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Sample records for 2,4-pentanedione

  1. Infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide.

    Science.gov (United States)

    Kong, Chang Yi; Siratori, Tomoya; Funazukuri, Toshitaka; Wang, Guosheng

    2014-10-03

    The effects of temperature and density on retention of platinum(II) 2,4-pentanedionate in supercritical fluid chromatography were investigated at temperatures of 308.15-343.15K and pressure range from 8 to 40MPa by the chromatographic impulse response method with curve fitting. The retention factors were utilized to derive the infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide. The determined partial molar volumes were small and positive at high pressures but exhibited very large and negative values in the highly compressible near critical region of carbon dioxide.

  2. Optimization of photoluminescence of Y(2)O(3):Eu and Gd(2)O(3):Eu phosphors synthesized by thermolysis of 2,4-pentanedione complexes.

    Science.gov (United States)

    Antic, B; Rogan, J; Kremenovic, A; Nikolic, A S; Vucinic-Vasic, M; Bozanic, D K; Goya, G F; Colomban, P H

    2010-06-18

    Spherical shaped nanoparticles of series Y(2 - x)Eu(x)O(3) (x = 0.06, 0.10, 0.20, and 2) and Gd(2 - x)Eu(x)O(3) (x = 0.06, 0.10) were prepared by thermolysis of 2,4-pentanedione complexes of Y, Gd, and Eu. The bixbyite phase of Gd(2 - x)Eu(x)O(3) samples was formed at 500 degrees C, whereas the thermal decomposition of Y and Eu complexes' mixtures occurred at higher temperatures. Linearity in the concentration dependence on lattice parameter confirmed the formation of solid solutions. The distribution of Eu(3+) in Gd(2 - x)Eu(x)O(3) was changed with thermal annealing: in the as-prepared sample (x = 0.10) the distribution was preferential at C(3i) sites while in the annealed samples, Eu(3+) were distributed at both C(2) and C(3i) sites. Rietveld refinement of site occupancies as well as emission spectra showed a random distribution of cations in Y(2 - x)Eu(x)O(3). The photoluminescence (PL) measurements of the sample showed red emission with the main peak at 614 nm ((5)D(0)-(7)F(2)). The PL intensity increased with increasing concentration of Eu(3+) in both series. Infrared excitation was required to obtain good Raman spectra. The linear dependence of the main Raman peak wavenumber offers a non-destructive method for monitoring the substitution level and its homogeneity at the micron scale.

  3. Effects of Eu3+ concentration on structural, optical and vibrational properties of multifunctional Ce(1-x)Eu(x)O2-delta) nanoparticles synthesized by thermolysis of 2,4-pentanedione complexes.

    Science.gov (United States)

    Kremenovic, A; Bozanic, D K; Welsch, A M; Jancar, B; Nikolic, A S; Boskovic, M; Colomban, Ph; Fabian, Martin; Antic, B

    2012-12-01

    The 5-10 nm Ce(1-x)Eu(x)O(2-delta) (0 < or = x < or = 0.30) nanoparticles with fluorite structure were synthesized by thermal decomposition of Eu- and Ce-2,4-pentanedione complexes mixtures. X-ray line broadening analysis of mixed samples Ce(1-x)Eu(x)O(2-delta) (0.05 < or = x < or = 0.30) showed that the crystallite size was lower and root mean square strain higher than in pure ceria. However, within mixed samples Ce(1-x)Eu(x)O(2-delta) (0.05 < or = x < or = 0.30) crystallite size and root mean square strain were independent of Eu3+ concentration. Raman spectroscopy results indicated that europium ions yield disorder by breaking the phonon propagation and therefore making the non-centre Brillouin zone modes Raman active. The absorption bands in the spectra of mixed oxides were blue-shifted in comparison to pure CeO(2-delta) nanopowder. The samples show red emission typical for Eu ions. The biggest photoluminescent intensity was observed for the highest Eu3+ concentration (x = 0.30) and further enhanced with the increase in crystallinity.

  4. 3-(3,4,5-Trimethoxybenzylidene)-2,4-pentanedione: Design of a novel photostabilizer with in vivo SPF boosting properties and its use in developing broad-spectrum sunscreen formulations.

    Science.gov (United States)

    Chaudhuri, R K; Ollengo, M A; Singh, P; Martincigh, B S

    2017-02-01

    The study concerned the synthesis of a novel photostabilizer based on benzylidenepentanedione chemistry and the evaluation of its potential in developing a broad-spectrum sunscreen formulation containing avobenzone. 3-(3,4,5-Trimethoxybenzylidene)-2-4-pentanedione (TMBP) was synthesized through a condensation reaction and incorporated into a sunscreen formulation containing, inter alia, avobenzone. The SPF, critical wavelength and in vitro photostability of the product were measured. The photostability was compared with that afforded by current avobenzone photostabilizers, namely octocrylene, ethylhexylmethoxycrylene and diethylhexylsyringylidenemalonate. The photostability of TMBP either alone or in the presence of avobenzone in a methanolic solution was also evaluated by UV spectrophotometric and HPLC analyses. The optical properties of TMBP were estimated experimentally and supported by time-dependent density functional theory (TD-DFT) calculations. The ability of TMBP to stabilize avobenzone under ultraviolet (UV) light exposure was shown both in formulated products and in solution. A comparative stability study incorporating various combinations of avobenzone, TMBP (vs. three commercial photostabilizers) and UVB sunscreens clearly showed TMBP to be a very effective stabilizer. The photostabilizing effect of TMBP arises from triplet-state energy transfer from avobenzone to TMBP and through light-induced reactions that preserve the main chromophores. Interestingly, a 50% in vivo SPF boosting was observed when TMBP was used with organic and inorganic sunscreens when alone it has no contribution to SPF. TMBP-containing sunscreen formulations clearly showed a critical wavelength of well over 370 nm and can thus be categorized as broad-spectrum sunscreens. We were able to design a very effective photostabilizer, trimethoxybenzylidene pentanedione (INCI name), based on benzylidenepentanedione chemistry. TMBP is very efficient in stabilizing avobenzone in formulated

  5. Fabrication and Properties of Organic-Inorganic Nanolaminates Using Molecular and Atomic Layer Deposition Techniques

    Science.gov (United States)

    2012-02-01

    55, 1030-1039 (2009).* 2. B.B. Burton, D.N. Goldstein and S.M. George, "Atomic Layer Deposition of MgO Using Bis(ethylcyclopentadienyl) magnesium ...Atomic Layer Deposition Using Tin 2,4-Pentanedionate and Hydrogen Sulfide , J. Phys. Chem. C 114, 17597-17603 (2010).* 28. L.A. Riley, A.S

  6. 4-Acetyl-2-hydroxy-2,5-dimethylfuran-3(2H-one

    Directory of Open Access Journals (Sweden)

    Chiaki Akazaki

    2016-10-01

    Full Text Available The facile synthesis of 4-acetyl-2-hydroxy-2,5-dimethylfuran-3(2H-one (4 was achieved by the Mn(OAc3-mediated aerobic oxidation of 2,4-pentanedione or the direct reaction of Mn(acac3 in AcOH-TFE at room temperature under a dried air stream.

  7. Synthesis of two sup 14 C-labeled catechol-o-methyltransferase inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Karlsson, Carita; Honkanen, Erkki (Orion Corporation Ltd., Espoo (Finland). Research Center)

    1991-02-01

    {sup 14}C-labelled 3-(3,4-dihydroxy-5-nitrophenylmethylidene)-2,4-pentanedione and {sup 14}C-labelled E-N,N-diethyl-2-cyano-3-(3,4-dihydroxy-5-nitrophenyl)acrylamide have been synthesized from (carbonyl-{sup 14}C)vanillin. (author).

  8. Synthesis and Processing of Ultra-High Temperature Metal Carbide and Metal Diboride Nanocomposite Materials

    Science.gov (United States)

    2008-04-15

    Synthesis and Processing of Ultra-High Temperature Metal Carbide and Metal Diboride Nanocomposite Materials Final Performance Report Contract Number...sintered commercially-available powders. Each project is summarized below: Synthesis : Zirconium diboride and a zirconium diboride/tantalum diboride...mixture were synthesized by solution-based processing. Zirconium n-propoxide was refluxed with 2,4-pentanedione to form zirconium diketonate . This compound

  9. Microwave-Assisted Synthesis of 3,5-Dibenzyl-4-amino-1,2,4-triazole and its Diazo Ligand, Metal Complexes Along with Anticancer Activity

    Directory of Open Access Journals (Sweden)

    Anjali Jha

    2010-01-01

    Full Text Available Synthesis of 3,5-dibenzyl-4-amino-1,2,4-triazole was accomplished via a conventional method as well as microwave irradiation method, followed by diazotization and coupling with 2,4-pentanedione. The dinucleating ligand was isolated and complexed with Ni(II, Cu(II and Ru(III chlorides. These complexes were screened on Jurkat, Raji & PBMC cell lines for anticancer activity. Ruthenium complexes showed potential anticancer activities.

  10. Microwave-Assisted Synthesis of 3,5-Dibenzyl-4-amino-1,2,4-triazole and its Diazo Ligand, Metal Complexes Along with Anticancer Activity

    OpenAIRE

    Anjali Jha; Murthy, Y. L. N.; Durga, G.; Sundari, T. T.

    2010-01-01

    Synthesis of 3,5-dibenzyl-4-amino-1,2,4-triazole was accomplished via a conventional method as well as microwave irradiation method, followed by diazotization and coupling with 2,4-pentanedione. The dinucleating ligand was isolated and complexed with Ni(II), Cu(II) and Ru(III) chlorides. These complexes were screened on Jurkat, Raji & PBMC cell lines for anticancer activity. Ruthenium complexes showed potential anticancer activities.

  11. Synthesis and structure of new mononuclear octahedral cobalt(III) dioximates derived from isonicotinic hydrazide

    Science.gov (United States)

    Cocu, Maria; Bulhac, Ion; Coropceanu, Eduard; Melnic, Elena; Shova, Sergiu; Ciobanica, Olga; Gutium, Victoria; Bourosh, Paulina

    2014-04-01

    New organic ligand L (1) resulting from isonicotinic hydrazide and 2,4-pentanedione has been prepared and investigated by physicochemical methods, including elemental analysis, 1H and 13C NMR, IR spectroscopy and X-ray studies. The X-ray investigation revealed that the condensation of 2,4-pentanedione with isonicotinic hydrazide is accompanied by the formation of a five-membered ring including three carbon atoms of 2,4-pentanedione and two nitrogen atoms of the isonicotinic hydrazide fragment. The reaction between [Co(DfgH)2Br(H2O)] (DfgH2 = diphenylglyoxime) and L resulted in the formation of the mononuclear octahedral complex [Co(DfgH)2BrL] (2) with the substitution of the water molecule in the apical position by the ligand L. The reaction starting from [Co(DmgH)2Cl(H2O)] (DmgH = dimethylglyoxime) and L resulted in the mononuclear octahedral Co(III) complex with the composition [Co(DmgH)2ClL‧] (3), where L‧ unexpectedly represents a dehydrated derivative of L. The two coordination compounds are characterized by X-ray diffraction method. The IR, 1H NMR spectral studies of new compounds are also reported.

  12. Energy transfer and light yield properties of a new highly loaded indium(III) β-diketonate organic scintillator system

    Science.gov (United States)

    Buck, C.; Hartmann, F. X.; Motta, D.; Schoenert, S.

    2007-02-01

    We present combined experimental and model studies of the light yield and energy transfer properties of a newly developed high light yield scintillator based on indium(III)-tris(2,4-pentanedionate) in a 2-(4-biphenyl)-5-phenyloxazole (BPO), methoxybenzene organic liquid; of interest to the detection of solar electron neutrino oscillations. Optical measurements are made to understand the energy transfer properties and a model is advanced to treat the unusual conditions of high metal and fluor loadings. Such scintillator types are of interest to the exploration of novel luminescent materials and the development of large-scale detectors for studying fundamental properties of naturally occurring neutrinos.

  13. Microwave-accelerated synthesis of some 1-aroyl-3,5-dimethylpyrazoles

    Institute of Scientific and Technical Information of China (English)

    Aamer Saeed; Amara Mumtaz

    2008-01-01

    Rapid and highly efficient synthesis of some 1-aroy1-3,5-dimethylpyrazoles is achieved by the cyclocondensation of corresponding aroyl hydrazides with 2,4-pentanedione in the absence of solvent and catalyst,under microwave irradiation.The reaction proceeds rapidly and is completed within 40-70 s giving a series of 1-aroy1-3,5-dimethylpyrazoles derivatives in high yields.All of the compounds have been characterized by FTIR,1H NMR,and mass spectroscopy.

  14. Study on Synthesis, Characterization and Catalytic Activity of Polystyrene-supported Mo (VI) Complex in Epoxidation of Cyclohexene

    Institute of Scientific and Technical Information of China (English)

    章亚东; 高晓蕾; 陈霞; 王朝进; 蒋登高

    2003-01-01

    Molybdenum (VI) complex, namely molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] used as epoxidation catalyst species, was synthesized and characterized by elemental analysis and infrared spectrum.Polystyrene-supported molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] for synthesis of epoxycyclohexane was prepared by phase transfer catalysis method. Effects of various factors in synthesis of epoxycyclohexane by reaction of cyclohexene and t-BuOOH in the atmosphere of nitrogen catalyzed by polystyrene-supported MoO2 (acac)2 were aLso investigated. Under the following conditions, n(cyclohexene):n(t-BuOOH)=3.5:l (based on 0.1 mol of t-BuOOH), volume of solvent ~10 ml, reaction temperature ~80℃, reaction time ~60 min, and mass of molybdenum in the catalyst ~ 2.30 × 10-3 g, the yield of epoxycyclohexane on the basis of t-BuOOH is over 99.5%, and the purity of epoxycyclohexane is about 99.9% by gas chromatogram(GC )analysis.

  15. High performance of inverted polymer solar cells with cobalt oxide as hole-transporting layer

    Science.gov (United States)

    Wang, Xiangdong; Peng, Qing; Zhu, Weiguo; Lei, Gangtie

    2015-05-01

    Cobalt oxide (II, III) (CoOx) was inserted as efficient hole-transporting interlayer between the active layer and top electrode in inverted polymer solar cells (PSCs) with titanium (diisopropoxide) bis(2, 4-pentanedionate) (TIPD) as an electron selective layer. The work function of CoOx was measured by Kelvin probe and the device performances with different thicknesses of cobalt oxide were studied. The device with CoOx exhibited a remarkable improvement in power conversion efficiency compared with that without CoOx, which indicated that CoOx efficiently prevented the recombination of charge carriers at the organic/top electrode interface. The performance improvement was attributed to the fact that the CoOx thin film can module the Schottky barrier and form an ohmic contact at the organic/metal interface, which makes it a promising hole-transporting layer.

  16. Synthesis, structural, spectral, thermal and antimicrobial studies of palladium(II), platinum(II), ruthenium(III) and iridium(III) complexes derived from N,N,N,N-tetradentate macrocyclic ligand.

    Science.gov (United States)

    Rani, Soni; Kumar, Sumit; Chandra, Sulekh

    2011-05-01

    Palladium(II), platinum(II), ruthenium(III) and iridium(III) complexes of general stoichiometry [PdL]Cl(2), [PtL]Cl(2), [Ru(L)Cl(2)]Cl and [Ir(L)Cl(2)]Cl are synthesized with a tetradentate macrocyclic ligand, derived from 2,6-diaminopyridine with 3-ethyl 2,4-pentanedione. Ligand was characterized on the basis of elemental analyses, IR, mass, and (1)H NMR and (13)C NMR spectral studies. All the complexes were characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, mass, electronic spectral techniques and thermal studies. The value of magnetic moments indicates that all the complexes are diamagnetic except Ru(III) complex which shows magnetic moments corresponding its one unpaired electron. The macrocyclic ligand and all its metal complexes were also evaluated in vitro against some plant pathogenic fungi and bacteria to assess their biocidal properties.

  17. Synthesis and Thermal Decomposition Mechanism Study of a Novel Iridium Precursor

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    Yan Xin

    2016-01-01

    Full Text Available Ir(TFA3 (TFA=1,1,1-trifluoro-2,4-pentanedionate metal complexes with high purity was successfully synthesized. The metal complexes have been characterized by elemental analysis, infrared spectroscopy, nuclear magnetic resonance spectroscopy. The volatility of metal complexes was studied by thermogravimetry analysis. And a possible decomposition mechanism was studied by mass spectroscopic analysis method. The novel iridium complexes can be severed as precursor in metalorganic chemical vapor deposition of iridium films. iridium films were deposited by metalorganic chemical vapor deposition method, and the Ir(TFA3 complex was used as precursor. The iridium thin films were characterized by X-ray diffraction and scanning electron microscopy in order to determine crystallinity and surface morphology.

  18. Estimation of vapour pressure and partial pressure of subliming compounds by low-pressure thermogravimetry

    Indian Academy of Sciences (India)

    G V Kunte; Ujwala Ail; P K Ajikumar; A K Tyagi; S A Shivashankar; A M Umarji

    2011-12-01

    A method for the estimation of vapour pressure and partial pressure of subliming compounds under reduced pressure, using rising temperature thermogravimetry, is described in this paper. The method is based on our recently developed procedure to estimate the vapour pressure from ambient pressure thermogravimetric data using Langmuir equation. Using benzoic acid as the calibration standard, vapour pressure–temperature curves are calculated at 80, 160 and 1000 mbar for salicylic acid and vanadyl bis-2,4-pentanedionate, a precursor used for chemical vapour deposition of vanadium oxides. Using a modification of the Langmuir equation, the partial pressure of these materials at different total pressures is also determined as a function of temperature. Such data can be useful for the deposition of multi-metal oxide thin films or doped thin films by chemical vapour deposition (CVD).

  19. An iron(II) diketonate-diamine complex as precursor for thin film fabrication by atomic layer deposition

    Science.gov (United States)

    Bratvold, Jon E.; Carraro, Giorgio; Barreca, Davide; Nilsen, Ola

    2015-08-01

    A new divalent Fe precursor has been explored for deposition of iron-containing thin films by atomic layer deposition and molecular layer deposition (ALD/MLD). The Fe(II) β-diketonate-diamine complex, Fe(hfa)2TMEDA, (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, TMEDA = N,N,N‧,N‧-tetramethylethylenediamine) can be handled in air, and sublimation at 60 °C ensures a satisfactory vaporization rate. The reactivity of the precursor does not allow for direct reaction with water as co-reactant. Nevertheless, it reacts with carboxylic acids, resulting in organic-inorganic hybrid materials, and with ozone, yielding α-Fe2O3. The divalent oxidation state of iron was maintained during deposition when oxalic acid was used as co-reactant, demonstrating the first preservation of Fe(II) from precursor to film during an MLD process. A self-saturating growth mode was proven by in situ quartz crystal microbalance (QCM) measurements, and the films were further characterized by grazing incidence X-ray diffraction (GIXRD), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS).

  20. Surface functionalization of nanostructured Fe2O3 polymorphs: from design to light-activated applications.

    Science.gov (United States)

    Barreca, Davide; Carraro, Giorgio; Gasparotto, Alberto; Maccato, Chiara; Rossi, Francesca; Salviati, Giancarlo; Tallarida, Massimo; Das, Chittaranjan; Fresno, Fernando; Korte, Dorota; Stangar, Urška Lavrenčič; Franko, Mladen; Schmeisser, Dieter

    2013-08-14

    Nanostructured iron(III) oxide deposits are grown by chemical vapor deposition (CVD) at 400-500 °C on Si(100) substrates from Fe(hfa)2TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N',N'-tetramethylethylenediamine), yielding the selective formation of α-Fe2O3 or the scarcely studied ε-Fe2O3 polymorphs under suitably optimized preparative conditions. By using Ti(OPr(i))4 (OPr(i) = iso-propoxy) and water as atomic layer deposition (ALD) precursors, we subsequently functionalized the obtained materials at moderate temperatures (<300 °C) by an ultrathin titanomagnetite (Fe3-xTixO4) overlayer. An extensive multitechnique characterization, aimed at elucidating the system structure, morphology, composition and optical properties, evidenced that the photoactivated hydrophilic and photocatalytic behavior of the synthesized materials is dependent both on iron oxide phase composition and ALD surface modification. The proposed CVD/ALD hybrid synthetic approach candidates itself as a powerful tool for a variety of applications where semiconductor-based nanoarchitectures can benefit from the coupling with an ad hoc surface layer.

  1. Europium incorporated into titanium oxide by the sol-gel method

    Directory of Open Access Journals (Sweden)

    Lucas Alonso Rocha

    2005-09-01

    Full Text Available In this work titanium sol was prepared from tetraethylorthotitanate (TEOT in ethanol, stabilized with beta-diketonate 2,4 pentanedione in molar ratio 1:1 homogenized by magnetic stirring, europium ion was add as structural probe. The xerogels were heat treated at 500, 750 and 1000 °C and the characterization was realized by x-ray diffraction (XRD, transmission electron microscopy (TEM, thermogravimetric analysis (TGA/DSC and photoluminescence (PL. The excitation spectra of Eu (III ion present maximum in 394 nm correspondent to 5L6 level and emission spectra present bands characteristic transitions arising from the 5 D0 -> 7F J (J = 0, 1, 2, 3, 4 manifolds to samples treat at 500 and 750 °C. The Eu (III emission disappear, when heated at 1000 °C, probably due to phase transition anatase to rutile and migrations of ions to the external surface that was proved by x-ray diffraction, transmission electronic microscopy and the thermogravimetric analyses of xerogels.

  2. Composition-dependent electrocatalytic activity of palladium-iridium binary alloy nanoparticles supported on the multiwalled carbon nanotubes for the electro-oxidation of formic acid.

    Science.gov (United States)

    Bao, Jianming; Dou, Meiling; Liu, Haijing; Wang, Feng; Liu, Jingjun; Li, Zhilin; Ji, Jing

    2015-07-22

    Surface-functionalized multiwalled carbon nanotubes (MWCNTs) supported Pd100-xIrx binary alloy nanoparticles (Pd100-xIrx/MWCNT) with tunable Pd/Ir atomic ratios were synthesized by a thermolytic process at varied ratios of bis(acetylacetonate) palladium(II) and iridium(III) 2,4-pentanedionate precursors and then applied as the electrocatalyst for the formic acid electro-oxidation. The X-ray diffraction pattern (XRD) and transmission electron microscope (TEM) analysis showed that the Pd100-xIrx alloy nanoparticles with the average size of 6.2 nm were uniformly dispersed on the MWCNTs and exhibited a single solid solution phase with a face-centered cubic structure. The electrocatalytic properties were evaluated through the cyclic voltammetry and chronoamperometry tests, and the results indicated that both the activity and stability of Pd100-xIrx/MWCNT were strongly dependent on the Pd/Ir atomic ratios: the best electrocatalytic performance in terms of onset potential, current density, and stability against CO poisoning was obtained for the Pd79Ir21/MWCNT. Moreover, compared with pure Pd nanoparticles supported on MWCNTs (Pd/MWCNT), the Pd79Ir21/MWCNT exhibited enhanced steady-state current density and higher stability, as well as maintained excellent electrocatalytic activity in high concentrated formic acid solution, which was attributed to the bifunctional effect through alloying Pd with transition metal.

  3. The very covalent diammino(o-benzoquinonediimine) dichlororuthenium(II). An example of very strong pi-back-donation.

    Science.gov (United States)

    Rusanova, Julia; Rusanov, Eduard; Gorelsky, S I; Christendat, Dharamdat; Popescu, Raluca; Farah, Abdiaziz A; Beaulac, Rémi; Reber, Christian; Lever, A B P

    2006-08-07

    The syntheses and X-ray structures of the complexes Ru(S-dmso)Cl2(opda) (1) and Ru(NH3)2Cl2(bqdi) (2) are described (opda= o-phenylenediamine, bqdi= o-benzoquinonediimine). Optical absorption and emission, vibrational (resonance Raman), and electrochemical data are discussed. We explore the nature of the ruthenium benzoquinone electronic interaction in species 2 primarily within the framework of density functional theory (DFT) but also using INDO/S to extract Coulombic and exchange integrals. The resonance Raman and emission data were understood in terms of a common set of coupled vibrations localized primarily within the ruthenium metallacycle ring. Experimental and computational data were also compared among a select group of ruthenium bqdi species with other spectator ligands, specifically ammonia, 2,2'-bipyridine, and 2,4-pentanedione. The changes in the electrochemistry, optical spectroscopy, and vibrational spectra with changing spectator ligand donicity were explained within a common theoretical (DFT) model which further provided a detailed analysis of the variation in the molecular orbital descriptions. With the application of an extended charge decomposition analysis (ECDA), a detailed picture emerged of the bonding between the bqdi ligand and the metal atom, illustrating the coupling between the orbitals of each fragment as a function of orbital symmetry and charge transfer between the fragments of the complex. Metal-to-bqdi pi-back-donation is seen to be very important.

  4. Calcium copper-titanate thin film growth: tailoring of the operational conditions through nanocharacterization and substrate nature effects.

    Science.gov (United States)

    Lo Nigro, Raffaella; Toro, Roberta G; Malandrino, Graziella; Fragalà, Ignazio L; Losurdo, Maria; Giangregorio, Michelaria M; Bruno, Giovanni; Raineri, Vito; Fiorenza, Patrick

    2006-09-07

    A novel approach based on a molten multicomponent precursor source has been applied for the MOCVD fabrication of high-quality CaCu(3)Ti(4)O(12) (CCTO) thin films on various substrates. The adopted in situ strategy involves a molten mixture consisting of Ca(hfa)(2).tetraglyme, Ti(tmhd)(2)(O-iPr)(2), and Cu(tmhd)(2) [Hhfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; tetraglyme = 2,5,8,11,14-pentaoxapentadecane; Htmhd = 2,2,6,6-tetramethyl-3,5-heptandione; O-iPr = isopropoxide] precursors. Film structural and morphological characterizations have been carried out by several techniques [X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM)], and in particular the energy filtered TEM mapping and X-ray energy dispersive (EDX) analysis in TEM mode provided a suitable correlation between nanostructural properties of CCTO films and deposition conditions and/or the substrate nature. Correlation between the nanostructure and optical/dielectric properties has been investigated exploiting spectroscopic ellipsometry.

  5. Fast fluorometric flow injection analysis of formaldehyde in atmospheric water

    Energy Technology Data Exchange (ETDEWEB)

    Dong, S.; Dasgupta, P.K.

    1987-06-01

    Formaldehyde can be determined in aqueous solution at a rate of 45 samples/h with a small sample requirement (100 ..mu..L). The fluorescence of 3,5-diacetyl-1,4-dihydrolutidine formed upon reaction of formaldehyde with ammonium acetate and 2,4-pentanedione (25 s, 95 /sup 0/C) is monitored with a filter fluorometer. The detection limit is 0.1 ..mu..M (3 ..mu..g/L) or 10 pmol of HCHO. The response is linear up to 3.3 ..mu..M (100 ..mu..g/L), the departure from linearity at 0.33 mM is 21%, but high levels are satisfactorily determined with a second-order calibration equation. Interference from S(IV) has been investigated in detail and completely eliminated by addition of H/sub 2/O/sub 2/ before rendering the sample alkaline. There are no effects from commonly occurring metal ions and anions; the method is very selective to formaldehyde compared to other carbonyl compounds. A S(IV)-containing preservative has been formulated for the stabilization of low concentrations of HCHO. Results are presented for fogwater samples. 8 figures, 41 references.

  6. Bifunctional Molecular Photoswitches Based on Overcrowded Alkenes for Dynamic Control of Catalytic Activity in Michael Addition Reactions.

    Science.gov (United States)

    Pizzolato, Stefano F; Collins, Beatrice S L; van Leeuwen, Thomas; Feringa, Ben L

    2017-05-02

    The emerging field of artificial photoswitchable catalysis has recently shown striking examples of functional light-responsive systems allowing for dynamic control of activity and selectivity in organocatalysis and metal-catalysed transformations. While our group has already disclosed systems featuring first generation molecular motors as the switchable central core, a design based on second generation molecular motors is lacking. Here, the syntheses of two bifunctionalised molecular switches based on a photoresponsive tetrasubstituted alkene core are reported. They feature a thiourea substituent as hydrogen-donor moiety in the upper half and a basic dimethylamine group in the lower half. This combination of functional groups offers the possibility for application of these molecules in photoswitchable catalytic processes. The light-responsive central cores were synthesized by a Barton-Kellogg coupling of the prefunctionalized upper and lower halves. Derivatization using Buchwald-Hartwig amination and subsequent introduction of the thiourea substituent afforded the target compounds. Control of catalytic activity in the Michael addition reaction between (E)-3-bromo-β-nitrostyrene and 2,4-pentanedione is achieved upon irradiation of stable-(E) and stable-(Z) isomers of the bifunctional catalyst 1. Both isomers display a decrease in catalytic activity upon irradiation to the metastable state, providing systems with the potential to be applied as ON/OFF catalytic photoswitches. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Efficient perovskite/fullerene planar heterojunction solar cells with enhanced charge extraction and suppressed charge recombination

    Science.gov (United States)

    Li, Cong; Wang, Fuzhi; Xu, Jia; Yao, Jianxi; Zhang, Bing; Zhang, Chunfeng; Xiao, Min; Dai, Songyuan; Li, Yongfang; Tan, Zhan'ao

    2015-05-01

    Alcohol soluble titanium chelate TIPD (titanium (diisopropoxide) bis(2,4-pentanedionate)) was used as an electron transporting layer to form an ohmic contact with the negative electrode, aiming to enhance the charge extraction and suppress the charge recombination for high performance CH3NH3PbI3/PCBM-based PHJ perovskite solar cells. The TIPD layer shows excellent suitability to CH3NH3PbI3 perovskite synthesized by different methods. For one-step synthesized CH3NH3PbI3, the power conversion efficiency (PCE) of the device with the TIPD buffer reaches 8.75%, with a nearly 33% increase in comparison with the device without the buffer layer (6.58%). For two-step synthesized CH3NH3PbI3, an open-circuit voltage (Voc) of 0.89 V, a short-circuit current density (Jsc) of 22.57 mA cm-2, and a fill factor (FF) of 64.5%, corresponding to a PCE of 12.95% for the device with a TIPD buffer layer were achieved, which is among the best performances reported in the literature for CH3NH3PbI3/PCBM-based PHJ perovskite solar cells.Alcohol soluble titanium chelate TIPD (titanium (diisopropoxide) bis(2,4-pentanedionate)) was used as an electron transporting layer to form an ohmic contact with the negative electrode, aiming to enhance the charge extraction and suppress the charge recombination for high performance CH3NH3PbI3/PCBM-based PHJ perovskite solar cells. The TIPD layer shows excellent suitability to CH3NH3PbI3 perovskite synthesized by different methods. For one-step synthesized CH3NH3PbI3, the power conversion efficiency (PCE) of the device with the TIPD buffer reaches 8.75%, with a nearly 33% increase in comparison with the device without the buffer layer (6.58%). For two-step synthesized CH3NH3PbI3, an open-circuit voltage (Voc) of 0.89 V, a short-circuit current density (Jsc) of 22.57 mA cm-2, and a fill factor (FF) of 64.5%, corresponding to a PCE of 12.95% for the device with a TIPD buffer layer were achieved, which is among the best performances reported in the literature

  8. An iron(II) diketonate–diamine complex as precursor for thin film fabrication by atomic layer deposition

    Energy Technology Data Exchange (ETDEWEB)

    Bratvold, Jon E., E-mail: j.e.bratvold@kjemi.uio.no [Centre for Materials Science and Nanotechnology (SMN)/Department of Chemistry, University of Oslo, PO Box 1033, Blindern, N-0315 Oslo (Norway); Carraro, Giorgio [Department of Chemistry, University of Padova and INSTM, via F. Marzolo 1, I-35131 Padova (Italy); Barreca, Davide [CNR-IENI and INSTM, Department of Chemistry, University of Padova, via F. Marzolo 1, I-35131 Padova (Italy); Nilsen, Ola [Centre for Materials Science and Nanotechnology (SMN)/Department of Chemistry, University of Oslo, PO Box 1033, Blindern, N-0315 Oslo (Norway)

    2015-08-30

    Highlights: • First report of Fe(hfa){sub 2}TMEDA as precursor in ALD and MLD. • Hybrid organic–inorganic films with oxalic acid as co-reactant between 125 and 350 °C. • Surface saturation evidenced by quartz crystal microbalance (QCM) analysis. • XPS confirms complete preservation of Fe(II) from precursor to film. • Deposition of α-Fe{sub 2}O{sub 3} when using ozone as co-reactant. - Abstract: A new divalent Fe precursor has been explored for deposition of iron-containing thin films by atomic layer deposition and molecular layer deposition (ALD/MLD). The Fe(II) β-diketonate-diamine complex, Fe(hfa){sub 2}TMEDA, (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, TMEDA = N,N,N′,N′-tetramethylethylenediamine) can be handled in air, and sublimation at 60 °C ensures a satisfactory vaporization rate. The reactivity of the precursor does not allow for direct reaction with water as co-reactant. Nevertheless, it reacts with carboxylic acids, resulting in organic–inorganic hybrid materials, and with ozone, yielding α-Fe{sub 2}O{sub 3}. The divalent oxidation state of iron was maintained during deposition when oxalic acid was used as co-reactant, demonstrating the first preservation of Fe(II) from precursor to film during an MLD process. A self-saturating growth mode was proven by in situ quartz crystal microbalance (QCM) measurements, and the films were further characterized by grazing incidence X-ray diffraction (GIXRD), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS)

  9. Sintering of SiO{sub 2}-Al{sub 2}O{sub 3}-TiO{sub 2} and SiO{sub 2}-Al{sub 2}O{sub 3}-ZrO{sub 2} obtained by the sol-gel process

    Energy Technology Data Exchange (ETDEWEB)

    Mendoza-Serna, R.; Loyo-Arnaud, E.; Martinez-Fuentes, S.S.; Munoz-Duran, R.; Valdez-Castro, L. [Facultad de Estudios Superiores Zaragoza, UNAM, Mexico, D. F. (Mexico); Mendez-Vivar, J. [Univ. Autonoma Metropolitana-Iztapalapa, Depto. de Quimica, Mexico, D. F. (Mexico)

    2004-07-01

    An experimental strategy was developed to obtain Si-Al-Ti and Si-Al-Zr transparent sols via the sol-gel process. Acetylacetone (2, 4 pentanedione, acacH) and itaconic anhydride (2-methylenesuccinic anhydride, anhH) were employed separately as chelating agents to stabilize Al, Ti and Zr precursors, in order to slow down the chemical reactivity, avoiding precipitation. The molar ratio chelating agent/M (M: Al, Ti, and Zr) was 2.0. The starting materials were Si(OEt){sub 4} (TEOS), Ti(OEt){sub 4} (OEt: OCH{sub 2}CH{sub 3}), Al(OBu{sup s}){sub 3} (OBu{sup s}: C{sub 2}H{sub 5}CH(CH{sub 3})O) and Zr(OPr{sup n}){sub 4} (OPr{sup n}: OCH{sub 2}CH{sub 2}CH{sub 3}). The molar ratio Si:Al:Ti or Zr was 80:7:13, respectively. The sols were clear and homogeneous at macroscopic scale during gelation. The gels were dried at 423 K for 24 h in air. Xerogels were calcined at 673, 773, 873 and 1123 K for 24 h in air. The samples were analyzed by X-ray diffraction and found to be amorphous up to 873 K. The solids calcined have small pore size (micro and mesopores). The solids were also studied by scanning electron microscopy (SEM), and X-ray diffraction (XRD) to compare the influence of size and structure of the chelating agent in the particle size and the crystallite size distribution. (orig.)

  10. Antiproliferative and cancer-chemopreventive properties of sulfated glycosylated extract derived from Leucaena leucocephala

    Directory of Open Access Journals (Sweden)

    Gamal-Eldeen Amira

    2007-01-01

    Full Text Available This work aimed to prove that simple chemical modification could provide new cancer chemopreventive and/or anticancer properties to the inactive extracted polysaccharide derived from Leucaena leucocephala . Polysaccharides were extracted from Leucaena leucocephala seeds and its 2,4-pentanedione-treated derivative (glycosylated form was prepared, which is further sulphated to give sulphated glycosylated form. Estimation of their anti-initiation activity, modulation of carcinogen metabolism, was indicated by the inhibition cytochrome P450 1A (CYP1A and the induction of glutathione-S-transferases (GSTs. Anti-proliferation activity was investigated by MTT assay against human hepatocarcinoma (HepG2, breast carcinoma (MCF-7 and lymphoblastic leukemia (1301. Apoptosis/necrosis and cell cycle were analyzed by flow cytometry. The results revealed that glycosylated form inhibited both CYP1A and GSTs, while sulphated glycosylated form not only inhibited CYP1A, but also induced the GSTs. Unlike GE, sulphated glycosylated form possessed a significant anti-proliferative activity against different cell lines. Analysis of HepG2 cell cycle phases demonstrated that glycosylated form led to a delay of G2/M-phase, while sulphated glycosylated form led to a concomitant arrest in S- and G2/M-phases. Investigation of apoptosis/necrosis ratio demonstrated that both of glycosylated form and sulphated glycosylated form induced HepG2 cell death by necrosis, but not apoptosis. Unmodified crude extract was neither active as cancer chemopreventive nor as anti-proliferative. In conclusion, chemical modification of Leucaena gum induced its cancer chemopreventive and anti-proliferative activities.

  11. X-ray Emission Spectroscopy to Study Ligand Valence Orbitals in Mn Coordination Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Smolentsev, Grigory; Soldatov, Alexander V; Messinger, Johannes; Merz, Kathrin; Weyhermuller, Thomas; Bergmann, Uwe; Pushkar, Yulia; Yano, Junko; Yachandra, Vittal K.; Glatzel, Pieter

    2009-03-02

    We discuss a spectroscopic method to determine the character of chemical bonding and for the identification of metal ligands in coordination and bioinorganic chemistry. It is based on the analysis of satellite lines in X-ray emission spectra that arise from transitions between valence orbitals and the metal ion 1s level (valence-to-core XES). The spectra, in connection with calculations based on density functional theory (DFT), provide information that is complementary to other spectroscopic techniques, in particular X-ray absorption (XANES and EXAFS). The spectral shape is sensitive to protonation of ligands and allows ligands, which differ only slightly in atomic number (e.g., C, N, O...), to be distinguished. A theoretical discussion of the main spectral features is presented in terms of molecular orbitals for a series of Mn model systems: [Mn(H2O)6]2+, [Mn(H2O)5OH]+, [Mn(H2O)5NH2]+, and [Mn(H2O)5NH3]2+. An application of the method, with comparison between theory and experiment, is presented for the solvated Mn2+ ion in water and three Mn coordination complexes, namely [LMn(acac)N3]BPh4, [LMn(B2O3Ph2)(ClO4)], and [LMn(acac)N]BPh4, where L represents 1,4,7-trimethyl-1,4,7-triazacyclononane, acac stands for the 2,4-pentanedionate anion, and B2O3Ph2 represents the 1,3-diphenyl-1,3-dibora-2-oxapropane-1,3-diolato dianion.

  12. A new route for the synthesis of titanium silicalite-1

    Energy Technology Data Exchange (ETDEWEB)

    Vasile, Aurelia, E-mail: aurelia_vasile@yahoo.com [Laboratory of Materials Chemistry, Faculty of Chemistry, ' Al.I. Cuza' University of Iasi, B-dul Carol I, No. 11, 700506 Iasi (Romania); Busuioc-Tomoiaga, Alina Maria [Laboratory of Materials Chemistry, Faculty of Chemistry, ' Al.I. Cuza' University of Iasi, B-dul Carol I, No. 11, 700506 Iasi (Romania); Catalysis Research Department, ChemPerformance SRL, Iasi 700337 (Romania)

    2012-01-15

    Graphical abstract: Well-prepared TS-1 was synthesized by an innovative procedure using inexpensive reagents such as fumed silica and TPABr as structure-directing agent. This is the first time when highly crystalline TS-1 is obtained in basic medium, using sodium hydroxide as HO{sup -} ion source required for the crystallization process. Hydrolysis of titanium source has been prevented by titanium complexation with acetylacetone before structuring gel. Highlights: Black-Right-Pointing-Pointer TS-1 was obtained using cheap reagents as fumed silica and tetrapropylammonium bromide. Black-Right-Pointing-Pointer First time NaOH was used as source of OH{sup -} ions required for crystallization process. Black-Right-Pointing-Pointer The hydrolysis Ti alkoxides was controlled by Ti complexation with 2,4-pentanedione. -- Abstract: A new and efficient route using inexpensive reagents such as fumed silica and tetrapropylammonium bromide is proposed for the synthesis of titanium silicalite-1. High crystalline titanium silicalite-1 was obtained in alkaline medium, using sodium hydroxide as HO{sup -} ion source required for the crystallization process. Hydrolysis of titanium source with formation of insoluble oxide species was prevented by titanium complexation with before structuring gel. The final solids were fully characterized by powder X-ray diffraction, scanning electron microscopy, Fourier transform infrared, ultraviolet-visible diffuse reflectance, Raman and atomic absorption spectroscopies, as well as nitrogen sorption analysis. It was found that a molar ratio Ti:Si of about 0.04 in the initial reaction mixture is the upper limit to which well formed titanium silicalite-1 with channels free of crystalline or amorphous material can be obtained. Above this value, solids with MFI type structure containing both Ti isomorphously substituted in the network and extralattice anatase nanoparticles inside of channels is formed.

  13. Single-step fabrication of nanolamellar structured oxide ceramic coatings by metal-organic chemical vapor deposition.

    Science.gov (United States)

    Eils, Nadine K; Mechnich, Peter; Keune, Hartmut; Wahl, Georg; Klages, Claus-Peter

    2011-09-01

    Oxide ceramic coatings in the system Y2O3-Al2O3-ZrO2 were fabricated in laboratory scale by using a MOCVD unit. A hot wall reactor was used along with different precursor feeding systems. Most experiments were carried out by using powder flash evaporation including a screw feeder for precursor powder delivery. For comparison, further samples were fabricated by using band flash evaporation and continuous evaporation from a crucible. Oxygen was used in all cases as reactant gas. Aluminium-tris-2,4-pentanedione (Al(acac)3), yttrium-tris-2,2,6,6-tetramethyl-3,5-heptanedione (Y(thd)3) and zirconium-tetrakis-2,2,6,6-tetramethyl-3,5-heptanedione (Zr(thd)4) were applied as metal-organic precursors because of their similar vaporization behaviour under the given conditions. The coating stoichiometry was varied from pure alumina to complex ternary compositions in the system Y2O3-Al2O3-ZrO2. Both kinds of ternary coatings fabricated by using flash evaporation methods show a nanolamellar microstructure in the as deposited state. Heat treating experiments at 1200 degrees C for up to 5 days enhance the lamellar character of the coating deposited by using powder flash evaporation. The lamellar microstructure is due to alternating YSZ enriched layers and YAG enriched layers in this state. However, the coating fabricated by using band flash evaporation shows a dense interpenetrating network of YSZ and YAG after heat treating instead of a lamellar microstructure observed in the as deposited state.

  14. Atomic layer deposition of copper sulfide thin films

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, Nathanaelle, E-mail: n.schneider@chimie-paristech.fr; Lincot, Daniel; Donsanti, Frédérique

    2016-02-01

    Atomic Layer Deposition (ALD) of copper sulfide (Cu{sub x}S) thin films from Cu(acac){sub 2} (acac = acetylacetonate = 2,4-pentanedionate) and H{sub 2}S as Cu and S precursors is reported. Typical self-saturated reactions (“ALD window”) are obtained in the temperature range T{sub dep} = 130–200 °C for an average growth per cycle (GR) = 0.25 Å/cycle. The morphology, crystallographic structure, chemical composition, electrical properties and optical band gap of thin films were investigated using scanning electronic microscopy (SEM), X-ray diffraction under Grazing Incidence conditions (GI-XRD), X-ray reflectivity (XRR), energy dispersive spectrometry (EDS), Hall effect measurements, and UV–vis spectroscopy. The obtained copper sulfide films are heavily p-doped (charge carrier concentration ~ 10{sup 21} –10{sup 22} cm{sup −3}) with optical band gaps in the range of 2.2–2.5 eV for direct and 1.6–1.8 eV for indirect band gaps. Depending on the number of ALD cycles, multiphase compounds (made of digenite Cu{sub 1.8}S, chalcocite Cu{sub 2}S, djurleite Cu{sub 31}S{sub 16} and covellite CuS) or single-phase digenite Cu{sub 1.8}S films are obtained via a growth mechanism that involves in-situ copper reduction and loss of sulfur by evaporation. - Highlights: • Cu{sub x}S films were synthesized by atomic layer deposition from Cu(acac){sub 2} and H{sub 2}S. • Self-saturated reactions at T{sub dep} = 130–200 °C for growth = 0.25 Å/cycle • Multi- or single- phase films are obtained depending on the number of cycles. • Growth mechanism involves copper reduction and loss of sulfur by evaporation.

  15. 桥连双(酮亚胺)和双(二酮亚胺)及其铝配合物的合成与催化活性%Synthesis and Catalytic Activity of Aluminum Complexes Supported by Bis(β-ketimine) and Bis(β-diketimine) Ligands

    Institute of Scientific and Technical Information of China (English)

    黄庆东; 李春兰; 张宇; 崔立山; 朱百春; 义建军; 刘林; 郝海军

    2014-01-01

    Owing to its special physical and chemical properties as well as good coordination activity with transition metals, β-diketone-derived β-ketimines and β-diketimines have been extensively studied in recent years. In this work, five new bridged bis(β-ketimine)(1-5) and bis(β-diketimine) ligands(6,7) were syn-thesized by the condensation reaction of 3,3’-(1,4-phenylene) bis(2,4-pentanedione) with various anilines. Treatment of these ligands with AlMe3 afforded five new aluminum complexes(8-12). All these compounds were characterized via elemental analysis, 1 H NMR, 13 C NMR, ESI-MS and IR spectroscopy. Structures of two aluminium complexes were determined by the X-ray single-crystal diffraction analysis. The bridged β-keti-mine acted as a chelating N, O-bidentate ligand to the aluminium atom. Each aluminum atom showed a dis-torted tetrahedral coordination geometry. These aluminum complexes exhibited effective catalytic activity in the ring-opening polymerization of ε-caprolactone.%通过桥连双β-二酮类化合物与取代苯胺反应,合成了5个新的桥连双(β-单酮亚胺)化合物(1~5)和2个新的桥连双(β-二酮亚胺)化合物(6,7),它们与三甲基铝反应,得到了相应的3个双(β-酮亚胺基)二铝配合物(8~10)和2个双(β-二酮亚胺基)二铝配合物(11,12)。采用核磁共振、红外光谱和质谱等对这些化合物进行了表征,通过X射线单晶衍射分析证实了铝配合物的结构,并考察了这些铝配合物在ε-己内酯开环聚合反应中的催化活性。

  16. 基体匹配校正-顶空-气相色谱法测定食品塑料包装材料中挥发性有机物%Head-Space-GC Determination of Volatile Organic Compounds in Plastic Packaging Materials for Foodstuffs with Matrix Matching Calibration

    Institute of Scientific and Technical Information of China (English)

    程欲晓; 周宇艳; 马明

    2012-01-01

    Ten volatile organic compounds(VOC′s),i.e.,toluene,ethyl acetate,2,4-pentanedione,2-ethyl-1-hexanol,1-nanaldehyde,decanecarbaldehyde,dodecanacarbaldehyde,decane,octane and dodecane in soft plastic packaging materials were determined by head-space gas chromatography using matrix matching calibration to compensate the matrix interference.A representative portion of the sample(packaging film,ca.100 cm2) was taken and stoved in a vacuum oven at 90 ℃ for 24 h.This portion of the sample was cut and used as blank matrix for preparation of calibration curve and definita amounts of standard solutions of the 10 VOC′s wer added to it and treated in the same way as the sample.A similar portion of the sample was cut and transferred into the headspace bottle,closed the bottle immediately and equilibrized at 100 ℃ for 30 min.HP-INNOWAX chromatographic column was used for separation at programed temperature elevation from 20 ℃ to 220 ℃.FID was adopted for determination.Detection limits(3S/N) found for the 10 VOC′s were ranged from 0.2 to 2.0 μg·dm-2.Values of recovery and RSD′s(n=6) were in the ranges of 82.5%-97.6% and 1.0%-14.0% respectively.%采用顶空-气相色谱法测定了食品用软质塑料包装材料中具有代表的10种挥发性有机物(VOC′s),包括甲苯、乙酸乙酯、2,4-戊二酮、2-乙基-1-己醇、1-壬醛、癸烷醛、十二烷醛、癸烷、正辛烷及十二烷,并用基体匹配法抵消了样品本身的基体干扰。从待分析样品(包装膜)裁取约100cm2大小片样置于真空烘箱中,于90℃烘24h,此片试样即可作为空白基质,再加入一定量的上述VOC标准溶液制备校准曲线。另取同一样品一片,剪碎后移入顶空瓶中,立即盖紧,在100℃平衡30min。方法中用HP-INNOWAX色谱柱在20℃~220℃温度区间程序升温,对各VOC进行分离,采用火焰离子化检测器检测。测得10种VOC′s的检出限(3S/N)在0.2~2.0μg.dm-2之间。另测

  17. 钒掺杂二氧化钛薄膜制备与材料特性分析%Preparation and characterization of V-doped titanium oxide thin films

    Institute of Scientific and Technical Information of China (English)

    刘欢; 龚树萍; 刘剑桥; 万久晓; 周东祥

    2011-01-01

    V-doped TiO2 films were prepared by sol-gel method starting from tetrabutyl titanate and vanadium(Ⅲ) 2,4-pentanedionate.Their properties were characterized by XRD,UV-Vis absorption spectra,FT-IR,and XPS with the undoped film samples as the control.Both the V-doped and undoped TiO2 films are anatase and the band gap decreases from 3.28 to 3.15eV,with a red shift in the absorption of V-doped TiO2 film compared to the undoped samples.The V-doped films consist of vanadium atoms in the V4+ and V5+ oxidation states,generating deep defect levels and the valence bandedge might extend into the forbidden band gap,inducing the band gap narrowing effect and enhancing the bandedge absorption.At the grain boundaries of TiO2,those impurity defects located deep inside the gap become closer to the top of the valence band and hence tend to trap the photo-generated holes,which would contribute to inhibit the recombination of photogenerated carriers and become highly attractive for application in photocatalytic materials.%以钛酸四丁酯和乙酰丙酮钒(Ⅲ)为主要原料,采用溶胶-凝胶法制备了钒掺杂二氧化钛薄膜,利用XRD、紫外-可见吸收光谱、FT-IR及XPS等表征手段,将其与未掺杂二氧化钛薄膜进行了材料特性对比研究。结果表明两种薄膜均为锐钛矿结构,引入钒后二氧化钛的禁带宽度由3.28eV减小至3.15eV,吸收带边红移至可见光范围;XPS分析证实制备的钒掺杂二氧化钛薄膜中钒以四价和五价两种氧化价态存在,可能在二氧化钛禁带中引入较深的杂质能级而引起价带顶向禁带拓展,从而产生引起禁带宽度变窄效应,扩展了二氧化钛带边光吸收。理论分析还表明,钒掺杂引起的深能级杂质在二氧化钛晶界处易于形成有效的陷阱俘获光生空穴,从而抑制光生载流子的复合,尤其适于用作光催化材料。