-voltage and current-concentration profiles. The cation-anion selectivity ratio ranges from 8 to 25, depending on the ionic concentrations in the reservoirs.

  8. Pearl-necklace complexes of flexible polyanions with neutral-cationic diblock copolymers

    NARCIS (Netherlands)

    Golinska, M.D.; Wolf, de F.A.; Cohen Stuart, M.A.; Hernandez Garcia, A.; Vries, de R.J.

    2013-01-01

    We study the complexation of very asymmetric diblock copolymers (consisting of a cationic block of 12 lysines connected to a 400 amino acid long hydrophilic polypeptide block with a net charge that is nearly zero) with oppositely charged sodium poly(acrylic acid) (NaPAA) with a range of molar masses

  9. Periodic modeling of zeolite Ti-LTA.

    Science.gov (United States)

    Hernandez-Tamargo, Carlos E; Roldan, Alberto; Ngoepe, Phuti E; de Leeuw, Nora H

    2017-08-21

    We have proposed a combination of density functional theory calculations and interatomic potential-based simulations to study the structural, electronic, and mechanical properties of pure-silica zeolite Linde Type A (LTA), as well as two titanium-doped compositions. The energetics of the titanium distribution within the zeolite framework suggest that the inclusion of a second titanium atom with configurations Ti-(Si) 0 -Ti, Ti-(Si) 1 -Ti, and Ti-(Si) 2 -Ti is more energetically favorable than the mono-substitution. Infra-red spectra have been simulated for the pure-silica LTA, the single titanium substitution, and the configurations Ti-(Si) 0 -Ti and Ti-(Si) 2 -Ti, comparing against experimental benchmarks where available. The energetics of the direct dissociation of water on these Lewis acid sites indicate that this process is only favored when two titanium atoms form a two-membered ring (2MR) sharing two hydroxy groups, Ti-(OH) 2 -Ti, which suggests that the presence of water may tune the distribution of titanium atoms within the framework of zeolite LTA. The electronic analysis indicates charge transfer from H 2 O to the Lewis acid site and hybridization of their electronic states.

  10. Charge imbalance

    International Nuclear Information System (INIS)

    Clarke, J.

    1981-01-01

    This article provides a long theoretical development of the main ideas of charge imbalance in superconductors. Concepts of charge imbalance and quasiparticle charge are introduced, especially in regards to the use of tunnel injection in producing and detecting charge imbalance. Various mechanisms of charge relaxation are discussed, including inelastic scattering processes, elastic scattering in the presence of energy-gap anisotropy, and various pair-breaking mechanisms. In each case, present theories are reviewed in comparison with experimental data

  11. Interaction of cationic drugs with liposomes.

    Science.gov (United States)

    Howell, Brett A; Chauhan, Anuj

    2009-10-20

    Interactions between cationic drugs and anionic liposomes were studied by measuring binding of drugs and the effect of binding on liposome permeability. The measurements were analyzed in the context of a continuum model based on electrostatic interactions and a Langmuir isotherm. Experiments and modeling indicate that, although electrostatic interactions are important, the fraction of drug sequestered in the double-layer is negligible. The majority of drug enters the bilayer with the charged regions interacting with the charged lipid head groups and the lipophilic regions associated with the bilayer. The partitioning of the drug can be described by a Langmuir isotherm with the electrostatic interactions increasing the sublayer concentration of the drug. The binding isotherms are similar for all tricyclic antidepressants (TCA). Bupivacaine (BUP) binds significantly less compared to TCA because its structure is such that the charged region has minimal interactions with the lipid heads once the BUP molecule partitions inside the bilayer. Conversely, the TCAs are linear with distinct hydrophilic and lipophilic regions, allowing the lipophilic regions to lie inside the bilayer and the hydrophilic regions to protrude out. This conformation maximizes the permeability of the bilayer, leading to an increased release of a hydrophilic fluorescent dye from liposomes.

  12. Simultaneous anionic and cationic redox

    Science.gov (United States)

    Jung, Sung-Kyun; Kang, Kisuk

    2017-12-01

    It is challenging to unlock anionic redox activity, accompanied by full utilization of available cationic redox process, to boost capacity of battery cathodes. Now, material design by tuning the metal-oxygen interaction is shown to be a promising solution.

  13. Effects of charge density and hydrophobicity of poly(amido amine)s for non-viral gene delivery

    NARCIS (Netherlands)

    Piest, Martin; Engbersen, Johannes F.J.

    2010-01-01

    High cationic charge densities in polymeric vectors result in tight DNA condensation, leading to small highly positively charged polyplexes which show generally high cellular uptake in vitro. However, high cationic charge densities also introduce membrane-disruptive properties to the polymers,

  14. First-principles analysis of ferroelectric transition in MnSnO3 and MnTiO3 perovskites

    Science.gov (United States)

    Kang, Sung Gu

    2018-06-01

    The ferroelectric instabilities of an artificially adopted Pnma structure in low tolerance perovskites have been explored (Kang et al., 2017) [4], where an unstable A-site environment was reported to be the major driving source for the low tolerance perovskites to exhibit ferroelectric instability. This study examined the ferroelectric transition of two magnetic perovskite materials, MnSnO3 and MnTiO3, in Pnma phase. Phase transitions to the Pnma phase at elevated pressures were observed. MnSnO3, which has a lower (larger) tolerance factor (B-site cation radius), showed a higher ferroelectric mode amplitude than MnTiO3. The distribution of the bond length of Mn-O and the mean quadratic elongation (QE) of octahedra (SnO6 or TiO6) were investigated for structural analysis. However, MnTiO3 showed a larger spontaneous polarization than MnSnO3 due to high Born effective charges of titanium. This study is useful because it provides a valuable pathway to the design of promising multiferroic materials.

  15. Comparison of cation adsorption by isostructural rutile and cassiterite.

    Science.gov (United States)

    Machesky, Michael; Wesolowski, David; Rosenqvist, Jörgen; Předota, Milan; Vlcek, Lukas; Ridley, Moira; Kohli, Vaibhav; Zhang, Zhan; Fenter, Paul; Cummings, Peter; Lvov, Serguei; Fedkin, Mark; Rodriguez-Santiago, Victor; Kubicki, James; Bandura, Andrei

    2011-04-19

    Macroscopic net proton charging curves for powdered rutile and cassiterite specimens with the (110) crystal face predominant, as a function of pH in RbCl and NaCl solutions, trace SrCl(2) in NaCl, and trace ZnCl(2) in NaCl and Na Triflate solutions, are compared to corresponding molecular-level information obtained from static DFT optimizations and classical MD simulations, as well as synchrotron X-ray methods. The similarities and differences in the macroscopic charging behavior of rutile and cassiterite largely reflect the cation binding modes observed at the molecular level. Cation adsorption is primarily inner-sphere on both isostructural (110) surfaces, despite predictions that outer-sphere binding should predominate on low bulk dielectric constant oxides such as cassiterite (ε(bulk) ≈ 11). Inner-sphere adsorption is also significant for Rb(+) and Na(+) on neutral surfaces, whereas Cl(-) binding is predominately outer-sphere. As negative surface charge increases, relatively more Rb(+), Na(+), and especially Sr(2+) are bound in highly desolvated tetradentate fashion on the rutile (110) surface, largely accounting for enhanced negative charge development relative to cassiterite. Charging curves in the presence of Zn(2+) are very steep but similar for both oxides, reflective of Zn(2+) hydrolysis (and accompanying proton release) during the adsorption process, and the similar binding modes for ZnOH(+) on both surfaces. These results suggest that differences in cation adsorption between high and low bulk dielectric constant oxides are more subtly related to the relative degree of cation desolvation accompanying inner-sphere binding (i.e., more tetradentate binding on rutile), rather than distinct inner- and outer-sphere adsorption modes. Cation desolvation may be favored at the rutile (110) surface in part because inner-sphere water molecules are bound further from and less tightly than on the cassiterite (110) surface. Hence, their removal upon inner

  16. Cation exchange interaction between antibiotic ciprofloxacin and montmorillonite

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Chih-Jen [Department of Earth Sciences, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan (China); Department of Geosciences, National Taiwan University, Taipei 10617, Taiwan (China); Li, Zhaohui, E-mail: li@uwp.edu [Department of Earth Sciences, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan (China); Department of Geosciences, University of Wisconsin - Parkside, Kenosha, WI 53144 (United States); Jiang, Wei-Teh, E-mail: atwtj@mail.ncku.edu.tw [Department of Earth Sciences, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan (China); Jean, Jiin-Shuh; Liu, Chia-Chuan [Department of Earth Sciences, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan (China)

    2010-11-15

    Exploring the interactions between antibiotics and soils/minerals is of great importance in resolving their fate, transport, and elimination in the environment due to their frequent detection in wastewater, river water, sewage sludge and soils. This study focused on determining the adsorption properties and mechanisms of interaction between antibiotic ciprofloxacin and montmorillonite (SAz-1), a swelling dioctahedral mineral with Ca{sup 2+} as the main interlayer cation. In acidic and neutral aqueous solutions, a stoichiometric exchange between ciprofloxacin and interlayer cations yielded an adsorption capacity as high as 330 mg/g, corresponding to 1.0 mmol/g. When solution pH was above its pK{sub a2} (8.7), adsorption of ciprofloxacin was greatly reduced due to the net repulsion between the negatively charged clay surfaces and the ciprofloxacin anion. The uptake of ciprofloxacin expanded the basal spacing (d{sub 001}) of montmorillonite from 15.04 to 17.23 A near its adsorption capacity, confirming cation exchange within the interlayers in addition to surface adsorption. Fourier transform infrared results further suggested that the protonated amine group of ciprofloxacin in its cationic form was electrostatically attracted to negatively charged sites of clay surfaces, and that the carboxylic acid group was hydrogen bonded to the basal oxygen atoms of the silicate layers. The results indicate that montmorillonite is an effective sorbent to remove ciprofloxacin from water.

  17. Cation exchange interaction between antibiotic ciprofloxacin and montmorillonite

    International Nuclear Information System (INIS)

    Wang, Chih-Jen; Li, Zhaohui; Jiang, Wei-Teh; Jean, Jiin-Shuh; Liu, Chia-Chuan

    2010-01-01

    Exploring the interactions between antibiotics and soils/minerals is of great importance in resolving their fate, transport, and elimination in the environment due to their frequent detection in wastewater, river water, sewage sludge and soils. This study focused on determining the adsorption properties and mechanisms of interaction between antibiotic ciprofloxacin and montmorillonite (SAz-1), a swelling dioctahedral mineral with Ca 2+ as the main interlayer cation. In acidic and neutral aqueous solutions, a stoichiometric exchange between ciprofloxacin and interlayer cations yielded an adsorption capacity as high as 330 mg/g, corresponding to 1.0 mmol/g. When solution pH was above its pK a2 (8.7), adsorption of ciprofloxacin was greatly reduced due to the net repulsion between the negatively charged clay surfaces and the ciprofloxacin anion. The uptake of ciprofloxacin expanded the basal spacing (d 001 ) of montmorillonite from 15.04 to 17.23 A near its adsorption capacity, confirming cation exchange within the interlayers in addition to surface adsorption. Fourier transform infrared results further suggested that the protonated amine group of ciprofloxacin in its cationic form was electrostatically attracted to negatively charged sites of clay surfaces, and that the carboxylic acid group was hydrogen bonded to the basal oxygen atoms of the silicate layers. The results indicate that montmorillonite is an effective sorbent to remove ciprofloxacin from water.

  18. Cation disorder in Ga1212.

    Science.gov (United States)

    Greenwood, K B; Ko, D; Vander Griend, D A; Sarjeant, G M; Milgram, J W; Garrity, E S; DeLoach, D I; Poeppelmeier, K R; Salvador, P A; Mason, T O

    2000-07-24

    Substitution of calcium for strontium in LnSr2-xCaxCu2GaO7 (Ln = La, Pr, Nd, Gd, Ho, Er, Tm, and Yb) materials at ambient pressure and 975 degrees C results in complete substitution of calcium for strontium in the lanthanum and praseodymium systems and partial substitution in the other lanthanide systems. The calcium saturation level depends on the size of the Ln cation, and in all cases, a decrease in the lattice parameters with calcium concentration was observed until a common, lower bound, average A-cation size is reached. Site occupancies from X-ray and neutron diffraction experiments for LnSr2-xCaxCu2GaO7 (x = 0 and x = 2) confirm that the A-cations distribute between the two blocking-layer sites and the active-layer site based on size. A quantitative link between cation distribution and relative site-specific cation enthalpy for calcium, strontium, and lanthanum within the gallate structure is derived. The cation distribution in other similar materials can potentially be modeled.

  19. The incorporation of neptunium and plutonium in thorutite (ThTi{sub 2}O{sub 6})

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yingjie, E-mail: yzx@ansto.gov.au; Gregg, Daniel J.; Lumpkin, Gregory R.; Begg, Bruce D.; Jovanovic, Miodrag

    2013-12-25

    Highlights: •The incorporation of neptunium (Np) and plutonium (Pu) in thorutite (ThTi{sub 2}O{sub 6}) has been studied. •The effect of Np/Pu doping on the unit cell parameter changes has been discussed from the structure point of view. •The effect of Y as charge compensator to encourage the formation of higher valences of Np and Pu has been explored. •The resulting Np/Pu doped thorutite samples have been characterised by using XRD, SEM and DRS. -- Abstract: The incorporation of neptunium (Np) and plutonium (Pu) into the brannerite structured lattice was studied using thorutite (ThTi{sub 2}O{sub 6}) as host lattice and sintering in air. The uncompensated Np and Pu doped samples and the low Y-charge compensated Np and Pu doped samples showed main phases as designed together with trace amounts of rutile. Those samples with larger amounts of Y produced yttrium pyrochlores as an additional minor phase. XRD analyses reveal anisotropic changes of the cell parameters; the a-parameter contracts while b- and c-parameters expand with mean cationic radius. This is in reasonable agreement with previous experimental data on ThTi{sub 2}O{sub 6} and Ce{sub 0.975}Ti{sub 2}O{sub 5.95}. Attempts to form Np or Pu valences >4+ by adding Y as a charge compensator were unsuccessful, suggesting that tetravalent Np and Pu ions are favoured in air-fired thorutite.

  20. A Cationic Smart Copolymer for DNA Binding

    Directory of Open Access Journals (Sweden)

    Tânia Ribeiro

    2017-11-01

    Full Text Available A new block copolymer with a temperature-responsive block and a cationic block was prepared by reversible addition-fragmentation chain transfer (RAFT polymerization, with good control of its size and composition. The first block is composed by di(ethylene glycol methyl ether methacrylate (DEGMA and oligo(ethylene glycol methyl ether methacrylate (OEGMA, with the ratio DEGMA/OEGMA being used to choose the volume phase transition temperature of the polymer in water, tunable from ca. 25 to above 90 °C. The second block, of trimethyl-2-methacroyloxyethylammonium chloride (TMEC, is positively charged at physiological pH values and is used for DNA binding. The coacervate complexes between the block copolymer and a model single strand DNA are characterized by fluorescence correlation spectroscopy and fluorescence spectroscopy. The new materials offer good prospects for biomedical application, for example in controlled gene delivery.

  1. Ti, Al

    Indian Academy of Sciences (India)

    In the present study, authors report on the effect that substrate bias voltage has on the microstructure and mechanical properties of (Ti, Al)N hard coatings deposited with cathodic arc evaporation (CAE) technique. The coatings were deposited from a Ti0.5Al0.5 powder metallurgical target in a reactive nitrogen atmosphere at ...

  2. Cationic polymerization of styrene by means of pulse radiolysis

    International Nuclear Information System (INIS)

    Egusa, S.; Arai, S.; Kira, A.; Imamura, M.; Tabata, Y.

    1977-01-01

    The radiation-induced cationic polymerization of styrene has been studied by microsecond pulse radiolysis. It was possible to observe absorption bands of a monomer cation radical (St. + ) at 630 nm and at 350 nm in a mixture of isopentane and n-butyl chloride at - 165 0 C. Three absorption bands, around 1600 nm, at 600 nm and at 450 nm, grew in parallel with the decay of St. + after pulse. The 1600-nm and 600-nm bands were assigned to an associated dimer cation radical (St 2 . + ), and the 450-nm band to a bonded dimer cation radical (St-St. + ) by comparison of absorption spectra of α-methylstyrene, 1,2-dihydronaphthalene and trans-β-methylstyrene. The kinetic behaviour of these species suggests that St-St. + and a part of St 2 . + are formed by the reaction of St. + with a styrene monomer, and the rest of St 2 . + may be formed by positive charge transfer from a solvent cation radical to an auto-associated neutral dimer of styrene. A long-lived absorption band at 340 nm grew with the decay of St-St. + . This band is considered due to a growing polymer carbonium ion. (author)

  3. Liquid-solid extraction of cationic metals by cationic amphiphiles

    International Nuclear Information System (INIS)

    Muller, W.

    2010-01-01

    In the field of selective separation for recycling of spent nuclear fuel, liquid-liquid extraction processes are widely used (PUREX, DIAMEX..) in industrial scale. In order to guarantee a sustainable nuclear energy for the forthcoming generations, alternative reprocessing techniques are under development. One of them bases on the studies from Heckmann et al in the 80's and consists in selectively precipitating actinides from aqueous waste solutions by cationic surfactants (liquid-solid extraction). This technique has some interesting advantages over liquid-liquid extraction techniques, because several steps are omitted like stripping or solvent washing. Moreover, the amount of waste is decreased considerably, since no contaminated organic solvent is produced. In this thesis, we have carried out a physico-chemical study to understand the specific interactions between the metallic cations with the cationic surfactant. First, we have analysed the specific effect of the different counter-ions (Cl - , NO 3 - , C 2 O 4 2- ) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu 2+ , Zn 2+ , UO 2 2+ , Fe 3+ , Nd 3+ , Eu 3+ , Th 4+ ) were considered; we have concluded that depending on the anionic complex of these metals formed in acidic media, we can observe either an adsorption at the micellar interface or not. This adsorption has a large influence of the surfactant aggregation properties and determines the limits of the application in term of ionic strength, temperature and surfactant concentration. (author) [fr

  4. Anaerobic toxicity of cationic silver nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Gitipour, Alireza; Thiel, Stephen W. [Biomedical, Chemical, and Environmental Engineering, University of Cincinnati, Cincinnati, OH (United States); Scheckel, Kirk G. [USEPA, Office of Research and Development, Cincinnati, OH (United States); Tolaymat, Thabet, E-mail: tolaymat.thabet@epa.gov [USEPA, Office of Research and Development, Cincinnati, OH (United States)

    2016-07-01

    The microbial toxicity of silver nanoparticles (AgNPs) stabilized with different capping agents was compared to that of Ag{sup +} under anaerobic conditions. Three AgNPs were investigated: (1) negatively charged citrate-coated AgNPs (citrate-AgNPs), (2) minimally charged polyvinylpyrrolidone coated AgNPs (PVP-AgNPs) and (3) positively charged branched polyethyleneimine coated AgNPs (BPEI-AgNPs). The AgNPs investigated in this experiment were similar in size (10–15 nm), spherical in shape, but varied in surface charge which ranged from highly negative to highly positive. While, at AgNPs concentrations lower than 5 mg L{sup −1}, the anaerobic decomposition process was not influenced by the presence of the nanoparticles, there was an observed impact on the diversity of the microbial community. At elevated concentrations (100 mg L{sup −1} as silver), only the cationic BPEI-AgNPs demonstrated toxicity similar in magnitude to that of Ag{sup +}. Both citrate and PVP-AgNPs did not exhibit toxicity at the 100 mg L{sup −1} as measured by biogas evolution. These findings further indicate the varying modes of action for nanoparticle toxicity and represent one of the few studies that evaluate end-of-life management concerns with regards to the increasing use of nanomaterials in our everyday life. These findings also highlight some of the concerns with a one size fits all approach to the evaluation of environmental health and safety concerns associated with the use of nanoparticles. - Highlights: • At concentrations -1 the anaerobic decomposition process was not impacted. • An impact on the microbial community at concentrations -1 were observed. • At high concentrations (100 mg L{sup −1}), the cationic BPEI-AgNPs demonstrated toxicity. • Toxicity was demonstrated without the presence of oxidative dissolution of silver. • A one size fits all approach for the evaluation of NPs may not be accurate.

  5. Vibrational Spectroscopy of Cation and Anion Channelrhodopsins

    Science.gov (United States)

    Yi, Adrian S.

    Optogenetics is a technique to control and monitor cell activity with light by expression of specific microbial rhodopsins. Cation channelrhodopsins (CCRs) and anion channelrhodopsins (ACRs) have been demonstrated to activate and silence cell activity, respectively. In this dissertation, the molecular mechanisms of two channelrhodopsins are studied: a CCR from Chlamydomonas augustae (CaChR1) and an ACR from Guillardia theta (GtACR1). The recently discovered GtACR1is especially interesting, as it achieves neural silencing with 1/1000th of the light intensity compared to previous microbial rhodopsin silencing ion pumps. Static and time-resolved resonance Raman, FTIR difference, and UV-visible spectroscopies were utilized in addition to various biochemical and genetic techniques to explore the molecular mechanisms of these channelrhodopsins. In CaChR1, Glu169 and Asp299 residues are located nearby the Schiff base (SB) similar to the homologous residues Asp85 and Asp212, which exist in an ionized state in unphotolyzed bacteriorhodopsin (BR) and play a key role in proton pumping. We observe significant changes in the protonation states of the SB, Glu169, and Asp299 of CaChR1 leading up to the open-channel P2 state, where all three groups exist in a charge neutral state. This unusual charge neutrality along with the position of these groups in the CaChR1 ion channel suggests that charge neutrality plays an important role in cation gating and selectivity in these low efficiency CCRs. Significant differences exist in the photocycle and protonation/hydrogen bonding states of key residues inGtACR1compared to BR and CaChR1. Resonance Raman studies reveal that in the unphotolyzed state of GtACR1, residues Glu68, Ser97 (BR Asp85 homolog), and Asp234 (BR Asp212 homolog) located near the SB exist in charge neutral states. Furthermore, upon K formation, these residues do not change their protonation states. At room temperature, a slow decay of the red-shifted K intermediate is

  6. Positron annihilation lifetime characterization of oxygen ion irradiated rutile TiO2

    Science.gov (United States)

    Luitel, Homnath; Sarkar, A.; Chakrabarti, Mahuya; Chattopadhyay, S.; Asokan, K.; Sanyal, D.

    2016-07-01

    Ferromagnetic ordering at room temperature has been induced in rutile phase of TiO2 polycrystalline sample by O ion irradiation. 96 MeV O ion induced defects in rutile TiO2 sample has been characterized by positron annihilation spectroscopic techniques. Positron annihilation results indicate the formation of cation vacancy (VTi, Ti vacancy) in these irradiated TiO2 samples. Ab initio density functional theoretical calculations indicate that in TiO2 magnetic moment can be induced either by creating Ti or O vacancies.

  7. Cationic Polymers Inhibit the Conductance of Lysenin Channels

    Directory of Open Access Journals (Sweden)

    Daniel Fologea

    2013-01-01

    Full Text Available The pore-forming toxin lysenin self-assembles large and stable conductance channels in natural and artificial lipid membranes. The lysenin channels exhibit unique regulation capabilities, which open unexplored possibilities to control the transport of ions and molecules through artificial and natural lipid membranes. Our investigations demonstrate that the positively charged polymers polyethyleneimine and chitosan inhibit the conducting properties of lysenin channels inserted into planar lipid membranes. The preservation of the inhibitory effect following addition of charged polymers on either side of the supporting membrane suggests the presence of multiple binding sites within the channel's structure and a multistep inhibition mechanism that involves binding and trapping. Complete blockage of the binding sites with divalent cations prevents further inhibition in conductance induced by the addition of cationic polymers and supports the hypothesis that the binding sites are identical for both multivalent metal cations and charged polymers. The investigation at the single-channel level has shown distinct complete blockages of each of the inserted channels. These findings reveal key structural characteristics which may provide insight into lysenin’s functionality while opening innovative approaches for the development of applications such as transient cell permeabilization and advanced drug delivery systems.

  8. Photoelectrocatalytic property of microporous Pt-TiO2/Ti electrodes

    International Nuclear Information System (INIS)

    Hung, Chung-Hsuang; Wu, Kee-Rong; Yeh, Chung-Wei; Sun, Jui-Ching; Hsu, Chuan-Jen

    2013-01-01

    This study investigates the photoelectrocatalytic (PEC) property of microporous WO 3 -loaded TiO 2 /Ti layer, prepared via micro-arc oxidation (MAO) of Ti plate, followed by sputtering deposition of a thin Pt layer as a Pt-TiO 2 /Ti electrode. The WO 3 -loaded TiO 2 layer which is associated with a more acidic surface forms many local electrochemical cells on its micro-pores immersed in cationic dye solution. The electrocatalytic (EC) reactions can take place in the local cells by the applied electrons. A low resistivity that is accomplished by MAO technique and by platinization offers an easy path for the electron motions in the Pt-TiO 2 /Ti electrode. All these features make the EC oxidation of aqueous dye pollutants practically feasible without using counter electrodes and supporting electrolytes. Our experiments demonstrate that, under PEC condition, the Pt-TiO 2 /Ti shows the highest degradation rate constant of 0.83 h − 1 at an applied bias of 1.0 V and exhibits significantly high PEC and EC oxidation activities at a low applied bias of 0.25 V. This is attributable to high anodic currents generated in the Pt-TiO 2 /Ti even at low bias. The modified microporous electrodes conclusively reveal a very interesting EC property as a two double-sided device that functions the PEC and EC oxidation simultaneously without a need of supporting electrolyte and expensive Pt cathode. - Highlights: ► Pt-TiO 2 /Ti exhibits enhanced photoelectrocatalytic (PEC) activity at low applied bias. ► The proposed device uses low applied bias (< 1.0 V) with no explicit cathode. ► PEC oxidation can be performed without supporting electrolyte and Pt cathode

  9. Ab initio charge analysis of pure and hydrogenated perovskites

    DEFF Research Database (Denmark)

    Bork, Nicolai Christian; Bonanos, Nikolaos; Rossmeisl, Jan

    2011-01-01

    We present a density functional theory based Bader analysis on the charge distribution in pure and hydrogenated SrTiO3. We find the hydrogen defect carries a +0.56e charge and the OH defect carrying a +0.50e charge compared to the host oxygen. Calculations on BaNbO3, CaTiO3, and SrZrO3 support th...

  10. Conserved Aromatic Residue Confers Cation Selectivity in Claudin-2 and Claudin-10b*

    Science.gov (United States)

    Li, Jiahua; Zhuo, Min; Pei, Lei; Yu, Alan S. L.

    2013-01-01

    In tight junctions, both claudin-2 and claudin-10b form paracellular cation-selective pores by the interaction of the first ECL 1 with permeating ions. We hypothesized that a highly conserved aromatic residue near the pore selectivity filter of claudins contributes to cation selectivity by cation-π interaction with the permeating cation. To test this, we generated MDCK I Tet-off cells stably transfected with claudin-2 Tyr67 mutants. The Y67L mutant showed reduced cation selectivity compared with wild-type claudin-2 due to a decrease in Na+ permeability, without affecting the Cl− permeability. The Y67A mutant enlarged the pore size and further decreased the charge selectivity due to an increase in Cl− permeability. The Y67F mutant restored the Na+ permeability, Cl− permeability, and pore size back to wild-type. The accessibility of Y67C to methanethiosulfonate modification indicated that its side chain faces the lumen of the pore. In claudin-10b, the F66L mutant reduced cation selectivity, and the F66A mutant lost pore conductance. We conclude that the conserved aromatic residue near the cation pore domain of claudins contributes to cation selectivity by a dual role of cation-π interaction and a luminal steric effect. Our findings provide new insight into how ion selectivity is achieved in the paracellular pore. PMID:23760508

  11. Potential effect of cationic liposomes on interactions with oral bacterial cells and biofilms.

    Science.gov (United States)

    Sugano, Marika; Morisaki, Hirobumi; Negishi, Yoichi; Endo-Takahashi, Yoko; Kuwata, Hirotaka; Miyazaki, Takashi; Yamamoto, Matsuo

    2016-01-01

    Although oral infectious diseases have been attributed to bacteria, drug treatments remain ineffective because bacteria and their products exist as biofilms. Cationic liposomes have been suggested to electrostatically interact with the negative charge on the bacterial surface, thereby improving the effects of conventional drug therapies. However, the electrostatic interaction between oral bacteria and cationic liposomes has not yet been examined in detail. The aim of the present study was to examine the behavior of cationic liposomes and Streptococcus mutans in planktonic cells and biofilms. Liposomes with or without cationic lipid were prepared using a reverse-phase evaporation method. The zeta potentials of conventional liposomes (without cationic lipid) and cationic liposomes were -13 and 8 mV, respectively, and both had a mean particle size of approximately 180 nm. We first assessed the interaction between liposomes and planktonic bacterial cells with a flow cytometer. We then used a surface plasmon resonance method to examine the binding of liposomes to biofilms. We confirmed the binding behavior of liposomes with biofilms using confocal laser scanning microscopy. The interactions between cationic liposomes and S. mutans cells and biofilms were stronger than those of conventional liposomes. Microscopic observations revealed that many cationic liposomes interacted with the bacterial mass and penetrated the deep layers of biofilms. In this study, we demonstrated that cationic liposomes had higher affinity not only to oral bacterial cells, but also biofilms than conventional liposomes. This electrostatic interaction may be useful as a potential drug delivery system to biofilms.

  12. EXAFS determination of cation local order in layered perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Montero C, M. E.; Fuentes M, L.; Duarte M, J. A.; Fuentes C, L. [Centro de Investigacion en Materiales Avanzados S. C., Miguel de Cervantes Saavedra 120, Complejo Industrial Chihuahua, 31109 Chihuahua (Mexico); Garcia G, M. [Instituto de Fisica, UNAM, Ciudad Universitaria, 04510 Mexico D. F. (Mexico); Mehta, A.; Webb, S. [Stanford Synchrotron Radiation Laboratory, CA (United States)

    2008-02-15

    EXAFS analysis of Bi{sub 6}Ti{sub 3}Fe{sub 2}O{sub 18} Aurivillius ceramic was performed to elucidate the local environment of Fe cations. Experiments were performed at Stanford Synchrotron Radiation Laboratory, at T = 10, 30, 50, 75, 100 and 298 K, in fluorescence regime. EXAFS spectra were processed using the ab initio multiple scattering program FEFF6. Distances among representative atomic pairs were refined. As a basic result, the previous hypothesis suggested by X-ray diffraction experiments, regarding a preference of iron atoms for the centered perovskite layer of the unit cell, was confirmed. (Author)

  13. Density functional study of carbon monoxide adsorption on small cationic, neutral, and anionic aluminum nitride clusters

    Science.gov (United States)

    Guo, Ling

    CO adsorption on small cationic, neutral, and anionic (AlN)n (n = 1-6) clusters has been investigated using density functional theory in the generalized gradient approximation. Among various possible CO adsorption sites, an N on-top (onefold coordinated) site is found to be the most favorable one, irrespective of the charge state of the clusters. The adsorption energies of CO on the anionic (AlN)nCO (n = 2-4) clusters are greater than those on the neutral and cationic complexes. The adsorption energies on the cationic and neutral complexes reflect the odd-even oscillations, and the adsorption energies of CO on the cationic (AlN)nCO (n = 5, 6) clusters are greater than those on the neutral and anionic complexes. The adsorption energies for the different charge states decrease with increasing cluster size.

  14. The kinetics of Cr layer coated on TiNi films for hydrogen absorption

    Indian Academy of Sciences (India)

    Abstract. The effect of hydrogen absorption on electrical resistance with temperature ... pressure by thermal evaporation on the glass substrate at room temperature. ... and charging rate becomes faster in comparison to FeTi and TiNi thin films.

  15. Preparation and characterization of UV-curable cationic composite adhesive

    International Nuclear Information System (INIS)

    Shen Yan; Yang Wenbin; Li Yintao; Xie Changqiong; Li Yingjun; Cheng Yafei; Zhou Yuanlin; Lu Zhongyuan

    2011-01-01

    UV-curable cationic composite adhesives containing TiO 2 nanostructures were prepared by using 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate(CE) as monomer, triphenylsulfonium hexafluorophosphate salt (PI-432) as photoinitiator and titanium isopropoxide (TIP) as inorganic precursor. The morphology of the composite adhesives was characterized by atom force microscopy (AFM). The effect of TIP content on refractive index and transmittance of adhesives were studied. The results show that TiO 2 nanostructures, the average diameter of which is 20 nm or so, can be uniformly dispersed in polymers of composite adhesives. The refractive index of adhesives can be adjusted from 1.501 9 to 1.544 9 with the change of TIP content. The transmittance of adhesives has a slight reduce with the increase of TIP content. When TIP content is up to 40%, the transmittance of composite adhesives remains around 90% or so. (authors)

  16. Fractional charges

    International Nuclear Information System (INIS)

    Saminadayar, L.

    2001-01-01

    20 years ago fractional charges were imagined to explain values of conductivity in some materials. Recent experiments have proved the existence of charges whose value is the third of the electron charge. This article presents the experimental facts that have led theorists to predict the existence of fractional charges from the motion of quasi-particles in a linear chain of poly-acetylene to the quantum Hall effect. According to the latest theories, fractional charges are neither bosons nor fermions but anyons, they are submitted to an exclusive principle that is less stringent than that for fermions. (A.C.)

  17. Ammonia vapor sensing properties of polyaniline-titanium(IV)phosphate cation exchange nanocomposite.

    Science.gov (United States)

    Khan, Asif Ali; Baig, Umair; Khalid, Mohd

    2011-02-28

    In this study, the electrically conducting polyaniline-titanium(IV)phosphate (PANI-TiP) cation exchange nanocomposite was synthesized by sol-gel method. The cation exchange nanocomposite based sensor for detection of ammonia vapors was developed at room temperature. It was revealed that the sensor showed good reversible response towards ammonia vapors ranging from 3 to 6%. It was found that the sensor with p-toluene sulphonic acid (p-TSA) doped exhibited higher sensing response than hydrochloric acid doped. This sensor has detection limit ≤1% ammonia. The response of resistivity changes of the cation exchange nanocomposite on exposure to different concentrations of ammonia vapors shows its utility as a sensing material. These studies suggest that the cation exchange nanocomposite could be a good material for ammonia sensor at room temperature. Copyright © 2010 Elsevier B.V. All rights reserved.

  18. Organic solvation of intercalated cations in V/sub 2/O/sub 5/ xerogels

    International Nuclear Information System (INIS)

    Lemordant, D.; Bouhaouss, A.; Aldbert, P.; Baffier, N.

    1986-01-01

    V/sub 2/O/sub 5/ xerogels (V/sub 2/O/sub 5/, 1.6H/sub 2/O) undergo a topotactic reversible exchange reaction at room temperature in organic solvents containing monovalent alkali or divalent (Mn/sup 2+/) cations. Basal spacing are dependent on solvent type and charge-to-radius ratio of guest cations. From the interlayer distances, two solvation stages have been inferred, depending on the nature of the solvent and of the cation, except with Cs/sup +/ for which no intracrystalline swelling by organic solvents is observed

  19. Solar Hydrogen Production Coupled with the Degradation of a Dye Pollutant Using TiO2 Modified with Platinum and Nafion

    Directory of Open Access Journals (Sweden)

    Jungwon Kim

    2014-01-01

    Full Text Available The simultaneous production of molecular hydrogen (H2 and degradation of rhodamine B (RhB was successfully achieved using TiO2 modified with platinum and nafion (Pt/TiO2/Nf under visible light (λ>420 nm. Pt/TiO2/Nf exhibited high activity for H2 production in the presence of RhB and EDTA as a photosensitizer (also an organic dye pollutant and an electron donor, respectively. However, the activity of TiO2 modified with either platinum or nafion for H2 production was negligible under the same experimental conditions. The negatively charged nafion layer enhances the adsorption of cationic RhB and pulls protons, a source of hydrogen, to the surface of TiO2 through electrostatic attraction. On the other hand, platinum deposits on TiO2 can act as an electron sink and a temporary electron reservoir for the reduction of protons. With the production of H2, RhB was gradually degraded through N-deethylation, which was confirmed by the spectral blue shift of the maximum absorption wavelength (λmax from 556 to 499 nm (corresponding to the λmax of rhodamine 110. With Pt/TiO2/Nf employed at [RhB]=20 μM (0.6 μmol, approximately 70 μmol of H2 was produced and RhB and its intermediates were completely removed over a 12 h period. A detailed reaction mechanism was discussed.

  20. Electrostatically driven resonance energy transfer in "cationic" biocompatible indium phosphide quantum dots.

    Science.gov (United States)

    Devatha, Gayathri; Roy, Soumendu; Rao, Anish; Mallick, Abhik; Basu, Sudipta; Pillai, Pramod P

    2017-05-01

    Indium Phosphide Quantum Dots (InP QDs) have emerged as an alternative to toxic metal ion based QDs in nanobiotechnology. The ability to generate cationic surface charge, without compromising stability and biocompatibility, is essential in realizing the full potential of InP QDs in biological applications. We have addressed this challenge by developing a place exchange protocol for the preparation of cationic InP/ZnS QDs. The quaternary ammonium group provides the much required permanent positive charge and stability to InP/ZnS QDs in biofluids. The two important properties of QDs, namely bioimaging and light induced resonance energy transfer, are successfully demonstrated in cationic InP/ZnS QDs. The low cytotoxicity and stable photoluminescence of cationic InP/ZnS QDs inside cells make them ideal candidates as optical probes for cellular imaging. An efficient resonance energy transfer ( E ∼ 60%) is observed, under physiological conditions, between the cationic InP/ZnS QD donor and anionic dye acceptor. A large bimolecular quenching constant along with a linear Stern-Volmer plot confirms the formation of a strong ground state complex between the cationic InP/ZnS QDs and the anionic dye. Control experiments prove the role of electrostatic attraction in driving the light induced interactions, which can rightfully form the basis for future nano-bio studies between cationic InP/ZnS QDs and anionic biomolecules.

  1. New double-cation borohydrides

    Energy Technology Data Exchange (ETDEWEB)

    Lindemann, Inge; Domenech Ferrer, Roger; Schultz, Ludwig; Gutfleisch, Oliver [IFW Dresden, Institute for Metallic Materials, P.O. Box 270016, 01171 Dresden (Germany); Filinchuk, Yaroslav [Swiss-Norwegian Beam Lines at ESRF, BP-220, 38043 Grenoble (France); Hagemann, Hans; Cerny, Radovan [Department of Physical Chemistry and Crystallography, University of Geneva, 1211 Geneva (Switzerland)

    2011-07-01

    Complex hydrides are under consideration for on-board hydrogen storage due to their high hydrogen density. However, up to now conventional borohydrides are either too stable or unstable for applications as in PEM fuel cells (60-120 C). Recently, double-cation borohydride systems have attracted great interest. The desorption temperature of the borohydrides decreases with increasing electronegativity of the cation. Consequently, it is possible to tailor a feasible on-board hydrogen storage material by the combination of appropriate cations. The stability was found to be intermediate between the single-cation borohydride systems. Two combinations were sucessfully synthesised by metathesis reaction via high energy ball milling. Al-Li-borohydride shows desorption at about 70 C combined with a very high hydrogen density (17.2 wt.%) and the Na-Al-borohydride (14.2 wt.%) decomposes around 90 C. Both desorption temperatures are in the target range for applications. The decomposition pathways were observed by in-situ-Raman spectroscopy, DSC (Differential Scanning Calorimetry), TG (Thermogravimetry) and thermal desorption measurements.

  2. Exchanged cations and water during reactions in polypyrrole macroions from artificial muscles.

    Science.gov (United States)

    Valero, Laura; Otero, Toribio F; Martínez, José G

    2014-02-03

    The movement of the bilayer (polypyrrole-dodecylbenzenesulfonate/tape) during artificial muscle bending under flow of current square waves was studied in aqueous solutions of chloride salts. During current flow, polypyrrole redox reactions result in variations in the volumes of the films and macroscopic bending: swelling by reduction with expulsion of cations and shrinking by oxidation with the insertion of cations. The described angles follow a linear function, different in each of the studied salts, of the consumed charge: they are faradaic polymeric muscles. The linearity indicates that cations are the only exchanged ions in the studied potential range. By flow of the same specific charge in every electrolyte, different angles were described by the muscle. The charge and the angle allow the number and volume of both the exchanged cations and the water molecules (related to a reference) between the film to be determined, in addition to the electrolyte per unit of charge during the driving reaction. The attained apparent solvation numbers for the exchanged cations were: 0.8, 0.7, 0.6, 0.5, 0.5, 0.4, 0.25, and 0.0 for Na(+), Mg(2+), La(3+), Li(+), Ca(2+), K(+), Rb(+), and Cs(+), respectively. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Understanding the impact of the central atom on the ionic liquid behavior: Phosphonium vs ammonium cations

    International Nuclear Information System (INIS)

    Carvalho, Pedro J.; Ventura, Sónia P. M.; Batista, Marta L. S.; Schröder, Bernd; Coutinho, João A. P.; Gonçalves, Fernando; Esperança, José; Mutelet, Fabrice

    2014-01-01

    The influence of the cation's central atom in the behavior of pairs of ammonium- and phosphonium-based ionic liquids was investigated through the measurement of densities, viscosities, melting temperatures, activity coefficients at infinite dilution, refractive indices, and toxicity against Vibrio fischeri. All the properties investigated are affected by the cation's central atom nature, with ammonium-based ionic liquids presenting higher densities, viscosities, melting temperatures, and enthalpies. Activity coefficients at infinite dilution show the ammonium-based ionic liquids to present slightly higher infinite dilution activity coefficients for non-polar solvents, becoming slightly lower for polar solvents, suggesting that the ammonium-based ionic liquids present somewhat higher polarities. In good agreement these compounds present lower toxicities than the phosphonium congeners. To explain this behavior quantum chemical gas phase DFT calculations were performed on isolated ion pairs at the BP-TZVP level of theory. Electronic density results were used to derive electrostatic potentials of the identified minimum conformers. Electrostatic potential-derived CHelpG and Natural Population Analysis charges show the P atom of the tetraalkylphosphonium-based ionic liquids cation to be more positively charged than the N atom in the tetraalkylammonium-based analogous IL cation, and a noticeable charge delocalization occurring in the tetraalkylammonium cation, when compared with the respective phosphonium congener. It is argued that this charge delocalization is responsible for the enhanced polarity observed on the ammonium based ionic liquids explaining the changes in the thermophysical properties observed

  4. Internal Charging

    Science.gov (United States)

    Minow, Joseph I.

    2014-01-01

    (1) High energy (>100keV) electrons penetrate spacecraft walls and accumulate in dielectrics or isolated conductors; (2) Threat environment is energetic electrons with sufficient flux to charge circuit boards, cable insulation, and ungrounded metal faster than charge can dissipate; (3) Accumulating charge density generates electric fields in excess of material breakdown strenght resulting in electrostatic discharge; and (4) System impact is material damage, discharge currents inside of spacecraft Faraday cage on or near critical circuitry, and RF noise.

  5. Liquid-solid extraction of metallic cations by cationic amphiphiles

    International Nuclear Information System (INIS)

    Mueller, Wolfram; Sievers, Torsten K.; Zemb, Thomas; Diat, Olivier; Sievers, Torsten K.; Dejugnat, Christophe

    2012-01-01

    In the field of selective metal ion separation, liquid-liquid extraction is usually conducted through an emulsion mixing of hydrophobic complexants dispersed in an organic phase and acidic water containing the ionic species. Recently, it has been shown that amphiphilic complexants could influence strongly extraction efficiency by enhancing the interfacial interaction between the metal ion in the aqueous and the complexant in the organic phase. Moreover, these amphiphiles can also substitute the organic phase if an appropriate aliphatic chain is chosen. The dispersion of such amphiphilic complexants in an aqueous solution of salt mixtures is not only attractive for studying specific interactions but also to better the understanding of complex formation in aqueous solution of multivalent metal ions, such as lanthanides and actinides. This understanding is of potential interest for a broad range of industries including purification of rare earth metals and pollute treatment e.g. of fission byproducts. This principle can also be applied to liquid-solid extraction, where the final state of the separation is a solid phase containing the selectively extracted ions. Indeed, a novel solid-liquid extraction method exploits the selective precipitation of metal ions from an aqueous salt mixture using a cationic surfactant, below its Krafft point (temperature below which the long aliphatic chains of surfactant crystallize). This technique has been proven to be highly efficient for the separation of actinides and heavy metal using long chain ammonium or pyridinium amphiphiles. The most important point in this process is the recognition of cationic metal ions by cationic surfactants. By computing the free energy of the polar head group per micelle as a function of the different counter-anions, we have demonstrated for the first time that different interactions exist between the micellar surface and the ions. These interactions depend on the nature of the cation but also on

  6. Cation-Inhibited Transport of Graphene Oxide Nanomaterials in Saturated Porous Media: The Hofmeister Effects.

    Science.gov (United States)

    Xia, Tianjiao; Qi, Yu; Liu, Jing; Qi, Zhichong; Chen, Wei; Wiesner, Mark R

    2017-01-17

    Transport of negatively charged nanoparticles in porous media is largely affected by cations. To date, little is known about how cations of the same valence may affect nanoparticle transport differently. We observed that the effects of cations on the transport of graphene oxide (GO) and sulfide-reduced GO (RGO) in saturated quartz sand obeyed the Hofmeister series; that is, transport-inhibition effects of alkali metal ions followed the order of Na + cations having large ionic radii (and thus being weakly hydrated) interacted with quartz sand and GO and RGO more strongly than did cations of small ionic radii. In particular, the monovalent Cs + and divalent Ca 2+ and Ba 2+ , which can form inner-sphere complexes, resulted in very significant deposition of GO and RGO via cation bridging between quartz sand and GO and RGO, and possibly via enhanced straining, due to the enhanced aggregation of GO and RGO from cation bridging. The existence of the Hofmeister effects was further corroborated with the interesting observation that cation bridging was more significant for RGO, which contained greater amounts of carboxyl and phenolic groups (i.e., metal-complexing moieties) than did GO. The findings further demonstrate that transport of nanoparticles is controlled by the complex interplay between nanoparticle surface functionalities and solution chemistry constituents.

  7. Primary processes of the radiation-induced cationic polymerization of aromatic olefins studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Brede, O.; Boes, J.; Helmstreit, W.; Mehnert, R.

    1982-01-01

    By pulse radiolysis of solutions of aromatic olefins (styrene, 1-methylstyrene, 1,1-diphenylethylene) in non-polar solvents (cyclohexane, carbon tetrachloride, n-butylchloride) the mechanism and kinetics of primary processes of radiation-induced cationic polymerization were investigated. In cyclohexane, radical cations of the olefins are generated by charge transfer from solvent cations. These cations dimerize in a diffusion-controlled reaction. The next step of chain-growth is slower by 3 to 4 orders of magnitude. In carbon tetrachloride and in n-butyl chloride growing olefin cations are produced by a reaction of radical cations with solvent as well as by addition of solvent carbonium ions to the monomer. In strongly acidic aqueous solution of olefins radical cations produced indirectly from hydroxycyclohexadienyl radicals dimerize and react in a subsequent step by deprotonation forming non-saturated dimer radicals. The reaction mechanism established shows that in the case of radiation-induced cationic polymerization it is not possible to define a uniform first step of the chain reaction. (author)

  8. Primary processes of the radiation-induced cationic polymerization of aromatic olefins studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Brede, O.; Boes, J.; Helmstreit, W.; Mehnert, R.

    1981-01-01

    By pulse radiolysis of solutions of aromatic olefins (styrene, 1-methylstyrene, 1,1-diphenylethylene) in nonpolar solvents (cyclohexane, carbon tetrachloride, n-butyl chloride) the mechanism and kinetics of primary processes of radiation-induced cationic polymerization were investigated. In cyclohexane, radical cations of the olefins are generated by charge transfer from solvent cations (k about 10 11 l mol -1 s -1 ). These cations dimerize in a diffusion-controlled reaction (k approximately 10 10 l mol -1 s -1 ). The next step of chain-growth is slower by 3 to 4 orders of magnitude. Furthermore, in carbon tetrachloride and in n-butyl chloride growing olefin cations are produced by a reaction of the radical cations with the solvent as well as by addition of solvent carbonium ions to the monomer. In strongly acidic aqueous solution of olefins radical cations produced indirectly from hydroxycyclohexadienyl radicals dimerize and react in a subsequent step by deprotonation forming non-saturated dimer radicals. The established reaction mechanism shows that in the case of radiation-induced cationic polymerization it is not possible to define a uniform first step of the chain reaction. (author)

  9. Experimental and theoretical study on cation-pi interaction of the univalent silver cation with [7]helicene in the gas phase and in the solid state

    Czech Academy of Sciences Publication Activity Database

    Makrlík, E.; Klepetářová, Blanka; Sýkora, D.; Böhm, S.; Vaňura, P.; Storch, Jan

    2015-01-01

    Roč. 635, Aug 16 (2015), s. 355-359 ISSN 0009-2614 R&D Projects: GA ČR GP13-21409P; GA ČR GAP207/10/1124; GA TA ČR TA01010646; GA MPO FR-TI3/628 Institutional support: RVO:61388963 ; RVO:67985858 Keywords : [7]helicene * univalent silver cation * crystal structure Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.860, year: 2015

  10. Preparation, characterization, and efficient transfection of cationic liposomes and nanomagnetic cationic liposomes

    Directory of Open Access Journals (Sweden)

    Samadikhah HR

    2011-10-01

    Full Text Available Hamid Reza Samadikhah1,*, Asia Majidi2,*, Maryam Nikkhah2, Saman Hosseinkhani11Department of Biochemistry, 2Department of Nanobiotechnology, Faculty of Biological Sciences, Tarbiat Modares University, Tehran, Iran *These authors contributed equally to this work Purpose: Cationic liposomes (CLs are composed of phospholipid bilayers. One of the most important applications of these particles is in drug and gene delivery. However, using CLs to deliver therapeutic nucleic acids and drugs to target organs has some problems, including low transfection efficiency in vivo. The aim of this study was to develop novel CLs containing magnetite to overcome the deficiencies. Patients and methods: CLs and magnetic cationic liposomes (MCLs were prepared using the freeze-dried empty liposome method. Luciferase-harboring vectors (pGL3 were transferred into liposomes and the transfection efficiencies were determined by luciferase assay. Firefly luciferase is one of most popular reporter genes often used to measure the efficiency of gene transfer in vivo and in vitro. Different formulations of liposomes have been used for delivery of different kinds of gene reporters. Lipoplex (liposome–plasmid DNA complexes formation was monitored by gel retardation assay. Size and charge of lipoplexes were determined using particle size analysis. Chinese hamster ovary cells were transfected by lipoplexes (liposome-pGL3; transfection efficiency and gene expression level was evaluated by luciferase assay. Results: High transfection efficiency of plasmid by CLs and novel nanomagnetic CLs was achieved. Moreover, lipoplexes showed less cytotoxicity than polyethyleneimine and Lipofectamine™. Conclusion: Novel liposome compositions (1,2-dipalmitoyl-sn-glycero-3-phosphocholine [DPPC]/dioctadecyldimethylammonium bromide [DOAB] and DPPC/cholesterol/DOAB with high transfection efficiency can be useful in gene delivery in vitro. MCLs can also be used for targeted gene delivery, due to

  11. Tripodal receptors for cation and anion sensors

    NARCIS (Netherlands)

    Kuswandi, Bambang; Nuriman, [Unknown; Verboom, Willem; Reinhoudt, David

    2006-01-01

    This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing

  12. Biomineralisation with Saos-2 bone cells on TiSiN sputtered Ti alloys.

    Science.gov (United States)

    V V, Anusha Thampi; Bendavid, Avi; Martin, P J; Vaithilingam, Vijay; Bean, Penelope A; Evans, Margaret D M; Subramanian, B

    2017-07-01

    Surface modifications of metallic implants are important in order to protect the underlying metals from the harsh corrosive environment inside the human body and to minimize the losses caused by wear. Recently, researches are carried out in developing bioactive surfaces on metallic implants, which supports the growth and proliferation of cells on to these surfaces. Titanium silicon nitride (TiSiN) hard nanocomposites thin films were fabricated on Ti alloys (Ti-6Al-4V) by pulsed direct current (DC) reactive magnetron sputtering. The films were characterized for its microstructural and electrochemical behavior. The higher charge transfer resistance (Rct) and positive shift in Ecorr value of TiSiN/Ti alloys than the bare Ti-alloys indicates a better corrosion resistance offered by the TiSiN thin films to the underlying substrates. The biological response to TiSiN/Ti alloys and control bare Ti-alloys was measured in vitro using cell-based assays with two main outcomes. Firstly, neither the Ti alloy nor the TiSiN thin film was cytotoxic to cells. Secondly, the TiSiN thin film promoted differentiation of human bone cells above the bare control Ti alloy as measured by alkaline phosphatase and calcium production. TiSiN thin films provide better corrosion resistance and protect the underlying metal from the corrosive environment. The thin film surface is both biocompatible and bioactive as indicated from the cytotoxicity and biomineralization studies. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Heavy metal cations permeate the TRPV6 epithelial cation channel.

    Science.gov (United States)

    Kovacs, Gergely; Danko, Tamas; Bergeron, Marc J; Balazs, Bernadett; Suzuki, Yoshiro; Zsembery, Akos; Hediger, Matthias A

    2011-01-01

    TRPV6 belongs to the vanilloid family of the transient receptor potential channel (TRP) superfamily. This calcium-selective channel is highly expressed in the duodenum and the placenta, being responsible for calcium absorption in the body and fetus. Previous observations have suggested that TRPV6 is not only permeable to calcium but also to other divalent cations in epithelial tissues. In this study, we tested whether TRPV6 is indeed also permeable to cations such as zinc and cadmium. We found that the basal intracellular calcium concentration was higher in HEK293 cells transfected with hTRPV6 than in non-transfected cells, and that this difference almost disappeared in nominally calcium-free solution. Live cell imaging experiments with Fura-2 and NewPort Green DCF showed that overexpression of human TRPV6 increased the permeability for Ca(2+), Ba(2+), Sr(2+), Mn(2+), Zn(2+), Cd(2+), and interestingly also for La(3+) and Gd(3+). These results were confirmed using the patch clamp technique. (45)Ca uptake experiments showed that cadmium, lanthanum and gadolinium were also highly efficient inhibitors of TRPV6-mediated calcium influx at higher micromolar concentrations. Our results suggest that TRPV6 is not only involved in calcium transport but also in the transport of other divalent cations, including heavy metal ions, which may have toxicological implications. Copyright © 2010 Elsevier Ltd. All rights reserved.

  14. Interfacial electron-transfer equilibria and flat-band potentials of α-Fe2O3 and TiO2 colloids studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Dimitrijevic, N.M.; Savic, D.; Micic, O.I.; Nozik, A.J.

    1984-01-01

    The kinetics and equilibria of electron transfer between methylviologen cation radicals and α-Fe 2 O 3 or TiO 2 colloidal particles were studied with the pulse-radiolysis technique. The rates of electron transfer to both colloids are lower than those predicted for a diffusion-controlled reaction. For higher pHs (TiO 2 , pH > 2; α-Fe 2 O 3 , pH > 9) the established equilibrium MV + in equilibrium MV 2+ + (e - )/sub coll/ is strongly influenced by the MV 2+ concentration and pH. The MV + equilibrium concentration can be exploited to derive the flat-band potential of the semiconductor colloids. The method for determining the flat-band potential of the particles is independent of whether the injected electrons are free or trapped, and whether the electrons raise the bulk Fermi level toward the conduction band or just produce a space charge. The flat-band potentials for both colloids appear to be somewhat more negative (-0.1 to -0.2 V) than the corresponding single-crystal electrodes. Also, the flat-band potentials become slightly more negative with increasing radiation dose (initial MV + concentration). The effect of absorbed radiation dose is explained by the corresponding changes in the ratio of oxidized to reduced forms of the redox couple, which in turn changes the adsorbed ionic charge on the semiconductor surface. For colloidal particles of TiO 2 stabilized by poly(vinyl alcohol) (PVA), the flat-band potentials were almost the same as those for PVA-free TiO 2 sols. The decrease of particle diameter from 800 to 70 A does not affect the value of the flat-band potentials for TiO 2 and α-Fe 2 O 3 colloids. 28 references, 9 figures

  15. Charge preamplifier

    International Nuclear Information System (INIS)

    Chaminade, R.; Passerieux, J.P.

    1961-01-01

    We describe a charge preamplifier having the following properties: - large open loop gain giving both stable gain and large input charge transfer; - stable input grid current with aging and without any adjustment; - fairly fast rise; - nearly optimum noise performance; - industrial material. (authors)

  16. Charge Meter

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 19; Issue 4. Charge Meter: Easy Way to Measure Charge and Capacitance: Some Interesting Electrostatic Experiments. M K Raghavendra V Venkataraman. Classroom Volume 19 Issue 4 April 2014 pp 376-390 ...

  17. Charging machine

    International Nuclear Information System (INIS)

    Medlin, J.B.

    1976-01-01

    A charging machine for loading fuel slugs into the process tubes of a nuclear reactor includes a tubular housing connected to the process tube, a charging trough connected to the other end of the tubular housing, a device for loading the charging trough with a group of fuel slugs, means for equalizing the coolant pressure in the charging trough with the pressure in the process tubes, means for pushing the group of fuel slugs into the process tube and a latch and a seal engaging the last object in the group of fuel slugs to prevent the fuel slugs from being ejected from the process tube when the pusher is removed and to prevent pressure liquid from entering the charging machine. 3 claims, 11 drawing figures

  18. Cationic electrodepositable coating composition comprising lignin

    Science.gov (United States)

    Fenn, David; Bowman, Mark P; Zawacky, Steven R; Van Buskirk, Ellor J; Kamarchik, Peter

    2013-07-30

    A cationic electrodepositable coating composition is disclosed. The present invention in directed to a cationic electrodepositable coating composition comprising a lignin-containing cationic salt resin, that comprises (A) the reaction product of: lignin, an amine, and a carbonyl compound; (B) the reaction product of lignin, epichlorohydrin, and an amine; or (C) combinations thereof.

  19. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong

    2017-01-01

    The employment of metal salts is quite limited in asymmetric catalysis, although it would provide an additional arsenal of safe and inexpensive reagents to create molecular functions with high optical purity. Cation chelation by polyethers increases the salts' solubility in conventional organic...... solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...... highly enantioselective silylation reactions in polyether-generated chiral environments, and leading to a record-high turnover in asymmetric organocatalysis. This can lead to further applications by the asymmetric use of other inorganic salts in various organic transformations....

  20. Bactericidal and Hemocompatible Coating via the Mixed-Charged Copolymer.

    Science.gov (United States)

    Fan, Xiao-Li; Hu, Mi; Qin, Zhi-Hui; Wang, Jing; Chen, Xia-Chao; Lei, Wen-Xi; Ye, Wan-Ying; Jin, Qiao; Ren, Ke-Feng; Ji, Jian

    2018-03-28

    Cationic antibacterial coating based on quaternary ammonium compounds, with an efficient and broad spectrum bactericidal property, has been widely used in various fields. However, the high density of positive charges tends to induce weak hemocompatibility, which hinders the application of the cationic antibacterial coating in blood-contacting devices and implants. It has been reported that a negatively charged surface can reduce blood coagulation, showing improved hemocompatibility. Here, we describe a strategy to combine the cationic and anionic groups by using mixed-charged copolymers. The copolymers of poly (quaternized vinyl pyridine- co- n-butyl methacrylate- co-methacrylate acid) [P(QVP- co- nBMA- co-MAA)] were synthesized through free radical copolymerization. The cationic group of QVP, the anionic group of MAA, and the hydrophobic group of nBMA were designed to provide bactericidal capability, hemocompatibility, and coating stability, respectively. Our findings show that the hydrophilicity of the copolymer coating increased, and its zeta potential decreased from positive charge to negative charge with the increase of the anionic/cationic ratio. Meanwhile, the bactericidal property of the copolymer coating was kept around a similar level compared with the pure quaternary ammonium copolymer coating. Furthermore, the coagulation time, platelet adhesion, and hemolysis tests revealed that the hemocompatibility of the copolymer coating improved with the addition of the anionic group. The mixed-charged copolymer combined both bactericidal property and hemocompatibility and has a promising potential in blood-contacting antibacterial devices and implants.

  1. Modulating macrophage polarization with divalent cations in nanostructured titanium implant surfaces

    International Nuclear Information System (INIS)

    Lee, Chung-Ho; Kim, Youn-Jeong; Jang, Je-Hee; Park, Jin-Woo

    2016-01-01

    Nanoscale topographical modification and surface chemistry alteration using bioactive ions are centrally important processes in the current design of the surface of titanium (Ti) bone implants with enhanced bone healing capacity. Macrophages play a central role in the early tissue healing stage and their activity in response to the implant surface is known to affect the subsequent healing outcome. Thus, the positive modulation of macrophage phenotype polarization (i.e. towards the regenerative M2 rather than the inflammatory M1 phenotype) with a modified surface is essential for the osteogenesis funtion of Ti bone implants. However, relatively few advances have been made in terms of modulating the macrophage-centered early healing capacity in the surface design of Ti bone implants for the two important surface properties of nanotopography and and bioactive ion chemistry. We investigated whether surface bioactive ion modification exerts a definite beneficial effect on inducing regenerative M2 macrophage polarization when combined with the surface nanotopography of Ti. Our results indicate that nanoscale topographical modification and surface bioactive ion chemistry can positively modulate the macrophage phenotype in a Ti implant surface. To the best of our knowledge, this is the first demonstration that chemical surface modification using divalent cations (Ca and Sr) dramatically induces the regenerative M2 macrophage phenotype of J774.A1 cells in nanostructured Ti surfaces. In this study, divalent cation chemistry regulated the cell shape of adherent macrophages and markedly up-regulated M2 macrophage phenotype expression when combined with the nanostructured Ti surface. These results provide insight into the surface engineering of future Ti bone implants that are harmonized between the macrophage-governed early wound healing process and subsequent mesenchymal stem cell-centered osteogenesis function. (paper)

  2. Modulating macrophage polarization with divalent cations in nanostructured titanium implant surfaces

    Science.gov (United States)

    Lee, Chung-Ho; Kim, Youn-Jeong; Jang, Je-Hee; Park, Jin-Woo

    2016-02-01

    Nanoscale topographical modification and surface chemistry alteration using bioactive ions are centrally important processes in the current design of the surface of titanium (Ti) bone implants with enhanced bone healing capacity. Macrophages play a central role in the early tissue healing stage and their activity in response to the implant surface is known to affect the subsequent healing outcome. Thus, the positive modulation of macrophage phenotype polarization (i.e. towards the regenerative M2 rather than the inflammatory M1 phenotype) with a modified surface is essential for the osteogenesis funtion of Ti bone implants. However, relatively few advances have been made in terms of modulating the macrophage-centered early healing capacity in the surface design of Ti bone implants for the two important surface properties of nanotopography and and bioactive ion chemistry. We investigated whether surface bioactive ion modification exerts a definite beneficial effect on inducing regenerative M2 macrophage polarization when combined with the surface nanotopography of Ti. Our results indicate that nanoscale topographical modification and surface bioactive ion chemistry can positively modulate the macrophage phenotype in a Ti implant surface. To the best of our knowledge, this is the first demonstration that chemical surface modification using divalent cations (Ca and Sr) dramatically induces the regenerative M2 macrophage phenotype of J774.A1 cells in nanostructured Ti surfaces. In this study, divalent cation chemistry regulated the cell shape of adherent macrophages and markedly up-regulated M2 macrophage phenotype expression when combined with the nanostructured Ti surface. These results provide insight into the surface engineering of future Ti bone implants that are harmonized between the macrophage-governed early wound healing process and subsequent mesenchymal stem cell-centered osteogenesis function.

  3. Charge independence and charge symmetry

    Energy Technology Data Exchange (ETDEWEB)

    Miller, G A [Washington Univ., Seattle, WA (United States). Dept. of Physics; van Oers, W T.H. [Manitoba Univ., Winnipeg, MB (Canada). Dept. of Physics; [TRIUMF, Vancouver, BC (Canada)

    1994-09-01

    Charge independence and charge symmetry are approximate symmetries of nature, violated by the perturbing effects of the mass difference between up and down quarks and by electromagnetic interactions. The observations of the symmetry breaking effects in nuclear and particle physics and the implications of those effects are reviewed. (author). 145 refs., 3 tabs., 11 figs.

  4. Charge independence and charge symmetry

    International Nuclear Information System (INIS)

    Miller, G.A.

    1994-09-01

    Charge independence and charge symmetry are approximate symmetries of nature, violated by the perturbing effects of the mass difference between up and down quarks and by electromagnetic interactions. The observations of the symmetry breaking effects in nuclear and particle physics and the implications of those effects are reviewed. (author). 145 refs., 3 tabs., 11 figs

  5. Low temperature oxidative desulfurization with hierarchically mesoporous titaniumsilicate Ti-SBA-2 single crystals.

    Science.gov (United States)

    Shi, Chengxiang; Wang, Wenxuan; Liu, Ni; Xu, Xueyan; Wang, Danhong; Zhang, Minghui; Sun, Pingchuan; Chen, Tiehong

    2015-07-21

    Hierarchically porous Ti-SBA-2 with high framework Ti content (up to 5 wt%) was firstly synthesized by employing organic mesomorphous complexes of a cationic surfactant (CTAB) and an anionic polyelectrolyte (PAA) as templates. The material exhibited excellent performance in oxidative desulfurization of diesel fuel at low temperature (40 °C or 25 °C) due to the unique hierarchically porous structure and high framework Ti content.

  6. Enhanced desorption of Cs from clays by a polymeric cation-exchange agent

    Energy Technology Data Exchange (ETDEWEB)

    Park, Chan Woo, E-mail: park85@gmail.com [Decontamination & Decommissioning Research Division, Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon (Korea, Republic of); Kim, Bo Hyun [Decontamination & Decommissioning Research Division, Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon (Korea, Republic of); Department of Chemical Engineering, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon (Korea, Republic of); Yang, Hee-Man; Seo, Bum-Kyoung [Decontamination & Decommissioning Research Division, Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon (Korea, Republic of); Lee, Kune-Woo, E-mail: nkwlee@kaeri.re.kr [Decontamination & Decommissioning Research Division, Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon (Korea, Republic of)

    2017-04-05

    Highlights: • A cationic polyelectrolyte has excellent ability to desorb Cs bound strongly to clay. • The polycation desorbed significantly more Cs from the clay than did single cations. • Additional NH{sub 4}{sup +} treatment following the polycation treatment enhanced desorption of Cs. • The reaction yielded efficient desorption (95%) of an extremely low concentration of Cs-137 in the clay. - Abstract: We report on a new approach to increase the removal of cesium from contaminated clays based on the intercalation of a cationic polyelectrolyte into the clay interlayers. A highly charged cationic polyelectrolyte, polyethyleneimine (PEI), was shown to intercalate into the negatively charged interlayers and readily replaced Cs ions adsorbed on the interlayers of montmorillonite. The polycation desorbed significantly more Cs strongly bound to the clay than did single cations. Moreover, additional NH{sub 4}{sup +} treatment following the PEI treatment enhanced desorption of Cs ions that were less accessible by the bulky polyelectrolyte. This synergistic effect of PEI with NH{sub 4}{sup +} yielded efficient desorption (95%) of an extremely low concentration of radioactive {sup 137}Cs in the clay, which is very difficult to remove by simple cation-exchange methods due to the increased stability of the binding of Cs to the clay at low Cs concentrations.

  7. Multi-signalling cation sensing behaviour of a bis(pyridin-2-yl methyl)aniline based hetarylazo dye

    International Nuclear Information System (INIS)

    Kaur, Paramjit; Sareen, Divya; Kaur, Mandeep; Singh, Kamaljit

    2013-01-01

    Graphical abstract: The chromogenic and electrochemical behaviour of bis(pyridine-2-yl methyl)aniline based hetarylazo dye gets perturbed in the presence of cations, most effective being Cu 2+ . The conversion of ICT to ICT/MLCT is witnessed by TD-DFT calculations. -- Highlights: •Cation sensing of hetarylazo dye based upon visual, absorption and electrochemical changes is described. •Sensing mechanism is based upon perturbation in intramolecular charge-transfer upon interaction with cations. •Sensing protocol is supported by 1 H NMR studies as well as theoretical calculations. •Hetarylazo dye acts as a multichannel sensor. •Response of the dye towards various cations has also been explored in acidic pH window. -- Abstract: We investigated the cation sensing behaviour of a bis(pyridin-2-yl methyl)aniline appended hetarylazo dye via chromogenic and electrochemical transduction channels. The binding pocket constituting both the pyridyl as well as aniline nitrogen atoms acts as recognition site for the cations and consequent perturbation in the intramolecular charge-transfer prevailing in the dye results in the chromogenic response manifested in the form of hypsochromic shift in the intramolecular charge-transfer band and the attendant naked-eye color changes. The dye exhibits significant changes in its electrochemical behaviour in the presence of cations. The experimental results are also rationalized by time-dependent density functional theory (TD-DFT) calculations

  8. Electrochemical sensing and photocatalysis using Ag–TiO2 ...

    Indian Academy of Sciences (India)

    temperature chemical route carried out for the prepara- tion of Ag–TiO2. ..... tions at pH 5, 7 and 11. practical sensors for detection of cationic industrial dyes. .... as detection of toxic entities in aqueous conditions. Apart from environmental ...

  9. Analysis of adsorption behavior of cations onto quartz surface by electrical double-layer model

    International Nuclear Information System (INIS)

    Kitamura, Akira; Yamamoto, Tadashi; Fujiwara, Kenso; Nishikawa, Sataro; Moriyama, Hirotake

    1999-01-01

    In a study of the adsorption behavior of cations onto quartz, the distribution coefficient of a variety of cations was determined using the batch method, and using the titration method, the surface charge densities of quartz in a number of electrolyte solutions. The two values thus determined were analyzed applying the electrical double-layer model, from which optimum parameter values were derived for double-layer electrostatics and intrinsic adsorption equilibrium constants. Based on these parameter values, the mechanism of cation adsorption is discussed: A key factor governing this mechanism proved to be the hydration behavior of cations. Consideration of the Coulomb interaction between the adsorbate ions and adsorbent surface led to the finding of a simple rule governing in common the adsorption equilibrium constants of different metal ions. (author)

  10. Preparation of Iron-nickel Alloy Nanostructures via Two Cationic Pyridinium Derivatives as Soft Templates

    Directory of Open Access Journals (Sweden)

    Jingxin Zhou

    2015-09-01

    Full Text Available In this paper, crystalline iron-nickel alloy nanostructures were successfully prepared from two cationic pyridinium derivatives as soft templates in solution. The crystal structure and micrograph of FeNi alloy nanostructures were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy, and the content was confirmed by energy-dispersive spectrometry. The results indicated that the as-prepared nanostructures showed slightly different diameter ranges with the change of cationic pyridinium derivatives on the surface. The experimental data indicated that the adsorption of cationic pyridinium compounds on the surface of particles reduces the surface charge, leading to an isotropic distribution of the residual surface charges. The magnetic behaviours of as-prepared FeNi alloy nanostructures exhibited disparate behaviours, which could be attributed to their grain sizes and distinctive structures. The present work may give some insight into the synthesis and character of new alloy nanomaterials with special nanostructures using new soft templates.

  11. Facile synthesis of surface-functionalized magnetic nanocomposites for effectively selective adsorption of cationic dyes

    Science.gov (United States)

    Hua, Yani; Xiao, Juan; Zhang, Qinqin; Cui, Chang; Wang, Chuan

    2018-04-01

    A new magnetic nano-adsorbent, polycatechol modified Fe3O4 magnetic nanoparticles (Fe3O4/PCC MNPs) were prepared by a facile chemical coprecipitation method using iron salts and catechol solution as precursors. Fe3O4/PCC MNPs owned negatively charged surface with oxygen-containing groups and showed a strong adsorption capacity and fast adsorption rates for the removal of cationic dyes in water. The adsorption capacity of methylene blue (MB), cationic turquoise blue GB (GB), malachite green (MG), crystal violet (CV) and cationic pink FG (FG) were 60.06 mg g- 1, 70.97 mg g- 1, 66.84 mg g- 1, 66.01 mg g- 1 and 50.27 mg g- 1, respectively. The adsorption mechanism was proposed by the analyses of the adsorption isotherms and adsorption kinetics of cationic dyes on Fe3O4/PCC MNPs. Moreover, the cationic dyes adsorbed on the MNPs as a function of contact time, pH value, temperature, coexisting cationic ions and ion strength were also investigated. These results suggested that the Fe3O4/PCC MNPs is promising to be used as a magnetic adsorbent for selective adsorption of cationic dyes in wastewater treatment.

  12. A Novel Method for the Determination of Membrane Hydration Numbers of Cations in Conducting Polymers

    DEFF Research Database (Denmark)

    Jafeen, M.J.M.; Careem, M.A.; Skaarup, Steen

    2012-01-01

    Polypyrrole polymer films doped with the large, immobile dodecy lbenzene sulfonate anions operating in alkali halide aqueous electroly tes has beenused as a novel physico-chemical environment to develop a more direct way of obtaining reliable values for the hydration numbers of cations. Simultane......Polypyrrole polymer films doped with the large, immobile dodecy lbenzene sulfonate anions operating in alkali halide aqueous electroly tes has beenused as a novel physico-chemical environment to develop a more direct way of obtaining reliable values for the hydration numbers of cations....... The number of water moleculesentering the polymer during the initial part of the first reduction was found to be constant and independent of the concentration of the electrolyte below ∼1 M. This well-defined value can be considered as the primarymembrane hydration number of the cation involved...... in the reduction process. The goal was to investigate both the effects of cation size and of cation charge. The membrane hydration number values obtained by this simple and direct method for a number of cations are: The hydration number for all of these cations seems to follow the same simple relation....

  13. Understanding weakly coordinating anions: tetrakis(pentafluorophenyl)borate paired with inorganic and organic cations.

    Science.gov (United States)

    Andreeva, Nadezhda A; Chaban, Vitaly V

    2017-03-01

    Efficient design of ionic compounds requires a systematic understanding of cation-anion interactions. Weakening of electrostatic attraction is essential to increase the liquid range of the ionic compound and decrease its melting point. Here, we report simulations of the closest-approach cation-anion distances in a variety of ion pairs containing the tetrakis(pentafluorophenyl)borate (TFPB - ) anion. Small alkali cations (Li + , Na + ) penetrate the TFPB - core, whereas K + and larger organic cations do not. In the latter case, the shortest possible distance from the cations to the boron atom of TFPB - ranges from 0.50 nm to 0.63 nm. TFPB - was shown to be substantially rigid, providing a steric hindrance to thermodynamically efficient cation-anion coordination. Our results prove that TFPB - is more efficient for electrostatic charge confinement than the tetraoctylammonium cation, whereas the perfluorophenyl group is more efficient than linear alkyl chains. These simulations will motivate development of TFPB - -based ionic liquids with low phase transition points. Graphical Abstract Ionic configuration of the equilibrated "TFPB + K"system.

  14. The role of cell walls and pectins in cation exchange and surface area of plant roots.

    Science.gov (United States)

    Szatanik-Kloc, A; Szerement, J; Józefaciuk, G

    2017-08-01

    We aimed to assess role of cell walls in formation of cation exchange capacity, surface charge, surface acidity, specific surface, water adsorption energy and surface charge density of plant roots, and to find the input of the cell wall pectins to the above properties. Whole roots, isolated cell walls and the residue after the extraction of pectins from the cell walls of two Apiaceae L. species (celeriac and parsnip) were studied using potentiometric titration curves and water vapor adsorption - desorption isotherms. Total amount of surface charge, as well as the cation exchange capacity were markedly higher in roots than in their cell walls, suggesting large contribution of other cell organelles to the binding of cations by the whole root cells. Significantly lower charge of the residues after removal of pectins was noted indicating that pectins play the most important role in surface charge formation of cell walls. The specific surface was similar for all of the studied materials. For the separated cell walls it was around 10% smaller than of the whole roots, and it increased slightly after the removal of pectins. The surface charge density and water vapor adsorption energy were the highest for the whole roots and the lowest for the cell walls residues after removal of pectins. The results indicate that the cell walls and plasma membranes are jointly involved in root ion exchange and surface characteristics and their contribution depends upon the plant species. Copyright © 2017 Elsevier GmbH. All rights reserved.

  15. Correlation between photoelectrochemical behaviour and photoelectrocatalytic activity and scaling-up of P25-TiO2 electrodes

    International Nuclear Information System (INIS)

    Pablos, Cristina; Marugán, Javier; Grieken, Rafael van; Adán, Cristina; Riquelme, Ainhoa; Palma, Jesús

    2014-01-01

    The use of TiO 2 electrodes may solve the two main drawbacks of photocatalytic processes: i) the necessity of recovering the catalyst and ii) the low quantum yield in the use of the radiation. This work focuses on the correlation between the photoelectrochemical properties of TiO 2 electrodes and their activity for the photoelectrocatalytic oxidation of methanol. Particulate TiO 2 electrodes prepared by deposition of P25-TiO 2 nanoparticles on titanium (TiO 2 /Ti) or conductive glass support (TiO 2 /ITO) seem to be effective for charge carrier transference on TiO 2 surface favouring the formation of ·OH radicals and consequently, the oxidation of molecules. In contrast, thermal TiO 2 electrodes prepared by annealing of titanium (Ti) present better properties for charge carrier separation as a consequence of the application of a potential bias. Despite reducing charge carrier recombination by applying an electric potential bias, the activity of thermal electrodes remains lower than that of P25-particulate electrodes. TiO 2 structure of P25-particulate electrodes does not completely allow developing a potential gradient. However, their adequate TiO 2 layer characteristics for charge carrier transfer lead to a reduction in charge carrier recombination making up for the lack of charge carrier separation when applying an electric potential bias. TiO 2 /Ti showed the highest values of activity. Therefore, the combination of the suitable TiO 2 surface properties for charge carrier transfer with an adequate conductive support seems to increase the properties of the electrode for allowing charge carrier separation. The scaling-up calculations for a TiO 2 /ITO electrode do lead to good estimations of the activity and photocurrent of larger electrodes since this photoanode made from ITO as conductive support does not seem to be significantly affected by the applied potential bias

  16. Single Vs Mixed Organic Cation for Low Temperature Processed Perovskite Solar Cells

    International Nuclear Information System (INIS)

    Mahmud, Md Arafat; Elumalai, Naveen Kumar; Upama, Mushfika Baishakhi; Wang, Dian; Wright, Matthew; Chan, Kah Howe; Xu, Cheng; Haque, Faiazul; Uddin, Ashraf

    2016-01-01

    Highlights: • Low temperature processed ZnO based single & mixed organic cation perovskite device. • 37% higher PCE in mixed cation perovskite solar cells (PSCs) than single cation ones. • Mixed cation PSCs exhibit significantly reduced photocurrent hysteresis. • Mixed cation PSCs demonstrate three fold higher device stability than single cation PSCs. • Electronic properties are analyzed using Electrochemical Impedance Spectroscopy. - Abstract: The present work reports a comparative study between single and mixed organic cation based MAPbI 3 and MA 0.6 FA 0.4 PbI 3 perovskite devices fabricated in conjunction with low temperature processed (<150 °C) ZnO electron transport layers. MA 0.6 FA 0.4 PbI 3 perovskite devices demonstrate 37% higher power conversion efficiency compared to MAPbI 3 perovskite devices developed on the ZnO ETL. In addition, MA 0.6 FA 0.4 PbI 3 devices exhibit very low photocurrent hysteresis and they are three-fold more stable than conventional MAPbI 3 PSCs (perovskite solar cells). An in-depth analysis on the charge transport properties in both fresh and aged devices has been carried out using electrochemical impedance spectroscopy analysis to comprehend the enhanced device stability of the mixed perovskite devices developed on the ZnO ETL. The study also investigates into the interfacial charge transfer characteristics associated with the ZnO/mixed organic cation perovskite interface and concomitant influence on the inherent electronic properties.

  17. Cation-Coupled Bicarbonate Transporters

    OpenAIRE

    Aalkjaer, Christian; Boedtkjer, Ebbe; Choi, Inyeong; Lee, Soojung

    2014-01-01

    Cation-coupled HCO3− transport was initially identified in the mid-1970s when pioneering studies showed that acid extrusion from cells is stimulated by CO2/HCO3− and associated with Na+ and Cl− movement. The first Na+-coupled bicarbonate transporter (NCBT) was expression-cloned in the late 1990s. There are currently five mammalian NCBTs in the SLC4-family: the electrogenic Na,HCO3-cotransporters NBCe1 and NBCe2 (SLC4A4 and SLC4A5 gene products); the electroneutral Na,HCO3-cotransporter NBCn1 ...

  18. Cation disorder in shocked orthopyroxene.

    Science.gov (United States)

    Dundon, R. W.; Hafner, S. S.

    1971-01-01

    The study of cation distributions over nonequivalent lattice sites in minerals may reveal information on the history of temperature and pressure in rocks. Chemically homogeneous orthopyroxene specimens were shocked under well-controlled conditions in the laboratory in order to provide a basis for the interpretation of more complex natural materials. As a result of the investigation it is concluded that the distribution of magnesium and iron over the M1 and M2 positions in Bamle enstatite shocked at 1 megabar is highly disordered. It corresponds to an equilibrium distribution of at least 1000 C.

  19. Cation coordination in oxychloride glasses

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, J A [Energy Technology Division, Argonne National Laboratory, Argonne, IL (United States); Holland, D [Physics Department, Warwick University, Coventry (United Kingdom); Bland, J [Physics Department, University of Liverpool, PO Box 147, Liverpool (United Kingdom); Johnson, C E [Physics Department, Northern Illinois University, DeKalb, IL (United States); Thomas, M F [Physics Department, University of Liverpool, PO Box 147, Liverpool (United Kingdom)

    2003-02-19

    Glasses containing mixtures of cations and anions of nominal compositions [Sb{sub 2}O{sub 3}]{sub x} - [ZnCl{sub 2}]{sub 1-x} where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Moessbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb){sub 2}(OZn)] and [Zn(ClZn){sub 2}(OSb){sub 2}].

  20. Cation coordination in oxychloride glasses

    International Nuclear Information System (INIS)

    Johnson, J A; Holland, D; Bland, J; Johnson, C E; Thomas, M F

    2003-01-01

    Glasses containing mixtures of cations and anions of nominal compositions [Sb 2 O 3 ] x - [ZnCl 2 ] 1-x where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Moessbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb) 2 (OZn)] and [Zn(ClZn) 2 (OSb) 2

  1. The Free Tricoordinated Silyl Cation Problem

    Directory of Open Access Journals (Sweden)

    Čičak, H.

    2010-03-01

    Full Text Available As the importance and abundance of silicon in our environment is large, it has been thought that silicon might take the place of carbon in forming a host of similar compounds and silicon-based life. However, until today there is no experimental evidence for such a hypothesis and carbon is still unique among the elements in the vast number and variety of compounds it can form. Also, the corresponding derivatives of the two elements show considerable differences in their chemical properties.The essential debate concerning organosilicon chemistry relates to the existence of the free planar tricoordinated silyl cations in condensed phase (R3Si+, in analogy to carbocations (R3C+ which have been known and characterized as free species. Although silyl cations are thermodynamically more stable than their carbon analogs, they are very reactive due to their high inherent electrophilicity and the ability of hypervalent coordination. On the other hand, stabilization by inductive and hyperconjugative effects and larger steric effects of carbocations make them less sensitive to solvation or other environmental effects than silyl cations. Hence, observation of free silyl cations in the condensed phase proved extremely difficult and the actual problem is the question of the degree of the (remaining silyl cation character.The first free silyl cation, trimesitylsilyl cation, and in analogy with it tridurylsilyl cation, were synthesized by Lambert et al. Free silyl cations based on analogy to aromatic ions (homocyclopropenylium and tropylium have also been prepared. However, in these silyl cations the cationic character is reduced by internal π -conjugation. Čičak et al. prepared some silyl-cationic intermediates (Me3Si--CH≡CR+in solid state. With the help of quantum-mechanical calculations it was concluded that these adducts have much more silyl cation than carbocation character.

  2. Hierarchical FeTiO3-TiO2 hollow spheres for efficient simulated sunlight-driven water oxidation.

    Science.gov (United States)

    Han, Taoran; Chen, Yajie; Tian, Guohui; Wang, Jian-Qiang; Ren, Zhiyu; Zhou, Wei; Fu, Honggang

    2015-10-14

    Oxygen generation is the key step for the photocatalytic overall water splitting and considered to be kinetically more challenging than hydrogen generation. Here, an effective water oxidation catalyst of hierarchical FeTiO3-TiO2 hollow spheres are prepared via a two-step sequential solvothermal processes and followed by thermal treatment. The existence of an effective heterointerface and built-in electric field in the surface space charge region in FeTiO3-TiO2 hollow spheres plays a positive role in promoting the separation of photoinduced electron-hole pairs. Surface photovoltage, transient-state photovoltage, fluorescence and electrochemical characterization are used to investigate the transfer process of photoinduced charge carriers. The photogenerated charge carriers in the hierarchical FeTiO3-TiO2 hollow spheres with a proper molar ratio display much higher separation efficiency and longer lifetime than those in the FeTiO3 alone. Moreover, it is suggested that the hierarchical porous hollow structure can contribute to the enhancement of light utilization, surface active sites and material transportation through the framework walls. This specific synergy significantly contributes to the remarkable improvement of the photocatalytic water oxidation activity of the hierarchical FeTiO3-TiO2 hollow spheres under simulated sunlight (AM1.5).

  3. ADSORPTION METHOD FOR SEPARATING METAL CATIONS

    Science.gov (United States)

    Khym, J.X.

    1959-03-10

    The chromatographic separation of fission product cations is discussed. By use of this method a mixture of metal cations containing Zr, Cb, Ce, Y, Ba, and Sr may be separated from one another. Mentioned as preferred exchange adsorbents are resins containing free sulfonic acid groups. Various eluants, such as tartaric acid, HCl, and citric acid, used at various acidities, are employed to effect the selective elution and separation of the various fission product cations.

  4. Electronic spectra of astrophysically interesting cations

    Energy Technology Data Exchange (ETDEWEB)

    Maier, John P., E-mail: j.p.maier@unibas.ch; Rice, Corey A., E-mail: j.p.maier@unibas.ch; Mazzotti, Fabio J., E-mail: j.p.maier@unibas.ch; Johnson, Anatoly, E-mail: j.p.maier@unibas.ch [Department of Chemistry, University of Basel, Klingelbergstr. 80, CH-4056 Basel (Switzerland)

    2015-01-22

    The electronic spectra of polyacetylene cations were recorded at 20K in the laboratory in an ion trap instrument. These can then be compared with diffuse interstellar band (DIB) absorptions. Examination of recently published data shows that the attribution of a weak DIB at ∼506.9 nm to diacetylene cation is not justified. Study of the higher excited electronic states of polyacetylene cations shows that their widths can still be sufficiently narrow for consideration as DIB carriers.

  5. Effect of TiO2 nano fillers on the electrical conductivity of PSAN/TiO2 polymer nanocomposites

    Science.gov (United States)

    Ningaraju, S.; Munirathnamma, L. M.; Kumar, K. V. Aneesh; Ravikumar, H. B.

    2016-05-01

    The microstructural characterization of Polystyrene co-acrylonitrile and Titanium dioxide (PSAN/TiO2) nanocomposites has been performed by Positron Annihilation Lifetime Spectroscopy. The decrease of positron lifetime parameters viz. o-Ps lifetime (τ3) and free volume size (Vf) up to 0.6 wt% of TiO2 is attributed to the filling of free volume holes by TiO2 nanoparticles. The increased free volume size (Vf) after 0.6 wt% of TiO2 indicates the formation of interface due to TiO2 nanoclusters. The variation of electrical conductivity at the lower and higher concentration of TiO2 in (PSAN/TiO2) nanocomposites is attributed to the blocking effect and space charge effect respectively.

  6. Ab Initio Study of the Atomic Level Structure of the Rutile TiO2(110)-Titanium Nitride (TiN) Interface.

    Science.gov (United States)

    Gutiérrez Moreno, José Julio; Nolan, Michael

    2017-11-01

    Titanium nitride (TiN) is widely used in industry as a protective coating due to its hardness and resistance to corrosion and can spontaneously form a thin oxide layer when it is exposed to air, which could modify the properties of the coating. With limited understanding of the TiO 2 -TiN interfacial system at present, this work aims to describe the structural and electronic properties of oxidized TiN based on a density functional theory (DFT) study of the rutile TiO 2 (110)-TiN(100) interface model system, also including Hubbard +U correction on Ti 3d states. The small lattice mismatch gives a good stability to the TiO 2 -TiN interface after depositing the oxide onto TiN through the formation of interfacial Ti-O bonds. Our DFT+U study shows the presence of Ti 3+ cations in the TiO 2 region, which are preferentially located next to the interface region as well as the rotation of the rutile TiO 2 octahedra in the interface structure. The DFT+U TiO 2 electronic density of states (EDOS) shows localized Ti 3+ defect states forming in the midgap between the top edge of the valence and the bottom of the conduction band. We increase the complexity of our models by the introduction of nonstoichiometric compositions. Although the vacancy formation energies for Ti in TiN (E vac (Ti) ≥ 4.03 eV) or O in the oxide (E vac (O) ≥ 3.40 eV) are quite high relative to perfect TiO 2 -TiN, defects are known to form during the oxide growth and can therefore be present after TiO 2 formation. Our results show that a structure with exchanged O and N can lie 0.82 eV higher in energy than the perfect system, suggesting the stability of structures with interdiffused O and N anions at ambient conditions. The presence of N in TiO 2 introduces N 2p states localized between the top edge of the O 2p valence states and the midgap Ti 3+ 3d states, thus reducing the band gap in the TiO 2 region for the exchanged O/N interface EDOS. The outcomes of these simulations give us a most comprehensive

  7. Uranium isotope separation using styrene cation exchangers

    International Nuclear Information System (INIS)

    Kahovec, J.

    1980-01-01

    The separation of 235 U and 238 U isotopes is carried out either by simple isotope exchange in the system uranium-cation exchanger (sulphonated styrene divinylbenzene resin), or by combination of isotope exchange in a uranium-cation exchanger (Dowex 50, Amberlite IR-120) system and a chemical reaction. A review is presented of elution agents used, the degree of cation exchanger cross-linking, columns length, and 235 U enrichment. The results are described of the isotope effect study in a U(IV)-U(VI)-cation exchanger system conducted by Japanese and Romanian authors (isotope exchange kinetics, frontal analysis, reverse (indirect) frontal analysis). (H.S.)

  8. Cation-π interactions in structural biology

    OpenAIRE

    Gallivan, Justin P.; Dougherty, Dennis A.

    1999-01-01

    Cation-pi interactions in protein structures are identified and evaluated by using an energy-based criterion for selecting significant sidechain pairs. Cation-pi interactions are found to be common among structures in the Protein Data Bank, and it is clearly demonstrated that, when a cationic sidechain (Lys or Arg) is near an aromatic sidechain (Phe, Tyr, or Trp), the geometry is biased toward one that would experience a favorable cation-pi interaction. The sidechain of Arg is more likely tha...

  9. Synthesis, structure and photocatalytic activity of calcined Mg-Al-Ti-layered double hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Hosni, Khaled; Abdelkarim, Omar; Srasra, Ezzeddine [Centre National des Recherches en Sciences des Matériaux (CNRSM), Soliman (Turkey); Frini-Srasra, Najoua [Faculté des Sciences de Tunis (FST), Tunis (Turkey)

    2015-01-15

    Mg-Al-Ti layered double hydroxides (LDH), consisting of di-, tri- and tetra-valent cations with different Al{sup 3+}/Ti{sup 4+} ratio, have been synthesized by co-precipitation which was demonstrated as efficient visible-light photocatalysts. The structure and chemical composition of the compound were characterized by PXRD, FT-IR, SAA, N{sub 2} adsorption-desorption isotherms, and DSC techniques. It is found that no hydrotalcites structure were formed for Ti{sup 4+}/(Ti{sup 4+}+ Al{sup 3+})>0.5 and the substitution of Ti(IV) for Al(III) in the layer increases the thermal stability of the resulting LDH materials. The calcined sample containing titanium showed relatively high adsorption capacity for MB as compared to that without titanium. Results show that the pseudo-second-order kinetic model and the Langmuir were found to correlate the experimental data well. The photocatalytic activity was evaluated for the degradation of the methylene blue. The photocatalytic activity increased with the increase of the Al/Ti cationic ratio. 71% of the dye could be removed by the Mg/Al/Ti-LDH with the cationic ratio Al/Ti=0 : 1 and calcined at 500 .deg. C.

  10. Gas-Phase Energetics of Actinide Oxides: An Assessment of Neutral and Cationic Monoxides and Dioxides from Thorium to Curium

    Science.gov (United States)

    Marçalo, Joaquim; Gibson, John K.

    2009-09-01

    An assessment of the gas-phase energetics of neutral and singly and doubly charged cationic actinide monoxides and dioxides of thorium, protactinium, uranium, neptunium, plutonium, americium, and curium is presented. A consistent set of metal-oxygen bond dissociation enthalpies, ionization energies, and enthalpies of formation, including new or revised values, is proposed, mainly based on recent experimental data and on correlations with the electronic energetics of the atoms or cations and with condensed-phase thermochemistry.

  11. Ion exchange centres of sorption of alkaline and alkaline-earth cations on hydrated titanium and tin dioxides

    International Nuclear Information System (INIS)

    Denisova, T.A.; Perekhozheva, T.N.; Sharigin, L.M.; Pletnev, R.N.

    1986-01-01

    The nature of exchange centres of one- and two-charged cations on hydrated titanium and tin dioxides by means of paramagnetic resonance method is studied. The sorption of cations of Na + , Cs + , Ca 2+ was carried out at 25 and 90 deg C at ph=5.0-10.4 on samples of hydrated titanium dioxide and hydrated tin dioxide, obtained by sol gel method and calcined at 150 deg C and 300 deg C accordingly.

  12. Ab initio calculation of Ti NMR shieldings for titanium oxides and halides

    Science.gov (United States)

    Tossell, J. A.

    Titanium NMR shielding constants have been calculated using ab initio coupled Hartree-Fock perturbation theory and polarized double-zeta basis sets for TiF 4, TiF 62-, TiCI 4, Ti(OH) 4, Ti(OH 2) 64+, Ti(OH) 4O, and Ti(OH) 3O -. In all cases the calculations were performed at Hartree-Fuck energy-optimized geometries. For Ti(OH) 4 a S4-symmetry geometry with nonlinear ∠ TiOH was employed. Relative shieldings are in reasonable agreement with experiment for TiF 62-, TiCI 4, and Ti(OR) 4, where R = H or alkyl. Ti(OH 2) 64+ is predicted to be more highly shielded than Ti(OH) 4 by about 340 ppm. The five-coordinate complex Ti(OH) 4O, whose calculated structure matches well that measured by extended X-ray absorption fine structure in K 2O · TiO 2 · SiO 2 glass, is actually deshielded compared to Ti(OH) 4 by about 40 ppm. X-ray absorption-near-edge spectral energies have also been calculated for TiF 4, TiCI 4, Ti(OH) 4, and Ti(OH) 4O using an equivalent ionic core virtual-orbital method and the observed reduction in term energy for the five-coordinate species compared to Ti(OH) 4 has been reproduced. Replacement of the H atoms in Ti(OH) 4 by point charges has only a slight effect upon σTi, suggesting a possible means of incorporating second-neighbor effects in NMR calculations for condensed phases.

  13. Distribution of isotopes produced in superconductor YBa2Cu3O7-x and ferroelectric PbZr0.54Ti0.46O3 under irradiation by high-energy charged particles

    International Nuclear Information System (INIS)

    Didik, V.A.; Malkovich, R.Sh.; Skoryatina, E.A.; Kozlovskij, V.V.

    1998-01-01

    The concentration profiles of transmutation radioactive isotopes, formed in the YBa 2 Cu 3 O 7-x superconductor and PbZr 0.54 Ti 0.46 O 3 ferroelectric under high-energy proton radiation (with 10 and 15 MeV energy), deuterons (4 MeV), the 3 He and 4 He nuclei (20 MeV), are studied. Two types of the concentration profiles: monotonous ones and profiles with the maximum are identified. It is shown that the isotope profile is determined by the character of energy dependence of the nuclear reaction cross section, leading to formation of the given isotope

  14. XPS Spectra Analysis of Ti2+, Ti3+ Ions and Dye Photodegradation Evaluation of Titania-Silica Mixed Oxide Nanoparticles

    Science.gov (United States)

    Chinh, Vu Duc; Broggi, Alessandra; Di Palma, Luca; Scarsella, Marco; Speranza, Giorgio; Vilardi, Giorgio; Thang, Pham Nam

    2018-04-01

    TiO2-SiO2 mixed oxides have been prepared by the sol-gel technique from tetrabutyl orthotitanate and tetraethyl orthosilicate. The prepared materials were characterized by x-ray diffraction, scanning electron microscopy, energy dispersive x-ray spectroscopy, nitrogen physisorption, Fourier-transform infrared spectroscopy (FT-IR) and x-ray photoelectron spectroscopy (XPS). The results indicate that the TiO2-SiO2 mixed oxides have a large surface area and a nanoscale size. FT-IR spectra show that Ti atoms are bonded to silica by oxygen bridging atoms in Ti-O-Si bonds. The titanium valence states in TiO2-SiO2 mixed oxides were investigated by XPS, and their spectra report the presence of Ti2+ and Ti3+ cations for high silica concentration, suggesting the formation of oxygen vacancies. The photocatalytic activity of the prepared materials has been evaluated for the photodegradation of methylene blue (MB). The mixed oxides were activated by means of a UV light source, and the concentration of MB was monitored by UV-Vis spectroscopy. The synthesized TiO2-SiO2 shows significantly higher MB removal efficiency in comparison with that of the commercial TiO2 Degussa, P25.

  15. Charge Trapping in Photovoltaically Active Perovskites and Related Halogenoplumbate Compounds.

    Science.gov (United States)

    Shkrob, Ilya A; Marin, Timothy W

    2014-04-03

    Halogenoplumbate perovskites (MeNH3PbX3, where X is I and/or Br) have emerged as promising solar panel materials. Their limiting photovoltaic efficiency depends on charge localization and trapping processes that are presently insufficiently understood. We demonstrate that in halogenoplumbate materials the holes are trapped by organic cations (that deprotonate from their oxidized state) and Pb(2+) cations (as Pb(3+) centers), whereas the electrons are trapped by several Pb(2+) cations, forming diamagnetic lead clusters that also serve as color centers. In some cases, paramagnetic variants of these clusters can be observed. We suggest that charge separation in the halogenoplumbates resembles latent image formation in silver halide photography. Electron and hole trapping by lead clusters in extended dislocations in the bulk may be responsible for accumulation of trapped charge observed in this photovoltaic material.

  16. Penetrating cation/fatty acid anion pair as a mitochondria-targeted protonophore

    Science.gov (United States)

    Severin, Fedor F.; Severina, Inna I.; Antonenko, Yury N.; Rokitskaya, Tatiana I.; Cherepanov, Dmitry A.; Mokhova, Elena N.; Vyssokikh, Mikhail Yu.; Pustovidko, Antonina V.; Markova, Olga V.; Yaguzhinsky, Lev S.; Korshunova, Galina A.; Sumbatyan, Nataliya V.; Skulachev, Maxim V.; Skulachev, Vladimir P.

    2010-01-01

    A unique phenomenon of mitochondria-targeted protonophores is described. It consists in a transmembrane H+-conducting fatty acid cycling mediated by penetrating cations such as 10-(6’-plastoquinonyl)decyltriphenylphosphonium (SkQ1) or dodecyltriphenylphosphonium (C12TPP). The phenomenon has been modeled by molecular dynamics and directly proved by experiments on bilayer planar phospholipid membrane, liposomes, isolated mitochondria, and yeast cells. In bilayer planar phospholipid membrane, the concerted action of penetrating cations and fatty acids is found to result in conversion of a pH gradient (ΔpH) to a membrane potential (Δψ) of the Nernstian value (about 60 mV Δψ at ΔpH = 1). A hydrophobic cation with localized charge (cetyltrimethylammonium) failed to substitute for hydrophobic cations with delocalized charge. In isolated mitochondria, SkQ1 and C12TPP, but not cetyltrimethylammonium, potentiated fatty acid-induced (i) uncoupling of respiration and phosphorylation, and (ii) inhibition of H2O2 formation. In intact yeast cells, C12TPP stimulated respiration regardless of the extracellular pH value, whereas a nontargeted protonophorous uncoupler (trifluoromethoxycarbonylcyanide phenylhydrazone) stimulated respiration at pH 5 but not at pH 3. Hydrophobic penetrating cations might be promising to treat obesity, senescence, and some kinds of cancer that require mitochondrial hyperpolarization. PMID:20080732

  17. Treatment of drinking water residuals: comparing sedimentation and dissolved air flotation performance with optimal cation ratios.

    Science.gov (United States)

    Bourgeois, J C; Walsh, M E; Gagnon, G A

    2004-03-01

    Spent filter backwash water (SFBW) and clarifier sludge generally comprise the majority of the waste residual volume generated and in relative terms, these can be collectively referred to as combined filter backwash water (CFBW). CFBW is essentially a low-solids wastewater with metal hydroxide flocs that are typically light and slow to settle. This study evaluates the impact of adding calcium and magnesium carbonates to CFBW in terms of assessing the impacts on the sedimentation and DAF separation processes. Representative CFBW samples were collected from two surface water treatment plants (WTP): Lake Major WTP (Dartmouth, Nova Scotia, Canada) and Victoria Park WTP (Truro, Nova Scotia, Canada). Bench-scale results indicated that improvements in the CFBW settled water quality could be achieved through the addition of the divalent cations, thereby adjusting the monovalent to divalent (M:D) ratios of the wastewater. In general, the DAF process required slightly higher M:D ratios than the sedimentation process. The optimum M:D ratios for DAF and sedimentation were determined to be 1:1 and 0.33:1, respectively. It was concluded that the optimisation of the cation balance between monovalent cations (e.g., Na(+), K(+)) and added divalent cations (i.e., Ca(2+), Mg(2+)) aided in the settling mechanism through charge neutralisation-precipitation. The increase in divalent cation concentrations within the waste residual stream promoted destabilisation of the negatively charged colour molecules within the CFBW, thereby causing the colloidal content to become more hydrophobic.

  18. Metal cation controls phosphate release in the myosin ATPase.

    Science.gov (United States)

    Ge, Jinghua; Huang, Furong; Nesmelov, Yuri E

    2017-11-01

    Myosin is an enzyme that utilizes ATP to produce a conformational change generating a force. The kinetics of the myosin reverse recovery stroke depends on the metal cation complexed with ATP. The reverse recovery stroke is slow for MgATP and fast for MnATP. The metal ion coordinates the γ phosphate of ATP in the myosin active site. It is accepted that the reverse recovery stroke is correlated with the phosphate release; therefore, magnesium "holds" phosphate tighter than manganese. Magnesium and manganese are similar ions in terms of their chemical properties and the shell complexation; hence, we propose to use these ions to study the mechanism of the phosphate release. Analysis of octahedral complexes of magnesium and manganese show that the partial charge of magnesium is higher than that of manganese and the slightly larger size of manganese ion makes its ionic potential smaller. We hypothesize that electrostatics play a role in keeping and releasing the abstracted γ phosphate in the active site, and the stronger electric charge of magnesium ion holds γ phosphate tighter. We used stable myosin-nucleotide analog complex and Raman spectroscopy to examine the effect of the metal cation on the relative position of γ phosphate analog in the active site. We found that in the manganese complex, the γ phosphate analog is 0.01 nm further away from ADP than in the magnesium complex. We conclude that the ionic potential of the metal cation plays a role in the retention of the abstracted phosphate. © 2017 The Protein Society.

  19. CO 2 adsorption in mono-, di- and trivalent cation-exchanged metal-organic frameworks: A molecular simulation study

    KAUST Repository

    Chen, Yifei

    2012-02-28

    A molecular simulation study is reported for CO 2 adsorption in rho zeolite-like metal-organic framework (rho-ZMOF) exchanged with a series of cations (Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, and Al 3+). The isosteric heat and Henry\\'s constant at infinite dilution increase monotonically with increasing charge-to-diameter ratio of cation (Cs + < Rb + < K + < Na + < Ca 2+ < Mg 2+ < Al 3+). At low pressures, cations act as preferential adsorption sites for CO 2 and the capacity follows the charge-to-diameter ratio. However, the free volume of framework becomes predominant with increasing pressure and Mg-rho-ZMOF appears to possess the highest saturation capacity. The equilibrium locations of cations are observed to shift slightly upon CO 2 adsorption. Furthermore, the adsorption selectivity of CO 2/H 2 mixture increases as Cs + < Rb + < K + < Na + < Ca 2+ < Mg 2+ ≈ Al 3+. At ambient conditions, the selectivity is in the range of 800-3000 and significantly higher than in other nanoporous materials. In the presence of 0.1% H 2O, the selectivity decreases drastically because of the competitive adsorption between H 2O and CO 2, and shows a similar value in all of the cation-exchanged rho-ZMOFs. This simulation study provides microscopic insight into the important role of cations in governing gas adsorption and separation, and suggests that the performance of ionic rho-ZMOF can be tailored by cations. © 2012 American Chemical Society.

  20. Afrikaans Syllabification Patterns

    Directory of Open Access Journals (Sweden)

    Tilla Fick

    2010-01-01

    Full Text Available In contrast to English, automatic hyphenation by computer of Afrikaans words is a problem that still needs to be addressed, since errors are still often encountered in printed text. An initial step in this task is the ability to automatically syllabify words. Since new words are created continuously by joining words, it is necessary to develop an “intelligent” technique for syllabification. As a first phase of the research, we consider only the orthographic information of words, and disregard both syntactic and morphological information. This approach allows us to use machine-learning techniques such as artificial neural networks and decision trees that are known for their pattern recognition abilities. Both these techniques are trained with isolated patterns consisting of input patterns and corresponding outputs (or targets that indicate whether the input pattern should be split at a certain position, or not. In the process of compiling a list of syllabified words from which to generate training data for the  syllabification problem, irregular patterns were identified. The same letter patterns are split differently in different words and complete words that are spelled identically are split differently due to meaning. We also identified irregularities in and between  the different dictionaries that we used. We examined the influence range of letters that are involved in irregularities. For example, for their in agter-ente and vaste-rente we have to consider three letters to the left of r to be certain where the hyphen should be inserted. The influence range of the k in verstek-waarde and kleinste-kwadrate is four to the left and three to the right. In an analysis of letter patterns in Afrikaans words we found that the letter e has the highest frequency overall (16,2% of all letters in the word list. The frequency of words starting with s is the highest, while the frequency of words ending with e is the highest. It is important to

  1. EPR investigation of Ti2+ in SrCl2 single crystals.

    Science.gov (United States)

    Herrington, J. R.; Estle, T. L.; Boatner, L. A.

    1972-01-01

    The observation of 'double quantum' transitions which made it possible to determine the charge state of Ti as 2+ is reported. The EPR spectrum observed at 1.2 K is presented in a graph. The first derivative of the absorption is shown vs the magnetic field. The hyperfine patterns for the Ti-47 and Ti-49 isotopes are identified. Spin-Hamiltonian parameters for Ti(2+) in various cubic hosts are listed.

  2. Local vs Nonlocal States in FeTiO3 Probed with 1s2pRIXS: Implications for Photochemistry.

    Science.gov (United States)

    Hunault, Myrtille O J Y; Khan, Wilayat; Minár, Jan; Kroll, Thomas; Sokaras, Dimosthenis; Zimmermann, Patric; Delgado-Jaime, Mario U; de Groot, Frank M F

    2017-09-18

    Metal-metal charge transfer (MMCT) is expected to be the main mechanism that enables the harvesting of solar light by iron-titanium oxides for photocatalysis. We have studied FeTiO 3 as a model compound for MMCT with 1s2pRIXS at the Fe K-edge. The high-energy resolution XANES enables distinguishing five pre-edge features. The three first well distinct RIXS features are assigned to electric quadrupole transitions to the localized Fe* 3d states, shifted to lower energy by the 1s core-hole. Crystal field multiplet calculations confirm the speciation of divalent iron. The contribution of electric dipole absorption due to local p-d mixing allowed by the trigonal distortion of the cation site is supported by DFT and CFM calculations. The two other nonlocal features are assigned to electric dipole transitions to excited Fe* 4p states mixed with the neighboring Ti 3d states. The comparison with DFT calculations demonstrates that MMCT in ilmenite is favored by the hybridization between the Fe 4p and delocalized Ti 3d orbitals via the O 2p orbitals.

  3. Crystal structure of Mo/sub 0.975/Ti/sub 0.025/O2 between 24 and 9000C

    International Nuclear Information System (INIS)

    Ghedira, M.; Do-Dinh, C.; Marezio, M.; Mercier, J.

    1985-01-01

    Structure of Mo/sub 0.975/Ti/sub 0.025/O 2 has been refined from single-crystal X-ray data at room temperature, 300, 500, 700, and 900 0 C. The variation of the lattice parameters as a function of temperature has been measured up to 1100 0 C. The existence of the Mo-Mo bonds of second order across the shared octahedral edge is confirmed. The bond strength-bond length method of Zachariasen gives the correct valence for the cations, but yields 2.168 for O(1) and 1.832 for O(2). These unreal charges are attributed to the presence of the Mo-Mo double bonds. The same calculation applied to the isostructural VO 2 gives the correct valences for all atoms. The structure of Mo/sub 0.975/Ti/sub 0.025/O 2 remains almost unchanged up to 900 0 C. The observed small variations indicate that at a temperature higher than 1100 0 C, Mo/sub 0.975/Ti/sub 0.025/O 2 should undergo a phase transition where the double bonds would become either single or be broken completely, in which case the tetragonal rutile structure would be obtained. 11 references, 2 figures, 5 tables

  4. Effects of charging and electric field on graphene functionalized with titanium

    International Nuclear Information System (INIS)

    Gürel, H Hakan; Ciraci, S

    2013-01-01

    Titanium atoms are adsorbed to graphene with a significant binding energy and render diverse functionalities to it. Carrying out first-principles calculations, we investigated the effects of charging and static electric field on the physical and chemical properties of graphene covered by Ti adatoms. When uniformly Ti covered graphene is charged positively, its antiferromagnetic ground state changes to ferromagnetic metal and attains a permanent magnetic moment. Static electric field applied perpendicularly causes charge transfer between Ti and graphene, and can induce metal–insulator transition. While each Ti adatom adsorbed to graphene atom can hold four hydrogen molecules with a weak binding, these molecules can be released by charging or applying electric field perpendicularly. Hence, it is demonstrated that charging and applied static electric field induce quasi-continuous and side specific modifications in the charge distribution and potential energy of adatoms absorbed to single-layer nanostructures, resulting in fundamentally crucial effects on their physical and chemical properties. (paper)

  5. High charge-discharge performance of Pb{sub 0.98}La{sub 0.02}(Zr{sub 0.35}Sn{sub 0.55}Ti{sub 0.10}){sub 0.995}O{sub 3} antiferroelectric ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Chenhong [Key Laboratory of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050 (China); University of the Chinese Academy of Sciences, Beijing 100049 (China); Liu, Zhen; Chen, Xuefeng; Yan, Shiguang; Cao, Fei; Dong, Xianlin; Wang, Genshui, E-mail: genshuiwang@mail.sic.ac.cn [Key Laboratory of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050 (China)

    2016-08-21

    The energy storage performance and charge-discharge properties of Pb{sub 0.98}La{sub 0.02}(Zr{sub 0.35}Sn{sub 0.55}Ti{sub 0.10}){sub 0.995}O{sub 3} (PLZST) antiferroelectric ceramics were investigated through directly measuring the hysteresis loops and pulse discharge current-time curves. The energy density only varies 0.2% per degree from 25 °C to 85 °C, and the energy efficiency maintains at about 90%. Furthermore, an approximate calculating model of maximum power density p{sub max} was established for the discharge process. Under a relatively high working electric field (8.2 kV/mm), this ceramics possess a greatly enhanced power density of 18 MW/cm{sup 3}. Moreover, the pulse power properties did not show degradation until 1500 times of charge-discharge cycling. The large released energy density, high energy efficiency, good temperature stability, greatly enhanced power density, and excellent fatigue endurance combined together make this PLZST ceramics an ideal candidate for pulse power applications.

  6. Capability of cation exchange technology to remove proven N-nitrosodimethylamine precursors.

    Science.gov (United States)

    Li, Shixiang; Zhang, Xulan; Bei, Er; Yue, Huihui; Lin, Pengfei; Wang, Jun; Zhang, Xiaojian; Chen, Chao

    2017-08-01

    N-nitrosodimethylamine (NDMA) precursors consist of a positively charged dimethylamine group and a non-polar moiety, which inspired us to develop a targeted cation exchange technology to remove NDMA precursors. In this study, we tested the removal of two representative NDMA precursors, dimethylamine (DMA) and ranitidine (RNTD), by strong acidic cation exchange resin. The results showed that pH greatly affected the exchange efficiency, with high removal (DMA>78% and RNTD>94%) observed at pHMg 2+ >RNTD + >K + >DMA + >NH 4 + >Na + . The partition coefficient of DMA + to Na + was 1.41±0.26, while that of RNTD + to Na + was 12.1±1.9. The pseudo second-order equation fitted the cation exchange kinetics well. Bivalent inorganic cations such as Ca 2+ were found to have a notable effect on NA precursor removal in softening column test. Besides DMA and RNTD, cation exchange process also worked well for removing other 7 model NDMA precursors. Overall, NDMA precursor removal can be an added benefit of making use of cation exchange water softening processes. Copyright © 2017. Published by Elsevier B.V.

  7. Cationic polymers and their therapeutic potential

    NARCIS (Netherlands)

    Samal, S.K.; Dash, M.; van Vlierberghe, S.; Kaplan, D.; Chiellini, E.; van Blitterswijk, Clemens; Moroni, Lorenzo; Dubruel, P.

    2012-01-01

    The last decade has witnessed enormous research focused on cationic polymers. Cationic polymers are the subject of intense research as non-viral gene delivery systems, due to their flexible properties, facile synthesis, robustness and proven gene delivery efficiency. Here, we review the most recent

  8. Tripodal Receptors for Cation and Anion Sensors

    Directory of Open Access Journals (Sweden)

    David N. Reinhoudt

    2006-08-01

    Full Text Available This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing are emphasised, along with their potential applications in optical sensors or optodes.

  9. Asymmetric Aminalization via Cation-Binding Catalysis

    DEFF Research Database (Denmark)

    Park, Sang Yeon; Liu, Yidong; Oh, Joong Suk

    2018-01-01

    Asymmetric cation-binding catalysis, in principle, can generate "chiral" anionic nucleophiles, where the counter cations are coordinated within chiral environments. Nitrogen-nucleophiles are intrinsically basic, therefore, its use as nucleophiles is often challenging and limiting the scope of the...

  10. Study of interactions between hyaluronan and cationic surfactants by means of calorimetry, turbidimetry, potentiometry and conductometry.

    Science.gov (United States)

    Krouská, J; Pekař, M; Klučáková, M; Šarac, B; Bešter-Rogač, M

    2017-02-10

    The thermodynamics of the micelle formation of the cationic surfactants tetradecyltrimethylammonium bromide (TTAB) and cetyltrimethylammonium bromide (CTAB) with and without the addition of hyaluronan of two molecular weights was studied in aqueous solution by titration calorimetry. Macroscopic phase separation, which was detected by calorimetry and also by conductometry, occurs when charges on the surfactant and hyaluronan are balanced. In contrast, turbidimetry and potentiometry showed hyaluronan-surfactant interactions at very low surfactant concentrations. The observed differences between systems prepared with CTAB and TTAB indicate that besides the electrostatic interactions, which probably predominate, hydrophobic effects also play a significant role in hyaluronan interactions with cationic surfactants. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Structural changes induced by lattice-electron interactions: SiO2 stishovite and FeTiO3 ilmenite.

    Science.gov (United States)

    Yamanaka, Takamitsu

    2005-09-01

    The bright source and highly collimated beam of synchrotron radiation offers many advantages for single-crystal structure analysis under non-ambient conditions. The structure changes induced by the lattice-electron interaction under high pressure have been investigated using a diamond anvil pressure cell. The pressure dependence of electron density distributions around atoms is elucidated by a single-crystal diffraction study using deformation electron density analysis and the maximum entropy method. In order to understand the bonding electrons under pressure, diffraction intensity measurements of FeTiO3 ilmenite and gamma-SiO2 stishovite single crystals at high pressures were made using synchrotron radiation. Both diffraction studies describe the electron density distribution including bonding electrons and provide the effective charge of the cations. In both cases the valence electrons are more localized around the cations with increasing pressure. This is consistent with molecular orbital calculations, proving that the bonding electron density becomes smaller with pressure. The thermal displacement parameters of both samples are reduced with increasing pressure.

  12. Theoretical study on the correlation between the nature of atomic Li intercalation and electrochemical reactivity in TiS2 and TiO2.

    Science.gov (United States)

    Kim, Yang-Soo; Kim, Hee-Jin; Jeon, Young-A; Kang, Yong-Mook

    2009-02-12

    The electronic structures of LiTiS(2) and LiTiO(2) (having alpha-NaFeO(2) structure) have been investigated using discrete variational Xalpha molecular orbital methods. The alpha-NaFeO(2) structure is the equilibrium structure for LiCoO(2), which is widely used as a commercial cathode material for lithium secondary batteries. This study especially focused on the charge state of Li ions and the magnitude of covalency around Li ions. When the average voltage of lithium intercalation was calculated using pseudopotential methods, the average intercalation voltage of LiTiO(2) (2.076 V) was higher than that of LiTiS(2) (1.958 V). This can be explained by the differences in Mulliken charge of lithium and the bond overlap population between the intercalated Li ions and anion in LiTiO(2) as well as LiTiS(2). The Mulliken charge, which is the ionicity of Li atom, was approximately 0.12 in LiTiS(2), and the bond overlap population (BOP) indicating the covalency between Ti and S was about 0.339. When compared with the BOP (0.6) of C-H, which is one of the most famous example of covalent bonding, the intercalated Li ions in LiTiS(2) tend to form a quite strong covalent bond with the host material. In contrast, the Mulliken charge of lithium was about 0.79, which means that Li is fully ionized and the BOP, the covalency between Ti and O, was 0.181 in LiTiO(2). Because of the high ionicity of Li and the weak covalency between Ti and the nearest anion, LiTiO(2) has a higher intercalation voltage than LiTiS(2).

  13. Decondensation behavior of DNA chains induced by multivalent cations at high salt concentrations: Molecular dynamics simulations and experiments

    International Nuclear Information System (INIS)

    Jiang Yang-Wei; Zhang Lin-Xi; Ran Shi-Yong; He Lin-Li; Wang Xiang-Hong

    2015-01-01

    Using molecular dynamics simulations and atomic force microscopy (AFM), we study the decondensation process of DNA chains induced by multivalent cations at high salt concentrations in the presence of short cationic chains in solutions. The typical simulation conformations of DNA chains with varying salt concentrations for multivalent cations imply that the concentration of salt cations and the valence of multivalent cations have a strong influence on the process of DNA decondensation. The DNA chains are condensed in the absence of salt or at low salt concentrations, and the compacted conformations of DNA chains become loose when a number of cations and anions are added into the solution. It is explicitly demonstrated that cations can overcompensate the bare charge of the DNA chains and weaken the attraction interactions between the DNA chains and short cationic chains at high salt concentrations. The condensation-decondensation transitions of DNA are also experimentally observed in mixing spermidine with λ-phage DNA at different concentrations of NaCl/MgCl 2 solutions. (paper)

  14. The effect of ultralow temperature on olefin cation formation by ionic fragmentation in the radiolysis of 2,3-dimethylbutane

    International Nuclear Information System (INIS)

    Miyazaki, Tetsuo

    1991-01-01

    The formation of olefin cations in the radiolysis of 2,3-dimethylbutane (DMB) was studied by ESR at 4.2 and 77 K. When a DMB-SF 6 mixture is γ-irradiated at 77 K, tetramethylethylene (TME) cations are formed remarkably. The formation of the TME cations, however, is suppressed at 4.2 K. When the DMB-SF 6 mixture is γ-irradiated at 4.2 K and then warmed to 77 K, TME cations are formed by thermal annealing. The TME cations are not formed by a charge transfer to olefinic impurities or olefinic products in radiolysis, but by H 2 elimination from parent DMB cations in the ground state. The remarkable formation of olefin cations at 77 K corresponds to the large yields of unsaturated dimers in the radiolysis of DMB at 77 K. The suppression of olefin cation formation at 4.2 K corresponds to the low yields of unsaturated dimers in the radiolysis of DMB at 4.2 K. (author)

  15. Exploring backbone-cation alkyl spacers for multi-cation side chain anion exchange membranes

    Science.gov (United States)

    Zhu, Liang; Yu, Xuedi; Hickner, Michael A.

    2018-01-01

    In order to systematically study how the arrangement of cations on the side chain and length of alkyl spacers between cations impact the performance of multi-cation AEMs for alkaline fuel cells, a series of polyphenylene oxide (PPO)-based AEMs with different cationic side chains were synthesized. This work resulted in samples with two or three cations in a side chain pendant to the PPO backbone. More importantly, the length of the spacer between cations varied from 3 methylene (-CH2-) (C3) groups to 8 methylene (C8) groups. The highest conductivity, up to 99 mS/cm in liquid water at room temperature, was observed for the triple-cation side chain AEM with pentyl (C5) or hexyl (C6) spacers. The multi-cation AEMs were found to have decreased water uptake and ionic conductivity when the spacer chains between cations were lengthened from pentyl (C5) or hexyl (C6) to octyl (C8) linking groups. The triple-cation membranes with pentyl (C5) or hexyl (C6) groups between cations showed greatest stability after immersion in 1 M NaOH at 80 °C for 500 h.

  16. The Role of Dopant Ions on Charge Injection and Transport in Electrochemically Doped Quantum Dot Films.

    Science.gov (United States)

    Gudjonsdottir, Solrun; van der Stam, Ward; Kirkwood, Nicholas; Evers, Wiel H; Houtepen, Arjan J

    2018-05-16

    Control over the charge density is very important for implementation of colloidal semiconductor nanocrystals into various optoelectronic applications. A promising approach to dope nanocrystal assemblies is charge injection by electrochemistry, in which the charge compensating electrolyte ions can be regarded as external dopant ions. To gain insight into the doping mechanism and the role of the external dopant ions, we investigate charge injection in ZnO nanocrystal assemblies for a large series of charge compensating electrolyte ions with spectroelectrochemical and electrochemical transistor measurements. We show that charge injection is limited by the diffusion of cations in the nanocrystal films as their diffusion coefficient are found to be ∼7 orders of magnitude lower than those of electrons. We further show that the rate of charge injection depends strongly on the cation size and cation concentration. Strikingly, the onset of electron injection varies up to 0.4 V, depending on the size of the electrolyte cation. For the small ions Li + and Na + the onset is at significantly less negative potentials. For larger ions (K + , quaternary ammonium ions) the onset is always at the same, more negative potential, suggesting that intercalation may take place for Li + and Na + . Finally, we show that the nature of the charge compensating cation does not affect the source-drain electronic conductivity and mobility, indicating that shallow donor levels from intercalating ions fully hybridize with the quantum confined energy levels and that the reorganization energy due to intercalating ions does not strongly affect electron transport in these nanocrystal assemblies.

  17. Corrosion behavior of TiN, TiAlN, TiAlSiN thin films deposited on tool steel in the 3.5 wt.% NaCl solution

    International Nuclear Information System (INIS)

    Yoo, Yun Ha; Le, Diem Phuong; Kim, Jung Gu; Kim, Sun Kyu; Vinh, Pham Van

    2008-01-01

    TiN, TiAlN and TiAlSiN hard coatings were deposited onto AISI H13 tool steel by cathodic arc plasma method. X-ray diffraction (XRD) analysis confirmed that incorporation of Al and Si into TiN led to refinement of microstructure. From the results of potentiodynamic polarization test and electrochemical impedance spectroscopy (EIS) test conducted in an aerated 3.5% NaCl solution, the TiAlSiN film showed the best corrosion resistance with the lowest corrosion current density and porosity, the highest protective efficiency and total resistance (pore resistance plus charge transfer resistance)

  18. Engineering the TiO2 -graphene interface to enhance photocatalytic H2 production.

    Science.gov (United States)

    Liu, Lichen; Liu, Zhe; Liu, Annai; Gu, Xianrui; Ge, Chengyan; Gao, Fei; Dong, Lin

    2014-02-01

    In this work, TiO2 -graphene nanocomposites are synthesized with tunable TiO2 crystal facets ({100}, {101}, and {001} facets) through an anion-assisted method. These three TiO2 -graphene nanocomposites have similar particle sizes and surface areas; the only difference between them is the crystal facet exposed in TiO2 nanocrystals. UV/Vis spectra show that band structures of TiO2 nanocrystals and TiO2 -graphene nanocomposites are dependent on the crystal facets. Time-resolved photoluminescence spectra suggest that the charge-transfer rate between {100} facets and graphene is approximately 1.4 times of that between {001} facets and graphene. Photoelectrochemical measurements also confirm that the charge-separation efficiency between TiO2 and graphene is greatly dependent on the crystal facets. X-ray photoelectron spectroscopy reveals that Ti-C bonds are formed between {100} facets and graphene, while {101} facets and {001} facets are connected with graphene mainly through Ti-O-C bonds. With Ti-C bonds between TiO2 and graphene, TiO2 -100-G shows the fastest charge-transfer rate, leading to higher activity in photocatalytic H2 production from methanol solution. TiO2 -101-G with more reductive electrons and medium interfacial charge-transfer rate also shows good H2 evolution rate. As a result of its disadvantageous electronic structure and interfacial connections, TiO2 -001-G shows the lowest H2 evolution rate. These results suggest that engineering the structures of the TiO2 -graphene interface can be an effective strategy to achieve excellent photocatalytic performances. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Net charge fluctuations and local charge compensation

    International Nuclear Information System (INIS)

    Fu Jinghua

    2006-01-01

    We propose net charge fluctuation as a measure of local charge correlation length. It is demonstrated that, in terms of a schematic multiperipheral model, net charge fluctuation satisfies the same Quigg-Thomas relation as satisfied by charge transfer fluctuation. Net charge fluctuations measured in finite rapidity windows depend on both the local charge correlation length and the size of the observation window. When the observation window is larger than the local charge correlation length, the net charge fluctuation only depends on the local charge correlation length, while forward-backward charge fluctuations always have strong dependence on the observation window size. Net charge fluctuations and forward-backward charge fluctuations measured in the present heavy ion experiments show characteristic features similar to those from multiperipheral models. But the data cannot all be understood within this simple model

  20. Cation transport in isomeric pentanes

    International Nuclear Information System (INIS)

    Gyoergy, Istvan; Gee, Norman; Freeman, G.R.

    1985-01-01

    The cation mobility μsub(+) is measured in n-pentane, isopentane, neo-pentane, and mixtures of n- and neo-pentane over conditions from the normal liquid, through the critical fluid, to the low density gas. Most of the liquid data correlate with the reduced temperature T/Tsub(c). The T/Tsub(c) reflects free volume and viscosity changes. Comparison is made to neutral molecule diffusion. The transition from viscosity control of mobility in the liquid to density control in the dilute gas occurs over the reduced viscosity region 3 > eta/etasub(c) > 0.6, which corresponds to the reduced density region 1.9 > eta/etasub(c) > 0.5. In the saturated gas etaμsub(+) is similar in all pentanes, but iso- approximately> n- > neo-pentane. At constant density dμsub(+)/dT >= 0 for gases. The average gas nμsub(+) is similar in all pentanes, but iso- approximately> n- > neo-pentane. At constant density dμsub(+)/dT >= 0 for gases. The average momentum transfer cross sections in the n-/neo-pentane mixtures are similar to those in neo-pentane at low T but similar to those in n-pentane at high T. The present findings are combined with previous electron mobility data in addressing the effect of hydrocarbon molecular (external) shape on the electric breakdown strength of gases

  1. Cationic Bolaamphiphiles for Gene Delivery

    Science.gov (United States)

    Tan, Amelia Li Min; Lim, Alisa Xue Ling; Zhu, Yiting; Yang, Yi Yan; Khan, Majad

    2014-05-01

    Advances in medical research have shed light on the genetic cause of many human diseases. Gene therapy is a promising approach which can be used to deliver therapeutic genes to treat genetic diseases at its most fundamental level. In general, nonviral vectors are preferred due to reduced risk of immune response, but they are also commonly associated with low transfection efficiency and high cytotoxicity. In contrast to viral vectors, nonviral vectors do not have a natural mechanism to overcome extra- and intracellular barriers when delivering the therapeutic gene into cell. Hence, its design has been increasingly complex to meet challenges faced in targeting of, penetration of and expression in a specific host cell in achieving more satisfactory transfection efficiency. Flexibility in design of the vector is desirable, to enable a careful and controlled manipulation of its properties and functions. This can be met by the use of bolaamphiphile, a special class of lipid. Unlike conventional lipids, bolaamphiphiles can form asymmetric complexes with the therapeutic gene. The advantage of having an asymmetric complex lies in the different purposes served by the interior and exterior of the complex. More effective gene encapsulation within the interior of the complex can be achieved without triggering greater aggregation of serum proteins with the exterior, potentially overcoming one of the great hurdles faced by conventional single-head cationic lipids. In this review, we will look into the physiochemical considerations as well as the biological aspects of a bolaamphiphile-based gene delivery system.

  2. Characterization of TiO{sub 2} thin films obtained by metal-organic chemical vapour deposition; Caracterizacao de filmes finos de TiO{sub 2} obtidos por deposicao quimica em fase vapor

    Energy Technology Data Exchange (ETDEWEB)

    Carriel, Rodrigo Crociati

    2015-07-01

    Titanium dioxide (TiO{sub 2}) thin films were grown on silicon substrate (100) by MOCVD process (chemical deposition of organometallic vapor phase). The films were grown at 400, 500, 600 and 700 ° C in a conventional horizontal equipment. Titanium tetraisopropoxide was used as source of both oxygen and titanium. Nitrogen was used as carrier and purge gas. X-ray diffraction technique was used for the characterization of the crystalline structure. Scanning electron microscopy with field emission gun was used to evaluate the morphology and thickness of the films. The films grown at 400 and 500°C presented anatase phase. The film grown at 600ºC presented rutile besides anatase phase, while the film grown at 700°C showed, in addition to anatase and rutile, brookite phase. In order to evaluate the electrochemical behavior of the films cyclic voltammetry technique was used. The tests revealed that the TiO2 films formed exclusively by the anatase phase exhibit strong capacitive character. The anodic current peak is directly proportional to the square root of the scanning rate for films grown at 500ºC, suggesting that linear diffusion is the predominant mechanism of cations transport. It was observed that in the film grown during 60 minutes the Na+ ions intercalation and deintercalation easily. The films grown in the other conditions did not present the anodic current peak, although charge was accumulated in the film. (author)

  3. Stressor states and the cation crossroads.

    Science.gov (United States)

    Weber, Karl T; Bhattacharya, Syamal K; Newman, Kevin P; Soberman, Judith E; Ramanathan, Kodangudi B; McGee, Jesse E; Malik, Kafait U; Hickerson, William L

    2010-12-01

    Neurohormonal activation involving the hypothalamic-pituitary-adrenal axis and adrenergic nervous and renin-angiotensin-aldosterone systems is integral to stressor state-mediated homeostatic responses. The levels of effector hormones, depending upon the degree of stress, orchestrate the concordant appearance of hypokalemia, ionized hypocalcemia and hypomagnesemia, hypozincemia, and hyposelenemia. Seemingly contradictory to homeostatic responses wherein the constancy of extracellular fluid would be preserved, upregulation of cognate-binding proteins promotes coordinated translocation of cations to injured tissues, where they participate in wound healing. Associated catecholamine-mediated intracellular cation shifts regulate the equilibrium between pro-oxidants and antioxidant defenses, a critical determinant of cell survival. These acute and chronic stressor-induced iterations in extracellular and intracellular cations are collectively referred to as the cation crossroads. Intracellular cation shifts, particularly excessive accumulation of Ca2+, converge on mitochondria to induce oxidative stress and raise the opening potential of their inner membrane permeability transition pores (mPTPs). The ensuing loss of cationic homeostasis and adenosine triphosphate (ATP) production, together with osmotic swelling, leads to organellar degeneration and cellular necrosis. The overall impact of iterations in extracellular and intracellular cations and their influence on cardiac redox state, cardiomyocyte survival, and myocardial structure and function are addressed herein.

  4. Ab initio calculations of PbTiO{sub 3}/SrTiO{sub 3} (001) heterostructures

    Energy Technology Data Exchange (ETDEWEB)

    Eglitis, R.I.; Piskunov, S.; Zhukovskii, Yu.F. [Institute of Solid State Physics, University of Latvia, 8 Kengaraga Str., 1063 Riga (Latvia)

    2016-12-15

    We performed ab initio calculations for the PbTiO{sub 3}/SrTiO{sub 3} (001) heterostructures. For both PbO and TiO{sub 2}-terminations of the PbTiO{sub 3} (001) thin film, augmented on the SrTiO{sub 3} (001) substrate, the magnitudes of atomic relaxations Δz increases as a function of the number of augmented monolayers. For both terminations of the augmented PbTiO{sub 3} (001) nanothin film, all upper, third and fifth monolayers are displaced inwards (Δz is negative), whereas all second, fourth and sixth monolayers are displaced outwards (Δz is positive). The B3PW calculated PbTiO{sub 3}/SrTiO{sub 3} (001) heterostructure band gaps, independently from the number of augmented layers, are always smaller than the PbTiO{sub 3} and SrTiO{sub 3} bulk band gaps. For both PbO and TiO{sub 2}-terminated PbTiO{sub 3}/SrTiO{sub 3}(001) heterostructures, their band gaps are reduced due to the increased number of PbTiO{sub 3} (001) monolayers. The band gaps of PbO-terminated augmented PbTiO{sub 3} (001) films are always larger than those for TiO{sub 2}-terminated PbTiO{sub 3} (001) thin films. The only exception is the case of 7-layer PbO-terminated and 8-layer TiO{sub 2}-terminated augmented PbTiO{sub 3} (001) thin films, where their band gaps both are equal to 2.99 eV. For each monolayer of the SrTiO{sub 3} (001) substrate, charge magnitudes always are more than several times larger, than for each monolayer in the augmented PbTiO{sub 3} (001) thin film. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Investigation into Photoconductivity in Single CNF/TiO2-Dye Core–Shell Nanowire Devices

    Directory of Open Access Journals (Sweden)

    Rochford Caitlin

    2010-01-01

    Full Text Available Abstract A vertically aligned carbon nanofiber array coated with anatase TiO2 (CNF/TiO2 is an attractive possible replacement for the sintered TiO2 nanoparticle network in the original dye-sensitized solar cell (DSSC design due to the potential for improved charge transport and reduced charge recombination. Although the reported efficiency of 1.1% in these modified DSSC’s is encouraging, the limiting factors must be identified before a higher efficiency can be obtained. This work employs a single nanowire approach to investigate the charge transport in individual CNF/TiO2 core–shell nanowires with adsorbed N719 dye molecules in dark and under illumination. The results shed light on the role of charge traps and dye adsorption on the (photo conductivity of nanocrystalline TiO2 CNF’s as related to dye-sensitized solar cell performance.

  6. Cation distributions on rapidly solidified cobalt ferrite

    Science.gov (United States)

    De Guire, Mark R.; Kalonji, Gretchen; O'Handley, Robert C.

    1990-01-01

    The cation distributions in two rapidly solidified cobalt ferrites have been determined using Moessbauer spectroscopy at 4.2 K in an 8-T magnetic field. The samples were obtained by gas atomization of a Co0-Fe2O3-P2O5 melt. The degree of cation disorder in both cases was greater than is obtainable by cooling unmelted cobalt ferrite. The more rapidly cooled sample exhibited a smaller departure from the equilibrium cation distribution than did the more slowly cooled sample. This result is explained on the basis of two competing effects of rapid solidification: high cooling rate of the solid, and large undercooling.

  7. Radioimmunoassay of human eosinophil cationic protein

    International Nuclear Information System (INIS)

    Venge, P.; Roxin, L.E.; Olsson, I.

    1977-01-01

    A radioimmunosorbent assay has been developed which allows the detection in serum of a cationic protein derived from eosinophil granulocytes. In 34 healthy individuals the mean level was 31 μg/l. with a range of 5 to 55 μg/l. The serum concentration of 'eosinophil' cationic protein was correlated (P<0.001) to the number of eosinophil granulocytes in peripheral blood. Quantitiation of 'eosinophil' cationic protein in serum might be useful in the study of eosinophil granulocyte turnover and function in vivo. (author)

  8. Biosorption of silver cations onto Lactococcus lactis and Lactobacillus casei isolated from dairy products.

    Directory of Open Access Journals (Sweden)

    Maciej Milanowski

    Full Text Available The current work deals with the phenomenon of silver cations uptake by two kinds of bacteria isolated from dairy products. The mechanism of sorption of silver cations by Lactococcus lactis and Lactobacillus casei bacteria was investigated. Inductively coupled plasma-mass spectrometry (ICP-MS was used for determination of silver concentration sorbed by bacteria. Analysis of charge distribution was conducted by diffraction light scattering method. Changes in the ultrastructure of Lactococcus lactis and Lactobacillus casei cells after treatment with silver cations were investigated using transmission electron microscopy observation. Molecular spectroscopy methods, namely Fourier transform-infrared spectroscopy (FT-IR and matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS were employed for description of the sorption mechanism. Moreover, an analysis of volatile organic compounds (VOCs extracted from bacterial cells was performed.

  9. The net charge at interfaces between insulators

    International Nuclear Information System (INIS)

    Bristowe, N C; Littlewood, P B; Artacho, Emilio

    2011-01-01

    The issue of the net charge at insulating oxide interfaces is briefly reviewed with the ambition of dispelling myths of such charges being affected by covalency and related charge density effects. For electrostatic analysis purposes, the net charge at such interfaces is defined by the counting of discrete electrons and core ion charges, and by the definition of the reference polarization of the separate, unperturbed bulk materials. The arguments are illustrated for the case of a thin film of LaAlO 3 over SrTiO 3 in the absence of free carriers, for which the net charge is exactly 0.5e per interface formula unit, if the polarization response in both materials is referred to zero bulk values. Further consequences of the argument are extracted for structural and chemical alterations of such interfaces, in which internal rearrangements are distinguished from extrinsic alterations (changes of stoichiometry, redox processes), only the latter affecting the interfacial net charge. The arguments are reviewed alongside the proposal of Stengel and Vanderbilt (2009 Phys. Rev. B 80 241103) of using formal polarization values instead of net interfacial charges, based on the interface theorem of Vanderbilt and King-Smith (1993 Phys. Rev. B 48 4442-55). Implications for non-centrosymmetric materials are discussed, as well as for interfaces for which the charge mismatch is an integer number of polarization quanta. (viewpoint)

  10. Stability of anionic polymers in presence of multivalent cations

    International Nuclear Information System (INIS)

    Sabbagh, Imad

    1997-01-01

    The objectives of this research thesis were to study the stability of poly-electrolytes in saline environments, and the interactions between ions and poly-electrolytes of different charge densities. After a recall of the properties of neutral polymers and of poly-electrolytes in solution, the author evokes the interactions between poly-electrolytes and counter-ions, and briefly presents two models of stability of poly-electrolytes in saline solutions. Then, he presents different experimental techniques (scattering techniques and electrochemical techniques) and the results obtained when characterizing the used compounds. In the next part, the author discusses the basic differences of solubility between poly-electrolytes with sulfonate or sulfate groups and those with carboxylate groups. A simple model, inspired by the electrostatic model, allows poly-electrolyte phase diagram to be generalised with respect to the chemical affinity of its functional group with ions of opposed sign. The author then reports the study of the behaviour of non-charged poly-acrylic acid in various saline solutions, and then checks the behaviour of this acid within an intermediate range of dissociation level. The poly-acrylic acid structure and the distribution of ions before de-mixing are studied by X-ray and neutron scattering. The author finally tries to understand what is going on when multivalent cations are replaced by positively charged nano-metric particles (dendrimers) [fr

  11. Rietveld refinement of KLaTiO4 from X-ray powder data

    Directory of Open Access Journals (Sweden)

    Bai-Chuan Zhu

    2011-04-01

    Full Text Available Potassium lanthanum titanate(IV, KLaTiO4, has been synthesized by conventional solid-state reaction. It crystallizes isotypically with the NaLnTiO4 (Ln = La, Pr, Nd, Sm, Eu, Gd, Y and Lu family. Five of the six atoms in the asymmetric unit (one K, one La, one Ti and two O atoms are situated on sites with 4mm symmetry, whereas one O atom has 2mm. site symmetry. The crystal structure can be described as being composed of single layers of distorted corner-sharing TiO6 octahedra extending parallel to (001. The layers are alternately separated by K+ and La3+ cations along [001]. The coordination number of both K+ and La3+ cations is nine, resulting in distorted KO9 and LaO9 polyhedra.

  12. Cationization of heparin for film applications

    Czech Academy of Sciences Publication Activity Database

    Šimkovic, I.; Mendichi, R.; Kelnar, Ivan; Filip, J.; Hricovíni, M.

    2015-01-01

    Roč. 115, 22 January (2015), s. 551-558 ISSN 0144-8617 Institutional support: RVO:61389013 Keywords : heparin * cationization * NMR Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.219, year: 2015

  13. Test procedure for cation exchange chromatography

    International Nuclear Information System (INIS)

    Cooper, T.D.

    1994-01-01

    The purpose of this test plan is to demonstrate the synthesis of inorganic antimonate ion exchangers and compare their performance against the standard organic cation exchangers. Of particular interest is the degradation rate of both inorganic and organic cation exchangers. This degradation rate will be tracked by determining the ion exchange capacity and thermal stability as a function of time, radiation dose, and chemical reaction

  14. Cycloaliphatic epoxide resins for cationic UV - cure

    International Nuclear Information System (INIS)

    Verschueren, K.; Balwant Kaur

    1999-01-01

    This paper introduces the cyclo - aliphatic epoxide resins used for the various applications of radiation curing and their comparison with acrylate chemistry. Radiation curable coatings and inks are pre - dominantly based on acrylate chemistry but over the last few years, cationic chemistry has emerged successfully with the unique properties inherent with cyclo - aliphatic epoxide ring structures. Wide variety of cationic resins and diluents, the formulation techniques to achieve the desired properties greatly contributes to the advancement of UV - curing technology

  15. Chemical reactivity of cation-exchanged zeolites

    OpenAIRE

    Pidko, E.A.

    2008-01-01

    Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed by Brønsted acid sites in the hydrogen forms of zeolites, the nature of chemical reactivity, and related, the structure of the metal-containing ions in cation-exchanged zeolites remains the subject...

  16. On the real performance of cation exchange resins in wastewater treatment under conditions of cation competition: the case of heavy metal pollution.

    Science.gov (United States)

    Prelot, Benedicte; Ayed, Imen; Marchandeau, Franck; Zajac, Jerzy

    2014-01-01

    Sorption performance of cation-exchange resins Amberlite® IRN77 and Amberlite™ IRN9652 toward Cs(I) and Sr(II) has been tested in single-component aqueous solutions and simulated waste effluents containing other monovalent (Effluent 1) or divalent (Effluent 2) metal cations, as well as nitrate, borate, or carbonate anions. The individual sorption isotherms of each main component were measured by the solution depletion method. The differential molar enthalpy changes accompanying the ion-exchange between Cs+ or Sr2+ ions and protons at the resin surface from single-component nitrate solutions were measured by isothermal titration calorimetry and they showed a higher specificity of the two resins toward cesium. Compared to the retention limits of both resins under such idealized conditions, an important depression in the maximum adsorption capacity toward each main component was observed in multication systems. The overall effect of ion exchange process appeared to be an unpredictable outcome of the individual sorption capacities of the two resins toward various cations as a function of the cation charge, size, and concentration. The cesium retention capacity of the resins was diminished to about 25% of the "ideal" value in Effluent 1 and 50% in Effluent 2; a further decrease to about 15% was observed upon concomitant strontium addition. The uptake of strontium by the resins was found to be less sensitive to the addition of other metal components: the greatest decrease in the amount adsorbed was 60% of the ideal value in the two effluents for Amberlite® IRN77 and 75% for Amberlite™ IRN9652. It was therefore demonstrated that any performance tests carried out under idealized conditions should be exploited with much caution to predict the real performance of cation exchange resins under conditions of cation competition.

  17. Enhancement of localization phenomena driven by covalency in the SrBiMn{sub 1.75}Ti{sub 0.25}O{sub 6} manganite

    Energy Technology Data Exchange (ETDEWEB)

    Asensio de Lucas, E.; Alvarez-Serrano, I. [Depto. Quimica Inorganica I, Facultad Ciencias Quimicas, Universidad Complutense de Madrid, E-28040 Madrid (Spain); Cuello, G.J. [Institut Laue-Langevin, 6 rue Jules Horowitz, F-38042 Grenoble (France); Garcia-Hernandez, M. [Instituto de Ciencia de Materiales de Madrid, CSIC, E-28049 Cantoblanco, Madrid (Spain); Lopez, M.L., E-mail: marisal@quim.ucm.es [Depto. Quimica Inorganica I, Facultad Ciencias Quimicas, Universidad Complutense de Madrid, E-28040 Madrid (Spain); Pico, C.; Veiga, M.L. [Depto. Quimica Inorganica I, Facultad Ciencias Quimicas, Universidad Complutense de Madrid, E-28040 Madrid (Spain)

    2012-05-05

    Graphical abstract: Enhancement of localization phenomena driven by covalency in the BiSrMn{sub 1.75}Ti{sub 0.25}O{sub 6} manganite. The CO/OO phenomena and magnetic clusters (Mn{sub 4}) stabilization at temperatures up to 520 K in BiSrMn{sub 1.75}Ti{sub 0.25}O{sub 6} are connected to a structural transition. The observed enhancement of electronic localization is interpreted considering covalent effects of Ti{sup 4+} and Bi{sup 3+} cations as the main driving force. Highlights: Black-Right-Pointing-Pointer The structural, electronic and magnetic behaviour of the new SrBiMn{sub 1.75}Ti{sub 0.25}O{sub 6} manganite is reported. Black-Right-Pointing-Pointer A structural transition above 520 K takes place, coinciding with relevant changes in the transport properties. Black-Right-Pointing-Pointer The electronic behavior is interpreted in terms of a remarkably high orbital and charge ordering temperature and cluster models. Black-Right-Pointing-Pointer The observed features are explained considering a scenario in which bonds covalence is enhanced by the Bi{sup 3+} and Ti{sup 4+} cations. - Abstract: Manganites are materials that show remarkable phenomena related to charge orbital ordering (CO/OO) and it is extremely important to understand the fundamental nature of this behaviour. This paper reports on the structural, electronic and magnetic behaviour of the new SrBiMn{sub 1.75}Ti{sub 0.25}O{sub 6} manganite and the dependence of these properties with temperature. A detailed structural analysis has been carried out by electron, X-ray, neutron diffraction between 4 and 700 K. The electron diffraction patterns obtained at room temperature (RT) evidence that the average structure (a{approx}b{approx}{radical}(2)a{sub p} and c {approx} 2a{sub p}) presents a modulation that doubles the a and c lattice parameters. A very high charge ordering (CO) transition temperature of 510 K, similar to that found for the non-doped material, SrBiMn{sub 2}O{sub 6}, is observed. Above this

  18. A Cation-containing Polymer Anion Exchange Membrane based on Poly(norbornene)

    Science.gov (United States)

    Beyer, Frederick; Price, Samuel; Ren, Xiaoming; Savage, Alice

    Cation-containing polymers are being studied widely for use as anion exchange membranes (AEMs) in alkaline fuel cells (AFCs) because AEMs offer a number of potential benefits including allowing a solid state device and elimination of the carbonate poisoning problem. The successful AEM will combine high performance from several orthogonal properties, having robust mechanical strength even when wet, high hydroxide conductivity, and the high chemical stability required for long device lifetimes. In this study, we have synthesized a model cationic polymer that combines three of the key advantages of Nafion. The polymer backbone based on semicrystalline atactic poly(norbornene) offers good mechanical properties. A flexible, ether-based tether between the backbone and fixed cation charged species (quaternary ammonium) should provide the low-Tg, hydrophilic environment required to facilitate OH- transport. Finally, methyl groups have been added at the beta position relative to the quaternary ammonium cation to prevent Hoffman elimination, one mechanism by which AEMs are neutralized in a high pH environment. In this poster, we will present our findings on mechanical properties, morphology, charge transport, and chemical stability of this material.

  19. Structure, thermodynamic and electronic properties of carbon-nitrogen cubanes and protonated polynitrogen cations

    Science.gov (United States)

    Chaban, Vitaly V.; Andreeva, Nadezhda A.

    2017-12-01

    Energy generation and storage are at the center of modern civilization. Energetic materials constitute quite a large class of compounds with a high amount of stored chemical energy that can be released. We hereby use a combination of quantum chemistry methods to investigate feasibility and properties of carbon-nitrogen cubanes and multi-charged polynitrogen cations in the context of their synthesis and application as unprecedented energetic materials. We show that the stored energy increases gradually with the nitrogen content increase. Nitrogen-poor cubanes retain their stabilities in vacuum, even at elevated temperatures. Such molecules will be probably synthesized at some point. In turn, polynitrogen cations are highly unstable, except N8H+, despite they are isoelectronic to all-carbon cubane. Kinetic stability of the cation decays drastically as its total charge increases. High-level thermodynamic calculations revealed that large amounts of energy are liberated upon decompositions of polynitrogen cations, which produce molecular nitrogen, acetylene, and protons. The present results bring a substantial insights to the design of novel high-energy compounds.

  20. Formation of radical cations of diaryloxadiazoles

    International Nuclear Information System (INIS)

    Helmstreit, W.

    1988-01-01

    The nature of the formation of the radical cation of the 2,5-bis-(p-diethylaminophenyl)-1,3,4-oxadiazole (PC) in liquid n-butyl chloride and acetonitrile has been investigated by observing excited state fluorescence and transient absorption using nanosecond pulse radiolysis and laser flash photolysis. The formation of solute oxonium ions has also been observed. At concentrations -4 mol dm -3 the growth time at which the transient absorption of the radical cation reaches the maximum follows the rise time of the electron pulse ( 2 laser yields the solute radical cation in an acetonitrile solution of 2 x 10 -4 mol dm -3 PC via an electronically excited state. Here, the generation time was smaller than 5 ns. The yield of the cation is increased by addition of CCl 4 . A reaction mechanism is proposed that explains the fast cation formation in terms of an exciplex formed by interaction between an electronically excited state of diaryloxadiazole and the ground state of the solvent. This exciplex yields the solute radical cation. (author)

  1. Luminescent sulfides of monovalent and trivalent cations

    International Nuclear Information System (INIS)

    1975-01-01

    The invention discloses a family of luminescent materials or phosphors having a rhombohedral crystal structure and consisting essentially of a mixed host sulfide of at least one monovalent host cation and at least one trivalent host cation, and containing, for each mole of phosphor, 0.0005 to 0.05 mole of at least one activating cation. The monovalent host cations may be Na, K or Rb and Cs. The trivalent host cations may be Gd, La, Lu, Sc and Y. The activating cations may be one or more of trivalent As, Bi, Ce, Dy, Er, Pr, Sb, Sm, Tb and Tm; divalent Lu, Mn, Pb and Sn; and monovalent Ag, Cu and Tl. The novel phosphors may be used in devices to convert electron-beam, ultraviolet or x-ray energy to light in the visible spectrum. Such energy conversion can be employed for example in fluoroscopic screens, and in viewing screens of cathode-ray tubes and other electron tubes

  2. Spin-polarized electron gas in Co2MSi/SrTiO3(M= Ti, V, Cr, Mn, and Fe) heterostructures

    KAUST Repository

    Nazir, S.

    2016-06-08

    Spin-polarized density functional theory is used to study the TiO2 terminated interfaces between the magnetic Heusler alloys Co2Si (M = Ti, V, Cr, Mn, and Fe) and the non-polar band insulator SrTiO3. The structural relaxation at the interface turns out to depend systematically on the lattice mis- match. Charge transfer from the Heusler alloys (mainly the M 3d orbitals) to the Ti dxy orbitals of the TiO2 interface layer is found to gradually grow from M = Ti to Fe, resulting in an electron gas with increasing density of spin-polarized charge carriers. (© 2016 WILEY-VCH Verlag GmbH &Co. KGaA, Weinheim). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  3. A density functional study of carbon monoxide adsorption on small cationic, neutral, and anionic gold clusters

    Science.gov (United States)

    Wu, X.; Senapati, L.; Nayak, S. K.; Selloni, A.; Hajaligol, M.

    2002-08-01

    CO adsorption on small cationic, neutral, and anionic Aun (n=1-6) clusters has been investigated using density functional theory in the generalized gradient approximation. Among various possible CO adsorption sites, the on-top (one-fold coordinated) is found to be the most favorable one, irrespective of the charge state of the cluster. In addition, planar structures are preferred by both the bare and the CO-adsorbed clusters. The adsorption energies of CO on the cationic clusters are generally greater than those on the neutral and anionic complexes, and decrease with size. The adsorption energies on the anions, instead, increase with cluster size and reach a local maximum at Au5CO-, in agreement with recent experiment. The differences in adsorption energies for the different charge states decrease with increasing cluster size.

  4. ETUDE DE LA DISTRIBUTION DES CATIONS ECHANGEABLES

    African Journals Online (AJOL)

    SEI Joseph

    Structural, optical and electrical properties of Cu-doped TiO2 thin films .... A partir des valeurs du coefficient d'extinction k de la couche mince, obtenu par ..... BARTEAU, ''Band gap tailoring of Nd3+-doped TiO2 nanoparticles'', Appl. Phys. Lett.

  5. Efficient H2 production over Au/graphene/TiO2 induced by surface plasmon resonance of Au and band-gap excitation of TiO2

    International Nuclear Information System (INIS)

    Liu, Yang; Yu, Hongtao; Wang, Hua; Chen, Shuo; Quan, Xie

    2014-01-01

    Highlights: • Both surface plasmon resonance and band-gap excitation were used for H 2 production. • Au/Gr/TiO 2 composite photocatalyst was synthesized. • Au/Gr/TiO 2 exhibited enhancement of light absorption and charge separation. • H 2 production rate of Au/Gr/TiO 2 was about 2 times as high as that of Au/TiO 2 . - Abstract: H 2 production over Au/Gr/TiO 2 composite photocatalyst induced by surface plasmon resonance of Au and band-gap excitation of TiO 2 using graphene (Gr) as an electron acceptor has been investigated. Electron paramagnetic resonance study indicated that, in this composite, Gr collected electrons not only from Au with surface plasmon resonance but also from TiO 2 with band-gap excitation. Surface photovoltage and UV–vis absorption measurements revealed that compared with Au/TiO 2 , Au/Gr/TiO 2 displayed more effective photogenerated charge separation and higher optical absorption. Benefiting from these advantages, the H 2 production rate of Au/Gr/TiO 2 composite with Gr content of 1.0 wt% and Au content of 2.0 wt% was about 2 times as high as that of Au/TiO 2 . This work represents an important step toward the efficient application of both surface plasmon resonance and band-gap excitation on the way to converting solar light into chemical energy

  6. Geminate electron--cation recombination in disordered solids

    International Nuclear Information System (INIS)

    Berlin, Y.A.; Chekunaev, N.I.; Goldanskii, V.I.

    1990-01-01

    A theory of a geminate electron--cation recombination has been developed using the percolation approach to the description of the electron transport in disordered solids. Following this approach all trapping sites are separated into two groups. The first group forms a diffusion cluster responsible for the macroscopic charge transfer in disordered media whilethe second group consists of isolated traps playing the role of origins and sinks for mobile electrons. In the framework of such a model an equation has been derived describing the electron motion in the Coulomb field of a parent cation. The solution of this equation in the long time limit shows that the recombination rate decreases vs time as t -(1+α/2) with α being a positive constant or a very weak function of t. In the particular case of Gaussian diffusion α=1 and the kinetic law obtained reduces to that predicted by the well-known Onsager--Smoluchowski theory. However for the dispersive (non-Gaussian) transport in highly disordered systems α<1 and its value depends on the type of disorder, on the energy level structure of trapped electrons and on the specific mechanism of electron migration through the medium

  7. Coordination phenomena of cationic uranium(iv) complexes

    International Nuclear Information System (INIS)

    Rohwer, H.E.

    1974-12-01

    The coordination properties of the cationic uranium(IV) complexes UCl 3 + , UCl 2 2+ , UCl 3+ , and U 4+ were studied in a non-aqueous medium in the presence of perchlorate as counterion which, however, proved to coordinate to a much greater extent than expected. The strong neutral ligand, HMPA, could successively displace some of the perchlorates. An electrostatic model for the U(CIO 4 ) 4 -HMPA-acetone system compared favourably with the actual results. This emphasized the high ionic content in the bonding with actenoid cations, even with such a high charge as +4 . These conclusions are in agreement with studies 75 in which nitrate acts as counter ion. Correspondingly the uranium (IV) chemistry is characterized by the absence of typical 3d-organometallic chemistry, for example, strong bonding with CO, P(Phi) 3 etc, which strongly depends on covalent bonding. This stresses the fact that the d and f orbitals are not readily available for strong bond formation with the actenoids. 76

  8. Organic non-aqueous cation-based redox flow batteries

    Science.gov (United States)

    Zhang, Lu; Huang, Jinhua; Burrell, Anthony

    2018-05-08

    The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturated moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte comprises a tetrafluorohydroquinone ether compound or a tetrafluorocatechol ether compound.

  9. Organic non-aqueous cation-based redox flow batteries

    Science.gov (United States)

    Jansen, Andrew N.; Vaughey, John T.; Chen, Zonghai; Zhang, Lu; Brushett, Fikile R.

    2016-03-29

    The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturated moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte is selected to have a higher redox potential than the redox reactant of the negative electrolyte.

  10. Selective adsorption of cationic dyes by UiO-66-NH{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Qi; He, Qinqin; Lv, Mengmeng; Xu, Yanli; Yang, Hanbiao; Liu, Xueting, E-mail: wmlxt@163.com; Wei, Fengyu, E-mail: weifyliuj@163.com

    2015-02-01

    Graphical abstract: - Highlights: • Two Zr(IV)-based MOFs can remove cationic dyes more effectively than anionic dyes. • UiO-66 has higher selectivity for cationic dyes after modification with NH{sub 2}. • The mechanism for adsorption selectivity is rationally proposed. - Abstract: Herein, two zirconium(IV)-based MOFs UiO-66 and UiO-66-NH{sub 2} had been successfully prepared by a facile solvothermal method and were characterized by X-ray diffraction (XRD), field emission transmission electron microscopy (FETEM), N{sub 2} adsorption–desorption (BET), X-ray photoelectron spectroscopy (XPS), and zeta potential. They exhibit small size, large surface area, and can remove cationic dyes from aqueous solution more effectively than anionic dyes. This adsorption selectivity is due to the favorable electrostatic interactions between the adsorbents and cationic dyes. Furthermore, owing to the individual micropore structure of UiO-66-NH{sub 2} and its more negative zeta potential resulted from the charge balance for the protonation of –NH{sub 2}, UiO-66-NH{sub 2} displays much higher adsorption capacity for cationic dyes and lower adsorption capacity for anionic dyes than UiO-66.

  11. Exchange of interlayer cations in micaceous minerals. Final report, February 1, 1967--August 31, 1976

    International Nuclear Information System (INIS)

    Scott, A.D.

    1976-08-01

    Laboratory experiments were carried out to establish a comprehensive understanding of the processes and factors governing the sorption and release of interlayer cations in micaceous minerals. A diverse approach with several lines of work was used to delineate the effects of different procedures, solution compositions and mineral properties. It was soon clear that the major factors controlling the exchange of interlayer cations are the blocking effects of dissolved fixable cations and the limiting effects of small particles. By using sodium tetraphenylboron to reduce the blocking effects and by excluding particles that were smaller than 2 μm, however, the subtle effects of many other factors were brought out. The redox status of structural iron, the hydroxyl groups, the interlayer spacing and the layer charge of the minerals are indicative of the type of factors involved and the fact that they are mainly interactive in nature. One conclusion from this work is that most experimental results for interlayer cation exchange are bound to reflect some combination of the controlling factors. More important, however, was the observation that proper management of interlayer cation exchange can make micaceous minerals a good sink for cesium and source of potassium

  12. Structure-transfection activity relationships in a series of novel cationic lipids with heterocyclic head-groups.

    Science.gov (United States)

    Ivanova, Ekaterina A; Maslov, Mikhail A; Kabilova, Tatyana O; Puchkov, Pavel A; Alekseeva, Anna S; Boldyrev, Ivan A; Vlassov, Valentin V; Serebrennikova, Galina A; Morozova, Nina G; Zenkova, Marina A

    2013-11-07

    Cationic liposomes are promising candidates for the delivery of various therapeutic nucleic acids. Here, we report a convenient synthesis of carbamate-type cationic lipids with various hydrophobic domains (tetradecanol, dialkylglycerol, cholesterol) and positively charged head-groups (pyridinium, N-methylimidazolium, N-methylmorpholinium) and data on the structure-transfection activity relationships. It was found that single-chain lipids possess high surface activity, which correlates with high cytotoxicity due to their ability to disrupt the cellular membrane by combined hydrophobic and electrostatic interactions. Liposomes containing these lipids also display high cytotoxicity with respect to all cell lines. Irrespective of chemical structures, all cationic lipids form liposomes with similar sizes and surface potentials. The characteristics of complexes composed of cationic liposomes and nucleic acids depend mostly on the type of nucleic acid and P/N ratios. In the case of oligodeoxyribonucleotide delivery, the transfection activity depends on the type of cationic head-group regardless of the type of hydrophobic domain: all types of cationic liposomes mediate efficient oligonucleotide transfer into 80-90% of the eukaryotic cells, and liposomes based on lipids with N-methylmorpholinium cationic head-group display the highest transfection activity. In the case of plasmid DNA and siRNA, the type of hydrophobic domain determines the transfection activity: liposomes composed of cholesterol-based lipids were the most efficient in DNA transfer, while liposomes containing glycerol-based lipids exhibited reasonable activity in siRNA delivery under serum-free conditions.

  13. CHARGE Association

    Directory of Open Access Journals (Sweden)

    Semanti Chakraborty

    2012-01-01

    Full Text Available We present here a case of 17-year-old boy from Kolkata presenting with obesity, bilateral gynecomastia, mental retardation, and hypogonadotrophic hypogonadism. The patient weighed 70 kg and was of 153 cm height. Facial asymmetry (unilateral facial palsy, gynecomastia, decreased pubic and axillary hair, small penis, decreased right testicular volume, non-palpable left testis, and right-sided congenital inguinal hernia was present. The patient also had disc coloboma, convergent squint, microcornea, microphthalmia, pseudohypertelorism, low set ears, short neck, and choanalatresia. He had h/o VSD repaired with patch. Laboratory examination revealed haemoglobin 9.9 mg/dl, urea 24 mg/dl, creatinine 0.68 mg/dl. IGF1 77.80 ng/ml (decreased for age, GH <0.05 ng/ml, testosterone 0.25 ng/ml, FSH-0.95 ΅IU/ml, LH 0.60 ΅IU/ml. ACTH, 8:00 A.M cortisol, FT3, FT4, TSH, estradiol, DHEA-S, lipid profile, and LFT was within normal limits. Prolactin was elevated at 38.50 ng/ml. The patient′s karyotype was 46XY. Echocardiography revealed ventricularseptal defect closed with patch, grade 1 aortic regurgitation, and ejection fraction 67%. Ultrasound testis showed small right testis within scrotal sac and undescended left testis within left inguinal canal. CT scan paranasal sinuses revealed choanalatresia and deviation of nasal septum to the right. Sonomammography revealed bilateral proliferation of fibroglandular elements predominantly in subareoalar region of breasts. MRI of brain and pituitary region revealed markedly atrophic pituitary gland parenchyma with preserved infundibulum and hypothalamus and widened suprasellar cistern. The CHARGE association is an increasingly recognized non-random pattern of congenital anomalies comprising of coloboma, heart defect, choanal atresia, retarded growth and development, genital hypoplasia, ear abnormalities, and/or deafness. [1] These anomalies have a higher probability of occurring together. In this report, we have

  14. Synthesis of a cationic thermoresponsive dendrimer and its self-assembly with apoferritin protein cage

    OpenAIRE

    Välimäki, Salla

    2015-01-01

    The aim of this work was to synthesize cationic dendrimer with a thermoresponsive polymer tail and complex the dendrimer with negatively charged apoferritin protein nanocage. These kind of systems are developed, for example, for biomedical applications. Spermine dendron with atom transfer radical polymerization initiator in focal point was synthesized successfully. Thermoresponsive poly(di(ethylene glycol) methyl ether methacrylate) was in situ polymerized to the dendron to form the therm...

  15. Dilute Al and V NMR in α-Ti

    International Nuclear Information System (INIS)

    Chou, L.H.; Rowland, T.J.

    1992-01-01

    We report a nuclear-magnetic-resonance investigation of four titanium alloys: Ti--1 at. % V, Ti--2 at. % V, Ti--1 at. % Al, and Ti--2 at. % Al. Interpretation of the experimental 51 V and 27 Al absorption curves was accomplished largely by comparison with computer-simulated curves. Since the latter include the effects of nuclear-quadrupole and anisotropic Knight-shift interactions, dipolar broadening, and inhomogeneous Knight shift for the V and Al solute nuclei, the comparison yields experimental values for the electric-field gradient, axially symmetric anistropic Knight shift, and isotropic Knight shift, from which we attempt to deduce the local charge distribution at the V or Al atoms in the hcp α-Ti matrix. We find that the localized states on an Al impurity exhibit very little of the character of the host Ti atomic structure. There is no orbital contribution to the Knight shift and the s conduction-electron density at Al sites is small. On the other hand, when vanadium is present as a dilute solute in the Ti lattice, only minor changes in its Knight shift are found. There is a large orbital-shift contribution, and the V nuclear absorption exhibits much the same character as in pure metallic V; there is, however, clear evidence of the V charge distribution assuming the hexagonal symmetry of the Ti lattice. The measured temperature dependences of the anisotropic Knight shift and electric-field-gradient values at V solute sites in Ti are also discussed. On partitioning the field gradient we find that the contribution from local non-s electrons is about two to five times larger in magnitude than the Ti-lattice ion value, a strong indication that the electronic structure near V (but not Al) resembles that of the matrix Ti

  16. A model for the electric conduction in metal/poly-TiO2/metal structure

    Science.gov (United States)

    Hossein-Babaei, Faramarz; Alaei-Sheini, Navid-

    2017-12-01

    Intensely studied memristive devices have M‧/MO/M″ structures, wherein MO is a nanometer-sized metal oxide crystallite sandwiched between the M‧ and M″ metal electrodes. The most widely used oxide for this purpose is TiO2 and the electrodes are of noble metals such as platinum, silver, and gold. The memristive features of the device is believed to originate from the motion of the ionized oxygen vacancies within the oxide crystal. The operation of the device is further complicated by the motion of the mobile cations originating from the metal electrodes. The complexity of the device performance increases further when the noble metal electrodes form Schottky barriers at their junctions with TiO2, as the conduction takes place through these energy barriers. In a recent publication, the authors have shown that, owing to the ohmicity of the Ti/TiO2 junctions, electronic observations on the devices with Ti/TiO2/Ti structure can be easier to model. The presented model clarified that in a Ti/poly-TiO2/Ti structure, the ionic motion and the electronic conduction take place on the TiO2 grain surfaces and grain boundaries rather than the grain interiors. Here, we show that the suggested model has important implications for chemical sensor design and fabrication.

  17. Accelerating rate calorimetry studies of the reactions between ionic liquids and charged lithium ion battery electrode materials

    International Nuclear Information System (INIS)

    Wang, Yadong; Zaghib, K.; Guerfi, A.; Bazito, Fernanda F.C.; Torresi, Roberto M.; Dahn, J.R.

    2007-01-01

    Using accelerating rate calorimetry (ARC), the reactivity between six ionic liquids (with and without added LiPF 6 ) and charged electrode materials is compared to the reactivity of standard carbonate-based solvents and electrolytes with the same electrode materials. The charged electrode materials used were Li 1 Si, Li 7 Ti 4 O 12 and Li 0.45 CoO 2 . The experiments showed that not all ionic liquids are safer than conventional electrolytes/solvents. Of the six ionic liquids tested, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMI-FSI) shows the worst safety properties, and is much worse than conventional electrolyte. 1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMI-TFSI) and 1-propyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (Py13-FSI) show similar reactivity to carbonate-based electrolyte. The three ionic liquids 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide (BMMI-TFSI), 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide (Pp14-TFSI) and N-trimethyl-N-butylammonium bis(trifluoromethanesulfonyl)imide (TMBA-TFSI) show similar reactivity and are much safer than the conventional carbonate-based electrolyte. A comparison of the reactivity of ionic liquids with common anions and cations shows that ionic liquids with TFSI - are safer than those with FSI - , and liquids with EMI + are worse than those with BMMI + , Py13 + , Pp14 + and TMBA +

  18. Modification of Ti6Al4V surface by diazonium compounds

    Science.gov (United States)

    Sandomierski, Mariusz; Buchwald, Tomasz; Strzemiecka, Beata; Voelkel, Adam

    2018-02-01

    Ti6Al4V alloy is the most commonly used in orthopedic industry as an endoprosthesis. Ti6Al4V exhibits good mechanical properties, except the abrasion resistance. Surface modification of Ti6Al4V in order to obtain organic layer, and then the attachment of the polymer, can allow for overcoming this problem. The aim of the work was the modification of Ti6Al4V surface by diazonium compounds: salt or cation generated in situ and examine the influence of the reducing agent - ascorbic acid, and the temperature of reaction on modification process. Moreover, the simulated body fluid was used for the assessment of the organic layer stability on Ti6Al4V surface. The evaluation of the modification was carried out using the following methods: Raman microspectroscopy, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Higher temperature of modification by 4-hydroxymethylbenzenediazonium cation, provides the largest amount of organic layer on the Ti6Al4V alloy. In the case of the Ti6Al4V modified by Variamine Blue B salt, the amount of organic layer is not dependent on the reaction condition. Moreover, the ascorbic acid and the presence of TiO2 does not effect on the modification. The modified surface is completely coated with the organic layer which is stable in simulated body fluid.

  19. A2TiF5.nH2O (A=K, Rb, or Cs; n=0 or 1): Synthesis, structure, characterization, and calculations of three new uni-dimensional titanium fluorides

    International Nuclear Information System (INIS)

    Jo, Vinna; Woo Lee, Dong; Koo, Hyun-Joo; Ok, Kang Min

    2011-01-01

    Three new uni-dimensional alkali metal titanium fluoride materials, A 2 TiF 5 .nH 2 O (A=K, Rb, or Cs; n=0 or 1) have been synthesized by hydrothermal reactions. The structures of A 2 TiF 5 .nH 2 O have been determined by single-crystal X-ray diffraction. The Ti 4+ cations have been reduced to Ti 3+ during the synthesis reactions. All three A 2 TiF 5 .nH 2 O materials contain novel 1-D chain structures that are composed of the slightly distorted Ti 3+ F 6 corner-sharing octahedra attributable to the Jahn-Teller distortion. The coordination environment of the alkali metal cations plays an important role to determine the degree of turning in the chain structures. Complete structural analyses, Infrared and UV-vis diffuse reflectance spectra, and thermal analyses are presented, as are electronic structure calculations. -- Graphical abstract: Ball-and-stick and polyhedral representations for (a) β-K 2 TiF 5 and (b) Rb 2 TiF 5 .H 2 O or Cs 2 TiF 5 .H 2 O with the K + and Rb + (or Cs + ) coordination environment emphasized. Display Omitted Research highlights: → Synthesis, structure, characterization, and calculation of new titanium fluorides. → Study of reduction of starting Ti 4+ cations to Ti 3+ by DMF. → Novel 1-D chain structures with Jahn-Teller distorted TiF 6 octahedra.

  20. Accelerators for forming cationic technetium complexes useful as radiodiagnostic images

    International Nuclear Information System (INIS)

    Tweedle, M.F.

    1985-01-01

    This invention relates to compositions for making cationic radiodiagnostic agents and, in particular, to accelerator compounds for labelling such cationic radiodiagnostic agents, kits for preparing such 99m Tc-labelled cationic radiodiagnostic agents with technetium, and methods for labelling such cationic radiodiagnostic agents with technetium

  1. Pulse radiolysis study of monomer and dimer cations of styrene, 1-methylstyrene and 1,1'-diphenylethylene

    International Nuclear Information System (INIS)

    Mehnert, R.; Helmstreit, W.; Boes, J.; Brede, O.

    1977-01-01

    In pulse-irradiated solutions of styrene, 1-methylstyrene and 1,1'-diphenylethylene, the decay kinetics of the olefin monomer cations and the formation kinetics of the corresponding dimer cations have been studied at room temperature. The solutions were irradiated with 15-nsec 15-ampere pulses of 1-MeV electrons from an Elit-type accelerator. The total dose per pulse was approximately 10 krad. The monomer cations were generated with rate constants of about 10 11 M -1 sec -1 . From the time decay of the monomer light absorption and the growth in time of the dimer absorption rate constants for the dimer formation between 0.8x10 10 and 1.2x10 10 M -1 sec -1 have been determined. (T.I.)

  2. Comparison Study on the Microstructure of Nanocrystalline TiO2 in Different Ti-Si Binary Oxides

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Three different Ti-Si oxide structuares, silica supported titania, silica coated titania and intimately mixed silicatitania, containing 10%-40% SiO2, were made by sol-gel process. The variations of microstructure parameters of nanocrystalline (nc) TiO2-anatase in the three kirds of binary oxides, including in-plane spacing d, cell constants (a0, CQ), cell volume V, cell axial ratio c0/a0 and crystal grain size, were comparatively investigated by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). It is found that the microstructure parameters vary remarkably with increasing SiO2 content and annealing temperature. Different structured Ti-Si binary oxides lead to different variation tendencies of microstructure parameters. The more SiO2 the binary oxide contains, the more lattice defects of nc TiO2-anatase appear; diffusion or migration of Si cations could be an important influential factor in the variations of microstructure. The grain size of nc TiO2 in the three kinds of binary oxides not only depends on SiO2 content and annealing temperature but also on the degree of lattice microstrain and distortion of nc TiO2-anatase. Both grain size and phase transformation of nc TiO2-anatase are effectively inhibited with increasing SiOa content.

  3. Hydrogen storage behavior of one-dimensional TiBx chains

    International Nuclear Information System (INIS)

    Li Fen; Zhao Jijun; Chen Zhongfang

    2010-01-01

    We designed a series of one-dimensional TiB x (x = 2-6) chains used for hydrogen storage. Among them, TiB 5 possesses the lowest heat of formation and the highest binding energy, and is the most energetically favorable configuration. The binding energy per atom in TiB 5 is even larger than that in a Ti dimer, which suggests the preference of Ti atoms to combine with B 5 clusters rather than clustering. Each Ti atom in the TiB 5 chain can host four hydrogen molecules (corresponding to a hydrogen storage capacity of 7.3 wt%) with an average binding energy of 43.7 kJ mol -1 /H 2 . The significant charge transfer and strong Kubas σ-H 2 interaction between H 2 and Ti atoms contribute to the ideal dihydrogen binding energies.

  4. Zeaxanthin Radical Cation Formation in Minor Light-Harvesting Complexes of Higher Plant Antenna

    Energy Technology Data Exchange (ETDEWEB)

    Avenson, Thomas H.; Ahn, Tae Kyu; Zigmantas, Donatas; Niyogi, Krishna K.; Li, Zhirong; Ballottari, Matteo; Bassi, Roberto; Fleming, Graham R.

    2008-01-31

    Previous work on intact thylakoid membranes showed that transient formation of a zeaxanthin radical cation was correlated with regulation of photosynthetic light-harvesting via energy-dependent quenching. A molecular mechanism for such quenching was proposed to involve charge transfer within a chlorophyll-zeaxanthin heterodimer. Using near infrared (880-1100 nm) transient absorption spectroscopy, we demonstrate that carotenoid (mainly zeaxanthin) radical cation generation occurs solely in isolated minor light-harvesting complexes that bind zeaxanthin, consistent with the engagement of charge transfer quenching therein. We estimated that less than 0.5percent of the isolated minor complexes undergo charge transfer quenching in vitro, whereas the fraction of minor complexes estimated to be engaged in charge transfer quenching in isolated thylakoids was more than 80 times higher. We conclude that minor complexes which bind zeaxanthin are sites of charge transfer quenching in vivo and that they can assume Non-quenching and Quenching conformations, the equilibrium LHC(N)<--> LHC(Q) of which is modulated by the transthylakoid pH gradient, the PsbS protein, and protein-protein interactions.

  5. Solid-state poly(ethylene glycol)-polyurethane/polymethylmethacrylate/rutile TiO2 nanofiber composite electrolyte-correlation between morphology and conducting properties

    International Nuclear Information System (INIS)

    Chilaka, Naresh; Ghosh, Sutapa

    2012-01-01

    Network. Power law exponents of individual phase of that semi Inter penetrating Polymer Network obtained by simulated fitting of the conductivity versus log frequency profile using universal power law reveals that cationic hopping in the polymethylmethacrylate phase and anionic hopping in the polyethylene glycol-polyurethane phase contribute significantly to the charge transport processes in these semi Inter penetrating Polymer Network.

  6. Gas phase chemistry of N-benzylbenzamides with silver(I) cations: characterization of benzylsilver cation.

    Science.gov (United States)

    Sun, Hezhi; Jin, Zhe; Quan, Hong; Sun, Cuirong; Pan, Yuanjiang

    2015-03-07

    The benzylsilver cation which emerges from the collisional dissociation of silver(I)-N-benzylbenzamide complexes was characterized by deuterium-labeling experiments, theoretical calculations, breakdown curves and substituent effects. The nucleophilic attack of the carbonyl oxygen on an α-hydrogen results in the generation of the benzylsilver cation, which is competitive to the AgH loss with the α-hydrogen.

  7. Effect of the internal pressure and the anti-site disorder on the structure and magnetic properties of ALaFeTiO6 (A=Ca, Sr, Ba) double perovskite oxides

    International Nuclear Information System (INIS)

    Elbadawi, A.A.; Yassin, O.A.; Gismelseed, Abbasher A.

    2013-01-01

    Successful preparation of double perovskite oxides of chemical formula ALaFeTiO 6 (A=Ba, Sr and Ca) has been achieved by following the precursor method. The samples were studied by means of X-ray diffraction and Mössbauer spectroscopy. The Rietveld analysis of the X-ray diffraction data showed that all the samples have anti-site disorder. The presence of anti-site disorder has altered the electronic environment around the Fe ion sites which creates electric field gradient between two different sites. Observation of quadruple splitting in the ideal cubic perovskite BaLaFeTiO 6 (its tolerance factor equals 1) is the evidence of this anti-site generated electric field gradient. The valence state of the Fe atom determined from the measurements of the Mössbauer effect of 57 Fe at room temperature and 80 K showed that the iron ion has the Fe 3+ high spin state as extracted from the values of the isomer shift for all the samples. It is evidenced that the anti-site disorder has no appreciable effect on the spin state of the Fe ion, but alters the charge densities at the Fe sites and influences the hyperfine parameters of the present samples. Weak ferromagnetism is observed in CaLaFeTiO 6 and SrLaFeTiO 6 and is related to both the internal pressure and the anti-site effect which facilitate the occurrence of the Fe 3+ ↑−O−Fe 3+ ↓ antiferromagnetic interaction with canted spin. - Highlights: ► Anti-site disorder was revealed in (Ca,Sr,Ba)LaFeTiO 6 double perovskites. ► Mössbauer spectroscopy revealed a dependence of the quadruple splitting and the cation size mismatch. ► Weak ferromagnetism is evidenced due to internal pressure and anti-site disorder.

  8. Effect of Divalent Cations on RED Performance and Cation Exchange Membrane Selection to Enhance Power Densities.

    Science.gov (United States)

    Rijnaarts, Timon; Huerta, Elisa; van Baak, Willem; Nijmeijer, Kitty

    2017-11-07

    Reverse electrodialysis (RED) is a membrane-based renewable energy technology that can harvest energy from salinity gradients. The anticipated feed streams are natural river and seawater, both of which contain not only monovalent ions but also divalent ions. However, RED using feed streams containing divalent ions experiences lower power densities because of both uphill transport and increased membrane resistance. In this study, we investigate the effects of divalent cations (Mg 2+ and Ca 2+ ) on RED and demonstrate the mitigation of those effects using both novel and existing commercial cation exchange membranes (CEMs). Monovalent-selective Neosepta CMS is known to block divalent cations transport and can therefore mitigate reductions in stack voltage. The new multivalent-permeable Fuji T1 is able to transport divalent cations without a major increase in resistance. Both strategies significantly improve power densities compared to standard-grade CEMs when performing RED using streams containing divalent cations.

  9. Charge ordering in the rare earth manganates: the experimental situation

    International Nuclear Information System (INIS)

    Rao, C.N.R.; Cheetham, A.K.; Raveau, Bernard

    2000-01-01

    Charge-ordered phases of rare earth manganates are novel manifestations arising from interactions between the charge carriers and phonons, giving rise to the localization of carriers at specific sites in the lattice below a certain temperature. Accompanying this phenomenon, the Mn 3+ (e g ) orbitals and the associated lattice distortions also exhibit long range ordering (orbital ordering). What makes the manganates even more interesting is the occurrence of complex spin ordering related to anisotropic magnetic interactions. In this article, we discuss the emerging scenario of charge-ordered rare earth manganates in the light of specific case studies and highlight some of the new experimental findings related to spin, orbital and charge ordering. We also examine features such as the charge stripes and phase separation found experimentally in these materials, and discuss the factors that affect charge-ordering such as the size of A-site cations and magnetic and electric fields, as well as isotopic and chemical substitutions. (author)

  10. PIIID-formed (Ti, O)/Ti, (Ti, N)/Ti and (Ti, O, N)/Ti coatings on NiTi shape memory alloy for medical applications

    Energy Technology Data Exchange (ETDEWEB)

    Sun Tao, E-mail: taosun@hotmail.com.hk [Department of Mechanical Engineering, University of Hong Kong, Pokfulam Road (Hong Kong); Institute of Microelectronics, Agency for Science, Technology and Research (A-STAR) (Singapore); Wang Langping, E-mail: aplpwang@hit.edu.cn [State Key Lab of Advanced Welding and Joining, Harbin Institute of Technology (China); Wang Min; Tong Howang [Department of Mechanical Engineering, University of Hong Kong, Pokfulam Road (Hong Kong); Lu, William W. [Department of Orthopedics and Traumatology, University of Hong Kong, Sassoon Road (Hong Kong)

    2012-08-01

    (Ti, O)/Ti, (Ti, N)/Ti and (Ti, O, N)/Ti composite coatings were fabricated on NiTi shape memory alloy via plasma immersion ion implantation and deposition (PIIID). Surface morphology of samples was investigated using atomic force microscopy (AFM) and scanning electron microscopy (SEM). Cross-sectional morphology indicated that the PIIID-formed coatings were dense and uniform. X-ray diffraction (XRD) was used to characterize the phase composition of samples. X-ray photoelectron spectroscopy (XPS) results showed that the surface of coated NiTi SMA samples was Ni-free. Nanoindentation measurements and pin-on-disc tests were carried out to evaluate mechanical properties and wear resistance of coated NiTi SMA, respectively. For the in vitro biological assessment of the composite coatings in terms of cell morphology and cell viability, osteoblast-like SaOS-2 cells and breast cancer MCF-7 cells were cultured on NiTi SMA samples, respectively. SaOS-2 cells attached and spread better on coated NiTi SMA. Viability of MCF-7 cells showed that the PIIID-formed composite coatings were noncytotoxic and coated samples were more biocompatible than uncoated samples. - Highlights: Black-Right-Pointing-Pointer PIIID-formed coatings were fabricated on NiTi SMA to improve its biocompatibility. Black-Right-Pointing-Pointer Microstructure, mechanical properties and biocompatibility of coatings were investigated. Black-Right-Pointing-Pointer All PIIID-formed composite coatings were noncytotoxic and cytocompatible.

  11. Low-temperature processed ultrathin TiO2 for efficient planar heterojunction perovskite solar cells

    International Nuclear Information System (INIS)

    Huang, Xiaokun; Hu, Ziyang; Xu, Jie; Wang, Peng; Zhang, Jing; Zhu, Yuejin

    2017-01-01

    Highlights: • An ultrathin and discrete TiO 2 (u-TiO 2 ) was fabricated at low temperature. • High-performance perovskite solar cells based u-TiO 2 was realized. • u-TiO 2 between perovskite and FTO functions as a bridge for electron transport. • u-TiO 2 accelerates electron transfer and alleviates charge recombination. - Abstract: A compact TiO 2 (c-TiO 2 ) layer fabricated by spin coating or spray pyrolysis following a high-temperature sintering is a routine in high-performance planar heterojunction perovskite solar cells. Here, we demonstrate an effective low-temperature approach to fabricate an ultrathin and discrete TiO 2 (u-TiO 2 ) for enhancing photovoltaic performance of perovskite solar cells. Via hydrolysis of low-concentration TiCl 4 solution at 70 °C, u-TiO 2 was grown on a fluorine doped tin oxide (FTO) substrate, forming the electron selective contact with the photoactive CH 3 NH 3 PbI 3 film. The perovskite solar cell using u-TiO 2 achieves an efficiency of 13.42%, which is compared to 13.56% of the device using c-TiO 2 prepared by high-temperature sintering. Cyclic voltammetry, steady-state photoluminescence spectroscopy and electrical impedance spectroscopy were conducted to study interface engineering and charge carrier dynamics. Our results suggest that u-TiO 2 functions as a bridge for electron transport between perovskite and FTO, which accelerates electron transfer and alleviates charge recombination.

  12. Determination of The Optimum Use of Cationic Starch on the Basis of the Mechanical Strengths of Mixed OCC and Virgin NSSC pulps

    Directory of Open Access Journals (Sweden)

    Mansour Ghaffari

    2012-01-01

    Full Text Available This study was carried out to optimize of cationic starch use for improvement of the mechanical properties of mixed OCC & NSSC pulps. NSSC pulps were mixed with the OCC pulps by following weight ratios: 80/20, 70/30 and 60/40, respectively. Cationic starch was used in different charges of 0.5, 1.25, 2 and 3 %. The produced paper strength properties were measured according to Tappi standard. The results obtained from normalized equation showed that treatment of C4 (60% NSSC+ 40% OCC using 3% Cationic starch is the best suitable samples. Also, by increasing the OCC proportion in mixed pulps, tensile, Tear, burst strengths increases, but Concora medium test (CMT and Ring crush test (RCT decreased. In general, by increasing of the cationic starch dosage, mechanical strengths has increased and its improved use had determined by 3% cationic starch.

  13. Workplace Charging. Charging Up University Campuses

    Energy Technology Data Exchange (ETDEWEB)

    Giles, Carrie [ICF International, Fairfax, VA (United States); Ryder, Carrie [ICF International, Fairfax, VA (United States); Lommele, Stephen [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2016-03-01

    This case study features the experiences of university partners in the U.S. Department of Energy's (DOE) Workplace Charging Challenge with the installation and management of plug-in electric vehicle (PEV) charging stations.

  14. Forging Colloidal Nanostructures via Cation Exchange Reactions.

    Science.gov (United States)

    De Trizio, Luca; Manna, Liberato

    2016-09-28

    Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field.

  15. Forging Colloidal Nanostructures via Cation Exchange Reactions

    Science.gov (United States)

    2016-01-01

    Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field. PMID:26891471

  16. Effects of Cations on the Hydrogen Bond Network of Liquid Water: New Results from X-ray Absorption Spectroscopy of Liquid Microjets

    International Nuclear Information System (INIS)

    Cappa, Christopher D.; Smith, Jared D.; Messer, Benjamin M.; Cohen, Ronald C.; Saykally, Richard J.

    2005-01-01

    The oxygen K-edge absorption spectra (XAS) of aqueous chloride solutions are measured for Li + , Na + , K + , NH + , C(NH2) 3 + , Mg 2+ and Ca 2+ and 4 M cation concentrations. Density functional theory calculation have indicated that the ion-specific spectral variations arise from direct electronic perturbation of the unoccupied orbitals due to the presence of the ions, as a result of differences in charge transfer from the water molecules onto the divalent cations

  17. Association of alkali and alkaline earth metal cations with radical-anions of 9-fluorenone and 9.10-anthraquinone in dimethyl formamide medium

    International Nuclear Information System (INIS)

    Karpinets, A.P.; Bezuglyj, V.D.; Svetlichnaya, T.M.

    1988-01-01

    The polarographic method is used to estimate the stability of associates formed in dimethyl formamide by the products of one-electron reduction of 9-fluorenone and 9.10-anthraquinone with cations of alkali and alkali earth metals. It is shown that the strength of 9-fluorenone and 9.10-anthraquinone radical anion associates studied increases with cation charge increase and decrease of its crystallographic radius

  18. Hierarchical TiN nanoparticles-assembled nanopillars for flexible supercapacitors with high volumetric capacitance.

    Science.gov (United States)

    Qin, Ping; Li, Xingxing; Gao, Biao; Fu, Jijiang; Xia, Lu; Zhang, Xuming; Huo, Kaifu; Shen, Wenli; Chu, Paul K

    2018-05-10

    Titanium nitride (TiN) is an attractive electrode material in fast charging/discharging supercapacitors because of its excellent conductivity. However, the low capacitance and mechanical brittleness of TiN restricts its further application in flexible supercapacitors with high energy density. Thus, it is still a challenge to rationally design TiN electrodes with both high electrochemical and mechanical properties. Herein, the hierarchical TiN nanoparticles-assembled nanopillars (H-TiN NPs) array as binder free electrodes were obtained by nitriding of hierarchical titanium dioxide (TiO2) nanopillars, which was produced by a simple hydrothermal treatment of anodic TiO2 nanotubes (NTs) array in water. The porous TiN nanoparticles connected to each other to form ordered nanopillar arrays, effectively providing larger specific surface area and more active sites for charge storage. The H-TiN NPs delivered a high volumetric capacitance of 120 F cm-3 at 0.83 A cm-3, which is better than that of TiN NTs arrays (69 F cm-3 at 0.83 A cm-3). After assembling into all-solid-state devices, the H-TiN NPs based supercapacitors exhibited outstanding volumetric capacitance of 5.9 F cm-3 at 0.02 A cm-3 and a high energy density of 0.53 mW h cm-3. Our results reveal a new strategy to optimize the supercapacitive performance of metal nitrides.

  19. Y-doping TiO2 nanorod arrays for efficient perovskite solar cells

    Science.gov (United States)

    Deng, Xinlian; Wang, Yanqing; Cui, Zhendong; Li, Long; Shi, Chengwu

    2018-05-01

    To improve the electron transportation in TiO2 nanorod arrays and charge separation in the interface of TiO2/perovskite, Y-doping TiO2 nanorod arrays with the length of 200 nm, diameter of 11 nm and areal density of 1050 μm-2 were successfully prepared by the hydrothermal method and the influence of Y/Ti molar ratios of 0%, 3%, 5% in the hydrothermal grown solutions on the growth of TiO2 nanorod arrays was investigated. The results revealed that the appropriate Y/Ti molar ratios can increase the areal density of the corresponding TiO2 nanorod arrays and improve the charge separation in the interface of the TiO2/perovskite. The Y-doping TiO2 nanorod array perovskite solar cells with the Y/Ti molar ratio of 3% exhibited a photoelectric conversion efficiency (PCE) of 18.11% along with an open-circuit voltage (Voc) of 1.06 V, short-circuit photocurrent density (Jsc) of 22.50 mA cm-2 and fill factor (FF) of 76.16%, while the un-doping TiO2 nanorod array perovskite solar cells gave a PCE of 16.42% along with Voc of 1.04 V, Jsc of 21.66 mA cm-2 and FF of 72.97%.

  20. Syntheses and Photodynamic Activity of Pegylated Cationic Zn(II-Phthalocyanines in HEp2 Cells

    Directory of Open Access Journals (Sweden)

    Benson G. Ongarora, Xiaoke Hu, Susan D. Verberne-Sutton, Jayne C. Garno, M. Graça H. Vicente

    2012-01-01

    Full Text Available Di-cationic Zn(II-phthalocyanines (ZnPcs are promising photosensitizers for the photodynamic therapy (PDT of cancers and for photoinactivation of viruses and bacteria. Pegylation of photosensitizers in general enhances their water-solubility and tumor cell accumulation. A series of pegylated di-cationic ZnPcs were synthesized from conjugation of a low molecular weight PEG group to a pre-formed Pc macrocycle, or by mixed condensation involving a pegylated phthalonitrile. All pegylated ZnPcs were highly soluble in polar organic solvents but were insoluble in water; they have intense Q absorptions centered at 680 nm and fluorescence quantum yields of ca. 0.2 in DMF. The non-pegylated di-cationic ZnPc 6a formed large aggregates, which were visualized by atomic force microscopy. The cytotoxicity, cellular uptake and subcellular distribution of all cationic ZnPcs were investigated in human carcinoma HEp2 cells. The most phototoxic compounds were found to be the α-substituted Pcs. Among these, Pcs 4a and 16a were the most effective (IC50 ca. 10 μM at 1.5 J/cm2, in part due to the presence of a PEG group and the two positive charges in close proximity (separated by an ethylene group in these macrocycles. The β-substituted ZcPcs 6b and 4b accumulated the most within HEp2 cells but had low photocytoxicity (IC50 > 100 μM at 1.5 J/cm2, possibly as a result of their lower electron density of the ring and more extended conformations compared with the α-substituted Pcs. The results show that the charge distribution about the Pc macrocycle and the intracellular localization of the cationic ZnPcs mainly determine their photodynamic activity.

  1. Cationic peptide exposure enhances pulsed-electric-field-mediated membrane disruption.

    Science.gov (United States)

    Kennedy, Stephen M; Aiken, Erik J; Beres, Kaytlyn A; Hahn, Adam R; Kamin, Samantha J; Hagness, Susan C; Booske, John H; Murphy, William L

    2014-01-01

    The use of pulsed electric fields (PEFs) to irreversibly electroporate cells is a promising approach for destroying undesirable cells. This approach may gain enhanced applicability if the intensity of the PEF required to electrically disrupt cell membranes can be reduced via exposure to a molecular deliverable. This will be particularly impactful if that reduced PEF minimally influences cells that are not exposed to the deliverable. We hypothesized that the introduction of charged molecules to the cell surfaces would create regions of enhanced transmembrane electric potential in the vicinity of each charged molecule, thereby lowering the PEF intensity required to disrupt the plasma membranes. This study will therefore examine if exposure to cationic peptides can enhance a PEF's ability to disrupt plasma membranes. We exposed leukemia cells to 40 μs PEFs in media containing varying concentrations of a cationic peptide, polyarginine. We observed the internalization of a membrane integrity indicator, propidium iodide (PI), in real time. Based on an individual cell's PI fluorescence versus time signature, we were able to determine the relative degree of membrane disruption. When using 1-2 kV/cm, exposure to >50 μg/ml of polyarginine resulted in immediate and high levels of PI uptake, indicating severe membrane disruption, whereas in the absence of peptide, cells predominantly exhibited signatures indicative of no membrane disruption. Additionally, PI entered cells through the anode-facing membrane when exposed to cationic peptide, which was theoretically expected. Exposure to cationic peptides reduced the PEF intensity required to induce rapid and irreversible membrane disruption. Critically, peptide exposure reduced the PEF intensities required to elicit irreversible membrane disruption at normally sub-electroporation intensities. We believe that these cationic peptides, when coupled with current advancements in cell targeting techniques will be useful tools in

  2. Influence of cationic lipid concentration on properties of lipid–polymer hybrid nanospheres for gene delivery

    Directory of Open Access Journals (Sweden)

    Bose RJC

    2015-09-01

    Full Text Available Rajendran JC Bose,1,2 Yoshie Arai,1 Jong Chan Ahn,1 Hansoo Park,2 Soo-Hong Lee11Department of Biomedical Science, College of Life Science, CHA University, Seongnam, 2Department of Integrative Engineering, Chung-Ang University, Seoul, South Korea Abstract: Nanoparticles have been widely used for nonviral gene delivery. Recently, cationic hybrid nanoparticles consisting of two different materials were suggested as a promising delivery vehicle. In this study, nanospheres with a poly(D,l-lactic-co-glycolic acid (PLGA core and cationic lipid shell were prepared, and the effect of cationic lipid concentrations on the properties of lipid polymer hybrid nanocarriers investigated. Lipid–polymer hybrid nanospheres (LPHNSs were fabricated by the emulsion-solvent evaporation method using different concentrations of cationic lipids and characterized for size, surface charge, stability, plasmid DNA-binding capacity, cytotoxicity, and transfection efficiency. All LPHNSs had narrow size distribution with positive surface charges (ζ-potential 52–60 mV, and showed excellent plasmid DNA-binding capacity. In vitro cytotoxicity measurements with HEK293T, HeLa, HaCaT, and HepG2 cells also showed that LPHNSs exhibited less cytotoxicity than conventional transfection agents, such as Lipofectamine and polyethyleneimine–PLGA. As cationic lipid concentrations increased, the particle size of LPHNSs decreased while their ζ-potential increased. In addition, the in vitro transfection efficiency of LPHNSs increased as lipid concentration increased. Keywords: core–shell hybrid nanospheres, lipid concentration, surface modification, low cytotoxicity, transfection efficiency

  3. Formation and fragmentation of quadruply charged molecular ions by intense femtosecond laser pulses.

    Science.gov (United States)

    Yatsuhashi, Tomoyuki; Nakashima, Nobuaki

    2010-07-22

    We investigated the formation and fragmentation of multiply charged molecular ions of several aromatic molecules by intense nonresonant femtosecond laser pulses of 1.4 mum with a 130 fs pulse duration (up to 2 x 10(14) W cm(-2)). Quadruply charged states were produced for 2,3-benzofluorene and triphenylene molecular ion in large abundance, whereas naphthalene and 1,1'-binaphthyl resulted only in up to triply charged molecular ions. The laser wavelength was nonresonant with regard to the electronic transitions of the neutral molecules, and the degree of fragmentation was strongly correlated with the absorption of the singly charged cation radical. Little fragmentation was observed for naphthalene (off-resonant with cation), whereas heavy fragmentation was observed in the case of 1,1'-binaphthyl (resonant with cation). The degree of H(2) (2H) and 2H(2) (4H) elimination from molecular ions increased as the charge states increased in all the molecules examined. A striking difference was found between triply and quadruply charged 2,3-benzofluorene: significant suppression of molecular ions with loss of odd number of hydrogen was observed in the quadruply charged ions. The Coulomb explosion of protons in the quadruply charged state and succeeding fragmentation resulted in the formation of triply charged molecular ions with an odd number of hydrogens. The hydrogen elimination mechanism in the highly charged state is discussed.

  4. Photochemical and photocatalytic evaluation of 1D titanate/TiO{sub 2} based nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Conceição, D.S.; Ferreira, D.P. [Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Graça, C.A.L. [Universidade de São Paulo, Avenida Prof. Luciano Gualberto, tr. 3, 380 São Paulo (Brazil); Júlio, M.F.; Ilharco, L.M. [Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Velosa, A.C. [Instituto Nacional de Tecnologia, Av. Venezuela 82, Rio de Janeiro (Brazil); Santos, P.F. [Centro de Química, Vila Real Universidade de Trás-os-Montes e Alto Douro, 5001-801 Vila Real (Portugal); Vieira Ferreira, L.F., E-mail: lfvieiraferreira@tecnico.ulisboa.pt [Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1049-001 Lisboa (Portugal)

    2017-01-15

    Highlights: • 1D titanate based nanomaterials were prepared via a hydrothermal approach. • The structural and photochemical evaluation of the nanomaterials was performed. • A fluorescent dye was used as a surface probe in visible excitation conditions. • Amicarbazone was used as the model contaminant for photodegradation studies. - Abstract: One-dimensional (1D) titanate based nanomaterials were synthesized following an alkaline hydrothermal approach of commercial TiO{sub 2} nanopowder. The morphological features of all materials were monitored by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and also Brunauer-Emmett-Teller (BET) technique. In addition the photochemical behaviour of these nanostructured materials were evaluated with the use of laser induced luminescence (LIL), ground-state diffuse reflectance (GSDR), and laser-flash photolysis in diffuse reflectance mode (DRLFP). The mixed titanate/TiO{sub 2} nanowires presented the least intense fluorescence spectra, suggesting the presence of surficial defects that can extend the lifetime of the excited charge carriers. A fluorescent ‘rhodamine-like’ dye was adsorbed onto different materials and examined via photoexcitation in the visible range to study the self-photosensitization mechanism. The presence of the radical cation of the dye and the degradation kinetics, when compared with a neutral substrate—cellulose, provided significant evidences regarding the photoactivity of the different materials. Regarding all the materials under study, the nanowires exhibited a strong photocatalytic efficiency, for the adsorbed fluorescent probe. The photocatalytic mechanism was also considered by studying the photodegradation capability of the titanate based materials in the presence of an herbicide, Amicarbazone, after ultraviolet (UVA) photoexcitation.

  5. Chemistry of alkali cation exchanged faujasite and mesoporous NaX using alkyl halides and phosphates

    Science.gov (United States)

    Lee, Min-Hong

    The purpose of this work was to increase the reactivity of Faujasite X (NaX) zeolite toward the reactive decontamination of materials subject to nucleophilic attack by means of zeolite cation optimization and by means of the synthesis of mesoporous Faujasite X. Primary alkyl halides and trialkyl phosphates have been the test materials on which the cation-optimized and mesoporous zeolites have been tested. In the alkali cation optimization work, reactions of methyl iodide and 1-chloropropane with alkali metal cation exchanged Faujasite zeolite X were investigated at room temperature. The reactivity of the framework and the product formation were shown to depend on zeolite framework counter-cation. A quantitative study of zeolite product formation has been carried out, primarily using solid-state NMR spectroscopy. Large alkali cations showed preference toward substitution chemistry. In contrast, alkyl halide exposed LiX and NaX zeolites underwent both substitution and elimination. Subsequently introduced water molecules led to hydrolysis of framework species that was sensitive to framework counter-cation. The mesoporous NaX zeolites work undertakes to test whether an improvement in surface chemical reactivity can be achieved by introducing mesopores into the already reactive nucleophilic microporous NaX zeolite. Incorporation of the polydiallyl dimethyl ammonium chloride (PDADMAC) template and the formation of mesopores in Faujasite X zeolite (NaX) were successful and well-characterized. The mesopores are proposed to have occurred from incorporation of the cationic PDADMAC polymer into the zeolite by compensating zeolite framework charge. Subsequent sodium cation exchange of calcined mesoporous NaX was shown to restore the chemical reactivity characteristic of as-synthesized NaX. Trialkyl organophosphorous compounds underwent substitution reactions. The reactivity of both microporous and mesoporous Faujasite zeolite X and the product formation was shown to depend on

  6. Stability of anionic polymers in presence of multivalent cations

    International Nuclear Information System (INIS)

    Sabbagh, Imad

    1997-01-01

    This research thesis aimed at studying the stability of poly-electrolytes in saline environments, and the interactions between ions and poly-electrolytes of different charge densities. For this purpose, the author more particularly studied specific interactions between anionic poly-electrolytes and multivalent cations. After a recall of properties of neutral polymers and poly-electrolytes in solution, the author evokes interactions between poly-electrolytes and counter-ions, and briefly presents two models of stability of poly-electrolytes in saline solutions. The next part presents various experimental spectroscopic and electrochemical techniques and results of the characterization of the used products. Spectroscopic techniques allow ion-polymer interactions at the atomic scale to be studied, and electrochemical techniques allow the behaviour of small ions to be studied. The author then discusses the main differences of solubility between poly-electrolytes containing sulphonate or sulphate groups and those containing carboxylate groups. A model is then developed to generalise phase diagrams of a poly-electrolyte with respect to the chemical affinity of its functional group with ions of opposite sign. The author then addresses the behaviour of a non charged polyacrylic acid in various saline solutions, and presents a phase diagram model [fr

  7. Propan-1-ol Oxidation Reaction on Au/TiO 2 Catalysts | Nuhu ...

    African Journals Online (AJOL)

    This was further investigated using Pulse Flow reactor, TPFRP, TPD, and XRD,. The adsorption of propan-1-ol over TiO2 (P25) indicated a full monolayer with much of it in a dissociated state, forming propoxy group on the cationic site and hydroxyl group at anions. The propoxy is relatively stable until about 250oC, at which ...

  8. Quick spacecraft charging primer

    International Nuclear Information System (INIS)

    Larsen, Brian Arthur

    2014-01-01

    This is a presentation in PDF format which is a quick spacecraft charging primer, meant to be used for program training. It goes into detail about charging physics, RBSP examples, and how to identify charging.

  9. Ferrocene-based diradicals of imino nitroxide, nitronyl nitroxide and verdazyl, and their cations are possible SMM: A quantum chemical study

    Science.gov (United States)

    Pal, Arun K.; Datta, Sambhu N.

    2017-05-01

    Six diradicals designed from imino nitroxide, verdazyl and nitronyl nitroxide monoradicals coupled via the ferrocene moiety and six corresponding triradical cations are quantum chemically investigated. The transoid conformation is employed for considerations of general stability. All biradicals are found as very weakly and antiferromagnetically coupled. This agrees with experiment. The cations have strong antiferromagnetic spin-coupling. The charge and spin population distributions, spin alternation pattern, and the disjoint nature of SOMOs can be used to explain the nature and extent of magnetic interaction. Calculated EPR characteristics identify the neutral species as well as their cations as possible single molecule magnets.

  10. Ti on GaAs(110)

    International Nuclear Information System (INIS)

    McCants, C.E.; Kendelewicz, T.; Williams, M.D.; List, R.S.; Lindau, I.; Spicer, W.E.

    1985-01-01

    The chemical and electronic properties of the Ti:GaAs interface have been studied using soft x-ray and ultraviolet photoemission spectroscopies. The Fermi level pinning position is observed to be 0.7 eV for n-type, consistent with both the Unified Defect Model and the charge transfer effects observed by Williams et. al. The interface is quite disrupted, as evidenced by shifts in both the Ga and As 3d core levels and marked changes in their lineshapes. The Ga core level moves to higher kinetic energy and shifts to a metallic-like state with increasing Ti coverages. The As core level also shifts to higher KE; in addition, as appears to diffuse through the Ti overlayer for thin (<10 monolayers) coverage. This, in addition to a change in the intensity ratio between the As 3d/sub 5/2/ and 3d/sub 3/2/ peaks suggests the formation of a Ti-arsenide, which is predicted by bulk thermodynamics. The room temperature data imply a laminar coverage, although annealing studies suggest the possibility of cluster formation with increasing temperature (0<10 monolayers). These results are also consistent with those obtained by Waldrop et. al. for Ti:GaAs(100) interfaces

  11. Visible-light-driven photoelectrochemical and photocatalytic performances of Cr-doped SrTiO3/TiO2 heterostructured nanotube arrays.

    Science.gov (United States)

    Jiao, Zhengbo; Chen, Tao; Xiong, Jinyan; Wang, Teng; Lu, Gongxuan; Ye, Jinhua; Bi, Yingpu

    2013-01-01

    Well-aligned TiO2 nanotube arrays have become of increasing significance because of their unique highly ordered array structure, high specific surface area, unidirectional charge transfer and transportation features. However, their poor visible light utilization as well as the high recombination rate of photoexcited electron-hole pairs greatly limited their practical applications. Herein, we demonstrate the fabrication of visible-light-responsive heterostructured Cr-doped SrTiO3/TiO2 nanotube arrays by a simple hydrothermal method, which facilitate efficient charge separation and thus improve the photoelectrochemical as well as photocatalytic performances.

  12. Modulation of Charge Recombination in CsPbBr3 Perovskite Films with Electrochemical Bias

    KAUST Repository

    Scheidt, Rebecca A; Samu, Gergely F.; Janá ky, Csaba; Kamat, Prashant V.

    2017-01-01

    The charging of mesoscopic TiO2 layer in a metal halide perovskite solar cell can influence the overall power conversion efficiency. By employing CsPbBr3 films deposited on a mesoscopic TiO2 film, we have succeeded in probing the influence

  13. Preparation and Characterization of Cationic PLA-PEG Nanoparticles for Delivery of Plasmid DNA

    Directory of Open Access Journals (Sweden)

    Zou Weiwei

    2009-01-01

    Full Text Available Abstract The purpose of the present work was to formulate and evaluate cationic poly(lactic acid-poly(ethylene glycol (PLA-PEG nanoparticles as novel non-viral gene delivery nano-device. Cationic PLA-PEG nanoparticles were prepared by nanoprecipitation method. The gene loaded nanoparticles were obtained by incubating the report gene pEGFP with cationic PLA-PEG nanoparticles. The physicochemical properties (e.g., morphology, particle size, surface charge, DNA binding efficiency and biological properties (e.g., integrity of the released DNA, protection from nuclease degradation, plasma stability, in vitro cytotoxicity, and in vitro transfection ability in Hela cells of the gene loaded PLA-PEG nanoparticles were evaluated, respectively. The obtained cationic PLA-PEG nanoparticles and gene loaded nanoparticles were both spherical in shape with average particle size of 89.7 and 128.9 nm, polydispersity index of 0.185 and 0.161, zeta potentials of +28.9 and +16.8 mV, respectively. The obtained cationic PLA-PEG nanoparticles with high binding efficiency (>95% could protect the loaded DNA from the degradation by nuclease and plasma. The nanoparticles displayed sustained-release properties in vitro and the released DNA maintained its structural and functional integrity. It also showed lower cytotoxicity than Lipofectamine 2000 and could successfully transfect gene into Hela cells even in presence of serum. It could be concluded that the established gene loaded cationic PLA-PEG nanoparticles with excellent properties were promising non-viral nano-device, which had potential to make cancer gene therapy achievable.

  14. Linear electro-optical properties of tetragonal BaTiO 3

    Indian Academy of Sciences (India)

    Linear optical susceptibility and clamped linear electro-optical tensor coefficients of tetragonal BaTiO3 are calculated using a formalism based on bond charge theory. Calculated values are in close agreement with experimental data. The covalent Ti–O bonds constituting distorted TiO6 octahedral groups are found to be ...

  15. Role of doping and CuO segregation in improving the giant permittivity of CaCu3Ti4O12

    International Nuclear Information System (INIS)

    Capsoni, D.; Bini, M.; Massarotti, V.; Chiodelli, G.; Mozzatic, M.C.; Azzoni, C.B.

    2004-01-01

    The dopant role on the electric and dielectric properties of the perovskite-type CaCu 3 Ti 4 O 12 (CCTO) compound is evidenced. Impedance spectroscopy measurements show that the relevant permittivity value attributed to sintered CCTO is due to grain boundary (g.b.) effects. The g.b. permittivity value of the pure CCTO can be increased of 1-2 orders of magnitude by cation substitution on Ti site and/or segregation of CuO phase, while the bulk permittivity keeps values 90εr180. Bulk and g.b. conductivity contributions are discussed: electrons are responsible for the charge transport and a mean bulk activation energy of 0.07eV is obtained at room temperature for all the examined samples. The g.b. activation energy ranges between 0.54 and 0.76eV. Defect models related to the transport properties are proposed, supported by electron paramagnetic resonance measurements

  16. Cationic Gelatin Nanoparticles for Drug Delivery to the Ocular Surface: In Vitro and In Vivo Evaluation

    Directory of Open Access Journals (Sweden)

    Ching-Li Tseng

    2013-01-01

    Full Text Available To develop an effective ocular drug delivery carrier, we prepared two different charged gelatin nanoparticles (GPs and evaluated particle size, surface charge, and morphology. The in vitro biocompatibility of GPs was assessed using human corneal epithelium (HCE cells and in vivo safety by administering them as eye drops to New Zealand rabbits. The GPs prepared using type A gelatin were positively charged (GP(+, +33 mV; size, 180.6±45.7 nm. Water-soluble tetrazolium salt (WST-1 assay showed that both GPs were nontoxic to HCE cells. The fluorescence intensity of HCE cells cultured with cationic GPs conjugated with a fluorescent dye was higher than that of the anionic GP-treated HCE cells. In vivo examination showed no serious irritation to the rabbit eyes. Furthermore, corneal thickness and ocular pressure in the eyes of the treated rabbits were similar to those in the eyes of normal rabbits. Microscopic examination of corneal cryosections showed widely distributed fluorescent nanocarriers, from the anterior to the posterior part of the cornea of the GP(+ group, and higher fluorescence intensity in the GP(+ group was also observed. In conclusion, GPs as cationic colloidal carriers were efficiently adsorbed on the negatively charged cornea without irritating the eyes of the rabbits and can be retained in the cornea for a longer time. Thus, GPs(+ have a great potential as vehicles for ocular drug delivery.

  17. Adsorption of cationic amylopectin on microcrystalline cellulose.

    NARCIS (Netherlands)

    Steeg, van de H.G.M.; Keizer, de A.; Cohen Stuart, M.A.; Bijsterbosch, B.H.

    1993-01-01

    The effects of electrolyte concentration and pH on the adsorption of cationic amylopectin on microcrystalline cellulose were investigated. The adsorbed amount in the pseudo-plateau of the isotherm showed a maximum as a function of the electrolyte concentration. We compared the data with a recent

  18. Alkynylcarbenium ions and related unsaturated cations

    Energy Technology Data Exchange (ETDEWEB)

    Lukyanov, Sergey M; Koblik, Alla V; Muradyan, Lyudmila A [Institute of Physical and Organic Chemistry, Rostov State University, Rostov-on-Don (Russian Federation)

    1998-10-31

    Published data on carbenium ions containing carbon-carbon triple bonds both directly conjugated with the carbenium centre and separated from it are surveyed and described systematically. Ammonium, diazonium, iminium, phosphonium and iodonium cations containing alkynyl groups, which can be regarded as heteroanalogues of alkynylcarbenium ions, are also considered. The bibliography includes 283 references.

  19. Alkynylcarbenium ions and related unsaturated cations

    International Nuclear Information System (INIS)

    Lukyanov, Sergey M; Koblik, Alla V; Muradyan, Lyudmila A

    1998-01-01

    Published data on carbenium ions containing carbon-carbon triple bonds both directly conjugated with the carbenium centre and separated from it are surveyed and described systematically. Ammonium, diazonium, iminium, phosphonium and iodonium cations containing alkynyl groups, which can be regarded as heteroanalogues of alkynylcarbenium ions, are also considered. The bibliography includes 283 references

  20. Mixed cation effect in sodium aluminosilicate glasses

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Smedskjær, Morten Mattrup; Mauro, John C.

    , network structure, and the resistances associated with the deformation processes in mixed cation glasses by partially substituting magnesium for calcium and calcium for lithium in sodium aluminosilicate glasses. We use Raman and 27Al NMR spectroscopies to obtain insights into the structural...

  1. Cationic flotation of some lithium ores

    International Nuclear Information System (INIS)

    Valadao, G.E.S.; Peres, A.E.C.; Silva, H.C. da

    1984-01-01

    The cationic flotation of some lithium ores (spodumene, amblygonite, petalite, lepidolite) is studied by the measure of zeta potential and micro-flotation tests in Hallimond tube. The effect of some modifier agents (corn starch, meta sodium silicate) on the lithium flotation is studied. (M.A.C.) [pt

  2. Letter: OCCO*+, NNCO*+ and NNNN*+ radical cations.

    Science.gov (United States)

    Flammang, R; Srinivas, R; Nguyen, M T; Gerbaux, P

    2007-01-01

    Chemical ionization of a mixture of nitrogen and carbon monoxide produces three stable isobaric species at m/z 56: OCCO, OCNN and NNNN radical cations. Separated at increased resolution, these ions are readily identified by collisional activation. Neutralization-reionization experiments performed on two different mass spectrometers have not allowed the detection of any recovery signals for the corresponding neutrals.

  3. Al cation induces aggregation of serum proteins.

    Science.gov (United States)

    Chanphai, P; Kreplak, L; Tajmir-Riahi, H A

    2017-07-15

    Al cation is known to induce protein fibrillation and causes several neurodegenerative disorders. We report the spectroscopic, thermodynamic analysis and AFM imaging for the Al cation binding process with human serum albumin (HSA), bovine serum albumin (BSA) and milk beta-lactoglobulin (b-LG) in aqueous solution at physiological pH. Hydrophobicity played a major role in Al-protein interactions with more hydrophobic b-LG forming stronger Al-protein complexes. Thermodynamic parameters ΔS, ΔH and ΔG showed Al-protein bindings occur via hydrophobic and H-bonding contacts for b-LG, while van der Waals and H-bonding interactions prevail in HSA and BSA adducts. AFM clearly indicated that aluminum cations are able to force BSA and b-LG into larger or more robust aggregates than HSA, with HSA 4±0.2 (SE, n=801) proteins per aggregate, for BSA 17±2 (SE, n=148), and for b-LG 12±3 (SE, n=151). Thioflavin T test showed no major protein fibrillation in the presence of Al cation. Al complexation induced major alterations of protein conformations with the order of perturbations b-LG>BSA>HSA. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Chemical reactivity of cation-exchanged zeolites

    NARCIS (Netherlands)

    Pidko, E.A.

    2008-01-01

    Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed

  5. Selective crystallization of cations with crown ethers

    International Nuclear Information System (INIS)

    Heffels, Dennis Egidius

    2014-01-01

    The aim of this work was to study the selectivity and preferences of the incorporation of differently sized cations in the cavities of various crown ethers and the characterization of the resulting compounds. The coordination preferences of crown ethers with different cavities have long been known, and the impact of other effects on the structure formation have increasingly become the focus of attention. In this work a comparative overview of the coordination preferences depending on various factors was undertaken. The focus was mainly on the variation of the cavity of the crown ether in the presence of differently sized cations. In addition, the effects of the solvent and differently coordinating anions have been investigated. Within the framework of this work, basic coordination preferences could be detected with rare earth nitrates, which are affected particularly by the choice of the solvent. The formation of different types of structures could be controlled by varying the conditions such that the incorporation of the cation in the cavity of the crown ether was influenced and the formation of a particular type of structure can be influenced partly by the choice of solvent. In this case no direct preferences for the incorporation into the cavity of the crown ether in relation to the cation size were observed for rare earth cations. However, the coordination of the crown ether leads in each case - for lanthanides - to rather high coordination numbers. A total of five new rare earth complexes and two structural variants could be observed with crown ethers. In the study of the selectivity of the incorporation into the cavity, known structures were also reproduced and further structures were characterized but the crystal structures not entirely solved. With the use of monovalent cations such as potassium, lithium or silver a total of nine new compounds could be synthesized, while no clear preferences for the incorporation of certain cations were detected. The

  6. CNDO/2-SCF and PCILO (MO) calculations on the 1-butene/NA/and (charge-transfer) complex

    Energy Technology Data Exchange (ETDEWEB)

    Lochmann, R; Meiler, W

    1977-01-01

    CNDO/2-SCF and PCILO (MO) calculations on the 1-Butene/Na/sup +/ (charge-transfer) complex involving the olefinic m electrons were made in connection with butene adsorption in zeolites, including the effect of the cation on the conformation of the butene in the zeolite cavity. Calculations were made of rotational energy barriers, preferred cation arrangements with respect to the butene molecule, and charge distributions by both methods. Taking into account systematic errors with the two methods, it is concluded that the PCILO method, which predicts a stabilization of the skew over the cis conformation by the cation, gives closer agreement with experiment. Graph, tables, diagrams, and 19 references.

  7. Ajuste teórico de las curvas PTCR de BaTiO3 dopado con niobio

    Directory of Open Access Journals (Sweden)

    Castro, M. S.

    2002-02-01

    Full Text Available In this work, a theoretical fitting to the experimental PTCR effect in slightly Nb-doped BaTiO3 from the Heywang-Jonker model is simulated. Besides, a qualitative approach was used to evaluate the GBBL characteristics of strongly Nb - doped BaTiO3. In both cases, a link between the electrical properties and the defect profile developed in these based - BaTiO3 ceramics was established. From the results, good agreement between experimental and calculated results was obtained for the PTCR ceramics. Asmall increment in Nb2O5 concentration leads to an increasing in the concentration of occupied acceptor states, the energy of the surface state and also the barrier height. In these cases, microstructural observations shown an important grain growth with average grain size between 10 and 100μm. EPR results clearly indicate low concentration of cationic vacancies for these materials. This phenomenon is associated to a charge-compensation mechanism in slightly-doped BaTiO3, that result in a semiconducting behaviour. On the other hand, the electrical behaviour of strongly–doped BaTiO3 moves away from the PTCR effect, and the material becomes insulating with noticeable GBBL characteristics. In this case, microstructural observations along defect structure analysis encourage the hypothesis in which barium vacancies act as acceptor at grain boundaries and play and important role in restricting grain growth of Nb2O5-BaTiO3 ceramics.En este trabajo se determinó la influencia de la concentración de Nb2O5 sobre el comportamiento PTCR de cerámicos basados en BaTiO3. Por otra parte, se estudió el impacto de una gran concentración del dopante sobre el comportamiento GBBL del BaTiO3. En ambos casos, se estableció una relación entre las propiedades eléctricas observadas y la estructura de defectos iónicos desarrollada. La aplicación del modelo de Heywang-Jonker permite el ajuste teórico de las curvas de resistividad – temperatura de los cerámicos PTCR

  8. Electronic structure of layered ferroelectric high-k titanate Pr2Ti2O7

    Science.gov (United States)

    Atuchin, V. V.; Gavrilova, T. A.; Grivel, J.-C.; Kesler, V. G.; Troitskaia, I. B.

    2012-11-01

    The spectroscopic parameters and electronic structure of binary titanate Pr2Ti2O7 have been studied by IR-, Raman and X-ray photoelectron spectroscopy (XPS) for the powder sample prepared by solid state synthesis. The spectral features of valence band and all constituent element core levels have been considered. The Auger parameters of titanium and oxygen in Pr2Ti2O7 have been determined as αTi=872.8 and αO=1042.3 eV. Variations of cation-anion bond ionicity have been discussed using binding energy differences ΔTi=(BE O 1s-BE Ti 2p3/2)=71.6 eV and ΔPr=BE(Pr 3d5/2)-BE(O 1s)=403.8 eV as key parameters in comparison with those of other titanium- and praseodymium-bearing oxides.

  9. A.C. impedance, XRD, DSC, SEM and charge/discharge studies on Al2O3, TiO2, SiO2 dispersoid LiPF6/PVC/PVdF-co-HFP composite polymer electrolytes by phase inversion

    Science.gov (United States)

    Vickraman, P.; Gopukumar, S.

    2017-07-01

    The PVC/PVdF-co-HFP composite polymer electrolyte membranes (CPEMs) by varying blend ratios 1:1, 1:2, and 2:1 with fixed content of Al2O3, TiO2 and SiO2 having soaked in 0.5 M LiPF6 in EC/DEC (1:1) v/v) have been prepared by phase inversion. CPEMs of higher ionic conductivity (not dependent on electrolyte uptake as observed in our study) ASA4 (3.61×10-4 Scm-1), TSA3 (1.53×10-4 Scm-1), and SSA3 (4.81×10-4 Scm-1) have been only chosen for XRD, DSC, SEM and electrochemical studies. In XRD, crystalline peaks (phases) of PVdF have been noted with/without change in intensity as well as FWHM which correspond to type of filler interaction with host matrix. In DSC, it is observed that shifts in baseline, melting endotherms, and area under the endotherms indicating the thermal hist ory of PVC (Tg = 82 ° C) and melting of VdF crystallites varied with nature of the filler dispersoid. In SEM, the coagulated fibrils of the polymer coiled with the sponge like structure has been mapped. The charge/discharge studies are carried out on these CPEMs at C/10 rate in the voltage range 2.8 V - 4.2 V, and it is noted that the TSA3 showed better cycling performance with good capacity retention i.e., 50 cycles with 66% capacity retention than ASA4 of 28 cycles with 65% and SSA3 of 5 cycles with 56%. In the present study Coulombic efficiency is concerned only for first cycle and it is noted that the TSA3 showed 71% than 66% and 62% respectively for SSA3 and ASA4.

  10. Design of Perovskite Oxides as Anion-Intercalation-Type Electrodes for Supercapacitors: Cation Leaching Effect.

    Science.gov (United States)

    Liu, Yu; Dinh, Jim; Tade, Moses O; Shao, Zongping

    2016-09-14

    Oxygen ions can be exploited as a charge carrier to effectively realize a new type of anion-intercalation supercapacitor. In this study, to get some useful guidelines for future materials development, we comparatively studied SrCoO3-δ (SC), Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), and Co3O4 as electrodes in supercapacitors with aqueous alkaline electrolyte. The effect of interaction between the electrode materials with the alkaline solution was focused on the structure and specific surface area of the electrode material, and ultimately the electrochemical performance was emphasized. Both BSCF and SC were found to experience cation leaching in alkaline solution, resulting in an increase in the specific surface area of the material, but overleaching caused the damage of perovskite structure of BSCF. Barium leaching was more serious than strontium, and the cation leaching was component dependent. Although high initial capacitance was achieved for BSCF, it was not a good candidate as intercalation-type electrode for supercapacitor because of poor cycling stability from serious Ba(2+) and Sr(2+) leaching. Instead, SC was a favorable electrode candidate for practical use in supercapacitors due to its high capacity and proper cation leaching capacity, which brought beneficial effect on cycling stability. It is suggested that cation leaching effect should be seriously considered in the development of new perovskite materials as electrodes for supercapacitors.

  11. Photocatalytic decouloration of malachite green dye by application of TiO2 nanotubes

    International Nuclear Information System (INIS)

    Prado, Alexandre G.S.; Costa, Leonardo L.

    2009-01-01

    The nanotubes of titania were synthesized in a hydrothermal system and characterized by scanning electronic microscopy (SEM), FT-IR, FT-Raman, and surface charge density by surface area analyzer. These nanomaterials were applied to photocatalyse malachite green dye degradation. Photodegradation capacity of TiO 2 nanotubes was compared to TiO 2 anatase photoactivity. Malachite dye was completely degraded in 75 and 105 min of reaction photocatalysed by TiO 2 nanotubes and TiO 2 anatase, respectively. Catalysts displayed high photodegradation activity at pH 4. TiO 2 nanotubes were easily recycled whereas the reuse of TiO 2 anatase was not effective. Nanotubes maintained 80% of their activity after 10 catalytic cycles and TiO 2 anatase presented only 8% of its activity after 10 cycles.

  12. Estimation of the basicity of the donor strength of terminal groups in cationic polymethine dyes

    Science.gov (United States)

    Kachkovsky, Alexey; Obernikhina, Nataliya; Prostota, Yaroslav; Naumenko, Antonina; Melnyk, Dmitriy; Yashchuk, Valeriy

    2018-02-01