Solvothermal synthesis, crystal structure, and second-order nonlinear optical properties of a new noncentrosymmetric gallium-organic framework material, [N(C{sub 3}H{sub 7}){sub 4}]{sub 3}Ga{sub 3}[C{sub 6}H{sub 3}(CO{sub 2}){sub 3}]{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Lee, Dong Woo; Jo, Vinna [Department of Chemistry, Chung-Ang University, Seoul, 156-756 (Korea, Republic of); Ok, Kang Min, E-mail: kmok@cau.ac.kr [Department of Chemistry, Chung-Ang University, Seoul, 156-756 (Korea, Republic of)

2012-10-15

A novel noncentrosymmetric (NCS) gallium-organic framework material, [N(C{sub 3}H{sub 7}){sub 4}]{sub 3}Ga{sub 3}[C{sub 6}H{sub 3}(CO{sub 2}){sub 3}]{sub 4} (CAUMOF-11) has been synthesized by a solvothermal reaction using Ga(NO{sub 3}){sub 3}{center_dot}xH{sub 2}O, 1,3,5-C{sub 6}H{sub 3}(CO{sub 2}H){sub 3}, N(C{sub 3}H{sub 7}){sub 4}Cl, HNO{sub 3}, and HCON(CH{sub 3}){sub 2} at 180 Degree-Sign C. The structure of the reported material has been determined by single-crystal X-ray diffraction. CAUMOF-11 has an anionic three-dimensional framework with aligned four-coordinate GaO{sub 4} tetrahedra and 1,3,5-benzenetricarboxylate groups. Tetrapropylammonim cations reside within the channel and maintain the charge balance. Detailed structural analyses with full characterization including infrared spectroscopy, thermogravimetric analysis, elemental analysis, ion-exchange reactions, topotactic decomposition, and gas adsorption experiments are reported. Powder second-harmonic generating (SHG) measurements on CAUMOF-11, using 1064 nm radiation, exhibit SHG efficiency of 15 times that of {alpha}-SiO{sub 2} and the material is phase-matchable (type-1). - Graphical Abstract: Second-order nonlinear optical measurements on CAUMOF-11 reveal that the material is phase-matchable (type-1) with SHG efficiency of 15 times that of {alpha}-SiO{sub 2}. Highlights: Black-Right-Pointing-Pointer A new NCS Ga-organic framework was solvothermally synthesized. Black-Right-Pointing-Pointer CAUMOF-11 exhibits SHG efficiency of 15 times that of {alpha}-SiO{sub 2}. Black-Right-Pointing-Pointer Thermal decomposition of CAUMOF-11 crystal maintains the original morphology.

Interactions of methylamine and ammonia with atmospheric nucleation precursor H{sub 2}SO{sub 4} and common organic acids: Thermodynamics and atmospheric implications

Energy Technology Data Exchange (ETDEWEB)

Xu, Y.; Jiang, L.; Bai, Z. [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Science, Beijing 100012 (China); Nadykto, A. B., E-mail: anadykto@gmail.com [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Science, Beijing 100012 (China); Department of Applied Mathematics, Moscow State University of Technology “STANKIN”, Vadkovsky per. 1, Moscow 127055 (Russian Federation); Atmospheric Science Research Center, State University of New York at Albany, 251 Fuller Road, Albany, NY 12203 (United States)

2016-06-08

Interactions of the two common atmospheric bases, ammonia (NH{sub 3}) and methylamine MA (CH{sub 3}NH{sub 2}), which are considered to be important stabilizers of binary clusters in the Earth’s atmosphere, with H{sub 2}SO{sub 4}, the key atmospheric precursor, and 14 common atmospheric organic acids (COA) (formic (CH{sub 2}O{sub 2}), acetic (C{sub 2}H{sub 4}O{sub 2}), oxalic (C{sub 2}H{sub 2}O{sub 4}), malonic (C{sub 3}H{sub 4}O{sub 4}), succinic (C{sub 4}H{sub 6}O{sub 4}), glutaric acid (C{sub 5}H{sub 8}O{sub 4}), adipic (C{sub 6}H{sub 10}O{sub 4}), benzoic (C{sub 6}H{sub 5}COOH), phenylacetic (C{sub 6}H{sub 5}CH{sub 2}COOH), pyruvic (C{sub 3}H{sub 4}O{sub 3}), maleic acid (C{sub 4}H{sub 4}O{sub 4}), malic (C{sub 4}H{sub 6}O{sub 5}), tartaric (C{sub 4}H{sub 6}O{sub 6}) and pinonic acid (C{sub 10}H{sub 16}O{sub 3})) have been studied using the composite high-accuracy G3MP2 method. The thermodynamic stability of mixed (COA) (H{sub 2}SO{sub 4}), (COA)(B1) and (COA)(B2) dimers and (COA) (H{sub 2}SO{sub 4}) (B1) and (COA) (H{sub 2}SO{sub 4}) (B1) trimers, where B1 and B2 represent methylamine (CH{sub 3}NH{sub 2}) and ammonia (NH{sub 3}), respectively, have been investigated and their impacts on the thermodynamic stability of clusters containing H{sub 2}SO{sub 4} have been analyzed. It has been shown that in many cases the interactions of H{sub 2}SO{sub 4} with COA, ammonia and methylamine lead to the formation of heteromolecular dimers and trimers, which are certainly more stable than (H{sub 2}SO{sub 4}){sub 2} and (H{sub 2}SO{sub 4}){sub 3}. It has also been found that free energies of (COA) (H{sub 2}SO{sub 4})+ CH{sub 3}NH{sub 2}⇔(COA) (H{sub 2}SO{sub 4})(CH{sub 3}NH{sub 2}) reactions exceed 10-15 kcal mol{sup −1}. This is a clear indication that mixed trimers composed of COA, H{sub 2}SO{sub 4} and methylamine are very stable and can thus serve as possible nucleation sites. The present study leads us to conclude that the interactions of COA coexisting with H{sub

Inhibition by Ginkgo leaves extract of the corrosion of steel in HCl and H{sub 2}SO{sub 4} solutions

Energy Technology Data Exchange (ETDEWEB)

Deng Shuduan, E-mail: dengshuduan@163.com [Faculty of Materials Engineering, Southwest Forestry University, Kunming 650224 (China); Li Xianghong [Faculty of Science, Southwest Forestry University, Kunming 650224 (China)

2012-02-15

Highlights: Black-Right-Pointing-Pointer Ginkgo leaves extract (GLE) acts as a good inhibitor for steel in HCl and H{sub 2}SO{sub 4} media. Black-Right-Pointing-Pointer The inhibition efficiency follows the order: HCl > H{sub 2}SO{sub 4}. Black-Right-Pointing-Pointer The adsorption of GLE on steel surface obeys Langmuir adsorption isotherm. Black-Right-Pointing-Pointer GLE behaves as a mixed-type inhibitor in 1.0 M HCl, while cathodic inhibitor in 0.5 M H{sub 2}SO{sub 4}. - Abstract: The inhibition effect of Ginkgo leaves extract (GLE) on the corrosion of cold rolled steel (CRS) in 1.0-5.0 M HCl and 0.5-2.5 M H{sub 2}SO{sub 4} solutions was investigated for the first time by weight loss, potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) methods. The results show that GLE is a good inhibitor, and exhibits more efficient in 1.0 M HCl than 0.5 M H{sub 2}SO{sub 4}. The adsorption of GLE on CRS surface obeys Langmuir adsorption isotherm. GLE acts as a mixed-type inhibitor in 1.0 M HCl, while a cathodic inhibitor in 0.5 M H{sub 2}SO{sub 4}.

A study on H{sub 2}S permeability of CsHSO{sub 4} membranes

Energy Technology Data Exchange (ETDEWEB)

Mbah, Jonathan; Wolan, John T. [Department of Chemical and Biomedical Engineering, College of Engineering, University of South Florida, Tampa, FL 33620 (United States); Clean Energy Research Center, College of Engineering, University of South Florida, Tampa, FL 33617 (United States); Krakow, Burton [Clean Energy Research Center, College of Engineering, University of South Florida, Tampa, FL 33617 (United States); Stefanakos, Elias [Clean Energy Research Center, College of Engineering, University of South Florida, Tampa, FL 33617 (United States); Department of Electrical Engineering, College of Engineering, University of South Florida, Tampa, FL 33617 (United States)

2009-03-15

The gas permeability of H{sub 2}S gas at 150 C through ultra-thin cesium hydrogen sulfate (CsHSO{sub 4}) membranes has been investigated. Gas chromatography-mass spectrometry analyses indicate that CsHSO{sub 4} membrane is impermeable to H{sub 2}S gas under test conditions. The apparent micropore diameter of the membrane averaged between 9.5 and 11.5 Aa with a maximum permeance of 0.09 Barrer (6.75 x 10{sup -19} m{sup 2} s{sup -1} Pa{sup -1}). Atomic force microscope and X-ray diffraction analyses show respectively that the surface morphology and crystal structure of the membranes are preserved, with no adverse effect from prolonged exposure to H{sub 2}S gas. Electrochemical impedance spectroscopy analysis confirm over a 30% decrease in membrane resistance via an 80% reduction in membrane thickness. (author)

A 3d-4f complex constructed by the assembly of a cationic template, [Cu(en){sub 2}]{sup 2+}, and a 3D anionic coordination polymer, [Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}(C{sub 5}O{sub 5})(H{sub 2}O){sub 2}]{sup 2-}

Energy Technology Data Exchange (ETDEWEB)

Ke, Szu-Yu; Yeh, Chang-Tsung; Wang, Chih-Chieh [Department of Chemistry, Soochow University, Taipei, Taiwan (China); Lee, Gene-Hsiang [Instrumentation Center, National Taiwan University, Taipei, Taiwan (China); Sheu, Hwo-Shuenn [National Synchrotron Radiation Research Center, Hsinchu, Taiwan (China)

2017-05-18

A three-dimensional (3D) 3d-4f complex, [Cu(en){sub 2}][Sm{sub 2}(C{sub 5}O{sub 5})(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 2}].8H{sub 2}O (1) (en = ethylenediamine, C{sub 5}O{sub 5}{sup 2-} = dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione), were prepared via the in-situ ring-opening oxidation reaction of croconate in the presence of the template-directed complex, [Cu(en){sub 2}]{sup 2+} cation. The structural characterization determined by X-ray diffraction determination reveals that the 3D anionic coordination polymer of [Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}(C{sub 5}O{sub 5})(H{sub 2}O){sub 2}]{sup 2-} in 1 can be describe in terms of in-plane 2D honeycomb-like [Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}] layered frameworks bridged by oxalate with bis-chelating mode, being mutually interlinked via the bridge of μ{sub 1,2,3,4}-croconate ligands with bis-chelating coordination mode to complete the 3D open framework, which gives rise to 1D channels with pore size of 14.023 x 11.893 Aa (longest atom-atom contact distances) along the b axis. The structure-directing complex, [Cu(en){sub 2}]{sup 2+}, and solvated water molecules are resided into these honeycomb-type hexagonal channels. The thermal stability of 1 was further studied by TGA and in-situ powder X-ray diffraction measurement. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Biological reduction-deposition and luminescent properties of nanostructured CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) and CePO{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Yu, Xiaoniu [School of Materials Science and Engineering, Southeast University, Nanjing 211189 (China); Research Institute of Green Construction Materials, Southeast University, Nanjing 211189 (China); Qian, Chunxiang, E-mail: cxqian@seu.edu.cn [School of Materials Science and Engineering, Southeast University, Nanjing 211189 (China); Research Institute of Green Construction Materials, Southeast University, Nanjing 211189 (China)

2016-03-01

Nano-sized CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) and CePO{sub 4} with hexagonal phase have been prepared by simply varying the reactant P/Ce molar ratio in bacterial liquid. The phase composition of two samples was checked via Fourier transform infrared spectroscopy (FTIR), energy dispersive analysis of X-rays (EDS) and X-ray diffraction (XRD) analyses, displaying the presence of CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) and CePO{sub 4} with average crystallite size are 32.34 and 15.61 nm, respectively. The scanning electron microscopy (SEM) images show that nano-clusters and sphere-like in shape with a narrow diameter distribution were observed in two samples. The transmission electron microscopy (TEM) photographs further indicate obtained CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) and CePO{sub 4} nanoparticles correspond to nanosheets and nanorods, respectively. The emission spectra of CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) and CePO{sub 4} display a broad band of 300–380 nm range with the strongest emission at 342 nm in the violet region. - Highlights: • A new method was found to synthesize CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) and CePO{sub 4} nanoparticles. • CePO{sub 4}@NaCe(SO{sub 4}){sub 2}(H{sub 2}O) nanoparticles have good luminescent properties. • Size and luminescent properties of two samples have been studied and compared.

High yield and facile microwave-assisted synthesis of conductive H{sub 2}SO{sub 4} doped polyanilines

Energy Technology Data Exchange (ETDEWEB)

Gizdavic-Nikolaidis, Marija R., E-mail: m.gizdavic@auckland.ac.nz [School of Chemical Sciences, The University of Auckland, Private Bag 92019, Auckland Mail Centre, Auckland, 1142 (New Zealand); Faculty of Physical Chemistry, Studentski Trg 12-16, PO Box 137, 11001, Belgrade (Serbia); Jevremovic, Milutin M. [Public Company Nuclear Facilities of Serbia, 12-14 Mike Petrovica Alasa, Vinca, 11351, Belgrade (Serbia); Milenkovic, Maja [Faculty of Physical Chemistry, Studentski Trg 12-16, PO Box 137, 11001, Belgrade (Serbia); Allison, Morgan C. [School of Chemical Sciences, The University of Auckland, Private Bag 92019, Auckland Mail Centre, Auckland, 1142 (New Zealand); Stanisavljev, Dragomir R. [Faculty of Physical Chemistry, Studentski Trg 12-16, PO Box 137, 11001, Belgrade (Serbia); Bowmaker, Graham A. [School of Chemical Sciences, The University of Auckland, Private Bag 92019, Auckland Mail Centre, Auckland, 1142 (New Zealand); Zujovic, Zoran D. [School of Chemical Sciences, The University of Auckland, Private Bag 92019, Auckland Mail Centre, Auckland, 1142 (New Zealand); MacDiarmid Institute for Advanced Materials and Nanotechnology, Victoria University of Wellington, PO Box 600, Wellington, 6140 (New Zealand); Institute of General and Physical Chemistry, Studentski Trg 12-16, 11001, Belgrade (Serbia)

2016-04-15

The microwave-assisted synthesis of polyaniline (PANI) was performed using ammonium persulphate (APS) as oxidizing agent in 0.5 M–2.5 M concentration range of aqueous sulphuric acid (H{sub 2}SO{sub 4}) at 93 W applied microwave power of 10 min duration. The microwave (MW) synthesized PANIs had 3 times higher yield in comparison to PANI samples prepared using a classical method, CS (0 W MW power) at the same temperature for 10 min synthesis duration period. Fourier Transform Infrared (FTIR) and UV–Vis spectroscopies confirmed the formation of PANI structure in all products. The influence of H{sub 2}SO{sub 4} acid dopant on the spin concentration of MW and CS H{sub 2}SO{sub 4} doped PANI samples were examined by EPR spectroscopy, while the morphological characteristics were investigated by using scanning electron microscopy (SEM). XRD results showed amorphous phases in both MW and CS H{sub 2}SO{sub 4} doped PANI samples. Conductivity measurements revealed ∼1.5 times higher conductivity values for MW H{sub 2}SO{sub 4} doped PANI samples in comparison with PANI samples prepared by the CS method under same condition. The influence of sulfate anion in comparison to chloride anion as a dopant on morphological, dopant levels and conductivity properties of MW PANI samples were also investigated. - Highlights: • Nanoporous microwave synthesized doped polyanilines as chemical sensor material. • Morphology and physical properties of polyanilines depend on acid concentration. • Spin concentration is determined by the nature of the polyaniline synthesis.

Long-term stability of FeSO{sub 4} and H{sub 2}SO{sub 4} treated chromite ore processing residue (COPR): Importance of H{sup +} and SO{sub 4}{sup 2−}

Energy Technology Data Exchange (ETDEWEB)

Wang, Xin [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Zhang, Jingdong [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Wang, Linling, E-mail: wanglinling@mail.hust.edu.cn [School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Chen, Jing, E-mail: chenjing@mail.hust.edu.cn [School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Hou, Huijie; Yang, Jiakuan [School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Lu, Xiaohua [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

2017-01-05

Highlights: • The long-term stability of the FeSO{sub 4}-H{sub 2}SO{sub 4} treated COPR was evaluated. • Reliable long-term stability for samples curing 400 days was achieved. • H{sub 2}SO{sub 4} significantly enhanced the stabilization efficiency of COPR using FeSO{sub 4}. • H{sup +} and SO{sub 4}{sup 2−} both reinforced Cr(VI) release from COPR core to react with Fe(II). - Abstract: In this study, the long-term stability of Cr(VI) in the FeSO{sub 4} and H{sub 2}SO{sub 4} (FeSO{sub 4}-H{sub 2}SO{sub 4}) treated chromite ore processing residue (COPR) after 400 curing days and the stabilization mechanisms were investigated. FeSO{sub 4}-H{sub 2}SO{sub 4} treatment significantly reduced toxicity characteristic leaching procedure (TCLP) and synthetic precipitation leaching procedure (SPLP) Cr(VI) concentrations to lower than the regulatory limit of 1.5 mg L{sup −1} (HJ/T 301-2007, China EPA) even for the samples curing 400 days, achieving an outstanding long-term stability. Our independent leaching tests revealed that H{sup +} and SO{sub 4}{sup 2−} have synergistic effect on promoting the release of Cr(VI), which would make Cr(VI) easier accessed by Fe(II) during stabilization. The contributions of H{sup +} and SO{sub 4}{sup 2−} to Cr(VI) release ratio were 25%–44% and 19%–38%, respectively, as 5 mol H{sub 2}SO{sub 4} per kg COPR was used. X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and alkaline digestion analyses were also employed to interpret the possible stabilization mechanism. Cr(VI) released from COPR solid was reduced to Cr(III) by Fe(II), and then formed stable Fe{sub x}Cr{sub (1−x)}(OH){sub 3} precipitate. This study provides a facile and reliable scheme for COPR stabilization, and verifies the excellent long-term stability of the FeSO{sub 4}-H{sub 2}SO{sub 4} treated COPR.

Description and crystal structure of albrechtschraufite, MgCa{sub 4}F{sub 2}[UO{sub 2}(CO{sub 3}){sub 3}]{sub 2}.17-18H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Mereiter, K. [Vienna Univ. of Technology (Austria). Inst. of Chemical Technologies and Analytics

2013-04-15

Albrechtschraufite, MgCa{sub 4}F{sub 2}[UO{sub 2}(CO{sub 3}){sub 3}]{sub 2}.17-18H{sub 2}O, triclinic, space group P anti 1, a = 13.569(2), b = 13.419(2), c = 11.622(2) Aa, α = 115.82(1), β = 107.61(1), γ = 92.84(1) (structural unit cell, not reduced), V = 1774.6(5) Aa{sup 3}, Z = 2, Dc = 2.69 g/cm{sup 3} (for 17.5 H{sub 2}O), is a mineral that was found in small amounts with schroeckingerite, NaCa{sub 3}F[UO{sub 2}(CO{sub 3}){sub 3}](SO{sub 4}).10H{sub 2}O, on a museum specimen of uranium ore from Joachimsthal (Jachymov), Czech Republic. The mineral forms small grain-like subhedral crystals (= 0.2 mm) that resemble in appearance liebigite, Ca{sub 2}[UO{sub 2}(CO{sub 3}){sub 3}]. ∝ 11H{sub 2}O. Colour pale yellow-green, luster vitreous, transparent, pale bluish green fluorescence under ultraviolet light. Optical data: Biaxial negative, nX = 1.511(2), nY = 1.550(2), nZ = 1.566(2), 2V = 65(1) (λ = 589 nm), r < v weak. After qualitative tests had shown the presence of Ca, U, Mg, CO{sub 2} and H{sub 2}O, the chemical formula was determined by a crystal structure analysis based on X-ray four-circle diffractometer data. The structure was later on refined with data from a CCD diffractometer to R1 = 0.0206 and wR2 = 0.0429 for 9,236 independent observed reflections. The crystal structure contains two independent [UO{sub 2}(CO{sub 3}){sub 3}]{sup 4-} anions of which one is bonded to two Mg and six Ca while the second is bonded to only one Mg and three Ca. Magnesium forms a MgF{sub 2}(O{sub carbonate}){sub 3}(H{sub 2}O) octahedron that is linked via the F atoms with three Ca atoms so as to provide each F atom with a flat pyramidal coordination by one Mg and two Ca. Calcium is 7- and 8-coordinate forming CaFO{sub 6}, CaF{sub 2}O{sub 2}(H{sub 2}O){sub 4}, CaFO{sub 3}(H{sub 2}O){sub 4} and CaO{sub 2}(H{sub 2}O){sub 6} coordination polyhedra. The crystal structure is built up from MgCa{sub 3}F{sub 2}[UO{sub 2}(CO{sub 3}){sub 3}].8H{sub 2}O layers parallel to (001) which

Rate of hydrogen motion in Ni-substituted LaNi{sub 5}H{sub x} from NMR

Energy Technology Data Exchange (ETDEWEB)

Mendenhall, Michael P. [Washington University, Department of Physics, Saint Louis, MO 63130 (United States); Bowman, Robert C. [Jet Propulsion Laboratory, California Institute of Technology, Mail Stop 79-24, 4800 Oak Grove Drive, Pasadena, CA 91109 (United States); Ivancic, Timothy M. [Washington University, Department of Physics, Saint Louis, MO 63130 (United States); Conradi, Mark S. [Washington University, Department of Physics, Saint Louis, MO 63130 (United States)], E-mail: msc@wuphys.wustl.edu

2007-10-31

Partial substitution of Sn, Ge, or Si for Ni in LaNi{sub 5}H{sub x} greatly enhances the stability under repeated hydrogen-cycling. Proton NMR relaxation measurements are reported here to determine the rates of H hopping in the substituted metals LaNi{sub 4.6}M{sub 0.4}H{sub x} with M = Sn, Ge, and Si, for comparison to bare LaNi{sub 5}H{sub x}. The relaxation times T{sub 2}{sup *} (FID), T{sub 2} (Hahn echo), T{sub 2}-CPMG, T{sub 1}, and T{sub 1{rho}} were determined from 130 to 375 K. The three substituents result in only small increases in the average rate of motion at a given temperature but with a broader distribution of rates over the many inequivalent H sites and hopping paths. Evidently, the average energy barriers along the paths for H motion are only little affected by these substituents. Changes of H content x produce only minor changes in the relaxation times.

Extended analysis of the 5g. -->. 4f emissions in H/sub 2/

Energy Technology Data Exchange (ETDEWEB)

Chang, E.S.; Pulchtopek, S.; Eyler, E.E.

1984-01-15

An analysis starting from Hund's case d has been used to extend the work of Herzberg and Jungen on the 5g..-->..4f emissions in H/sub 2/. A simple analytical expression for the line intensities is presented that agrees with their calculations is about 1%. All of the experimentally observed lines have been accounted for by including higher vibrational levels in our calculations.

Molecular dynamics and quantum chemical calculation studies on 4,4-dimethyl-3-thiosemicarbazide as corrosion inhibitor in 2.5 M H{sub 2}SO{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Musa, Ahmed Y., E-mail: ahmed.musa@ymail.com [Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, Bangi 43600, Selangor (Malaysia); Kadhum, Abdul Amir H.; Mohamad, Abu Bakar; Takriff, Mohd Sobri [Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, Bangi 43600, Selangor (Malaysia)

2011-09-15

Highlights: {yields} This work deals with a study of chemical additives for corrosion inhibition of mild steel in acidic conditions. {yields} The effects of the additive 4,4-dimethyl-3-thiosemicarbazide (DTS) on mild steel were studied by means of electrochemical techniques. {yields} Quantum chemical calculations and molecular dynamic model were performed to characterize the inhibition mechanism. {yields} The calculations provided information that helps in the analysis/interpretation of the experimental work. - Abstract: The inhibition of mild steel corrosion in a 2.5 M H{sub 2}SO{sub 4} solution by 4,4-dimethyl-3-thiosemicarbazide (DTS) was studied at 30 deg. C using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Quantum chemical parameters were calculated for DTS using PM3-SCF method. The molecular dynamic method was performed to simulate the adsorption of the DTS molecules on Fe surface. Results showed that DTS performed excellent as inhibitor for mild steel corrosion in a 2.5 M H{sub 2}SO{sub 4} solution and indicated that the inhibition efficiencies increase with the concentration of inhibitor. Theoretical results indicated that DTS could adsorb on the mild steel surface firmly through heteroatoms.

Structural, mechanical, and electronic properties of monoclinic N{sub 2}H{sub 5}N{sub 3} under pressure

Energy Technology Data Exchange (ETDEWEB)

Qi-Jun, Liu; Fu-Sheng, Liu, E-mail: qijunliu@home.swjtu.edu.cn [School of Physical Science and Technology, Southwest Jiaotong University, Key Laboratory of Advanced Technologies of Materials, Ministry of Education of China, Chengdu (China); Bond and Band Engineering Group, Sichuan Provincial Key Laboratory (for Universities) of High Pressure Science and Technology, Southwest Jiaotong University, Chengdu (China); Zheng-Tang, Liu [State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi' an, (China)

2015-08-15

Structural, elastic, mechanical, and electronic properties of monoclinic N{sub 2}H{sub 5}N{sub 3} at zero and high pressure have been investigated using the plane-wave ultrasoft pseudopotential method within the density-functional theory (DFT). The pressure dependences of structural parameters, elastic constants, mechanical properties, band gaps, and density of states of monoclinic N{sub 2}H{sub 5}N{sub 3} have been calculated and discussed. The obtained results show that monoclinic N{sub 2}H{sub 5}N{sub 3} is unstable at pressures exceeding the value 126.1 GPa. The ratio of B/G and the Cauchy’s pressure indicate that monoclinic N{sub 2}H{sub 5}N{sub 3} behaves in ductile nature with pressure ranging from 0 to 200 GPa. (author)

Modeling impacts of NH{sub 3} on uptake of H{sub 2}SO{sub 4} by charged nucleating nanoparticles in the Earth's atmosphere

Energy Technology Data Exchange (ETDEWEB)

Nadykto, A. B., E-mail: anadykto@gmail.com [Atmospheric Science Research Center, State University of New York at Albany, 251 Fuller Road, Albany, NY 12203 (United States); Department of Applied Mathematics, Moscow State University of Technology “STANKIN”, Vadkovsky per. 1, Moscow 127055 (Russian Federation); Nazarenko, K. M.; Markov, P. N. [Department of Applied Mathematics, Moscow State University of Technology “STANKIN”, Vadkovsky per. 1, Moscow 127055 (Russian Federation); Yu, F. [Atmospheric Science Research Center, State University of New York at Albany, 251 Fuller Road, Albany, NY 12203 (United States)

2016-06-08

The understanding of the role of ammonia, a well-known stabilizer of binary sulfuric acid-water clusters, in the gas-to-nanoparticle conversion in the Earth atmosphere is critically important for the assessment of aerosol radiative forcing associated with the climate changes. The sulfuric acid H{sub 2}SO{sub 4} is present in the atmosphere in the form of the gas-phase hydrates (H{sub 2}SO{sub 4})(H{sub 2}O){sub n}, whose interaction with NH{sub 3} leads to the formation of more stable bisulfate clusters (NH{sub 3})(H{sub 2}SO{sub 4})(H{sub 2}O){sub n}. Although the impact of NH{sub 3} on the thermochemical stability of binary clusters nucleating homogeneously has been studied in some detail in the past, the effect of ammonia on other microphysical properties relevant to nucleation remains insufficiently well understood. In the present study, the effect of ammonia on the electrical dipole moment controlling the nucleation of airborne ions via the dipole-charge interaction has been investigated using the Density Functional Theory (DFT), ab initio MP2 and model chemistry G3 methods. The presence of ammonia in (H{sub 2}SO{sub 4})(H{sub 2}O){sub n} is found to lead to very large enhancement in the dipole moment, which exceeds 2.0-2.5 Debyes (∼60-80%), 3.7-5.0 Debyes (∼90-180%), 1.4-4.5 Debyes (∼50-150%) and 2.1-5.5 Debyes (∼60-700%) for n = 0, n = 1, n = 2 and n = 3, respectively. The implications of this include the significantly increased uptake of the sulfuric acid, the key atmospheric nucleation precursor, by airborne ions and neutrals (due to dipole-dipole interaction), enhanced nucleation rates and the elevated production of ultrafine particles, which cause adverse health impacts.

Copper(II) perrhenate Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2}: Synthesis from isopropanol and CuReO{sub 4}, structure and properties

Energy Technology Data Exchange (ETDEWEB)

Mikhailova, D., E-mail: d.mikhailova@ifw-dresden.de [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM), Hermann-von-Helmholtz-Platz 1, D-76434 Eggenstein-Leopoldshafen (Germany); Institute for Complex Materials, IFW Dresden, Helmholtzstrasse 20, D-01069 Dresden (Germany); Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, D-01187 Dresden (Germany); Engel, J.M. [Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 2, D-64287 Darmstadt (Germany); Schmidt, M. [Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, D-01187 Dresden (Germany); Tsirlin, A.A. [National Institute of Chemical Physics and Biophysics, Akadeemia tee 23, 12618 Tallinn (Estonia); Ehrenberg, H. [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM), Hermann-von-Helmholtz-Platz 1, D-76434 Eggenstein-Leopoldshafen (Germany); Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 2, D-64287 Darmstadt (Germany)

2015-12-15

The crystal structure of Cu{sup +}Re{sup 7+}O{sub 4} is capable of a quasi-reversible incorporation of C{sub 3}H{sub 7}OH molecules. A room-temperature reaction between CuReO{sub 4} and C{sub 3}H{sub 7}OH under oxidizing conditions leads to the formation of a novel metal-organic hybrid compound Cu{sup 2+}(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2}. Upon heating under reducing conditions, this compound transforms back into CuReO{sub 4}, albeit with ReO{sub 2} and metallic Cu as by-products. The crystal structure of Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2} solved from single-crystal X-ray diffraction (Pbca, a=10.005(3) Å, b=7.833(2) Å, and c=19.180(5) Å) reveals layers of corner-sharing CuO{sub 6}-octahedra and ReO{sub 4}-tetrahedra, whereas isopropyl groups are attached to both sides of these layers, thus providing additional connections within the layers through hydrogen bonds. Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2} is paramagnetic down to 4 K because the spatial arrangement of the Cu{sup 2+} half-filled orbitals prevents magnetic superexchange. The paramagnetic effective moment of 2.0(1) μ{sub B} is slightly above the spin-only value and typical for Cu{sup 2+} ions. - Highlights: • Novel Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2} compound has a sequence of inorganic and organic layers. • Hydrogen bonds provide an additional bonding Isopropanol molecules serve as a reducing agent during decomposition. • No direct Cu-O-Re-O-Cu connections via d{sub x2-y2} orbital of Cu{sup 2+} explain paramagnetism. • Hydrogen bonds provide an additional bonding. • Isopropanol molecules serve as a reducing agent during decomposition.

Nature of active centers of catalytic system of VOCl/sub 3/ - Al(C/sub 2/H/sub 5/)/sub 2/Cl

Energy Technology Data Exchange (ETDEWEB)

Dubnikova, I L; Meshkova, I N [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

1977-05-01

To investigate the nature of the active sites of the catalyst VOCl/sub 3/-Al(C/sub 2/H/sub 5/)/sub 2/Cl during olefine polymerization, the following factors have been studied: composition and catalytic activity of homogeneous and heterogeneous components of the system, valent state of vanadium entering into the composition of the catalytic sites, effect of an organoaluminium component on the catalytic activity of the system, and the properties of the polymeric products being formed. It has been shown that the catalytic sites of the system VOCl/sub 3/-Al(C/sub 4/H/sub 5/)/sub 2/Cl are located, predominantly, in the heterogeneus phase of the catalyst. A conclusion has been made that heterogeneous catalytic sites are bimetal complexes of alkyl derivatives of vanadium trichloride and aluminuim alkylchlorides and that polycentral mechanism of catalysis of olefine polymerization in the presence of VOCl/sub 3/-Al(C/sub 2/H/sub 5/)/sub 2/Cl is caused by two types of active vanadium-aluminium complexes differing in the nature of an organoaluminium component.

Stability and isomerization reactions of phenyl cation C{sub 6}H{sub 5}{sup +} isomers

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Shi, Dandan [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Yang, Xue [College of Science, Jilin Institute of Chemical Technology, Jilin 132022 (China); Zhang, Xiaomei; Shan, Shimin [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Xu, Haifeng, E-mail: xuhf@jlu.edu.cn [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Yan, Bing, E-mail: yanbing@jlu.edu.cn [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China)

2016-03-01

Highlights: • A total of 60 isomers of C{sub 6}H{sub 5}{sup +} cations were obtained at density functional theory. • The stability and isomerization reactions of C{sub 6}H{sub 5}{sup +} isomers were performed. • The structures, frequencies, thermodynamic properties of isomers were summarized. • Ring to ring or chain isomerization pathways were investigated using IRC method. • Result shows reactions contain hydrogen transfer, bond broken and reconstruction. - Abstract: As a key polyatomic molecular cation that plays a pivotal role in growth of the polycyclic aromatic hydrocarbons, phenyl cation C{sub 6}H{sub 5}{sup +} exhibits various isomers and isomerization reactions. Investigation on the structure and stability of the isomers as well as the isomerization is important for better understanding the chemical reactions involving C{sub 6}H{sub 5}{sup +} cations. In this work, we have performed a theoretical study on the stability and isomerization reactions of C{sub 6}H{sub 5}{sup +} isomers at density functional theory B3LYP/6-311G (d, p) level. We have obtained a total of 60 isomers of C{sub 6}H{sub 5}{sup +} cations, most of which are reported for the first time. The geometries, vibrational frequencies, thermodynamic properties and stability of 28 out of 60 isomers have been summarized in detail. Different ring-to-ring and ring-to-chain isomerization pathways, which are connected via 28 transition states, have been investigated using the intrinsic reaction coordinate method. The results show that the isomerization reactions occur via hydrogen migration followed by bond-breaking and reconstruction.

X-ray and NQR studies of bromoindate(III) complexes. [C{sub 2}H{sub 5}NH{sub 3}]{sub 4}InBr{sub 7}, [C(NH{sub 2}){sub 3}]{sub 3}InBr{sub 6}, and [H{sub 3}NCH{sub 2}C(CH{sub 3}){sub 2}CH{sub 2}NH{sub 3}]InBr{sub 5}

Energy Technology Data Exchange (ETDEWEB)

Iwakiri, Takeharu; Ishihara, Hideta [Saga Univ. (Japan). Faculty of Culture and Education; Terao, Hiromitsu [Tokushima Univ. (Japan). Faculty of Integrated Arts and Sciences; Lork, Enno; Gesing, Thorsten M. [Bremen Univ. (Germany). Inst. of Inorganic Chemistry and Crystallography

2017-03-01

The crystal structures of [C{sub 2}H{sub 5}NH{sub 3}]{sub 4}InBr{sub 7}(1), [C(NH{sub 2}){sub 3}]{sub 3}InBr{sub 6}(2), and [H{sub 3}NCH{sub 2}C(CH{sub 3}){sub 2}CH{sub 2}NH{sub 3}]InBr{sub 5}(3) were determined at 100(2) K: monoclinic, P2{sub 1}/n, a=1061.94(3), b=1186.40(4), c=2007.88(7) pm, β= 104.575(1) , Z=4 for 1; monoclinic, C2/c, a=3128.81(12), b=878.42(3), c=2816.50(10) pm, β=92.1320(10) , Z=16 for 2; orthorhombic, P2{sub 1}2{sub 1}2{sub 1}, a=1250.33(5), b=1391.46(6), c=2503.22(9) pm, Z=4 for 3. The structure of 1 contains an isolated octahedral [InBr{sub 6}]{sup 3-} ion and a Br{sup -} ion. The structure of 2 contains three different isolated octahedral [InBr{sub 6}]{sup 3-} ions. The structure of 3 has a corner-shared double-octahedral [In{sub 2}Br{sub 11}]{sup 5-} ion and an isolated tetrahedral [InBr{sub 4}]{sup -} ion. The {sup 81}Br nuclear quadrupole resonance (NQR) lines of the terminal Br atoms of the compounds are widely spread in frequency, and some of them show unusual positive temperature dependence. These observations manifest the N-H..Br-In hydrogen bond networks developed between the cations and anions to stabilize the crystal structures. The {sup 81}Br NQR and differential thermal analysis (DTA) measurements have revealed the occurrence of unique phase transitions in 1 and 3. When the bond angles were estimated from the electric field gradient (EFG) directions calculated by the molecular orbital (MO) methods, accurate values were obtained for [InBr{sub 6}]{sup 3-} of 1 and for [In{sub 2}Br{sub 11}]{sup 5-} and [InBr{sub 4}]{sup -} of 3, except for several exceptions in those for the latter two ions. On the other hand, the calculations of {sup 81}Br NQR frequencies have produced up to 1.4 times higher values than the observed ones.

Comparative study of the catalytic activity of the complexes Cp{sup *}RuCl(PAr{sub 3}){sub 2} [Ar = -C{sub 6H}5 and 4-CF{sub 3}-C{sub 6}H{sub 4}] in the ATRP of styrene

Energy Technology Data Exchange (ETDEWEB)

Villa-Hernandez, Alejandro M.; Rosales-Velazquez, Claudia P.; Torres-Lubian, Jose R., E-mail: rtorres@ciqa.mx [Departamento de Sintesis de Polimeros, Centro de Investigacion en Quimica Aplicada, Coah. (Mexico); Saldivar-Guerra, Enrique [Departamento de Procesos de Polimerizacion, Centro de Investigacion en Quimica Aplicada, Coah. (Mexico)

2011-09-15

Styrene polymerization by ATRP was conducted independently using the complexes Cp{sup *}RuCl(PPh{sub 3}){sub 2}, and Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2} as catalysts, in order to evaluate the influence of the electronic properties of the phosphine ligands on the rate and control of the polymerization. The kinetic data for polymerizations carried out with Cp{sup *}RuCl(PPh{sub 3}){sub 2}, show that molecular weights increase linearly with conversion with an average initiation efficiency of 0.77. The molecular weights obtained in the kinetic study with Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2} also increase with conversion but show a marked deviation below the theoretical molecular weights. This behavior was explained by the gradual, irreversible, oxidation of catalyst Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2} as confirmed by {sup 31}P-NMR spectroscopy. Catalyst Cp{sup *}RuCl(PPh{sub 3}){sub 2} promotes the polymerization with a rate of polymerization higher than that obtained using Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2}; this is consistent with the better electron donating properties of PPh{sub 3} versus P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}. Preliminary studies of styrene polymerization by ATRP in supercritical CO{sub 2}, shows that only catalyst Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2}, with fluorinated ligands, was active. (author)

In pursuit of the rhabdophane crystal structure: from the hydrated monoclinic LnPO{sub 4}.0.667H{sub 2}O to the hexagonal LnPO{sub 4} (Ln = Nd, Sm, Gd, Eu and Dy)

Energy Technology Data Exchange (ETDEWEB)

Mesbah, Adel, E-mail: adel.mesbah@cea.fr [ICSM, UMR 5257 CNRS – CEA – ENSCM – Université de Montpellier, Site de Marcoule - Bât 426, BP 17171, 30207 Bagnols/Cèze (France); Clavier, Nicolas [ICSM, UMR 5257 CNRS – CEA – ENSCM – Université de Montpellier, Site de Marcoule - Bât 426, BP 17171, 30207 Bagnols/Cèze (France); Elkaim, Erik [Synchrotron SOLEIL, L' Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex (France); Szenknect, Stéphanie; Dacheux, Nicolas [ICSM, UMR 5257 CNRS – CEA – ENSCM – Université de Montpellier, Site de Marcoule - Bât 426, BP 17171, 30207 Bagnols/Cèze (France)

2017-05-15

The dehydration process of the hydrated rhabdophane LnPO{sub 4}.0.667H{sub 2}O (Ln = La to Dy) was thoroughly studied over the combination of in situ high resolution synchrotron powder diffraction and TGA experiments. In the case of SmPO{sub 4}.0.667H{sub 2}O (monoclinic, C2), a first dehydration step was identified around 80 °C leading to the formation of SmPO{sub 4}.0.5H{sub 2}O (Monoclinic, C2) with Z =12 and a =17.6264(1) Å, b =6.9704(1) Å, c =12.1141(1) Å, β=133.74(1) °, V =1075.33(1) Å{sup 3}. In agreement with the TGA and dilatometry experiments, all the water molecules were evacuated above 220 °C yielding to the anhydrous form, which crystallizes in the hexagonal P3{sub 1}21 space group with a =7.0389(1) Å, c =6.3702(1) Å and V =273.34(1) Å{sup 3}. This study was extended to selected LnPO{sub 4}.0.667H{sub 2}O samples (Ln= Nd, Gd, Eu, Dy) and the obtained results confirmed the existence of two dehydration steps before the stabilization of the anhydrous form, with the transitory formation of LnPO{sub 4}.0.5H{sub 2}O. - Graphical abstract: The dehydration process of the rhabdophane SmPO{sub 4}.0.667H{sub 2}O was studied over combination of in situ high resolution synchrotron powder diffraction and TGA techniques, a first dehydration was identified around 80 °C leading to the formation of SmPO{sub 4}.0.5H{sub 2}O (Monoclinic, C2). Then above 220 °C, the anhydrous form of the rhabdophane SmPO{sub 4} was stabilized and crystallizes in the hexagonal P3{sub 1}21 space group. - Highlights: • In situ synchrotron powder diffraction was carried out during the dehydration of the rhabdopahe LnPO{sub 4}.0.667H{sub 2}O. • The heat of the rhabdophane LnPO{sub 4}.0.667H{sub 2}O leads to LnPO{sub 4}.0.5H{sub 2}O then to anhydrous rhabdophane LnPO{sub 4}. • LnPO{sub 4}.0.5H{sub 2}O (monoclinic, C2) and LnPO{sub 4} (Hexagonal, P3{sub 1}21) were solved over the use of direct methods.

Synthesis, structural characterization, and dehydration analysis of uranyl zinc mellitate, (UO{sub 2})Zn(H{sub 2}O){sub 4}(H{sub 2}mel).2H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Olchowka, Jakub; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry [Unite de Catalyse et Chimie du Solide (UCCS) - UMR CNRS 8181, Universite de Lille Nord de France, USTL-ENSCL, Villeneuve d' Ascq (France)

2013-04-15

A new heterometallic uranyl zinc carboxylate, (UO{sub 2})Zn(H{sub 2}O){sub 4}(H{sub 2}mel).2H{sub 2}O, has been hydrothermally prepared (150 C, 24 h) by using 1,2,3,4,5,6-benzenehexacarboxylic acid (mellitic acid) as organic linker in order to form a three-dimensional network. Four of the six carboxylate groups of the mellitate ligand interact with mononuclear uranyl or zinc cations, which are eightfold (hexagonal bipyramid, UO{sub 8}) or sixfold [octahedron, ZnO{sub 2}(H{sub 2}O){sub 4}] coordinated, respectively. The remaining free carboxylate arms of the mellitate species preferentially interact through hydrogen bonds with water molecules trapped within the framework. Thermogravimetric and X-ray thermodiffraction (up to 800 C) analyses and in situ infrared spectroscopy (up to 210 C) indicated that both free and bound water species are evacuated from the structure in one step between 80 and 170 C, followed by its transformation into an unknown, anhydrous, poorly crystalline phase [UO{sub 2}Zn(mel)] up to 320 C. After the formation of an amorphous phase, the re-crystallization of oxides α-ZnU{sub 3}O{sub 10} and ZnO was observed from 460 C. The fluorescence spectrum of the as-synthesized uranyl zinc mellitate shows the six bands that are typical for vibronic couplings of the [O=U=O]{sup 2+} moiety. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synthesis, crystal structure, thermal analysis and dielectric properties of [(C{sub 4}H{sub 9}){sub 4}N]{sub 3}Bi{sub 2}Cl{sub 9} compound

Energy Technology Data Exchange (ETDEWEB)

Trigui, W., E-mail: walatrigui@yahoo.fr; Oueslati, A.; Chaabane, I.; Hlel, F.

2015-07-15

A new organic–inorganic tri-tetrabutylammonium nonachlorobibismuthate(III) compound was prepared. It was found to crystallize in the monoclinic system (P2{sub 1}/n space group) with the following lattice parameters: a=11.32(2) Å, b=22.30(3) Å, c=28.53(2) Å and β=96.52(0)°. The [Bi{sub 2}Cl{sub 9}]{sup 3−} anions are surrounded by six [(C{sub 4}H{sub 9})N]{sup +} cations, forming an octahedral configuration. These octahedra are sharing corners in order to provide the tri-dimensional network cohesion. The differential scanning calorimetry reveals four order-disorder reversible phase transitions located at 214, 238, 434 and 477 K. The Raman and infrared spectra confirm the presence of both cationic [(C{sub 4}H{sub 9})N]{sup +} and anionic [Bi{sub 2}Cl{sub 9}]{sup 3−} parts. The dielectric parameters, real and imaginary dielectric permittivity (ε′ and ε″), and dielectric loss tangent (tg δ), were measured in the frequency range of 209 kHz–5 MHz at different temperatures. The variations of dielectric dispersion (ε') and dielectric absorption (ε″) with frequency show a distribution of relaxation times, which is probably related to the change in the dynamical state of the [(C{sub 4}H{sub 9}){sub 4}N]{sup +} cations and the [Bi{sub 2}Cl{sub 9}]{sup 3−} anions. - Graphical abstract: Projection of the atomic arrangement of the [(C{sub 4}H{sub 9}){sub 4}N]{sub 3}Bi{sub 2}Cl{sub 9} compound along the b axis. - Highlights: • The structure of the (TBA){sub 3}Bi{sub 2}Cl{sub 9} compound was solved and reported. • The cristal belongs to the monoclinic system with P2{sub 1}/n space group. • DSC discloses four order–disorder reversible phases transitions. • The temperature-dependent permittivity ε' and ε″ has been investigated.

Supramolecular assemblies in [Cu(L-Arg){sub 2}(H{sub 2}O)]C{sub 2}O{sub 4}·6H{sub 2}O complex – Structural, spectroscopic, magnetic and thermal behavior

Energy Technology Data Exchange (ETDEWEB)

Wojciechowska, Agnieszka, E-mail: agnieszka.wojciechowska@pwr.edu.pl [Faculty of Chemistry, Wroclaw University of Technology, Wybrzeze Wyspiańskiego 27, 50-370, Wrocław (Poland); Kochel, Andrzej [Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383, Wrocław (Poland); Duczmal, Marek [Faculty of Chemistry, Wroclaw University of Technology, Wybrzeze Wyspiańskiego 27, 50-370, Wrocław (Poland)

2016-10-01

The reaction of L-arginine and oxalate ions with copper(II) salts yields a new complex with formula of [Cu(L-Arg){sub 2}(H{sub 2}O)]·C{sub 2}O{sub 4}·6H{sub 2}O (1) (where L-Arg = L-arginine). Single crystals of 1 were synthesized by crystallization from aqueous solution. The complex properties were characterized by X-ray diffraction, spectroscopy (FT-IR, FT-Raman, NIR-Vis-UV and EPR) as well as thermal and magnetic methods. The square pyramidal (SP) geometry around Cu(II) ions in [Cu(L-Arg){sub 2}(H{sub 2}O)]{sup 2+} cation complex is formed by two cis-chelated L-arginine zwitterions and a water molecule coordinated in the apex of square pyramid. The trigonality distortion of SP geometry is relatively small, τ = 0.0087. The solid state EPR spectrum showed broad hyperfine splitting with g{sub ⊥} = 2.061 at 77 K. The copper centres distanced at 7.558(5) Å are joined in a single zig-zag structure via a chain based on the combination of Cu−O(5)−H(29)⋯O(2)−C1−O1−Cu hydrogen bonds along the b axis (d (O2⋯O5) = 2.812 Å). Taking into account the structural features, the magnetic susceptibility data were best-fitted, giving the exchange parameter J = −0.16 cm{sup −1}. Complex 1 is thermally stable up to 66 °C, where it was observed to lose the crystallization water molecules with an 11.7% mass loss (calc. 11.5%). - Highlights: • Crystal and molecular structure of [Cu(L-Arg){sub 2}(H{sub 2}O)]C{sub 2}O{sub 4}·6H{sub 2}O crystals have been studied. • The magnetic interactions of Cu(II) centres are assisted by the formation of single zig-zag chain. • Role of oxalate ions in completed relatively small square pyramid distortion is described. • The cis-fashioned L-arginine created the stronger ligand field than trans-configuration.

Hydrazinium(1+) hexafluorotitanate(IV), 2N[sub 2]H[sub 5][sup +]. TiF[sub 6][sup 2-]. [N[sub 2]H[sub 5]TiF[sub 6

Energy Technology Data Exchange (ETDEWEB)

Leban, I. (Dept. of Chemistry and Chemical Technology, Univ. Ljubljana (Slovenia))

1994-06-15

The crystals exhibit racemic twinning. The structure consists of hydrazinium(1+), N[sub 2]H[sub 5][sup +], cations and usual octahedral hexafluorotitanate(IV) anions. They are linked together via hydrogen bonds of the types N-H..F and N-H..N. (orig.).

/sup 13/C, /sup 17/O, and /sup 33/S NMR spectra of alkyl phenyl sulfones C/sub 6/H/sub 5/SO/sub 2/Alk

Energy Technology Data Exchange (ETDEWEB)

Bzhezovskii, V.M.; Valeev, R.B.; Kalabin, G.A.; Aliev, I.A.

1987-06-20

The /sup 13/C, /sup 17/O, and /sup 33/S NMR spectra of alkyl phenyl sulfones C/sub 6/H/sub 5/SO/sub 2/Alk were obtained. The changes in the screening of the /sup 13/C, /sup 17/O, and /sup 33/S nuclei in these compounds are determined by the effect of the alkyl substituents, which alternates in sign and decreases along the chain of atoms in the order: CH/sub 3/, C/sub 2/H/sub 5/, iso-C/sub 3/H/sub 7/, and tert-C/sub 4/H/sub 9/. In the alkyl phenyl sulfides C/sub 6/H/sub 5/SAlk the additional effect of disruption in the p,..pi.. interaction between the sulfur atom and the benzene ring as a result of conformational changes is superimposed on the screening of the /sup 13/C/sup ortho/ nuclei. For the changes in the screening of the /sup 13/C/sup para/ nuclei in C/sub 6/H/sub 5/SAlk the steric disruption of the p,..pi.. conjugation by the alkyl substituents is determining.

Spontaneous piezoelectric effect as order parameter in (NH{sub 4}){sub 2}CuBr{sub 4}·2H{sub 2}O crystal

Energy Technology Data Exchange (ETDEWEB)

Tylczyński, Z., E-mail: zbigtyl@amu.edu.pl; Wiesner, M.; Trzaskowska, A.

2016-11-01

Temperature change of piezoelectric properties of (NH{sub 4}){sub 2}CuBr{sub 4}·2H{sub 2}O crystal in the low-temperature ferroelastoelectric phase is studied. The macroscopic order parameter is proved to be the h{sub 36} component of the spontaneous piezoelectric tensor. The critical exponent related with the phase transition is α=0.60±0.05.

The electrochemical oxidation of lead in various H/sub 2/O-H/sub 2/SO/sub 4/ mixtures-II. Ring-disc electrode study

Energy Technology Data Exchange (ETDEWEB)

Danel, V; Plichon, V

1983-06-01

The rotating ring-disc electrode technique was used to study the generation of soluble Pb(II) species during the anodic oxidation of the lead electrode in various H/sub 2/O-H/sub 2/SO/sub 4/ media. The concentration range extended from 0.06 to 10.3 M H/sub 2/SO/sub 4/. For every concentration it was possible to detect small cathodic ring current variation which was attributable to the reduction of Pb(II) to Pb. Quantitative measurements of the collection efficiency showed that the small cycle life of the lead-acid batter in 5.6 M H/sub 2/SO/sub 4/ cannot be ascribed to the dissolution step.

Magnesium hexafluoridozirconates MgZrF{sub 6}.5H{sub 2}O, MgZrF{sub 6}.2H{sub 2}O, and MgZrF{sub 6}. Structures, phase transitions, and internal mobility of water molecules

Energy Technology Data Exchange (ETDEWEB)

Gerasimenko, Andrey V.; Gaivoronskaya, Kseniya A.; Slobodyuk, Arseny B.; Didenko, Nina A. [Institute of Chemistry, Russian Academy of Sciences, Vladivostok (Russian Federation)

2017-12-04

The MgZrF{sub 6}.nH{sub 2}O (n = 5, 2 and 0) compounds were studied by the methods of X-ray diffraction and {sup 19}F, MAS {sup 19}F, and {sup 1}H NMR spectroscopy. At room temperature, the compound MgZrF{sub 6}.5H{sub 2}O has a monoclinic C-centered unit cell and is composed of isolated chains of edge-sharing ZrF{sub 8} dodecahedra reinforced with MgF{sub 2}(H{sub 2}O){sub 4} octahedra and uncoordinated H{sub 2}O molecules and characterized by a disordered system of hydrogen bonds. In the temperature range 259 to 255 K, a reversible monoclinic <-> two-domain triclinic phase transition is observed. The phase transition is accompanied with ordering of hydrogen atoms positions and the system of hydrogen bonds. The structure of MgZrF{sub 6}.2H{sub 2}O comprises a three-dimensional framework consisting of chains of edge-sharing ZrF{sub 8} dodecahedra linked to each other through MgF{sub 4}(H{sub 2}O){sub 2} octahedra. The compound MgZrF{sub 6} belongs to the NaSbF{sub 6} type and is built from regular ZrF{sub 6} and MgF{sub 6} octahedra linked into a three-dimensional framework through linear Zr-F-Mg bridges. The peaks in {sup 19}F MAS spectra were attributed to the fluorine structural positions. The motions of structural water molecules were studied by variable-temperature {sup 1}H NMR spectroscopy. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Generation of H{sub 2} and CO by solar thermochemical splitting of H{sub 2}O and CO{sub 2} by employing metal oxides

Energy Technology Data Exchange (ETDEWEB)

Rao, C.N.R., E-mail: cnrrao@jncasr.ac.in; Dey, Sunita

2016-10-15

Generation of H{sub 2} and CO by splitting H{sub 2}O and CO{sub 2} respectively constitutes an important aspect of the present-day concerns with energy and environment. The solar thermochemical route making use of metal oxides is a viable means of accomplishing these reduction reactions. The method essentially involves reducing a metal oxide by heating and passing H{sub 2}O or CO{sub 2} over the nonstoichiometric oxide to cause reverse oxidation by abstracting oxygen from H{sub 2}O or CO{sub 2}. While ceria, perovskites and other oxides have been investigated for this purpose, recent studies have demonstrated the superior performance of perovskites of the type Ln{sub 1−x}A{sub x}Mn{sub 1−y}M{sub y}O{sub 3} (Ln=rare earth, A=alkaline earth, M=various +2 and +3 metal ions), in the thermochemical generation of H{sub 2} and CO. We present the important results obtained hitherto to point out how the alkaine earth and the Ln ions, specially the radius of the latter, determine the performance of the perovskites. The encouraging results obtained are exemplefied by Y{sub 0.5}Sr{sub 0.5}MnO{sub 3} which releases 483 µmol/g of O{sub 2} at 1673 K and produces 757 µmol/g of CO from CO{sub 2} at 1173 K. The production of H{sub 2} from H{sub 2}O is also quite appreciable. Modification of the B site ion of the perovskite also affects the performance. In addition to perovskites, we present the generation of H{sub 2} based on the Mn{sub 3}O{sub 4}/NaMnO{sub 2} cycle briefly. - Graphical abstract: Ln{sub 0.5}A{sub 0.5}Mn{sub 1−x}M{sub x}O{sub 3} (Ln=lanthanide; A=Ca, Sr; M=Al, Ga, Sc, Mg, Cr, Fe, Co) perovskites are employed for the two step thermochemical splitting of CO{sub 2} and H{sub 2}O for the generation of CO and H{sub 2}. - Highlights: • Perovskite oxides based on Mn are ideal for the two-step thermochemical splitting of CO{sub 2} and H{sub 2}O. • In Ln{sub 1−x}A{sub x}MnO{sub 3} perovskite (Ln=rare earth, A=alkaline earth) both Ln and A ions play major roles

Molecular Simulations and Theoretical Predictions for Adsorption and Diffusion of CH{sub 4}/H{sub 2} and CO{sub 2}/CH{sub 4} Mixtures in ZIFs

Energy Technology Data Exchange (ETDEWEB)

Liu, Jinchen; Keskin, Seda; Sholl, David S; Johnson, J. Karl

2011-05-01

Adsorption and diffusion of CO{sub 2}/CH{sub 4} and CH{sub 4}/H{sub 2} mixtures were computed in zeolite imidazolate frameworks (ZIFs), ZIF-68 and ZIF-70, using atomically detailed simulations. Adsorption selectivity, diffusion selectivity, and membrane selectivity of ZIFs were calculated based on the results of atomistic simulations. Mixture adsorption isotherms predicted by the ideal adsorbed solution theory agree well with the results of molecular simulations for both ZIFs. Mixture diffusivity calculations indicate that diffusion of CH{sub 4} is increased with increasing concentration of H{sub 2} in the CH{sub 4}/H{sub 2} mixture, while the diffusivity of H{sub 2} decreases with increasing CH{sub 4} concentration. In contrast, the diffusivity of CH{sub 4} is essentially independent of the concentration of CO{sub 2} in the CO{sub 2}/CH{sub 4} mixture, while CO{sub 2} diffusivity decreases with increased CH{sub 4} loading, even though the diffusivity of CH{sub 4} is substantially larger than that of CO{sub 2}. This unusual behavior can be explained in terms of differences in adsorption site preferences due to charge–quadrupole interactions.

Experimental Determination of Solubilities of Tri-calcium Di-Citrate Tetrahydrate [Ca<sub>3sub>[C>3sub>H>5sub>O(COO)>3sub>]>2sub>•4H>2sub>O] Earlandite in NaCl and MgCl<sub>2sub> Solutions to High Ionic Strengths and Its Pitzer Model: Applications to Nuclear Waste Isolation and Other Low Temperature Environments

Energy Technology Data Exchange (ETDEWEB)

Xiong, Yongliang [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States). Carlsbad Programs Group; Kirkes, Leslie Dawn [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States). Carlsbad Programs Group; Westfall, Terry [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States). Carlsbad Programs Group; Marrs, Cassandra [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States). Carlsbad Programs Group; Knox, Jandi [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States). Carlsbad Programs Group; Burton, Heather Lynn [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States). Carlsbad Programs Group

2017-09-01

In this study, solubility measurements on tri-calcium di-citrate tetrahydrate [Ca<sub>3sub>[C>3sub>H>5sub>O(COO)>3sub>]2•4H>2sub>O, abbreviated as Ca<sub>3sub>[Citrate]>2sub>•4H>2sub>O] as a function of ionic strength are conducted in NaCl solutions up to I = 5.0 mol•kg^–1 and in MgCl<sub>2sub> solutions up to I = 7.5 mol•kg^–1, at room temperature (22.5 ± 0.5°C). The solubility constant (log K$0\\atop{sp}$) for Ca<sub>3sub>[Citrate]>2sub>•4H>2sub>O and formation constant (logβ$0\\atop{1}$) for Ca[C<sub>3sub>H>5sub>O(COO)>3sub>]^–Ca>3sub>[C>3sub>H>5sub>O(COO)>3sub>]>2sub>•4H>2sub>O (earlandite) = 3Ca²⁺ + 2[C<sub>3sub>H>5sub>O(COO)>3sub>]^3– + 4H>2sub>O (1) Ca²⁺ + [C<sub>3sub>H>5sub>O(COO)>3sub>]^3– = Ca[C<sub>3sub>H>5sub>O(COO)>3sub>]^– (2) are determined as –18.11 ± 0.05 and 4.97 ± 0.05, respectively, based on the Pitzer model with a set of Pitzer parameters describing the specific interactions in NaCl and M<sub>gCl>2sub> media.

Sugar supported H/sub 2/ production and C/sub 2/H/sub 2/ reduction by the cyanobiont Anabaena azollae

Energy Technology Data Exchange (ETDEWEB)

Rozen, A.; Tel-Or, E.

1986-01-01

Sugar supported activities of H/sub 2/ production and C/sub 2/H/sub 2/ reduction were characterized in axenic cell cultures of the cyanobiont Anabaena azollae isolated from the water fern Azolla filiculoides. Fructose was found to be the favoured substrate, enhancing activities in both the light and the dark even at relatively low concentrations of 0.5-1.0 mM. Higher concentrations of sucrose, (10-20mM) also supported H/sub 2/ production and C/sub 2/H/sub 2/ reduction, while glucose was less effective. Levels of H/sub 2/ production were always lower than those of C/sub 2/H/sub 2/ reduction. 13 references.

Implications for Extraterrestrial Hydrocarbon Chemistry: Analysis of Ethylene (C{sub 2}H{sub 4}) and D4-Ethylene (C{sub 2}D{sub 4}) Ices Exposed to Ionizing Radiation via Combined Infrared Spectroscopy and Reflectron Time-of-flight Mass Spectrometry

Energy Technology Data Exchange (ETDEWEB)

Abplanalp, Matthew J.; Kaiser, Ralf I., E-mail: ralfk@hawaii.edu [W. M. Keck Research Laboratory in Astrochemistry, University of Hawaii at Manoa, Honolulu, HI 96822 (United States)

2017-02-20

The processing of the hydrocarbon ice, ethylene (C{sub 2}H{sub 4}/C{sub 2}D{sub 4}), via energetic electrons, thus simulating the processes in the track of galactic cosmic-ray particles, was carried out in an ultrahigh vacuum apparatus. The chemical evolution of the ices was monitored online and in situ utilizing Fourier transform infrared spectroscopy (FTIR) and during temperature programmed desorption, via a quadrupole mass spectrometer utilizing electron impact ionization (EI-QMS) and a reflectron time-of-flight mass spectrometer utilizing a photoionization source (PI-ReTOF-MS). Several previous in situ studies of ethylene ice irradiation using FTIR were substantiated with the detection of six products: [CH{sub 4} (CD{sub 4})], acetylene [C{sub 2}H{sub 2} (C{sub 2}D{sub 2})], the ethyl radical [C{sub 2}H{sub 5} (C{sub 2}D{sub 5})], ethane [C{sub 2}H{sub 6} (C{sub 2}D{sub 6})], 1-butene [C{sub 4}H{sub 8} (C{sub 4}D{sub 8})], and n -butane [C{sub 4}H{sub 10} (C{sub 4}D{sub 10})]. Contrary to previous gas phase studies, the PI-ReTOF-MS detected several groups of hydrocarbon with varying degrees of saturation: C{sub n}H{sub 2n+2} (n = 4–10), C{sub n}H{sub 2n} ( n = 2–12, 14, 16), C{sub n}H{sub 2n−2} ( n = 3–12, 14, 16), C{sub n}H{sub 2n−4} (n = 4–12, 14, 16), C{sub n}H{sub 2n−6} (n = 4–10, 12), C{sub n}H{sub 2n−8} ( n = 6–10), and C{sub n}H{sub 2n−10} ( n = 6–10). Multiple laboratory studies have shown the facile production of ethylene from methane, which is a known ice constituent in the interstellar medium. Various astrophysically interesting molecules can be associated with the groups detected here, such as allene/methylacetylene (C{sub 3}H{sub 4}) or 1, 3-butadiene (C{sub 4}H{sub 6}) and its isomers, which have been shown to lead to polycyclic aromatic hydrocarbons. Finally, several hydrocarbon groups detected here are unique to ethylene ice versus ethane ice and may provide understanding of how complex hydrocarbons form in astrophysical

Crystal-field energy level analysis for Nd{sup 3+} ions at the low symmetry C{sub 1} site in [Nd(hfa){sub 4}(H{sub 2}O)](N(C{sub 2}H{sub 5}){sub 4}) single crystals

Energy Technology Data Exchange (ETDEWEB)

Mech, Agnieszka; Gajek, Zbigniew [Institute of Low Temperature and Structure Research, Polish Academy Of Sciences, ulica Okolna 2, 54-422 Wroclaw (Poland); Karbowiak, Miroslaw [Faculty of Chemistry, University of Wroclaw, ulica F Joliot-Curie 14, 50-383 Wroclaw (Poland); Rudowicz, Czeslaw [Institute of Physics, Szczecin University of Technology, Aleja Piastow 17, 70-310 Szczecin (Poland)], E-mail: karb@wchuwr.pl

2008-09-24

Optical absorption measurements of Nd{sup 3+} ions in single crystals of [Nd(hfa){sub 4}(H{sub 2}O)](N(C{sub 2}H{sub 5}){sub 4}) (hfa = hexafluoroacetyloacetonate), denoted Nd(hfa) for short, have been carried out at 4.2 and 298 K. This compound crystallizes in the monoclinic system (space group P 2{sub 1}/n). Each Nd ion is coordinated to eight oxygen atoms that originate from the hexafluoroacetylacetonate ligands and one oxygen atom from the water molecule. A total of 85 experimental crystal-field (CF) energy levels arising from the Nd{sup 3+} (4f{sup 3}) electronic configuration were identified in the optical spectra and assigned. A three-step CF analysis was carried out in terms of a parametric Hamiltonian for the actual C{sub 1} symmetry at the Nd{sup 3+} ion sites. In the first step, a total of 27 CF parameters (CFPs) in the Wybourne notation B{sub kq}, admissible by group theory, were determined in a preliminary fitting constrained by the angular overlap model predictions. The resulting CFP set was reduced to 24 specific independent CFPs using appropriate standardization transformations. Optimizations of the second-rank CFPs and extended scanning of the parameter space were employed in the second step to improve reliability of the CFP sets, which is rather a difficult task in the case of no site symmetry. Finally, seven free-ion parameters and 24 CFPs were freely varied, yielding an rms deviation between the calculated energy levels and the 85 observed ones of 11.1 cm{sup -1}. Our approach also allows prediction of the energy levels of Nd{sup 3+} ions that are hidden in the spectral range overlapping with strong ligand absorption, which is essential for understanding the inter-ionic energy transfer. The orientation of the axis system associated with the fitted CF parameters w.r.t. the crystallographic axes is established. The procedure adopted in our calculations may be considered as a general framework for analysis of CF levels of lanthanide ions at low

Study of the reversible water vapour sorption process of MgSO{sub 4}.7H{sub 2}O and MgCl{sub 2}.6H{sub 2}O under the conditions of seasonal solar heat storage

Energy Technology Data Exchange (ETDEWEB)

Ferchaud, C.J.; De Boer, R. [Eindhoven University of Technology, Department of Mechanical Engineering, Eindhoven (Netherlands); Zondag, H.A.; Veldhuis, J.B.J. [ECN Biomass and Energy Efficiency, Petten (Netherlands)

2012-08-15

The characterization of the structural, compositional and thermodynamic properties of MgSO{sub 4}.7H{sub 2}O and MgCl{sub 2}.6H{sub O} has been done for seasonal heat storage using in-situ X-ray Diffraction and thermal analyses (TG/DSC) under practical conditions for seasonal heat storage (T{sub max} = 150C, p(H{sub 2}O)=13 mbar). This study showed that these two materials release heat after a dehydration/hydration cycle with energy densities of 0.38 GJ/m{sup 3} for MgSO{sub 4}.7H{sub 2}O and 0.71 GJ/m{sup 3} MgCl{sub 2}.6H{sub 2}O. The low heat release found for MgSO{sub 4}.7H2O is mainly attributed to the amorphization of the material during the dehydration performed at 13 mbar which reduces its sorption capacity during the rehydration. MgCl{sub 2}.6H{sub 2}O presents a high energy density which makes this material interesting for the seasonal heat storage in domestic applications. This material would be able to fulfil the winter heat demand of a passive house estimated at 6 GJ with a packed bed reactor of 8.5 m{sup 3}. However, a seasonal heat storage system based on the water vapour sorption process in MgCl{sub 2}.6H{sub 2}O should be carefully set with a restricted temperature of 40C for the hydration reaction to avoid the liquefaction of the material at ambient temperature which limits its performances for long term storage.

[6-chloro-3-pyridylmethyl-{sup 3}H]neonicotinoids as high-affinity radioligands for the nicotinic acetylcholine receptor: preparation using NaB{sup 3}H{sub 4} and LiB{sup 3}H{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Latli, Bachir; Casida, J.E. [California Univ., Berkeley, CA (United States). Dept. of Environmental Science Policy and Management; Chit Than; Morimoto, Hiromi; Williams, P.G. [Lawrence Berkeley National Lab., CA (United States)

1996-11-01

NaB{sup 3}H{sub 4} and LiB{sup 3}H{sub 4} at 78% and 97% isotopic enrichments, respectively, were used in the synthesis of {sup 3}H-labeled 1-(6-chloro-3-pyridyl)-methyl-2-nitromethyleneimidazolidine (CH-IMI) and N`-[(6-chloro-3-pyridyl)methyl]-n``-cyano-n`-methylacetamidine (acetamiprid) (two very potent insecticides) and of 1-(6-chloro-3-pyridyl)methyl-2-iminoimidazolidine (desnitro-IMI) (a metabolite of the commercial insecticides imidacloprid). 6-Chloronicotinoyl chloride was treated with either NaB{sup 3}H{sub 4} in methanol or LiB{sup 3}H{sub 4} in tetrahydrofuran and the resulting alcohol transformed to 2-chloro-5-chloromethylpyridine, which was then coupled to N-cyano-N`-methylacetamidine to give [{sup 3}H] acetamiprid (45 Ci/mmol). 2-Chloro-5-chloro[{sup 3}H]methylpyridine was also reacted with ethylenediamine and the product was either refluxed in absolute ethanol with 1,1-bis(methylthio)-2-nitro-ethylene to provide [{sup 3}H]CH-IMI or reacted in toluene with a solution of cyanogen bromide to produce [{sup 3}H] desnitro-IMI (each 55 Ci/mmol). (author).

Organic-inorganic hybrid supramolecular assemblies based on isomers [H{sub x}As{sub 2}Mo{sub 6}O{sub 26}]{sup (6-x)-} clusters

Energy Technology Data Exchange (ETDEWEB)

Zhao, Zhi-Feng [College of Material Science and Engineering, Heilongjiang University of Science and Technology, Harbin (China); Su, Zhan-Hua; Cong, Bo-Wen; Zhao, Wen-Qi; Ma, Xiu-Juan [School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin (China)

2017-08-16

The arsenomolybdates [H{sub 2}As{sub 2}Mo{sub 6}O{sub 26}(H{sub 2}O)].(H{sub 2}biyb){sub 2}.2H{sub 2}O (1) and [H{sub 3}As{sub 2}Mo{sub 6}O{sub 26}].(H{sub 3}pt){sub 2} (2) [biyb = 1,4-bis(imidazol-1-ylmethyl)benzene, pt = 4'-(3{sup ''}-pyridyl)-2,3':6'3{sup ''}-terpyridine] were synthesized via hydrothermal method. The structures of the compounds were characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR spectroscopy, and TG analysis. Compounds 1 and 2 exhibit two isomeric forms of [H{sub x}As{sub 2}Mo{sub 6}O{sub 26}]{sup (6-x)-}. The structure of 1 is constructed from the B-type [H{sub 2}As{sub 2}Mo{sub 6}O{sub 26}(H{sub 2}O)]{sup 4-} polyanions and free biyb ligands via weak interactions to form 3D supramolecular framework with a {3.4.5"3.6}{3.4"3.5"2}{3.5.6}{sup 2}{3.5"2}{sup 2} topology structure. In compound 2, the A-type [H{sub 3}As{sub 2}Mo{sub 6}O{sub 26}]{sup 3-} clusters are surrounded by pt ligands through hydrogen bond interactions forming 3D supramolecular framework with a {4"3.6"3}{sup 2}{4"6.6"6.8"3} topology structure. The electrochemical behaviors, electrocatalytic and photocatalytic activities of 1 and 2 are detected. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Magnetism of CuCl{sub 2}·2D{sub 2}O and CuCl{sub 2}·2H{sub 2}O, and of CuBr{sub 2}·6H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

DeFotis, G.C., E-mail: gxdefo@wm.edu [Department of Chemistry, College of William and Mary, Williamsburg, VA 23187 (United States); Hampton, A.S.; Van Dongen, M.J.; Komatsu, C.H.; Benday, N.S.; Davis, C.M. [Department of Chemistry, College of William and Mary, Williamsburg, VA 23187 (United States); Hays, K.; Wagner, M.J. [Department of Chemistry, George Washington University, Washington, D.C. 20052 (United States)

2017-07-15

Highlights: • CuCl{sub 2}·2D{sub 2}O is examined magnetically and compared with CuCl{sub 2}·2H{sub 2}O. • Slightly lower magnetic characteristic temperatures occur for deuterated dihydrate. • The new compound CuBr{sub 2}·6H{sub 2}O is examined magnetically. • Unexpected relationships appears between magnetic behaviors of CuBr{sub 2}·6H{sub 2}O and CuBr{sub 2}. • Two alternative monoclinic unit cells can account for diffraction data on CuBr{sub 2}·6H{sub 2}O. - Abstract: The magnetic properties of little examined CuCl{sub 2}·2D{sub 2}O are studied and compared with those of CuCl{sub 2}·2H{sub 2}O. New CuBr{sub 2}·6H{sub 2}O is also examined. Susceptibility maxima appear for chlorides at 5.35 and 5.50 K, in the above order, with estimated antiferromagnetic ordering at 4.15 and 4.25 K. Curie-Weiss fits yield g of 2.210 and 2.205, and Weiss θ of −6.0 and −4.7 K, respectively, in χ{sub M} = C/(T − θ). One-dimensional Heisenberg model fits to susceptibilities, including interchain exchange in a mean-field approximation, are performed. Interchain exchange is significant but much weaker than intrachain. The bromide hexahydrate strongly differs magnetically from any chloride hydrate, but exhibits notable similarities and differences compared to previously studied CuBr{sub 2}. A broad susceptibility maximum occurs near 218 K, only 4% lower than for CuBr{sub 2}, but with almost twice the magnitude. Powder X-ray diffraction data for CuBr{sub 2}·6H{sub 2}O may be best accounted for by a monoclinic unit cell that is metrically orthorhombic. The volume per formula unit is consistent with trends in metal ionic radii. However, an alternative monoclinic cell with 5% smaller volume more readily rationalizes the magnetism.

Synergistic inhibition effect of 5-aminotetrazole and 4,6-dihydroxypyrimidine on the corrosion of cold rolled steel in H{sub 3}PO{sub 4} solution

Energy Technology Data Exchange (ETDEWEB)

Li, Xianghong, E-mail: xianghong-li@163.com [Yunnan Key Laboratory of Wood Adhesives and Glue Products, Southwest Forestry University, Kunming 650224 (China); Faculty of Science, Southwest Forestry University, Kunming 650224 (China); Deng, Shuduan [Yunnan Key Laboratory of Wood Adhesives and Glue Products, Southwest Forestry University, Kunming 650224 (China); Xie, Xiaoguang [School of Chemical Science and Technology, Yunnan University, Kunming 650091 (China); Du, Guanben [Yunnan Key Laboratory of Wood Adhesives and Glue Products, Southwest Forestry University, Kunming 650224 (China)

2016-09-15

The synergistic inhibition effect of 5-aminotetrazole (AT) and 4,6-dihydroxypyrimidine (DHP) on the corrosion of cold rolled steel (CRS) in H{sub 3}PO{sub 4} solution was studied by weight loss, potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), scanning electron microscope (SEM), quantum chemical calculation and molecular dynamics (MD) methods. The results show that AT exhibits a moderate inhibitive effect, and DHP has a poor effect. However, incorporation AT with DHP significantly improves the inhibitive performance, and yields synergism. The adsorption of AT in the absence and presence of DHP obeys Langmuir adsorption isotherm. AT/DHP mixture acts as a mixed-type inhibitor. The combined AT and DHP molecules co-adsorb on the Fe (001) surface in the nearly flat manner, and the adsorption energy is larger than individual AT or DHP. - Highlights: • There is a synergistic inhibition effect of AT and DHP for steel in H{sub 3}PO{sub 4} solution. • The adsorption of AT whether it is mixed with DHP or not obeys Langmuir isotherm. • The AT/DHP mixture behaves as a mixed-type inhibitor. • E{sub HOMO} increases and E{sub LUMO} decreases in the combined AT and DHP. • AT and DHP co-adsorb on Fe (001) surface with the nearly flat manner.

(Solid + liquid) isothermal evaporation phase equilibria in the aqueous ternary system (Li{sub 2}SO{sub 4} + MgSO{sub 4} + H{sub 2}O) at T = 308.15 K

Energy Technology Data Exchange (ETDEWEB)

Wang Shiqiang [Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008 (China); Graduate University of Chinese Academy of Sciences, Beijing 100039 (China); Deng Tianlong [Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008 (China); College of Materials, Chemistry and Chemical Engineering, Chengdu University Technology, Chengdu 610059 (China)], E-mail: dtl@cdut.edu.cn

2008-06-15

The solubility and the density in the aqueous ternary system (Li{sub 2}SO{sub 4} + MgSO{sub 4} + H{sub 2}O) at T = 308.15 K were determined by the isothermal evaporation. Our experimental results permitted the construction of the phase diagram and the plot of density against composition. It was found that there is one eutectic point for (Li{sub 2}SO{sub 4} . H{sub 2}O + MgSO{sub 4} . 7H{sub 2}O), two univariant curves, and two crystallization regions corresponding to lithium sulphate monohydrate (Li{sub 2}SO{sub 4} . H{sub 2}O) and epsomite (MgSO{sub 4} . 7H{sub 2}O). The system belongs to a simple co-saturated type, and neither double salts nor solid solution was found. Based on the Pitzer ion-interaction model and its extended HW models of aqueous electrolyte solution, the solubility of the ternary system at T = 308.15 K has been calculated. The predicted solubility agrees well with the experimental values.

Design and syntheses of hybrid metal–organic materials based on K{sub 3}[M(C{sub 2}O{sub 4}){sub 3}]·3H{sub 2}O [M(III)=Fe, Al, Cr] metallotectons

Energy Technology Data Exchange (ETDEWEB)

Sun, Yayong; Zong, Yingxia; Ma, Haoran; Zhang, Ao; Liu, Kang; Wang, Debao, E-mail: dbwang@qust.edu.cn; Wang, Wenqiang; Wang, Lei, E-mail: inorchemwl@126.com

2016-05-15

By using K{sub 3}[M(C{sub 2}O{sub 4}){sub 3}]·3H{sub 2}O [M(III)=Fe, Al, Cr] (C{sub 2}O{sub 4}{sup 2−}=oxalate) metallotectons as the starting material, we have synthesized eight novel complexes with formulas [{Fe(C_2O_4)_2(H_2O)_2}{sub 2}]·(H–L{sub 1}){sub 2}·H{sub 2}O 1, [Fe(C{sub 2}O{sub 4})Cl{sub 2}]·(H{sub 2}–L{sub 2}){sub 0.5}·(L{sub 2}){sub 0.5}·H{sub 2}O 2, [{Fe(C_2O_4)_1_._5Cl_2}{sub 2}]·(H–L{sub 3}){sub 4}3, [Fe{sub 2}(C{sub 2}O{sub 4})Cl{sub 8}]·(H{sub 2}–L{sub 4}){sub 2}·2H{sub 2}O 4, K[Al(C{sub 2}O{sub 4}){sub 3}]·(H{sub 2}–L{sub 5})·2H{sub 2}O 5, K[Al(C{sub 2}O{sub 4}){sub 3}]·(H–L{sub 6}){sub 2}·2H{sub 2}O 6, K[Cr(C{sub 2}O{sub 4}){sub 3}]·2H{sub 2}O 7, Na[Fe(C{sub 2}O{sub 4}){sub 3}]·(H–L{sub 6}){sub 2}·2H{sub 2}O 8 (with L{sub 1}=4-dimethylaminopyridine, L{sub 2}=2,3,5,6-tetramethylpyrazine, L{sub 3}=2-aminobenzimidazole, L{sub 4}=1,4-bis-(1H-imidazol-1-yl)benzene, L{sub 5}=1,4-bis((2-methylimidazol-1-yl)methyl)benzene, L{sub 6}=2-methylbenzimidazole). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra and thermogravimetric analyses. Compound 3 is a 2D H-bonded supramolecular architecture. Others are 3D supramolecular structures. Compound 1 shows a [Fe(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O){sub 2}]{sup −} unit and 3D antionic H-bonded framework. Compound 2 features a [Fe(C{sub 2}O{sub 4})Cl{sub 2}]{sup -} anion and 1D iron-oxalate-iron chain. Compound 3 features a [Fe{sub 2}(C{sub 2}O{sub 4}){sub 3}Cl{sub 4}]{sup 4−} unit. Compound 4 features distinct [Fe{sub 2}(C{sub 2}O{sub 4})Cl{sub 8}]{sup 4−} units, which are mutual linked by water molecules to generated a 2D H-bonded network. Compound 5 features infinite ladder-like chains constructed by [Al(C{sub 2}O{sub 4}){sub 3}]{sup 3−} units and K{sup +} cations. The 1D chains are further extended into 3D antionic H-bonded framework through O–H···O H-bonds. Compounds 6–8 show 2D [KAl(C{sub 2}O{sub

Biological H{sub 2} from syngas and from H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Weaver, P.; Maness, P.C.; Markov, S.; Martin, S. [National Renewable Energy Lab., Golden, CO (United States)

1996-10-01

The two stand-alone objectives of the research are to economically produce neat H{sub 2} in the near term from biomass (thermally gasified to syngas) and in the mid term from H{sub 2}O using cyanobacteria or algae with an oxygen-tolerant bacterial hydrogenase. Photosynthetic bacteria have four different terminal enzymes that mediate their H{sub 2} metabolisms-nitrogenase, uptake hydrogenase, fermentative hydrogenase, and carbon monoxide-linked hydrogenase. Each has been microbiologically and biochemically examined for their potential to specifically generate H{sub 2} in large-scale processes. Based on measurements of maximal activities, stabilities, energy requirements, equilibria, and partial pressures of the H{sub 2} producing reactions, the CO-linked hydrogenase is easily the most suited for practical applications. The enzyme mediates H{sub 2} production from CO at rates up to 1.5 mmol/min/g cell dry weight at near ambient temperature and pressure. Hydrogen can be produced and evolved at linear rates up to at least 2 atmospheres of partial pressure (100% CO). The rate-limiting step with high cell density suspensions is the mass transfer of CO into the aqueous phase. Bioreactor designs have been examined which enhance the mass transfer. Hollow-fiber bioreactors with bacterial cells immobilized on the fiber surfaces evolve H{sub 2} at ambient pressure at rates of about 0.3-0.7 mmol/min/g cdw. One such reactor has been producing H{sub 2} from CO continuously for 9 months with only occasional changes of liquid medium. A trickle-filter reactor with bacteria immobilized on beads removed from a bulk water phase and a pumped-bubble coil reactor with bacteria in suspension are also being examined.

Comparison of the reactivity of 2-Li-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2} with MCl{sub 4} (M=Th, U). Isolation of a thorium aryl complex or a uranium benzyne complex

Energy Technology Data Exchange (ETDEWEB)

Seaman, Lani A.; Pedrick, Elizabeth A.; Wu, Guang; Hayton, Trevor W. [California Univ., Santa Barbara, CA (United States). Dept. of Chemistry and Biochemistry; Tsuchiya, Takashi; Jakubikova, Elena [North Carolina State Univ., Raleigh, NC (United States). Dept. of Chemistry

2013-09-27

Individualism under actinoids: The reaction of 2-Li-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2} with [MCl{sub 4} (dme) {sub n}] (M=Th, n=2; M=U, n=0) gives the thorium aryl complex [Th(2-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2}){sub 4}] or the uranium benzene complex Li[U(2,3-C{sub 6}H{sub 3}CH{sub 2}NMe{sub 2})(2-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2}){sub 3}]. A DFT analysis suggests that the formation of a benzyne complex with uranium but not with thorium is a kinetic and not thermodynamic effect. [German] Individualismus unter Actinoiden: Die Reaktion von 2-Li-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2} mit [MCl{sub 4} (dme) {sub n}] (M=Th, n=2; M=U, n=0) ergibt den Thoriumarylkomplex [Th(2-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2}){sub 4}] bzw. den Uranbenz-inkomplex Li[U(2,3-C{sub 6}H{sub 3}CH{sub 2}NMe{sub 2})(2-C{sub 6}H{sub 4}CH{sub 2}NMe{sub 2}){sub 3}]. Einer dichtefunktionaltheoretischen Analyse zufolge ist es kinetisch und nicht thermodynamisch bedingt, dass der Benz-inkomplex im Fall von Uran entsteht, nicht aber im Fall von Thorium.

X-ray crystal and molecular structure of (eta/sup 5/C/sub 5/H/sub 5/)UCl/sub 3/. 2PPh/sub 3/O thf: trichloro (eta/sup 5/cyclopentadienyl)bis(triphenylphosphine oxide) uranium(IV). thf

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Bombieri, G; De Paoli, G [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi; Del Pra, A; Bagnall, K W

1978-01-01

Following reports of the preparation of (eta/sup 5/C/sub 5/H/sub 5/)UCl/sub 3/.xL (x = 1, L = dimethoxyethane and x = 2, L = tetrahydrofuran (thf), a series of analogous oxygen-donor complexes were isolated. This paper describes the crystal and molecular structure of one of them, ((eta/sup 5/C/sub 5/H/sub 5/)UCl/sub 3/.2PPh/sub 3/O)thf.

On the Formation of the C{sub 2}H{sub 6}O Isomers Ethanol (C{sub 2}H{sub 5}OH) and Dimethyl Ether (CH{sub 3}OCH{sub 3}) in Star-forming Regions

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Bergantini, Alexandre; Maksyutenko, Pavlo; Kaiser, Ralf I., E-mail: ralfk@hawaii.edu [Department of Chemistry, University of Hawaii at Mānoa, Honolulu, HI 96822 (United States)

2017-06-01

The structural isomers ethanol (CH{sub 3}CH{sub 2}OH) and dimethyl ether (CH{sub 3}OCH{sub 3}) were detected in several low-, intermediate-, and high-mass star-forming regions, including Sgr B2, Orion, and W33A, with the relative abundance ratios of ethanol/dimethyl ether varying from about 0.03 to 3.4. Until now, no experimental data regarding the formation mechanisms and branching ratios of these two species in laboratory simulation experiments could be provided. Here, we exploit tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) to detect and analyze the production of complex organic molecules (COMs) resulting from the exposure of water/methane (H{sub 2}O/CH{sub 4}) ices to energetic electrons. The main goal is to understand the formation mechanisms in star-forming regions of two C{sub 2}H{sub 6}O isomers: ethanol (CH{sub 3}CH{sub 2}OH) and dimethyl ether (CH{sub 3}OCH{sub 3}). The results show that the experimental branching ratios favor the synthesis of ethanol versus dimethyl ether (31 ± 11:1). This finding diverges from the abundances observed toward most star-forming regions, suggesting that production routes on interstellar grains to form dimethyl ether might be missing; alternatively, ethanol can be overproduced in the present simulation experiments, such as via radical–radical recombination pathways involving ethyl and hydroxyl radicals. Finally, the PI-ReTOF-MS data suggest the formation of methylacetylene (C{sub 3}H{sub 4}), ketene (CH{sub 2}CO), propene (C{sub 3}H{sub 6}), vinyl alcohol (CH{sub 2}CHOH), acetaldehyde (CH{sub 3}CHO), and methyl hydroperoxide (CH{sub 3}OOH), in addition to ethane (C{sub 2}H{sub 6}), methanol (CH{sub 3}OH), and CO{sub 2} detected from infrared spectroscopy. The yield of all the confirmed species is also determined.

Influence of the pressure and power on the non-equilibrium plasma chemistry of C{sub 2}, C{sub 2}H, C{sub 2}H{sub 2}, CH{sub 3} and CH{sub 4} affecting the synthesis of nanodiamond thin films from C{sub 2}H{sub 2} (1%)/H{sub 2}/Ar-rich plasmas

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Gordillo-Vazquez, F J [Instituto de Optica, C.S.I.C., Serrano 121, 28006 Madrid (Spain); Albella, J M [Instituto de Materiales de Madrid, C.S.I.C., Cantoblanco, 28049 Madrid (Spain)

2004-02-01

We have used a kinetic model to investigate the influence of changing the pressure (0.1-0.8 Torr) and power (100-300 W) on the non-equilibrium plasma chemistry of RF (13.56 MHz) produced C{sub 2}H{sub 2} (1%)/H{sub 2}/Ar plasmas of interest for the synthesis of nanodiamond thin films. We found that the concentrations of the species C{sub 2}(X{sup 1}SIGMA{sup +}{sub g}), C{sub 2}(a{sup 3}PI{sub u}) and C{sub 2}H are not sensitive to variations in the power but they exhibit a significant increase when the pressure decreases at high argon content in the plasma. In addition, the concentrations of C{sub 2}H{sub 2}, CH{sub 4} and CH{sub 3} exhibit a slight (case of C{sub 2}H{sub 2}) or negligible (case of CH{sub 3} and CH{sub 4}) power-dependence although they decrease (case of C{sub 2}H{sub 2} and CH{sub 4}) or remain almost constant (case of CH{sub 3}) as the pressure decreases. A reasonable agreement is found when comparing the model predictions with available experimental results. These findings provide a basic understanding of the plasma chemistry of hydrocarbon/Ar-rich plasma environments and, at the same time, can be of interest to optimize the processing conditions of nanodiamond films from medium pressure RF hydrocarbon/Ar-rich plasmas.

Investigation into complexing in Re/sup 7/-H/sub 3/O/sup +/-SO/sub 4//sup 2 -/-H/sub 2/O system

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Sinyakova, G S [AN Latvijskoj SSR, Riga. Inst. Neorganicheskoj Khimii

1979-10-01

Using the methods of spectrophotometry and conductometry it is shown, that in the ReO/sub 4//sup -/-H/sub 3/O/sup +/-SO/sub 4//sup 2 -/-H/sub 2/O system interaction between rhenium (7) and sulfuric acid takes place in a wide concentration range. In low-acid solutions at pH 2.0-0.9 rhenium(7) complex with proton is formed at the ratio of 1:1 with lgK/sub 1/=3.30+-0.02. In 1-10 mol. sulfuric acid observed is consecutive complexing at the rhenium(7) - sulfuric acid ratio in the complex of 1:1 and 1:2 respectively with lgK/sub 2/=0.93+-0.13 and lgK/sub 3/=0.34+-0.03. At the background of concentrated perchloric acid rhenium (7) and sodium sulfate form two complex compounds at rhenium (7) - sodium sulfate ratio of 1:1 and 1:2 with lgK/sub 1/=1.86+-0.02 and lgK/sub 2/=2.35+-0.03.

ON THE FORMATION AND ISOMER SPECIFIC DETECTION OF PROPENAL (C{sub 2}H{sub 3}CHO) AND CYCLOPROPANONE (c-C{sub 3}H{sub 4}O) IN INTERSTELLAR MODEL ICES—A COMBINED FTIR AND REFLECTRON TIME-OF-FLIGHT MASS SPECTROSCOPIC STUDY

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Abplanalp, Matthew J.; Borsuk, Aleca; Jones, Brant M.; Kaiser, Ralf I., E-mail: ralfk@hawaii.edu [W. M. Keck Research Laboratory in Astrochemistry, University of Hawaii at Manoa, Honolulu, Hawaii, HI, 96822 (United States)

2015-11-20

The formation routes of two structural isomers—propenal (C{sub 2}H{sub 3}CHO) and cyclopropanone (c-C{sub 3}H{sub 4}O)—were investigated experimentally by exposing ices of astrophysical interest to energetic electrons at 5.5 K thus mimicking the interaction of ionizing radiation with interstellar ices in cold molecular clouds. The radiation-induced processing of these ices was monitored online and in situ via Fourier Transform Infrared spectroscopy and via temperature programmed desorption exploiting highly sensitive reflectron time-of-flight mass spectrometry coupled with single photon ionization in the post irradiation phase. To selectively probe which isomer(s) is/are formed, the photoionization experiments were conducted with 10.49 and 9.60 eV photons. Our studies provided compelling evidence on the formation of both isomers—propenal (C{sub 2}H{sub 3}CHO) and cyclopropanone (c-C{sub 3}H{sub 4}O)—in ethylene (C{sub 2}H{sub 4})—carbon monoxide (CO) ices forming propenal and cyclopropanone at a ratio of (4.5 ± 0.9):1. Based on the extracted reaction pathways, the cyclopropanone molecule can be classified as a tracer of a low temperature non-equilibrium chemistry within interstellar ices involving most likely excited triplet states, whereas propenal can be formed at ultralow temperatures, but also during the annealing phase via non-equilibrium as well as thermal chemistry (radical recombination). Since propenal has been detected in the interstellar medium and our laboratory experiments demonstrate that both isomers originated from identical precursor molecules our study predicts that the hitherto elusive second isomer—cyclopropanone—should also be observable toward those astronomical sources such as Sgr B2(N) in which propenal has been detected.

Hydrothermal synthesis and crystal structures of Na{sub 2}Be{sub 3}(SeO{sub 3}){sub 4}.H{sub 2}O and Cs{sub 2}[Mg(H{sub 2}O){sub 6}]{sub 3}(SeO{sub 3}){sub 4}

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Shen, Chen; Mei, Dajiang; Sun, Chuanling; Liu, Yunsheng; Wu, Yuandong [College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science (China)

2017-09-04

The selenites, Na{sub 2}Be{sub 3}(SeO{sub 3}){sub 4}.H{sub 2}O and Cs{sub 2}[Mg(H{sub 2}O){sub 6}]{sub 3}(SeO{sub 3}){sub 4}, were synthesized under hydrothermal conditions. The crystal structures of Na{sub 2}Be{sub 3}(SeO{sub 3}){sub 4}.H{sub 2}O and Cs{sub 2}[Mg(H{sub 2}O){sub 6}]{sub 3}(SeO{sub 3}){sub 4} were determined by single-crystal X-ray diffractions. Na{sub 2}Be{sub 3}(SeO{sub 3}){sub 4}.H{sub 2}O crystallizes in the triclinic space group P1 (no. 2) with unit cell parameters a = 4.8493(9), b = 12.013(2), c = 12.077(2) Aa, and Z = 2, whereas Cs{sub 2}[Mg(H{sub 2}O){sub 6}]{sub 3}(SeO{sub 3}){sub 4} crystallizes in the monoclinic space group C2/m (no. 12) with lattice cell parameters a = 12.596(6), b = 7.297(4), c = 16.914(8) Aa, and Z = 2. Na{sub 2}Be{sub 3}(SeO{sub 3}){sub 4}.H{sub 2}O features a three-dimensional open framework structure formed by BeO{sub 4} tetrahedra and SeO{sub 3} trigonal pyramids. Na cations and H{sub 2}O molecules are located in different tunnels. Cs{sub 2}[Mg(H{sub 2}O){sub 6}]{sub 3}(SeO{sub 3}){sub 4} has a structure composed of isolated [Mg(H{sub 2}O){sub 6}] octahedra and SeO{sub 3} trigonal pyramids interacted by hydrogen bonds, and Cs cations are resided in-between. Both compounds were characterized by thermogravimetric analysis and FT-IR spectroscopy. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Reaction of pyridine-N-oxides with halogens; Vzaimodejstvie piridin-N-oksidov s galogenami

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Kanibolotskij, A L; Mikhzajlov, V A; Savelova, V A [AN Ukrainskoj SSR, Donetsk (Ukraine). Inst. Fiziko-Organicheskoj Khimii i Uglekhimii

1994-12-31

By the methods of conductometry, NMR and IR spectroscopy it has been ascertained that interaction of pyridine-N-oxides with bromine, iodine and interhalides (ICl and IBr) gives rise to the formation of crystal complexes of 1:1 composition. The complexes mentioned are of presumably ionic structure: [RC{sub 5}H{sub 4}N-O...X...O-NC{sub 5}H{sub 4}R]{sup +}[Y-X-Y]{sup -},where X,Y = Cl,Br,I.

The first study of antiferromagnetic eosphorite-childrenite series (Mn{sub 1−x}Fe{sub x})AlP(OH){sub 2}H{sub 2}O (x=0.5)

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Behal, D. [Sektion Kristallographie, Department für Geo- und Umweltwissenschaften, Ludwig-Maximilians-Universität München (LMU), Theresienstrasse 41, D-80333 Munich (Germany); Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universität München (TUM), Lichtenbergstrasse 1, D-85748 Garching (Germany); Röska, B. [Sektion Kristallographie, Department für Geo- und Umweltwissenschaften, Ludwig-Maximilians-Universität München (LMU), Theresienstrasse 41, D-80333 Munich (Germany); Park, S.-H., E-mail: sohyun.park@lmu.de [Sektion Kristallographie, Department für Geo- und Umweltwissenschaften, Ludwig-Maximilians-Universität München (LMU), Theresienstrasse 41, D-80333 Munich (Germany); Pedersen, B. [Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universität München (TUM), Lichtenbergstrasse 1, D-85748 Garching (Germany); Benka, G.; Pfleiderer, Ch. [Chair E21, Physik-Department, Technische Universität München (TUM), James-Franck-Strasse 1, D-85748 Garching (Germany); Wakabayashi, Y.; Kimura, T. [Division of Materials Physics, Graduate School of Engineering Science, Osaka University, Toyonaka 560-8531 (Japan)

2017-04-15

This study presents for the first time the antiferromagnetic structure of the eosphorite-childrenite series (Mn{sub 1-x}Fe{sub x})AlPO{sub 4}(OH){sub 2}H{sub 2}O (x=0.5), based on neutron single crystal diffraction at 3 K in combination with group theoretical representation analysis. The new magnetic structure is described in the magnetic space group P{sub C}mnb, maintaining the atomistic unit cell size (a×b×c) with a ~6.9 Å, b ~10.4 Å, c ~13.4 Å. Mn-rich and Fe-rich zones within solid solution crystals are expanded up to several hundred micrometers, as seen in electron microprobe and polarisation microscopy. Magnetic susceptibility and specific heat measurements on two different eosphorite-childrenite crystals show the magnetic transition temperature between 6.5 K and 6.8 K as the Mn{sup 2+}/Fe{sup 2+} ratio varies over single compositional zones. Below the Néel temperature, a magnetic field between 1.5 T and 2 T parallel to the a-axis causes a 180° spin-flip, reaching the saturation (5.25 μ{sub B} pfu) toward high magnetic fields. - Highlights: • New magnetic structure of (Mn{sub 1-x}Fe{sub x})AlPO{sub 4}(OH){sub 2}H{sub 2}O (x=0.5). • Magnetic phase transition at 6.5–6.6 K. • Magnetic interaction anisotropy in (Mn{sub 0.5}Fe{sub 0.5})AlPO{sub 4}(OH){sub 2}H{sub 2}O. • Compositional zones in the eosphorite-childrenite series.

Variable temperature ion trap studies of CH{sub 4}{sup +} + H{sub 2}, HD and D{sub 2}: negative temperature dependence and significant isotope effect

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Asvany, O.; Savic, I.; Schlemmer, S.; Gerlich, D

2004-03-08

Reactions of methane cations, CH{sub 4}{sup +}, with H{sub 2}, HD and D{sub 2} have been studied in a variable temperature 22-pole ion trap from room temperature down to 15 K. The formation of CH{sub 5}{sup +} in collisions with H{sub 2} is slow at 300 K, but it becomes faster by at least one order of magnitude when the temperature is lowered to 15 K. This behavior is tentatively explained with a longer complex lifetime at low temperatures. However, since tunneling is most probably not responsible for product formation, other dynamical or statistical restrictions must be responsible for the negative temperature dependence. In collisions of CH{sub 4}{sup +} with HD, the CH{sub 5}{sup +} product ion (68% at 15 K) prevails over CH{sub 4}D{sup +} (32%). Reaction of CH{sub 4}{sup +} with D{sub 2} is found to be much slower than with H{sub 2} or HD. The rate coefficient for converting CH{sub 4}{sup +} into CH{sub 3}D{sup +} by H-D exchange has been determined to be smaller than 10{sup -12} cm{sup 3}/s, indicating that scrambling in the CH{sub 6}{sup +} complex is very unlikely.

Solid-state thermal decomposition of the [Co(NH{sub 3}){sub 5}CO{sub 3}]NO{sub 3}{center_dot}0.5H{sub 2}O complex: A simple, rapid and low-temperature synthetic route to Co{sub 3}O{sub 4} nanoparticles

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Farhadi, Saeid, E-mail: sfarhad2001@yahoo.com [Department of Chemistry, Lorestan University, Khorramabad 68135-465 (Iran, Islamic Republic of); Safabakhsh, Jalil [Department of Chemistry, Lorestan University, Khorramabad 68135-465 (Iran, Islamic Republic of)

2012-02-25

Highlights: Black-Right-Pointing-Pointer [Co(NH{sub 3}){sub 5}CO{sub 3}]NO{sub 3}{center_dot}0.5H{sub 2}O complex was used for preparing pure Co{sub 3}O{sub 4} nanoparticles. Black-Right-Pointing-Pointer Co{sub 3}O{sub 4} nanoparticles were prepared at low temperature of 175 Degree-Sign C. Black-Right-Pointing-Pointer Co{sub 3}O{sub 4} nanoparticles show a weak ferromagnetic behaviour at room temperature. Black-Right-Pointing-Pointer The method is simple, low-cost and suitable for the production of Co{sub 3}O{sub 4}. - Abstract: Co{sub 3}O{sub 4} nanoparticles were easily prepared via the decomposition of the pentammine(carbonato)cobalt(III) nitrate precursor complex [Co(NH{sub 3}){sub 5}CO{sub 3}]NO{sub 3}{center_dot}0.5H{sub 2}O at low temperature (175 Degree-Sign C). The product was characterized by thermal analysis, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), UV-visible spectroscopy, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, Brunauer-Emmett-Teller (BET) specific surface area measurements and magnetic measurements. The FT-IR, XRD, Raman and EDX results indicated that the synthesized Co{sub 3}O{sub 4} nanoparticles are highly pure and have a single phase. The TEM analysis revealed nearly uniform and quasi-spherical Co{sub 3}O{sub 4} nanoparticles with an average particle size of approximately 10 nm. The optical absorption spectrum of the Co{sub 3}O{sub 4} nanoparticles showed two direct band gaps of 2.18 and 3.52 eV with a red shift in comparison with previous reported values. The prepared Co{sub 3}O{sub 4} nanoparticles showed a weak ferromagnetic behaviour that could be attributed to uncompensated surface spins and/or finite-size effects. Using the present method, Co{sub 3}O{sub 4} nanoparticles can be produced without expensive organic solvents and complicated equipment. This simple, rapid, safe and low-cost synthetic route can be extended to the synthesis of other

Detonation study of two stoichiometric mixtures (CH{sub 4}/H{sub 2}/O{sub 2}/N{sub 2} and CH{sub 4}/C{sub 2}H{sub 6}/O{sub 2}/N{sub 2}). Influence of the relative proportion of both fuels and of the initially high temperature; Etude de la detonation de deux melanges stoechiometriques (CH{sub 4}/H{sub 2}/O{sub 2}/N{sub 2} et CH{sub 4}/C{sub 2}H{sub 6}/O{sub 2}/N{sub 2}). Influence de la proportion relative des deux combustibles et de la temperature initiale elevee

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Matignon, Ch.

2000-12-15

Detonations of gaseous reactive mixtures made of two fuels of very different detonability xH{sub 2}+(1-x)CH{sub 4} and xC{sub 2}H{sub 6}+(1-x)CH{sub 4} in stoichiometric proportion with oxygen and diluted with nitrogen (in proportions varying from pure oxygen to the air) are investigated. The parameters of the study are the relative proportion x of fuels, nitrogen dilution B = O{sub 2}/N{sub 2} and the initial conditions of temperature and pressure. This study takes place within the general context of the chemical process safety improvement. Detonability was evaluated by the comparison between the characteristic cell size measurement of the three-dimensional structure of the autonomous and stationary detonation front with the chemical induction length calculated on the assumptions of the ZND model by means of several detailed chemical kinetics mechanisms. The results obtained for the mixtures with single fuel show that the detonability of methane decreases according to the initial temperature whatever the dilution B, and that the one of ethane and hydrogen decreases with B = 0 but increases with B = 3,76 (air) (the inversion of behaviour occurs for B = 2 for ethane, and B=1 for hydrogen). The results obtained for the mixtures with two fuels show that their detonability is each time influenced by the heaviest fuel, i.e. that the detonability of H{sub 2}/CH{sub 4} mixtures is rather controlled by CH{sub 4} whereas the one of C{sub 2}H{sub 6}/CH{sub 4} mixtures is rather controlled by C{sub 2}H{sub 6}. With pure oxygen (B = 0), these mixtures are desensitized by the increase of the initial temperature. Beyond a certain value x, an inversion of detonability according to x is observed. (author)

The crystal structure of Cs{sub 2}S{sub 2}O{sub 3}.H{sub 2}O

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Winkler, Verena; Schlosser, Marc; Pfitzner, Arno [Regensburg Univ. (Germany). Inst. fuer Anorganische Chemie

2016-08-01

A reinvestigation of the alkali metal thiosulfates has led to the new phase Cs{sub 2}S{sub 2}O{sub 3}.H{sub 2}O. At first cesium thiosulfate monohydrate was obtained as a byproduct of the synthesis of Cs{sub 4}In{sub 2}S{sub 5}. Further investigations were carried out using the traditional synthesis reported by J. Meyer and H. Eggeling. Cs{sub 2}S{sub 2}O{sub 3}.H{sub 2}O crystallizes in transparent, colorless needles. The crystal structure of the title compound was determined by single crystal X-ray diffraction at room temperature: space group C2/m (No. 12), unit cell dimensions: a = 11.229(4), b = 5.851(2), c = 11.260(5) Aa, β = 95.89(2) , with Z = 4 and a cell volume of V = 735.9(5) Aa{sup 3}. The positions of all atoms including the hydrogen atoms were located in the structure refinement. Cs{sub 2}S{sub 2}O{sub 3}.H{sub 2}O is isotypic with Rb{sub 2}S{sub 2}O{sub 3}.H{sub 2}O. Isolated tetrahedra [S{sub 2}O{sub 3}]{sup 2-} are coordinated by the alkali metal cations, and in addition they serve as acceptors for hydrogen bonding. For both Cs atoms the shortest distances are observed to oxygen atoms of the S{sub 2}O{sub 3}{sup 2-} anions whereas the terminating sulfur atom has its shortest contacts to the water hydrogen atoms. Thus, an extended hydrogen bonding network is formed. The title compound has also been characterized by IR spectroscopy. IR spectroscopy reveals the vibrational bands of the water molecules at 3385 cm{sup -1}. They show a red shift in the OH stretching and bending modes as compared to free water. This is due both to the S..H hydrogen bonding and to the coordination of H{sub 2}O molecules to the cesium atoms.

Synthesis and photocatalytic property for H{sub 2} production of H{sub 1.78}Sr{sub 0.78}Bi{sub 0.22}Nb{sub 2}O{sub 7} nanosheets

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Zhang, Bing [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi, 830011 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Li, Yingxuan, E-mail: yxli@ms.xjb.ac.cn [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi, 830011 (China); Luo, Jianmin [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi, 830011 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Xinjiang Uygur Autonomous Region Academy of Instrument Analysis, Urumqi, 830011 (China); Zhao, He [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi, 830011 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Zhao, Jie; Dong, Guohui; Zhu, Yunqing [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi, 830011 (China); Wang, Chuanyi, E-mail: cywang@ms.xjb.ac.cn [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi, 830011 (China)

2017-01-01

Highlights: • Ultrathin HSN Ns were first synthesized based on molten salt synthesis method. • HSN Ns Exhibit 5.5 times higher activity than that of the HSN Ps. • The enhanced photocatalytic activity of HSN Ns is due to the reduction in thickness. - Abstract: The SrBi{sub 2}Nb{sub 2}O{sub 9} platelets with a thickness of about 600 nm were synthesized by molten salt synthesis method. The treatment of the SrBi{sub 2}Nb{sub 2}O{sub 9} platelets with hydrochloric acid resulted in the formation of the protonated H{sub 1.78}Sr{sub 0.78}Bi{sub 0.22}Nb{sub 2}O{sub 7} platelets. Through a top–down approach in ethylamine solution, the H{sub 1.78}Sr{sub 0.78}Bi{sub 0.22}Nb{sub 2}O{sub 7} platelets were exfoliated into H{sub 1.78}Sr{sub 0.78}Bi{sub 0.22}Nb{sub 2}O{sub 7} nanosheets with a thickness of about 2.6 nm. The evolution of the structure, composition, morphology, optical, and photocatalytic properties of SrBi{sub 2}Nb{sub 2}O{sub 9} platelets was studied as it is converted into H{sub 1.78}Sr{sub 0.78}Bi{sub 0.22}Nb{sub 2}O{sub 7} platelets and subsequently exfoliated into H{sub 1.78}Sr{sub 0.78}Bi{sub 0.22}Nb{sub 2}O{sub 7} nanosheets. The absorption edge shifts to a lower wavelength accompanied by the protonation and exfoliation. The photocatalytic H{sub 2} evolution of the three samples were evaluated under the irradiation of a 300 W Xenon lamp from CH{sub 3}OH/H{sub 2}O solution, indicating that H{sub 1.78}Sr{sub 0.78}Bi{sub 0.22}Nb{sub 2}O{sub 7} nanosheets Exhibit 5.5 and 26.2 times higher activity than that of the H{sub 1.78}Sr{sub 0.78}Bi{sub 0.22}Nb{sub 2}O{sub 7} and SrBi{sub 2}Nb{sub 2}O{sub 9} platelets, respectively. The enhanced activity for the H{sub 1.78}Sr{sub 0.78}Bi{sub 0.22}Nb{sub 2}O{sub 7} nanosheets is mainly attributed to the higher separation efficiency of the photogenerated carriers and the larger specific surface area caused by the significant reduction in thickness.

Selective photocatalytic reduction of CO{sub 2} by H{sub 2}O/H{sub 2} to CH{sub 4} and CH{sub 3}OH over Cu-promoted In{sub 2}O{sub 3}/TiO{sub 2} nanocatalyst

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Tahir, Muhammad, E-mail: mtahir@cheme.utm.my [Chemical Reaction Engineering Group (CREG), Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310, UTM, Johor Bahru, Johor (Malaysia); Department of Chemical Engineering, COMSATS Institute of Information Technology, Lahore, Punjab (Pakistan); Tahir, Beenish; Saidina Amin, Nor Aishah; Alias, Hajar [Chemical Reaction Engineering Group (CREG), Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310, UTM, Johor Bahru, Johor (Malaysia)

2016-12-15

Highlights: • Cu-promoted In{sub 2}O{sub 3}/TiO{sub 2} nanocatalysts tested for CO{sub 2} photoreduction with H{sub 2}O/H{sub 2}. • Production of CH{sub 4} and CH{sub 3}OH depends on reductants type and metal-loading to TiO{sub 2}. • CH{sub 4} production over Cu-In/TiO{sub 2} was 1.5 fold more than In/TiO{sub 2} and 5 times the TiO{sub 2}. • The Cu-promoted CH{sub 3}OH production while In gave more CH{sub 4} with water vapors. • The H{sub 2} reductant gave negative effect for CH{sub 4} but enhanced CH{sub 3}OH production. - Abstract: Photocatalytic CO{sub 2} reduction by H{sub 2}O and/or H{sub 2} reductant to selective fuels over Cu-promoted In{sub 2}O{sub 3}/TiO{sub 2} photocatalyst has been investigated. The samples, prepared via a simple and direct sol-gel method, were characterized by XRD, SEM, TEM, XPS, N{sub 2} adsorption-desorption, UV–vis diffuse reflectance, Raman and PL spectroscopy. Cu and In loaded into TiO{sub 2}, oxidized as Cu{sup 2+} and In{sup 3+}, promoted efficient separation of photo-generated electron/hole pairs (e{sup −}/h{sup +}). The results indicate that the reduction rate of CO{sub 2} by H{sub 2}O to CH{sub 4} approached to 181 μmol g{sup −1} h{sup −1} using 0.5% Cu-3% In{sub 2}O{sub 3}/TiO{sub 2} catalyst, a 1.53 fold higher than the production rate over the 3% In{sub 2}O{sub 3}/TiO{sub 2} and 5 times the amount produced over the pure TiO{sub 2}. In addition, Cu was found to promote efficient production of CH{sub 3}OH and yield rate reached to 68 μmol g{sup −1} h{sup −1} over 1% Cu-3% In{sub 2}O{sub 3}/TiO{sub 2} catalyst. This improvement was attributed to charge transfer property and suppressed recombination rate by Cu-metal. More importantly, H{sub 2} reductant was less favorable for CH{sub 4} production, yet a significant amount of CH{sub 4} and CH{sub 3}OH were obtained using a mixture of H{sub 2}O/H{sub 2} reductant. Therefore, Cu-loaded In{sub 2}O{sub 3}/TiO{sub 2} catalyst has shown to be capable for

Tunneling in the CH{sub 3} + H{sub 2} {yields} CH{sub 4} + H reaction and its isotopic analog: an anomalous isotope effect

Energy Technology Data Exchange (ETDEWEB)

Kurosaki, Yuzuru; Takayanagi, Toshiyuki [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

1998-10-01

Vibrationally adiabatic ground-state potential curves for the CH{sub 3} + H{sub 2} {yields} CH{sub 4} + H (I) and CD{sub 3} + H{sub 2} {yields} CD{sub 4}H + H (II) reactions were obtained by adding zero-point energies of harmonic vibrations orthogonal to intrinsic reaction coordinate (IRC) to bare potential curves along IRC. It was clarified that both the barrier height and barrier width of reaction II are smaller than those of reaction I. This computational result qualitatively explains the experimental observation of Momose et al. (J. Chem. Phys. 108 (1998) 7334) that reaction II occurs but reaction I does not occur in solid parahydrogen at 5 K. (author)

An experimental investigation of H{sub 2} emissions of a 2004 heavy-duty diesel engine supplemented with H{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Gatts, T.; Li, H.; Liew, C.; Liu, S.; Spencer, T.; Wayne, S.; Clark, N. [Department of Mechanical and Aerospace Engineering, West Virginia University, P.O. Box 6106, Morgantown, WV 26506 (United States)

2010-10-15

Hydrogen (H{sub 2}) emissions characteristics of H{sub 2}-diesel dual fuel engine were measured using a 2004 turbocharged heavy-duty diesel engine with H{sub 2} supplemented into the intake air. The emissions of H{sub 2} were measured using an Electron Pulse Ionization (EPI) Mass Spectrometer (MS). The effect of the amount of H{sub 2} added, the engine load, and diesel fuel flow rates on the emissions of H{sub 2} and its combustion efficiency in the engine were investigated. The addition of H{sub 2} under high load operation was notable for its ability to obtain high H{sub 2} combustion efficiency and improve brake thermal efficiency. However, the addition of H{sub 2} at low load resulted in high emissions of H{sub 2} due to the failure to initiate and support a sufficiently vigorous flame for the complete combustion of H{sub 2} present outside the diesel spray plume. The maximum H{sub 2} emissions of 1.4% (volume in dry exhaust gas) were observed with the addition of 6% H{sub 2} at 10% load. In comparison, the maximum H{sub 2} emissions of 0.13% were observed when operated at 70% load with the addition of 6% H{sub 2}. The slip of a large percentage of H{sub 2} at low load operation was shown to deteriorate the potential of H{sub 2} in improving the brake thermal efficiency. (author)

Sensors based on mesoporous SnO{sub 2}-CuWO{sub 4} with high selective sensitivity to H{sub 2}S at low operating temperature

Energy Technology Data Exchange (ETDEWEB)

Stanoiu, Adelina; Simion, Cristian E. [National Institute of Materials Physics, Atomistilor 405A, P.O. Box MG-7, 077125 Bucharest, Măgurele (Romania); Calderon-Moreno, Jose Maria; Osiceanu, Petre [“Ilie Murgulescu” Institute of Physical Chemistry, Romanian Academy, Surface Chemistry and Catalysis Laboratory, Spl. Independentei 202, 060021, Bucharest (Romania); Florea, Mihaela [University of Bucharest, Faculty of Chemistry, Department of Organic Chemistry, Biochemistry and Catalysis, B-dul Regina Elisabeta 4-12, Bucharest (Romania); National Institute of Materials Physics, Atomistilor 405A, P.O. Box MG-7, 077125 Bucharest, Măgurele (Romania); Teodorescu, Valentin S. [National Institute of Materials Physics, Atomistilor 405A, P.O. Box MG-7, 077125 Bucharest, Măgurele (Romania); Somacescu, Simona, E-mail: somacescu.simona@gmail.com [“Ilie Murgulescu” Institute of Physical Chemistry, Romanian Academy, Surface Chemistry and Catalysis Laboratory, Spl. Independentei 202, 060021, Bucharest (Romania)

2017-06-05

Highlights: • Mesoporous SnO{sub 2}-CuWO{sub 4} obtained by an inexpensive synthesis route. • Powders characterization performed by a variety of complementary techniques. • SnO{sub 2}-CuWO{sub 4} layers with high selective sensitivity to H{sub 2}S. • Low operating temperature and relative humidity influences. - Abstract: Development of new sensitive materials by different synthesis routes in order to emphasize the sensing properties for hazardous H{sub 2}S detection is one of a nowadays challenge in the field of gas sensors. In this study we obtained mesoporous SnO{sub 2}-CuWO{sub 4} with selective sensitivity to H{sub 2}S by an inexpensive synthesis route with low environmental pollution level, using tripropylamine (TPA) as template and polyvinylpyrrolidone (PVP) as dispersant/stabilizer. In order to bring insights about the intrinsic properties, the powders were characterized by means of a variety of complementary techniques such as: X-Ray Diffraction, XRD; Transmission Electron Microscopy, TEM; High Resolution TEM, HRTEM; Raman Spectroscopy, RS; Porosity Analysis by N{sub 2} adsorption/desorption, BET; Scanning Electron Microscopy, SEM and X-ray Photoelectron Spectroscopy, XPS. The sensors were fabricated by powders deposition via screen-printing technique onto planar commercial Al{sub 2}O{sub 3} substrates. The sensor signals towards H{sub 2}S exposure at low operating temperature (100 °C) reaches values from 10{sup 5} (for SnWCu600) to 10{sup 6} (for SnWCu800) over the full range of concentrations (5–30 ppm). The recovery processes were induced by a short temperature trigger of 500 °C. The selective sensitivity was underlined with respect to the H{sub 2}S, relative to other potential pollutants and relative humidity (10–70% RH).

Hydrates of the alkali trioxidomonosulfidomolybdates and -tungstates. K{sub 2}[(Mo/W)O{sub 3}S] . 1.5 H{sub 2}O and (Rb/Cs){sub 2}[(Mo/W)O{sub 3}S] . H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Lehner, Anna J.; Braitsch, Milan; Roehr, Caroline [Freiburg Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

2012-11-01

The trioxidomonosulfidomolybdate and -tungstate anions [(Mo/W)O{sub 3}S]{sup 2-} are the first products formed when passing H{sub 2}S gas through a solution of the oxidometalates. Their potassium, rubidium and cesium salt hydrates form as crystalline precipitates from these solutions depending on pH, the polarity of the solvent, educt concentrations and temperature. The structures of the sesqui- (K) and mono- (Rb, Cs) hydrates have been determined by means of X-ray single crystal diffraction data. The potassium sesquihydrates K{sub 2}[(Mo/W)O{sub 3}S] . 1.5 H{sub 2}O are isotypic and crystallize with a new structure type (monoclinic, space group C2/c, M = Mo/W: a = 987.0(2)/993.13(11), b = 831.75(14)/831.10(11), c = 1868.9(4)/1865.2(2) pm, {beta} = 99.34(2)/99.153(8) , R1 = 0.0352/0.0390). In the crystal structure the [(Mo/W)O{sub 3}S]{sup 2-} anions are connected via hydrogen bonds to form columns along the c direction. Channels containing only water molecules run along the [101] direction. The dehydration process proceeds in a topotactic reaction between 60 to 95 C and yields crystals of the anhydrous salts K{sub 2}[(Mo/W)O{sub 3}S]. The two different K+ cations exhibit a 5 + 3 and 5 + 2 O/S coordination. The heavier alkali metal cations form the four monohydrates (Rb/Cs){sub 2}[(Mo/W)O{sub 3}S] . H{sub 2}O (trigonal rhombohedral, space group R anti 3m) with lattice parameters for the Rb/Cs molybdates of a = 621.17(6)/624.62(10), c = 3377.9(4)/3388.6(8) pm (R1 = 0.0505/0.0734) and the tungstates of a = 642.80(3)/643.3(4), c = 3532.8(3)/3566(4) pm (R1 = 0.0348/0.0660). In the structures the 3m symmetrical tetrahedra are arranged to form double layers in such a way, that the O{sub 3} bases of the tetrahedra are pointing towards each other in a staggered conformation. These double layers are stacked in the c direction in a rhombohedral sequence. In these hydrates, there are no distinct hydrogen bonds. Instead, partially disordered pairs of H{sub 2}O molecules are

Synthesis and properties of compounds (Ln(NO/sub 3/)/sub 2/(OP(N(CH/sub 3/)/sub 2/)/sub 3/)/sub 4/)B(C/sub 6/H/sub 5/)/sub 4/ (Ln=Y,La, Ce-Lu)

Energy Technology Data Exchange (ETDEWEB)

Skopenko, V V; Zub, Yu L; Matishinets, I M [Kievskij Gosudarstvennyj Univ. (Ukrainian SSR)

1984-01-01

From acetone solutions with the yield 75-80% compounds of the composition (Ln(NO/sub 3/)/sub 2/(OP(Nx(CN/sub 3/)/sub 2/)/sub 3/))B(C/sub 6/H/sub 5/)/sub 4/ (Ln=Y, La, Ce-Lu) have been separated. Comparing diffractograms the existence of two isostructural series with morphotropic transition at the Nd/Sm boundary has been established. Using the data of conductometry and IR spectroscopy it has been shown that the cation coordination number of the central atom is eight: four O atoms from two bidentate-cyclic nitrate groups and four O atoms from four monodentate phosphineoxide ligands. Measurement of electric conductivity of the substances separated in nitromethane has shown that the value lambdasub(M) varies inconsiderably from the value 48 Ohm/sup -1/xcm/sup 2/xmol/sup -1/.

Comparison of the reactivities of H{sub 3}PW{sub 12}O{sub 40} and H{sub 4}SiW{sub 12}O{sub 40} and their K{sup +}, NH{sub 4}{sup +} and Cs{sup +} salts in liquid phase isobutane/butene alkylation

Energy Technology Data Exchange (ETDEWEB)

Essayem, N.; Kieger, S.; Coudurier, G. [Institut de Recherches sur la Catalyse, Villeurbanne (France)] [and others

1996-12-31

Aliphatic alkylation presents a great interest in petroleum refinery processes. Classic acid solid catalysts exhibit rapid deactivation. The aim of this work was to study different salts with varying compositions. Activity in n-butane isomerization reaction of various alkaline salts of H{sub 3}PW{sub 12}O{sub 40} and H{sub 4}SiW{sub l2}O{sub 40} was shown to be strongly dependent on the strength and number of accessible protons whereas the stability with time on stream was correlated to the presence of mesoporosity. For the liquid iC{sub 4}/C{sub 4}{sup =} continuous alkylation reaction, the strength and the number of acid sites appeared less important than the existence of mesoporosity indicating that the diffusion of the reactants and of the products plays an important role in this reaction.

Density-functional theory study of the pressure-induced phase transition in hydronitrogen compound N{sub 4}H{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Liu, Qi-Jun, E-mail: qijunliu@home.swjtu.edu.cn [Bond and Band Engineering Group, Sichuan Provincial Key Laboratory (for Universities) of High Pressure Science and Technology, School of Physical Science and Technology, Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Zhang, Ning-Chao; Sun, Yan-Yun; Zhang, Ming-Jian; Liu, Fu-Sheng [Bond and Band Engineering Group, Sichuan Provincial Key Laboratory (for Universities) of High Pressure Science and Technology, School of Physical Science and Technology, Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Liu, Zheng-Tang [State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi' an, Shaanxi 710072 (China)

2014-03-01

Using first-principles density-functional theory, we have investigated the pressure-induced phase transition in hydronitrogen compound N{sub 4}H{sub 4} and discussed the potential tetragonal structure. We find that tetragonal structure with P4{sub 2}/n space group is mechanically stable and ductile. The thermodynamic stability of Pmna>P1{sup ¯}>P4{sub 2}/n>P2{sub 1}/m has been obtained. With increasing pressure, the phase transition pressures of T{sub Pmna→P4{sub 2/n}}, T{sub P4{sub 2/n→Pmna}}, T{sub Pmna→P1{sup ¯}} and T{sub P1{sup ¯}→P2{sub 1/m}} are 5.6, 15.0, 30.0 and 69.2 GPa, respectively, which are in agreement with the available data. Moreover, the mechanical stability of four structures under pressure has been analyzed.

Hydrothermal synthesis and characterization of the praseodymium borate-nitrate Pr[B{sub 5}O{sub 8}(OH)(H{sub 2}O){sub 0.87}]NO{sub 3}.2H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Ortner, Teresa S.; Huppertz, Hubert [Innsbruck Univ. (Austria). Inst. fuer Allgemeine, Anorganische und Theoretische Chemie

2017-10-01

The praseodymium borate-nitrate Pr[B{sub 5}O{sub 8}(OH)(H{sub 2}O){sub 0.87}]NO{sub 3}.2H{sub 2}O was obtained in a hydrothermal synthesis. It crystallizes monoclinically in the space group P2{sub 1}/n (no. 14) with four formula units (Z=4) and unit cell parameters of a=641.9(3), b=1551.8(7), c=1068.4(5) pm, with β=90.54(2) yielding V=1.0643(8) nm{sup 3}. The defect variant constitutes the missing member in the series of isostructural, early rare earth borate-nitrates of the composition RE[B{sub 5}O{sub 8}(OH)(H{sub 2}O){sub x}]NO{sub 3}.2H{sub 2}O [RE=La (x=0; 1), Ce (x=1), Nd (x=0.85), Sm (x=0)]. In addition to powder and single-crystal X-ray diffraction data, the novel borate-nitrate was characterized through IR and Raman spectroscopy.

A novel iron-containing polyoxometalate heterogeneous photocatalyst for efficient 4-chlorophennol degradation by H{sub 2}O{sub 2} at neutral pH

Energy Technology Data Exchange (ETDEWEB)

Zhai, Qian; Zhang, Lizhong [Department of Chemistry and Applied Chemistry, Changji University, Changji 831100 (China); Zhao, Xiufeng, E-mail: zhaoxiufeng19670@126.com [Department of Chemistry and Applied Chemistry, Changji University, Changji 831100 (China); Chen, Han; Yin, Dongju [Department of Chemistry and Applied Chemistry, Changji University, Changji 831100 (China); Li, Jianhui [Department of Chemistry and Applied Chemistry, Changji University, Changji 831100 (China); National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)

2016-07-30

Graphical abstract: An iron-containing polyoxometalate (Fe{sup III}LysSiW) catalyst showes good performance in the degradation of 4-chlorophenol by H{sub 2}O{sub 2}, especially in irradiated system. The catalytic activity of Fe{sup III}LysSiW stems from synergetic effect of ferric iron for Fenton-like catalysis and SiW{sub 12}O{sub 40}{sup 4−} for photocatalysis, respectively. The chemisorption of H{sub 2}O{sub 2} on Fe{sup III}LysSiW surface by hydrogen bonding also promotes both the Fenton-like and photocatalytic processes. - Highlights: • An iron-containing POM was synthesized as heterogeneous Fenton-like catalyst. • The catalyst has both the Fenton-like and photocatalytic activity at neutral pH. • The activity stems from the co-existence of iron and heteropolyanion in the catalyst. • The hydrogen bonding of H{sub 2}O{sub 2} on the catalyst surface enhances the reaction rate. - Abstract: An iron-containing polyoxometalate (Fe{sup III}LysSiW) was synthesized from ferric chloride (Fe{sup III}), lysine (Lys) and silicotungstic acid (SiW), and characterized using ICP-AES, TG, FT-IR, UV–vis DRS, XRD and SEM. The chemical formula of Fe{sup III}LysSiW was determined as [Fe(H{sub 2}O){sub 5}(C{sub 6}H{sub 14}N{sub 2}O{sub 2})]HSiW{sub 12}O{sub 40}·8H{sub 2}O, with Keggin-structured SiW{sub 12}O{sub 40}{sup 4−} heteropolyanion and lysine moiety. As a heterogeneous catalyst, the as prepared Fe{sup III}LysSiW showed good performance in the degradation of 4-chlorophenol by H{sub 2}O{sub 2} in both the dark and irradiated systems. Under the conditions of 4-chlorophenol 100 mg/L, Fe{sup III}LysSiW 1.0 g/L, H{sub 2}O{sub 2} 20 mmol/L and pH 6.5, 4-chlorophenol could be completely degraded in ca. 40 min in the dark and ca. 15 min upon irradiation. Prolonging the reaction time to 3 h, the TOC removal reached to ca. 71.3% in the dark and ca. 98.8% under irradiation. The catalytic activity of Fe{sup III}LysSiW stems from synergetic effect of ferric iron and SiW{sub

A combined crossed molecular beams and theoretical study of the reaction CN + C{sub 2}H{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Balucani, Nadia, E-mail: nadia.balucani@unipg.it [Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, Perugia (Italy); Leonori, Francesca; Petrucci, Raffaele [Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, Perugia (Italy); Wang, Xingan [Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, Perugia (Italy); Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China); Casavecchia, Piergiorgio [Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, Perugia (Italy); Skouteris, Dimitrios [Scuola Normale Superiore, Pisa (Italy); Albernaz, Alessandra F. [Instituto de Física, Universidade de Brasília, Brasília (Brazil); Gargano, Ricardo [Instituto de Física, Universidade de Brasília, Brasília (Brazil); Departments of Chemistry and Physics, University of Florida, Quantum Theory Project, Gainesville, FL 32611 (United States)

2015-03-01

Highlights: • The CN + C{sub 2}H{sub 4} reaction was investigated in crossed beam experiments. • Electronic structure calculations of the potential energy surface were performed. • RRKM estimates qualitatively reproduce the experimental C{sub 2}H{sub 3}NC yield. - Abstract: The CN + C{sub 2}H{sub 4} reaction has been investigated experimentally, in crossed molecular beam (CMB) experiments at the collision energy of 33.4 kJ/mol, and theoretically, by electronic structure calculations of the relevant potential energy surface and Rice–Ramsperger–Kassel–Marcus (RRKM) estimates of the product branching ratio. Differently from previous CMB experiments at lower collision energies, but similarly to a high energy study, we have some indication that a second reaction channel is open at this collision energy, the characteristics of which are consistent with the channel leading to CH{sub 2}CHNC + H. The RRKM estimates using M06L electronic structure calculations qualitatively support the experimental observation of C{sub 2}H{sub 3}NC formation at this and at the higher collision energy of 42.7 kJ/mol of previous experiments.

Accessing alkali-free NASICON-type compounds through mixed oxoanion sol–gel chemistry: Hydrogen titanium phosphate sulfate, H{sub 1−x}Ti{sub 2}(PO{sub 4}){sub 3−x}(SO{sub 4}){sub x} (x=0.5–1)

Energy Technology Data Exchange (ETDEWEB)

Mieritz, Daniel; Davidowski, Stephen K.; Seo, Dong-Kyun, E-mail: dseo@asu.edu

2016-10-15

We report a direct sol–gel synthesis and characterization of new proton-containing, rhombohedral NASICION-type titanium compounds with mixed phosphate and sulfate oxoanions. The synthetic conditions were established by utilizing peroxide ion as a decomposable and stabilizing ligand for titanyl ions in the presence of phosphates in a strong acidic medium. Thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), induction-coupled plasma optical emission spectroscopic (ICP-OES) elemental analysis, and Raman and {sup 1}H magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopic studies have determined the presence of sulfate and proton ions in the structure, for which the compositional range has been found to be H{sub 1−x}Ti{sub 2}(PO{sub 4}){sub 3−x}(SO{sub 4}){sub x} (x=0.5–1). The particulate products exhibit a nanocrystalline nature observed through characterization with scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The N{sub 2} sorption isotherm measurements and subsequent Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH) analyses confirmed the presence of the textural meso- and macropores in the materials. Future studies would determine the potential of the new compounds in various applications as battery materials, proton conductors and solid acid catalysts. - Graphical abstract: A series of proton-containing NASICON-type compounds, H{sub 1−x}Ti{sub 2}(PO{sub 4}){sub 3−x}(SO{sub 4}){sub x} (x=0.5–1), were discovered through a new sol–gel synthetic method that utilizes peroxide ion as a decomposable and stabilizing ligand for titanyl ions in the presence of phosphates in a strong acidic medium.

Synthesis, crystal structure and characterization of a 1D polyoxometalate-based compound: {l_brace}[Pr(H{sub 2}O){sub 7}][CrMo{sub 6}H{sub 6}O{sub 24}]{r_brace} . 4H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Zhao Lijie; Shen Shuchang; Yu Haiming [Qiqihar Univ., HL (China). Dept. of Chemistry and Chemical Engineering

2008-07-15

A novel polyoxometalated-based compound, {l_brace}[Pr(H{sub 2}O){sub 7}][CrMo{sub 6}H{sub 6}O{sub 24}]{r_brace} . 4H{sub 2}O, was prepared and characterized by elemental analysis, infrared and ultraviolet spectroscopy, TG measurement and single crystal X-ray diffraction. A chain-like coordination polymer is formed from a heteropolyanion [CrMo{sub 6}H{sub 6}O{sub 24}]{sup 3} as a building unit and [Pr(H{sub 2}O){sub 7}]{sup 3+} cations as linker. The chains are linked into an extensive three-dimensional supramolecular network through hydrogen bonding. The synthesis of 1 is accomplished only from pre-synthesized Anderson clusters, but not from simple starting materials. (orig.)

Chemiluminescence of the Ce{sup 3+}* ions, and the {sup 1}ГђЕѕ{sub 2} and ({sup 1}ГђЕѕ{sub 2}){sub 2} molecular species of oxygen induced by active surface of the (NH{sub 4}){sub 2}Ce(NO{sub 3}){sub 6} crystals at reduction of Ce{sup 4+} to Ce{sup 3+} by water in heterogeneous system «(NH{sub 4}){sub 2}Ce(NO{sub 3}){sub 6}-C{sub 6}H{sub 6}-H{sub 2}O»

Energy Technology Data Exchange (ETDEWEB)

Bulgakov, Ramil G., E-mail: profbulgakov@yandex.ru [Laboratory of Negative Ions Mass Spectrometry, Institute of Molecule and Crystal Physics, Ufa Research Centre of the Russian Academy of Sciences, 71, Oktyabrya Prosp., 450054 Ufa (Russian Federation); Gazeeva, Dilara R., E-mail: galimovdi@mail.ru [Laboratory of High Energy Chemistry and Catalysis, Institute of Petrochemistry and Catalysis Russian Academy of Sciences, 141 Prosp. Oktyabrya, 450075 Ufa (Russian Federation); Galimov, Dim I. [Laboratory of High Energy Chemistry and Catalysis, Institute of Petrochemistry and Catalysis Russian Academy of Sciences, 141 Prosp. Oktyabrya, 450075 Ufa (Russian Federation)

2017-03-15

We have discovered an unusual new chemiluminescence (CL) in the title system, which is different from other known CL by unusual combination of various in nature emitters, namely, electronically excited state of the Ce{sup 3+}* ion (λ{sub max}=335 nm), singlet oxygen {sup 1}ГђЕѕ{sub 2} (emission near 1270 nm) and its dimer ({sup 1}ГђЕѕ{sub 2}){sub 2} (λ{sub max}=490, 645, 715 nm). The Ce{sup 3+}* ions and oxygen emitters {sup 1}O{sub 2} and ({sup 1}O{sub 2}){sub 2} are generated in the reaction of Ce{sup 4+} with water and hydrogen peroxide, respectively. CL is generated only in a heterogeneous system «(NH{sub 4}){sub 2}Ce(NO{sub 3}){sub 6}-C{sub 6}H{sub 6}-H{sub 2}O» and completely absent in a homogeneous solution (NH{sub 4}){sub 2}Ce(NO{sub 3}){sub 6} in water containing benzene. This is due to the fact that the redox processes and CL in the «(NH{sub 4}){sub 2}Ce(NO{sub 3}){sub 6}-C{sub 6}H{sub 6}-H{sub 2}O» system are induced by active surface of the (NH{sub 4}){sub 2}Ce(NO{sub 3}){sub 6} crystals. It is through the action of the active surface of the (NH{sub 4}){sub 2}Ce(NO{sub 3}){sub 6} crystals is carried out population of such a high energy level of 5d{sup 1} excited state of Ce{sup 3+}* ion (λ{sub max}=353 nm, 3.7 eV). Discovered CL is the first example of an experimental registration of the Ce{sup 3+}* ion emission in a chemical reaction, because formation of Ce{sup 3+}* ion previously assumed to be in a great many works on the study of CL in reactions of Ce{sup 4+} compounds with various reducing agents, including the reaction with water, initiated by light or catalysts. Possible mechanism generation of new CL in the system under study has been proposed in the paper. - Highlights: • A new chemiluminescence (CL) in the (NH{sub 4}){sub 2}Ce(NO{sub 3}){sub 2}-C{sub 6}H{sub 6}-H{sub 2}O system was discovered. • The emission of the Ce{sup 3+}* ion as a CL emitter has been registered for the first time. • Other emitters of this CL are

Facile synthesis technology of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C adding H{sub 2}O{sub 2} in ball mill process

Energy Technology Data Exchange (ETDEWEB)

Min, Xiujuan [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, Harbin Institute of Technology, School of Chemistry and Chemical Engineering, Harbin 150001 (China); Mu, Deying [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, Harbin Institute of Technology, School of Chemistry and Chemical Engineering, Harbin 150001 (China); Department of Environmental Engineering, Harbin University of Commerce, Harbin 150076 (China); Li, Ruhong [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, Harbin Institute of Technology, School of Chemistry and Chemical Engineering, Harbin 150001 (China); Dai, Changsong, E-mail: changsd@hit.edu.cn [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, Harbin Institute of Technology, School of Chemistry and Chemical Engineering, Harbin 150001 (China)

2016-11-15

Highlights: • Sintering time of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} reduced to 6 hours by adding hydrogen peroxide. • Electrochemical performance of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} was improved by reducing sintering time. • The Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} production process was simplified during material synthesis stage. - Abstract: Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C has stable structure, high theory specific capacity and good safety performance, therefore it has become the research focus of lithium-ion batteries in recent years. The facile synthesis technology of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C was characterized by adding different amounts of H{sub 2}O{sub 2}. Structure and morphology characteristics were examined by XRD, TG, Raman Spectroscopy, XPS and SEM. Electrochemical performance was investigated by constant current charging and discharging test. The results revealed that the Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C electrochemical performance of adding 15 mL H{sub 2}O{sub 2} was better after sintering during 6 h. At the charge cut-off voltage of 4.3 V, the first discharge capacity at 0.2 C rate reached 127 mAh g{sup −1}. Because of adding H{sub 2}O{sub 2} in the ball-mill dispersant, the vanadium pentoxide formed the wet sol. The molecular-leveled mixture increased the homogeneity of raw materials. Therefore, the addition of H{sub 2}O{sub 2} shortened the sintering time and significantly improved the electrochemical performance of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C.

Static susceptibility and heat capacity studies on V{sub 3}O{sub 7}.H{sub 2}O{sub 7} nanobelts

Energy Technology Data Exchange (ETDEWEB)

Hellmann, I., E-mail: i.hellmann@ifw-dresden.d [Leibniz-Institut fuer Festkoerper- und Werkstoffforschung (IFW) Dresden, Helmholtzstr. 20, D-01069 Dresden (Germany); Zakharova, G.S.; Volkov, V.L. [Institute of Solid State Chemistry, Ural Division, Russian Academy of Sciences, Pervomaiskaya ul. 91, Yekaterinburg 620219 (Russian Federation); Taeschner, C.; Leonhardt, A.; Buechner, B.; Klingeler, R. [Leibniz-Institut fuer Festkoerper- und Werkstoffforschung (IFW) Dresden, Helmholtzstr. 20, D-01069 Dresden (Germany)

2010-04-15

V{sub 3}O{sub 7}.H{sub 2}O nanobelts were prepared by a hydrothermal method at 190 deg. C using V{sub 2}O{sub 5}.nH{sub 2}O gel and H{sub 2}C{sub 2}O{sub 4}.2H{sub 2}O as starting agents. The obtained nanobelts have diameters ranging from 40 to 70 nm with lengths up to several micrometers. Measurements of the static magnetic susceptibility and the specific heat show a discontinuous phase transition at around T=145 K, which separates two regions of paramagnetic behavior.

Impact of CT attenuation correction method on quantitative respiratory-correlated (4D) PET/CT imaging

Energy Technology Data Exchange (ETDEWEB)

Nyflot, Matthew J., E-mail: nyflot@uw.edu [Department of Radiation Oncology, University of Washington, Seattle, Washington 98195-6043 (United States); Lee, Tzu-Cheng [Department of Bioengineering, University of Washington, Seattle, Washington 98195-6043 (United States); Alessio, Adam M.; Kinahan, Paul E. [Department of Radiology, University of Washington, Seattle, Washington 98195-6043 (United States); Wollenweber, Scott D.; Stearns, Charles W. [GE Healthcare, Waukesha, Wisconsin 53188 (United States); Bowen, Stephen R. [Department of Radiation Oncology, University of Washington, Seattle, Washington 98195-6043 and Department of Radiology, University of Washington, Seattle, Washington 98195-6043 (United States)

2015-01-15

Purpose: Respiratory-correlated positron emission tomography (PET/CT) 4D PET/CT is used to mitigate errors from respiratory motion; however, the optimal CT attenuation correction (CTAC) method for 4D PET/CT is unknown. The authors performed a phantom study to evaluate the quantitative performance of CTAC methods for 4D PET/CT in the ground truth setting. Methods: A programmable respiratory motion phantom with a custom movable insert designed to emulate a lung lesion and lung tissue was used for this study. The insert was driven by one of five waveforms: two sinusoidal waveforms or three patient-specific respiratory waveforms. 3DPET and 4DPET images of the phantom under motion were acquired and reconstructed with six CTAC methods: helical breath-hold (3DHEL), helical free-breathing (3DMOT), 4D phase-averaged (4DAVG), 4D maximum intensity projection (4DMIP), 4D phase-matched (4DMATCH), and 4D end-exhale (4DEXH) CTAC. Recovery of SUV{sub max}, SUV{sub mean}, SUV{sub peak}, and segmented tumor volume was evaluated as RC{sub max}, RC{sub mean}, RC{sub peak}, and RC{sub vol}, representing percent difference relative to the static ground truth case. Paired Wilcoxon tests and Kruskal–Wallis ANOVA were used to test for significant differences. Results: For 4DPET imaging, the maximum intensity projection CTAC produced significantly more accurate recovery coefficients than all other CTAC methods (p < 0.0001 over all metrics). Over all motion waveforms, ratios of 4DMIP CTAC recovery were 0.2 ± 5.4, −1.8 ± 6.5, −3.2 ± 5.0, and 3.0 ± 5.9 for RC{sub max}, RC{sub peak}, RC{sub mean}, and RC{sub vol}. In comparison, recovery coefficients for phase-matched CTAC were −8.4 ± 5.3, −10.5 ± 6.2, −7.6 ± 5.0, and −13.0 ± 7.7 for RC{sub max}, RC{sub peak}, RC{sub mean}, and RC{sub vol}. When testing differences between phases over all CTAC methods and waveforms, end-exhale phases were significantly more accurate (p = 0.005). However, these differences were driven by

Adsorption properties of CO, H{sub 2} and CH{sub 4} over Pd/γ-Al{sub 2}O{sub 3} catalyst: A density functional study

Energy Technology Data Exchange (ETDEWEB)

Song, Zijian; Wang, Ben, E-mail: benwang@hust.edu.cn; Yu, Jie; Ma, Chuan; Qu, Qinggong; Zeng, Zhao; Xiang, Jun; Hu, Song; Sun, Lushi, E-mail: sunlushi@hust.edu.cn

2016-11-30

Highlights: • Model of dimer Pd supported on γ-Al{sub 2}O{sub 3} (1 1 0) surface was established. • CO, H{sub 2} and CH{sub 4} adsorption on clean γ-Al{sub 2}O{sub 3} and on Pd/γ-Al{sub 2}O{sub 3} surface was studied by DFT calculations. • CO, H{sub 2} and CH{sub 4} adsorptions are energetically more favorable in the presence of dimer Pd. • Mechanism of CO, H{sub 2} and CH{sub 4} adsorption on Pd/γ-Al{sub 2}O{sub 3} (1 1 0) surface was explained. - Abstract: Density functional theory (DFT) calculations were employed to investigate the adsorption characteristics of carbon monoxide (CO), hydrogen (H{sub 2}), and methane (CH{sub 4}) on the surface of clean γ-Al{sub 2}O{sub 3} and Pd supported γ-Al{sub 2}O{sub 3}, which is of significant for catalytic combustion. The adsorption intensities of the three gas molecules in pure γ-Al{sub 2}O{sub 3} (1 1 0) and Pd/γ-Al{sub 2}O{sub 3} (1 1 0) were in the order of CO > H{sub 2} > CH{sub 4}. The corresponding adsorption energies on the Pd/γ-Al{sub 2}O{sub 3} (1 1 0) surface were at least three times higher than those on γ-Al{sub 2}O{sub 3} (1 1 0). Anlysis of Mulliken population and partial density of states (PDOS) showed that the adsorption mechanisms were as follow: (a) CO stably adsorbed on the bridge site of dimer Pd with two C−Pd bonds because of charges transfer from the surface to CO, and the triple bond (C≡O) was broken to a double bond (C=O); (b) H{sub 2} was dissociated into hydrogen atoms on the dimer Pd and produced a stable planar configuration; and (c) the tetrahedral structure of CH{sub 4} was destroyed on the surface and formed a −CH{sub 3} species bonded to the Pd atom, which contributes to the orbital hybridization between C and Pd atoms.

Syntheses, crystal structures, and properties of the isotypic pair [Cr(H{sub 2}O){sub 6}]{sub 2}[B{sub 12}H{sub 12}]{sub 3}.15H{sub 2}O and [In(H{sub 2}O){sub 6}]{sub 2}[B{sub 12}H{sub 12}]{sub 3}.15H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Van, Nguyen-Duc; Kleeberg, Fabian M.; Schleid, Thomas [Institut fuer Anorganische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany)

2015-11-15

Single crystals of [Cr(H{sub 2}O){sub 6}]{sub 2}[B{sub 12}H{sub 12}]{sub 3}.15H{sub 2}O and [In(H{sub 2}O){sub 6}]{sub 2}[B{sub 12}H{sub 12}]{sub 3}.15H{sub 2}O were obtained by reactions of aqueous solutions of the acid (H{sub 3}O){sub 2}[B{sub 12}H{sub 12}] with chromium(III) hydroxide and indium metal shot, respectively. The title compounds crystallize isotypically in the trigonal system with space group R anti 3c (a = 1157.62(3), c = 6730.48(9) pm for the chromium, a = 1171.71(3), c = 6740.04(9) pm for the indium compound, Z = 6). The arrangement of the quasi-icosahedral [B{sub 12}H{sub 12}]{sup 2-} dianions can be considered as stacking of two times nine layers with the sequence..ABCCABBCA.. and the metal trications arrange in a cubic closest packed..abc.. stacking sequence. The metal trications are octahedrally coordinated by six water molecules of hydration, while another fifteen H{sub 2}O molecules fill up the structures as zeolitic crystal water or second-sphere hydrating species. Between these free and the metal-bonded water molecules, bridging hydrogen bonds are found. Furthermore, there is also evidence of hydrogen bonding between the anionic [B{sub 12}H{sub 12}]{sup 2-} clusters and the free zeolitic water molecules according to B-H{sup δ-}..{sup δ+}H-O interactions. Vibrational spectroscopy studies prove the presence of these hydrogen bonds and also show slight distortions of the dodecahydro-closo-dodecaborate anions from their ideal icosahedral symmetry (I{sub h}). Thermal decomposition studies for the example of [Cr(H{sub 2}O){sub 6}]{sub 2}[B{sub 12}H{sub 12}]{sub 3}.15H{sub 2}O gave no hints for just a simple multi-stepwise dehydration process. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Photodissociation of van der Waals clusters of isoprene with oxygen, C{sub 5}H{sub 8}-O{sub 2}, in the wavelength range 213-277 nm

Energy Technology Data Exchange (ETDEWEB)

Vidma, Konstantin V.; Frederix, Pim W. J. M.; Parker, David H. [Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 ED Nijmegen (Netherlands); Baklanov, Alexey V. [Institute of Chemical Kinetics and Combustion, Institutskaja Street 3, Novosibirsk 630090 (Russian Federation) and Novosibirsk State University, Pirogova street 2, Novosibirsk 630090 (Russian Federation)

2012-08-07

The speed and angular distribution of O atoms arising from the photofragmentation of C{sub 5}H{sub 8}-O{sub 2}, the isoprene-oxygen van der Waals complex, in the wavelength region of 213-277 nm has been studied with the use of a two-color dissociation-probe method and the velocity map imaging technique. Dramatic enhancement in the O atoms photo-generation cross section in comparison with the photodissociation of individual O{sub 2} molecules has been observed. Velocity map images of these 'enhanced' O atoms consisted of five channels, different in their kinetic energy, angular distribution, and wavelength dependence. Three channels are deduced to be due to the one-quantum excitation of the C{sub 5}H{sub 8}-O{sub 2} complex into the perturbed Herzberg III state ({sup 3}{Delta}{sub u}) of O{sub 2}. This excitation results in the prompt dissociation of the complex giving rise to products C{sub 5}H{sub 8}+O+O when the energy of exciting quantum is higher than the complex photodissociation threshold, which is found to be 41740 {+-} 200 cm{sup -1} (239.6{+-}1.2 nm). This last threshold corresponds to the photodissociation giving rise to an unexcited isoprene molecule. The second channel, with threshold shifted to the blue by 1480 {+-} 280 cm{sup -1}, corresponds to dissociation with formation of rovibrationally excited isoprene. A third channel was observed at wavelengths up to 243 nm with excitation below the upper photodissociation threshold. This channel is attributed to dissociation with the formation of a bound O atom C{sub 5}H{sub 8}-O{sub 2}+hv{yields} C{sub 5}H{sub 8}-O{sub 2}({sup 3}{Delta}{sub u}) {yields} C{sub 5}H{sub 8}O + O and/or to dissociation of O{sub 2} with borrowing of the lacking energy from incompletely cooled complex internal degrees of freedom C{sub 5}H{sub 8}{sup *}-O{sub 2}+hv{yields} C{sub 5}H{sub 8}{sup *}-O{sub 2}({sup 3}{Delta}{sub u}) {yields} C{sub 5}H{sub 8}+ O + O. The kinetic energy of the O atoms arising in two other

Syntheses and luminescence study for La{sub 1−x}Eu{sub x}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O (0≤x≤0.40) and the dehydrated products β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9} (0≤x≤0.15)

Energy Technology Data Exchange (ETDEWEB)

Sun, Xiaorui; Zhou, Zhengyang; Yang, Haixia; Gao, Wenliang; Cong, Rihong, E-mail: congrihong@cqu.edu.cn; Yang, Tao, E-mail: taoyang@cqu.edu.cn

2016-05-15

La{sub 1−x}Eu{sub x}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O with the Eu{sup 3+}-doping upper limit of 40 atom% were synthesized hydrothermally. Thereafter, thermal treatments at 710 °C were applied to obtain β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9}. The solid solution range is even narrower, i.e. 0≤x≤0.15, due to the mismatch between La{sup 3+} and Eu{sup 3+}. The host borate system shows a typical concentration quenching effect at x=0.20 under CT excitation, and this is postponed to x=0.30 under the f−f excitation. β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9} shows a very intense absorption of charge transfer, and gives strong red emissions at 615 nm with large R/O ratios (1.9–2.4). The saturation effect appears at x=0.11, which is probably due to the lattice distortion. Eu{sup 3+} luminescence was applied as the structural probe to study the local coordination environment change during the dehydration and re-crystallization processes of La{sub 0.93}Eu{sub 0.07}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O. - Highlights: • La{sub 1−x}Eu{sub x}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O (0≤x≤0.40) were prepared by hydrothermal method. • The Eu{sup 3+}-doping limit in β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9} is 15 atom% proved by powder XRD. • La{sub 1−x}Eu{sub x}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O show relatively weaker red emissions. • β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9} shows an intense CT absorption together with strong red emissions. • Eu{sup 3+} luminescence was studied when annealing La{sub 0.93}Eu{sub 0.07}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O.

Enhanced visible light photocatalytic H{sub 2} evolution of metal-free g-C{sub 3}N{sub 4}/SiC heterostructured photocatalysts

Energy Technology Data Exchange (ETDEWEB)

Wang, Biao, E-mail: wangbiao@fjirsm.ac.cn [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); University of the Chinese Academy of Sciences, Beijing 100049 (China); Zhang, Jingtao, E-mail: zhangjtao@mail.sysu.edu.cn [State Key Laboratory of Optoelectronic Materials and Technologies, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510006 (China); Huang, Feng, E-mail: huangfeng@mail.sysu.edu.cn [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); State Key Laboratory of Optoelectronic Materials and Technologies, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510006 (China)

2017-01-01

Highlights: • Novel g-C{sub 3}N{sub 4}/SiC composite was prepared by synthesizing g-C{sub 3}N{sub 4} on the surface of SiC. • g-C{sub 3}N{sub 4}/SiC composites exhibit much higher H{sub 2} production activity than pure g-C{sub 3}N{sub 4}. • The g-C{sub 3}N{sub 4}/SiC heterojunction mainly accounts for improved photocatalytic activity. - Abstract: g-C{sub 3}N{sub 4} has been attracting much attention for application in visible light photocatalytic water splitting due to its suitable band structure, and high thermal and chemical stability. However, the rapid recombination of photogenerated carriers has inhibited its wide use. For this reason, novel g-C{sub 3}N{sub 4}/SiC composites were prepared via in situ synthesis of g-C{sub 3}N{sub 4} on the surface of SiC, with which g-C{sub 3}N{sub 4} shows tight interaction (chemical bonding). The g-C{sub 3}N{sub 4}/SiC composites exhibit high stability in H{sub 2} production under irradiation with visible light (λ ≥ 420 nm), demonstrating a maximum of 182 μmol g{sup −1} h{sup −1}, being 3.4 times higher than that of pure g-C{sub 3}N{sub 4}. The enhanced photocatalytic H{sub 2} production ability for g-C{sub 3}N{sub 4}/SiC photocatalysts is primarily ascribed to the combined effects of enhanced separation of photogenerated carriers through efficient migration of electron and enlarged surface areas, in addition to the possible contributions of increased hydrophilicity of SiC and polymerization degree of g-C{sub 3}N{sub 4}. This study may provide new insights into the development of g-C{sub 3}N{sub 4}-based composites as stable and efficient photocatalysts for H{sub 2} production from water splitting.

Observation of stimulated Raman scattering in polar tetragonal crystals of barium antimony tartrate trihydrate, Ba[Sb{sub 2}((+)C{sub 4}H{sub 2}O{sub 6}){sub 2}].3H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Kaminskii, Alexander A. [Institute of Crystallography, Russian Academy of Sciences, Moscow (Russian Federation); Rhee, Hanjo; Eichler, Hans J.; Lux, Oliver [Institute of Optics and Atomic Physics, Technical University of Berlin (Germany); Nemec, Ivan [Department of Inorganic Chemistry, Faculty of Science, Charles University, Prague (Czech Republic); Yoneda, Hitoki; Shirakawa, Akira [Institute for Laser Science, University of Electro-Communications, Tokyo (Japan); Becker, Petra; Bohaty, Ladislav [Section Crystallography, Institute of Geology and Mineralogy, University of Cologne (Germany)

2017-04-15

The non-centrosymmetric polar tetragonal (P4{sub 1}) barium antimony tartrate trihydrate, Ba[Sb{sub 2}((+)C{sub 4}H{sub 2}O{sub 6}){sub 2}].3H{sub 2}O, was found to be an attractive novel semi-organic crystal manifesting numerous χ{sup (2)}- and χ{sup (3)}-nonlinear optical interactions. In particular, with picosecond single- and dual-wavelength pumping SHG and THG via cascaded parametric four-wave processes were observed. High-order Stokes and anti-Stokes lasing related to two SRS-promoting vibration modes of the crystal, with ω{sub SRS1} ∼ 575 cm{sup -1} and ω{sub SRS2} ∼ 2940 cm{sup -1}, takes place. Basing on a spontaneous Raman investigation an assignment of the two SRS-active vibration modes is discussed. (copyright 2017 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

N{sub 2}H{sub 4} electrooxidation at negative potential on novel wearable nano-Ni-MWNTs-textile electrode

Energy Technology Data Exchange (ETDEWEB)

Zhang, Dongming; Wang, Bin; Cao, Dianxue; Ye, Ke; Xu, Yang; Yin, Jinling; Cheng, Kui; Wang, Guiling, E-mail: wangguiling@hrbeu.edu.cn

2014-10-15

Highlights: • The novel Ni-MWNTs-textile electrode is prepared by the facile “dipping and drying” and electrodeposition process. • The Ni-MWNTs-textile electrode exhibits a special three dimensional network structure. • The Ni-MWNTs-textile electrode exhibits excellent performance for N{sub 2}H{sub 4} electrooxidation. - Abstract: A new composite Ni electrode is simply prepared by electrodeposition of nano-scaled Ni particles onto multi-walled carbon nanotubes (MWNTs)-enabled conductive textile fiber (cosmetic cotton) which owns an especial three-dimensional (3D) network structure. The morphology and phase structure of the Ni-MWNTs-textile electrode are characterized by scanning electron microscope, transmission electron microscope and X-ray diffraction spectrometer, and the catalytic performance for the N{sub 2}H{sub 4} electrooxidation is tested by linear sweep voltammetry and chronoamperometry. The results show that the Ni-MWNTs-textile electrode exhibits a remarkably high catalytic activity and good stability for N{sub 2}H{sub 4} electrooxidation. The onset potential stays at around −0.9 V and the oxidation current density reaches as high as 12 mA cm{sup −2} in the solution containing 1 mol dm{sup −3} NaOH and 20 mmol dm{sup −3} N{sub 2}H{sub 4} at around −0.80 V, both of which outstrip the previous reports.

Hydrothermal synthesis of WO{sub 3}·0.5H{sub 2}O microtubes with excellent photocatalytic properties

Energy Technology Data Exchange (ETDEWEB)

Wang, Xiaozhou; Meng, Xiuqing, E-mail: xqmeng@semi.ac.cn; Zhong, Mianzeng; Wu, Fengmin; Li, Jingbo, E-mail: jbli@semi.ac.cn

2013-10-01

Pyrochlore WO{sub 3} microtubes were synthesized via a hydrothermal method for the first time. In this process, thiourea was employed to overcome the hydrogen bonds on the rim of WO{sub 3}·0.5H{sub 2}O and hydroxylamine hydrochloride was used as a viscosity regulator. Field-emission scanning electron microscopy and high-resolution transmission electron microscopy observations revealed that large amounts of uniform single-crystal WO{sub 3}·0.5H{sub 2}O microtubes with diameters ranging from 100 to 300 nm and length of tens of micrometers were obtained. The thickness of the tube wall was about 40 nm. A possible rolling mechanism was proposed to explain the formation of the tubular structures, and the influence of thiourea and hydroxylamine hydrochloride on the uniform tubular morphology was discussed. The WO{sub 3}·0.5H{sub 2}O microtubes showed excellent photocatalytic activity toward the degradation of organic molecules such as RhB, which may find potential applications in the fields of photocatalysts, sensors and transistors.

Thermodynamics of the Li{sub 4}SiO{sub 4}/H{sub 2}O system

Energy Technology Data Exchange (ETDEWEB)

Alvani, C; Casadio, S [ENEA, Casaccia (Italy); Johnson, C

1998-03-01

The chemical interaction of He or He+0.1%H{sub 2} purge gases with Li{sub 4}SiO{sub 4} pebbles has been examined as a function temperature and partial pressure of water vapor by Temperature Programmed Reduction (TPR) and Temperature Programmed Desorption (TPD) measurements. The experimental conditions were selected to be representative of those envisaged occurring in the HCPB (Helium-Cooled Pebble Bed) blanket. At constant partial pressure of moisture, water adsorption on Li{sub 4}SiO{sub 4} decreases with increasing temperature up to 973K. Above that temperature water absorption increases due of the increasing water solubility of lithium hydroxide with temperature. Using these data, thermodynamic calculations have been carried out to evaluate the behavior of lithium orthosilicate in a moisture-containing environment. The evaluation was done over the 773 to 1173K temperature range. In general, the behavior of lithium orthosilicate was similar to earlier studies on lithium oxide except that the orthosilicate is not as strong in its deviations from ideality as the oxide. (author)

Facile hydrothermal synthesis of polyhedral Fe{sub 3}O{sub 4} nanocrystals, influencing factors and application in the electrochemical detection of H{sub 2}O{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Yuan Kefeng [College of Chemistry and Materials Science, Anhui Key Laboratory of Functional Molecular Solids, Anhui Normal University, Wuhu 241000 (China); Ni Yonghong, E-mail: niyh@mail.ahnu.edu.cn [College of Chemistry and Materials Science, Anhui Key Laboratory of Functional Molecular Solids, Anhui Normal University, Wuhu 241000 (China); Zhang Li [College of Chemistry and Materials Science, Anhui Key Laboratory of Functional Molecular Solids, Anhui Normal University, Wuhu 241000 (China)

2012-08-15

Highlights: Black-Right-Pointing-Pointer Fe{sub 3}O{sub 4} polyhedra had been successfully synthesized by a facile hydrothermal technology. Black-Right-Pointing-Pointer The as-obtained product exhibited the room-temperature ferrimagnetic property. Black-Right-Pointing-Pointer The final product could be prepared into an electrochemical sensor for the detection of H{sub 2}O{sub 2}. - Abstract: Polyhedral Fe{sub 3}O{sub 4} nanocrystals have been successfully synthesized by a facile hydrothermal technique, employing FeSO{sub 4}{center_dot}7H{sub 2}O, N{sub 2}H{sub 4} and NH{sub 3}{center_dot}H{sub 2}O as the reactants without the assistance of any surfactant. The phase of the as-obtained Fe{sub 3}O{sub 4} was characterized by X-ray powder diffraction (XRD) and further proved by Rietveld refinement of XRD data. Energy dispersive spectrometry (EDS) and scanning electron microscopy (SEM) were used for the composition and morphology analyses of the final product. Some factors influencing the formation of polyhedral Fe{sub 3}O{sub 4} nanocrystals were systematically investigated, including the reaction temperature and time, and the original volume ratio of NH{sub 3}{center_dot}H{sub 2}O/N{sub 2}H{sub 4}{center_dot}H{sub 2}O. It was found that the as-prepared Fe{sub 3}O{sub 4} polyhedra exhibited a good electrochemical property in 0.1 M phosphate buffer solution (PBS) with pH 7.0 and could be prepared into an electrochemical sensor for the detection of H{sub 2}O{sub 2}. The linear response range of the sensor was 10.0 Multiplication-Sign 10{sup -6} to 140.0 Multiplication-Sign 10{sup -6} M and a sensitivity was 11.05 {mu}A/mM. Furthermore, the room-temperature magnetic property of the product was also investigated.

Effect of the reaction time on the microstructure and porous texture of carbon materials obtained by chlorination of Ti(C{sub 5}H{sub 5})Cl{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Araujo-Pérez, D.J. [Centro de Investigación en Micro y Nanotecnología, Universidad Veracruzana, 94294, Boca del Río, Veracruz (Mexico); González-García, P., E-mail: pedro.gonzalez@cidesi.edu.mx [CONACYT Research Fellow – Centro de Ingeniería y Desarrollo Industrial, 76130, Querétaro, Querétaro (Mexico); Poisot, M. [Instituto de Química Aplicada, Universidad del Papaloapan, 68301, San Juan Bautista Tuxtepec, Oaxaca (Mexico); García-González, L. [Centro de Investigación en Micro y Nanotecnología, Universidad Veracruzana, 94294, Boca del Río, Veracruz (Mexico)

2015-09-15

Carbon materials have been obtained by the chlorination reaction of Ti(C{sub 5}H{sub 5})Cl{sub 2} at 900 °C, varying the reaction time at 30, 60, 90 and 120 min. The average microstructure, studied by X ray powder diffraction, suggest that these materials consist mainly of disordered carbon with low graphitization degree (from 13.5 to 16.5%). These results are in agreement with the Raman data since the D band (at ≈ 1350 cm{sup −1}) indicates that disordered carbon networks have appeared. The calculated in-plane correlation length increases from 4.04 to 4.70 nm as the chlorination time increases from 30 to 120 min. The textural analyses reveal adsorption isotherms type 1 with hysteresis H4, microporous areas as high as 855 m{sup 2}/g and pore volume of 0.55 cm{sup 3}/g. Additionally, an important contribution of mesoporosity, around 3.6 nm, was also detected. - Highlights: • Micro-mesoporous carbon materials were obtained by chlorination of Ti(C{sub 5}H{sub 5}){sub 2}Cl{sub 2} at 900 °C. • The effect of chlorination exposure time on the microstructure and textural properties was studied. • Microstructural analysis by XRD and Raman showed that carbon samples are mainly disordered. • N{sub 2} adsorption/desorption isotherms showed isotherms type 1 with hysteresis H4. • Micropore size increases at longer chlorination time; in contrast, pore volume decreases.

Influence of preparation conditions on porous structures of olive stone activated by H{sub 3}PO{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Yavuz, Reha; Akyildiz, Hanife [Istanbul Technical University, Chemical and Metallurgical Engineering Faculty, 34469 Maslak, Istanbul (Turkey); Karatepe, Nilguen; Cetinkaya, Eda [Istanbul Technical University, Institute of Energy, Renewable Energy Division, 34469 Maslak, Istanbul (Turkey)

2010-01-15

An olive factory residue was used as a precursor in the preparation of granular activated carbon by chemical activation with H{sub 3}PO{sub 4}. Effects of final activation temperature, time, and H{sub 3}PO{sub 4} concentration used in the impregnation stage on the porous development were investigated. SO{sub 2} adsorption experiments were also performed for some of the activated carbon samples to represent their adsorption performance. Activation at low temperature represented that micropores were developed first at early stages of the temperatures. Mesoporosity developed at around 250 C, enhanced up to 400 C, and then started to decrease due to possibly shrinking of pores. The optimum temperature for olive stone was found to be around 400 C on the basis of total pore volume and BET surface area. It was clearly demonstrated that H{sub 3}PO{sub 4} concentration used in the impregnation stage was not only effective for development of surface area and pore volumes but also an effective tool for tailoring the pore structure and size distribution. (author)

Gauthierite, KPb[(UO{sub 2}){sub 7}O{sub 5}(OH){sub 7}].8H{sub 2}O, a new uranyl-oxide hydroxy-hydrate mineral from Shinkolobwe with a novel uranyl-anion sheet-topology

Energy Technology Data Exchange (ETDEWEB)

Olds, Travis A. [Notre Dame Univ., IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences; Plasil, Jakub [ASCR, Prague (Czech Republic). Inst. of Physics; Kampf, Anthony R. [Natural History Museum of Los Angeles County, Los Angeles, CA (United States). Mineral Sciences Dept.; Skoda, Radek [Masaryk Univ., Brno (Czech Republic). Dept. of Geological Sciences; Burns, Peter C. [Notre Dame Univ., IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences; Notre Dame Univ., IN (United States). Dept. of Chemistry and Biochemistry,; Cejka, Jiri [National Museum, Prague (Czech Republic). Dept. of Mineralogy and Petrology; Bourgoin, Vincent; Boulliard, Jean-Claude [Pierre et Marie Curie Univ., Paris (France). Association Jean Wyart, Collection des Mineraux de Jussieu

2017-03-15

Gauthierite, KPb[(UO{sub 2}){sub 7}O{sub 5}(OH){sub 7}].8H{sub 2}O, is a new uranyl-oxide hydroxy-hydrate mineral from the Shinkolobwe Mine, Democratic Republic of Congo, Africa. It occurs on a matrix of uraninite-bearing quartz gangue associated with soddyite and a minor metazeunerite.metatorbernite series mineral. It is a product of oxidation.hydration weathering of uraninite. Gauthierite is monoclinic, P2{sub 1}/c, with a = 29.844(2) Aa, b = 14.5368(8) Aa, c = 14.0406(7) Aa, β = 103.708(6) , V = 5917.8(6)Aa{sup 3} and Z = 8. Prismatic crystals have pronounced lengthwise striations and reach about 1mm in length. Gauthierite is yellowish orange with a light orange streak and vitreous lustre. The Mohs hardness is ∝ 3 to 4. It is brittle with an uneven fracture and perfect cleavage on {0 1 0}. The calculated density based on the empirical formula is 5.437 g/cm{sup 3}. Optically, gauthierite is biaxial (-), with α = 1.780(5), β = 1.815(5), γ = 1.825(5) (white light), 2V{sub meas.} = 58(1) ; dispersion is extreme (r>>v). The optical orientation is X = b, Y∼a{sup *}, Z∼c (or X = b, Y and a=14 in obtuse β); it is pleochroic with X very pale yellow, Y and Z orange-yellow; X<sub 2}O 1.29, PbO 7.17, UO{sub 3} 82.10, H{sub 2}O 8.78 (structure), total 99.34 wt.%. The empirical formula (based on 34 O a.p.f.u.) is: K{sub 0.67}Pb{sub 0.78}U{sub 7}O{sub 34}H{sub 23.77}. The ideal formula is KPb[(UO{sub 2}){sub 7}O{sub 5}(OH){sub 7}](H{sub 2}O){sub 8}, which requires K{sub 2}O 1.90, PbO 9.00, UO{sub 3} 80.74, H{sub 2}O 8.35, total 100 wt.%. Raman and infrared spectral data confirm the presence of UO{sub 2}{sup 2+}, OH{sup -} and molecular H{sub 2}O. The eight strongest powder X-ray diffraction lines are [d{sub obs} in Aa (hkl) I{sub rel}]: 7.28 (020,400) 49, 3.566 (040, -802, -204) 67, 3.192 (622, -224) 100, 2.541 (-842,-244) 18, 2.043 (406) 14, 2.001 (662,-264, 14.2.0) 23, 1.962 (426,-146) 14, and 1

Compound effect of CaCO{sub 3} and CaSO{sub 4}·2H{sub 2}O on the strength of steel slag: cement binding materials

Energy Technology Data Exchange (ETDEWEB)

Qi, Liqian; Liu, Jiaxiang; Liu, Qian, E-mail: ljxpost@263.net [Beijing Key Laboratory of Electrochemical Process and Technology for Materials, The State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing (China)

2016-03-15

In this study, we replaced 30% of the cement with steel slag to prepare binding material; additionally, small amounts of CaCO{sub 3} and CaSO{sub 4}·2H{sub 2}O were added. This was done to study the compound effect of CaCO{sub 3} and CaSO{sub 4}·2H{sub 2}O on the strength of steel slag-cement binding materials. The hydration degree of the steel slag cementitious material was analyzed by XRD, TG and SEM. The results showed that the optimum proportions of CaCO{sub 3} and CaSO{sub 4}·2H{sub 2}O were 3% and 2%, respectively. Compared with the steel slag-cement binders without adding CaCO{sub 3} and CaSO{sub 4}·2H{sub 2}O, the compressive strength increased by 59.9% at 3 days and by 17.8% at 28 days. Acting as the nucleation matrix, CaCO{sub 3} could accelerate the hydration of C{sub 3}S. In addition, CaCO{sub 3} was involved in the hydration reaction, generating a new hydration product, which could stably exist in a slurry. Meanwhile, CaSO{sub 4}·2H{sub 2}O could increase the number of AFt. The compound effect of CaCO{sub 3} and CaSO{sub 4}·2H{sub 2}O enhanced the intensity of steel slag-cement binding materials and improved the whole hydration behavior. (author)

Mesoporous Co{sub 3}O{sub 4} and CoO rate at C topotactically transformed from chrysanthemum-like Co(CO{sub 3}){sub 0.5}(OH).0.11H{sub 2}O and their lithium-storage properties

Energy Technology Data Exchange (ETDEWEB)

Xiong, Shenglin; Zeng, Hua Chun [Department of Chemical and Biomolecular Engineering, KAUST-NUS GCR Program, Faculty of Engineering, National University of Singapore, 10 Kent Ridge Crescent, Singapore (Singapore); Chen, Jun Song; Lou, Xiong Wen [School of Chemical and Biomedical Engineering, Nanyang Technological University, 70 Nanyang Drive, Singapore (Singapore)

2012-02-22

In this work, a novel hydrothermal route is developed to synthesize cobalt carbonate hydroxide, Co(CO{sub 3}){sub 0.5}(OH).0.11H{sub 2}O. In this method, sodium chloride salt is utilized to organize single-crystalline nanowires into a chrysanthemum-like hierarchical assembly. The morphological evolution process of this organized product is investigated by examining different reaction intermediates during the synthesis. The growth and thus the final assembly of the Co(CO{sub 3}){sub 0.5}(OH).0.11H{sub 2}O can be finely tuned by selecting preparative parameters, such as the molar ratio of the starting chemicals, the additives, the reaction time and the temperature. Using the flower-like Co(CO{sub 3}){sub 0.5}(OH).0.11H{sub 2}O as a solid precursor, quasi-single-crystalline mesoporous Co{sub 3}O{sub 4} nanowire arrays are prepared via thermal decomposition in air. Furthermore, carbon can be added onto the spinel oxide by a chemical-vapor-deposition method using acetylene, which leads to the generation of carbon-sheathed CoO nanowire arrays (CoO rate at C). Through comparing and analyzing the crystal structures, the resultant products and their high crystallinity can be explained by a sequential topotactic transformation of the respective precursors. The electrochemical performances of the typical cobalt oxide products are also evaluated. It is demonstrated that tuning of the surface texture and the pore size of the Co{sub 3}O{sub 4} products is very important in lithium-ion-battery applications. The carbon-decorated CoO nanowire arrays exhibit an excellent cyclic performance with nearly 100% capacity retention in a testing range of 70 cycles. Therefore, this CoO rate at C nanocomposite can be considered to be an attractive candidate as an anode material for further investigation. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

NQR and X-ray crystal structure studies of cadmium halide complexes: [C(NH{sub 2}){sub 3}]CdI{sub 3} and [4-ClC{sub 6}H{sub 5}NH{sub 3}]{sub 3}CdBr{sub 5}

Energy Technology Data Exchange (ETDEWEB)

Gesing, Thorsten M.; Lork, Enno [Bremen Univ. (Germany). MAPEX Center for Material and Processes; Terao, Hiromitsu [Tokushima Univ. (Japan). Faculty of Integrated Arts and Sciences; Ishihara, Hideta [Saga Univ. (Japan). Faculty of Culture and Education

2016-05-01

The crystal structures of [C(NH{sub 2}){sub 3}]CdI{sub 3} (1) and [4-ClC{sub 6}H{sub 5}NH{sub 3}]{sub 3}CdBr{sub 5} (2) have been determined at 100 K: monoclinic, Cc, a = 828.75(3) pm, b = 1615.31(5) pm, c = 810.64(3) pm, and β = 106.5820(10) for 1; monoclinic, P2{sub 1}/c, a = 1486.93(5) pm, b = 794.31(3) pm, c = 2290.59(7) pm, and β = 99.6830(10) for 2. The structure of 1 has an infinite chain of anions consisting of [CdI{sub 4}] tetrahedra sharing two corners. The structure of 2 has an infinite chain of anions consisting of [CdBr{sub 6}] octahedra sharing two corners in cis positions. In both structures, isolated cations are connected to the anion chains through weak hydrogen bonds Cd-X..H to result in three-dimensional network structures. In accordance with the crystal structures, three {sup 127}I (m = ±1/2 <-> m = ±3/2), five {sup 81}Br, and three {sup 35}Cl nuclear quadrupole resonance (NQR) lines were observed for 1 and 2. The NQR spectra reflect the anion chain structures and their weak hydrogen bonds. The MO calculations of the models [Cd{sub 5}I{sub 16}]{sup 6-} for 1 and [Cd{sub 3}Br{sub 16}]{sup 10-} for 2 estimate only about half the values for the NQR frequencies but give accurate electric field gradient directions.

Preparation and characterization of activated carbon from reedy grass leaves by chemical activation with H{sub 3}PO{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Xu, Jianzhong, E-mail: xjz8112@sina.com [College of Chemistry and Environmental Science, Hebei University, Baoding 071002, Hebei (China); Chen, Lingzhi [College of Chemistry and Environmental Science, Hebei University, Baoding 071002, Hebei (China); Department of Applied Chemistry, Hengshui University, Hengshui 053000, Hebei (China); Qu, Hongqiang; Jiao, Yunhong; Xie, Jixing [College of Chemistry and Environmental Science, Hebei University, Baoding 071002, Hebei (China); Xing, Guangen [Department of Applied Chemistry, Hengshui University, Hengshui 053000, Hebei (China)

2014-11-30

Highlights: • Activated carbons were produced from reedy grass leaves by activation with phosphoric acid. • The activated carbons have a large number of oxygen- and phosphorus-containing surface groups. • The structure of activated carbons was bight fibers features on the surface and the external surface of the activated carbons was slightly corrugated and abundant pores. - Abstract: Activated carbons were produced from reedy grass leaves by chemical activation with H{sub 3}PO{sub 4} in N{sub 2} atmosphere and their characteristics were investigated. The effects of activation temperature and time were examined. Adsorption capacity was demonstrated with BET and iodine number. Micropore volume and pore size distribution of activated carbons were characterized by N{sub 2} adsorption isotherms. The surface area and iodine number of the activated carbons produced at 500 °C for 2 h were 1474 m{sup 2}/g and 1128 mg/g, respectively. Thermal decomposition of pure reedy grass leaves and H{sub 3}PO{sub 4}-impregnated reedy grass leaves have been investigated with thermogravimetric/mass spectroscopy (TG–MS) technique. It was found that the temperature and intensity of maximum evolution of H{sub 2}O and CO{sub 2} of H{sub 3}PO{sub 4}-impregnated reedy grass leaves were lower than that of pure reedy grass leaves. This implies that H{sub 3}PO{sub 4} as an activating reagent changed the thermal degradation of the reedy grass leaves, stabilized the cellulose structure, leading to a subsequent change in the evolution of porosity. The results of X-ray photoelectron spectroscopy and Fourier-infrared spectroscopy analysis indicate that the produced activated carbons have rich functional groups on surface.

Electrical properties, phase transitions and conduction mechanisms of the [(C{sub 2}H{sub 5})NH{sub 3}]{sub 2}CdCl{sub 4} compound

Energy Technology Data Exchange (ETDEWEB)

Mohamed, C. Ben; Karoui, K. [Laboratory of Condensed Matter, Faculty of Science of Sfax, University of Sfax, BP1171- 3000 Sfax (Tunisia); Saidi, S. [Laboratory of Materials, Organization and Properties (LMOP), Faculty of Sciences of Tunis, Tunis-El Manar University, 2092 Tunis (Tunisia); Guidara, K. [Laboratory of Condensed Matter, Faculty of Science of Sfax, University of Sfax, BP1171- 3000 Sfax (Tunisia); Rhaiem, A. Ben, E-mail: abdallahrhaiem@yahoo.fr [Laboratory of Condensed Matter, Faculty of Science of Sfax, University of Sfax, BP1171- 3000 Sfax (Tunisia)

2014-10-15

The [(C{sub 2}H{sub 5})NH{sub 3}]{sub 2}CdCl{sub 4} hybrid material was prepared and its calorimetric study and electric properties were investigated at low temperature. The X-ray powder diffractogram has shown that the compound is crystallized in the orthorhombic system with Abma space group, and the refined unit cell parameters are a=7.546 Å, b=7.443 Å, and c=21.831 Å. The calorimetric study has revealed two endothermic peaks at 216 K and 357 K, which are confirmed by the variation of f{sub p} and σ{sub dc} as a function of temperature. The equivalent circuit based on the Z-View-software was proposed and the conduction mechanisms were determined. The obtained results have been discussed in terms of the correlated barrier hopping model (CBH) in phase I (low temperature (OLT)), non-overlapping small polaron tunneling model (NSPT) in phase II (room temperature (ORT)) and the overlapping large polaron tunneling model in phase III (high temperature (OHT)). The density of localized states N{sub F}(E) at the Fermi level and the binding energy W{sub m} were calculated. The variation of the dielectric loss log(ε″) with log(ω) was found to follow the empirical law, ε″=B ω{sup m(T)}.

Crystal structures and thermal decomposition of permanganates AE[MnO{sub 4}]{sub 2} . n H{sub 2}O with the heavy alkaline earth elements (AE=Ca, Sr and Ba)

Energy Technology Data Exchange (ETDEWEB)

Henning, Harald; Bauchert, Joerg M.; Conrad, Maurice; Schleid, Thomas [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie

2017-10-01

Reexamination of the syntheses and crystal structures as well as studies of the thermal decomposition of the heavy alkaline earth metal permanganates Ca[MnO{sub 4}]{sub 2} . 4 H{sub 2}O, Sr[MnO{sub 4}]{sub 2} . 3 H{sub 2}O and Ba[MnO{sub 4}]{sub 2} are the focus of this work. As an alternative to the very inelegant Muthmann method, established for the synthesis of Ba[MnO{sub 4}]{sub 2} a long time ago, we employed a cation-exchange column loaded with Ba{sup 2+} cations and passed through an aqueous potassium-permanganate solution. We later used this alternative also with strontium- and calcium-loaded columns and all the compounds synthesized this way were indistinguishable from the products of the established methods. Ca[MnO{sub 4}]{sub 2} . 4 H{sub 2}O exhibiting [CaO{sub 8}] polyhedra crystallizes in the orthorhombic space group Pccn with the lattice parameters a=1397.15(9), b=554.06(4) and c=1338.97(9) pm with Z=4, whereas Sr[MnO{sub 4}]{sub 2} . 3 H{sub 2}O with [SrO{sub 10}] polyhedra adopts the cubic space group P2{sub 1}3 with a=964.19(7) pm and Z=4. So the harder the AE{sup 2+} cation, the higher its demand for hydration in aqueous solution. Consequently, the crystal structure of Ba[MnO{sub 4}]{sub 2} in the orthorhombic space group Fddd with a=742.36(5), b=1191.23(7) and c=1477.14(9) pm with Z=8 lacks any crystal water, but contains [BaO{sub 12}] polyhedra. During the thermal decomposition of Ca[MnO{sub 4}]{sub 2} . 4 H{sub 2}O, the compound expels up to two water molecules of hydration, before the crystal structure collapses after the loss of the third H{sub 2}O molecule at 157 C. The crystal structure of Sr[MnO{sub 4}]{sub 2} . 3 H{sub 2}O breaks down after the expulsion of the third water molecule as well, but this already occurs at 148 C. For both the calcium and the strontium permanganate samples, orthobixbyite-type α-Mn{sub 2}O{sub 3} and the oxomanganates(III,IV) AEMn{sub 3}O{sub 6} (AE=Ca and Sr) remain as final decomposition products at 800 C

Sr{sub 2}CoMoO{sub 6} anode for solid oxide fuel cell running on H{sub 2} and CH{sub 4} fuels

Energy Technology Data Exchange (ETDEWEB)

Zhang, Ping [Engineering Research Center of Nano-GEO Materials of Education Ministry, China University of Geosciences, Wuhan 430074 (China); Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); Huang, Yun-Hui [Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); State Key Laboratory of Materials Processing and Die and Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan 430074 (China); Cheng, Jin-Guang; Goodenough, John B. [Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); Mao, Zong-Qiang [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China)

2011-02-15

The double perovskite Sr{sub 2}CoMoO{sub 6-{delta}} was investigated as a candidate anode for a solid oxide fuel cell (SOFC). Thermogravimetric analysis (TGA) and powder X-ray diffraction (XRD) showed that the cation array is retained to 800 C in H{sub 2} atmosphere with the introduction of a limited concentration of oxide-ion vacancies. Stoichiometric Sr{sub 2}CoMoO{sub 6} has an antiferromagnetic Neel temperature T{sub N} {approx} 37 K, but after reduction in H{sub 2} at 800 C for 10 h, long-range magnetic order appears to set in above 300 K. In H{sub 2}, the electronic conductivity increases sharply with temperature in the interval 400 C < T < 500 C due to the onset of a loss of oxygen to make Sr{sub 2}CoMoO{sub 6-{delta}} a good mixed oxide-ion/electronic conductor (MIEC). With a 300-{mu}m-thick La{sub 0.8}Sr{sub 0.12}Ga{sub 0.83}Mg{sub 0.17}O{sub 2.815} (LSGM) as oxide-ion electrolyte and SrCo{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} as the cathode, the Sr{sub 2}CoMoO{sub 6-{delta}} anode gave a maximum power density of 1017 mW cm{sup -2} in H{sub 2} and 634 mW cm{sup -2} in wet CH{sub 4}. A degradation of power in CH{sub 4} was observed, which could be attributed to coke build up observed by energy dispersive spectroscopy (EDS). (author)

Radiosynthesis and pre-clinical evaluation of [{sup 18}F]fluoro-[1,2-{sup 2}H{sub 4}]choline

Energy Technology Data Exchange (ETDEWEB)

Smith, Graham [Comprehensive Cancer Imaging Centre, Faculty of Medicine, Imperial College London, Hammersmith Hospital, Du Cane Road, London W12 0NN (United Kingdom); Zhao Yongjun [MDx Discovery (part of GE Healthcare) at Hammersmith Imanet, Ltd., Hammersmith Hospital, Du Cane Road, London W12 0NN (United Kingdom); Leyton, Julius [Comprehensive Cancer Imaging Centre, Faculty of Medicine, Imperial College London, Hammersmith Hospital, Du Cane Road, London W12 0NN (United Kingdom); Shan Bo [MDx Discovery (part of GE Healthcare) at Hammersmith Imanet, Ltd., Hammersmith Hospital, Du Cane Road, London W12 0NN (United Kingdom); Nguyen, Quang-de; Perumal, Meg [Comprehensive Cancer Imaging Centre, Faculty of Medicine, Imperial College London, Hammersmith Hospital, Du Cane Road, London W12 0NN (United Kingdom); Turton, David [GE-Imanet, Hammersmith Hospital, Du Cane Road, London, W12 0NN (United Kingdom); Arstad, Erik; Luthra, Sajinder K.; Robins, Edward G. [MDx Discovery (part of GE Healthcare) at Hammersmith Imanet, Ltd., Hammersmith Hospital, Du Cane Road, London W12 0NN (United Kingdom); Aboagye, Eric O., E-mail: eric.aboagye@imperial.ac.u [Comprehensive Cancer Imaging Centre, Faculty of Medicine, Imperial College London, Hammersmith Hospital, Du Cane Road, London W12 0NN (United Kingdom)

2011-01-15

Introduction: Choline radiotracers are widely used for clinical PET diagnosis in oncology. [{sup 11}C]Choline finds particular utility in the imaging of brain and prostate tumor metabolic status, where 2-[{sup 18}F]fluoro-2-deoxy-D-glucose ('FDG') shows high background uptake. More recently we have extended the clinical utility of [{sup 11}C]choline to breast cancer where radiotracer uptake correlates with tumor aggressiveness (grade). In the present study, a new choline analog, [{sup 18}F]fluoro-[1,2-{sup 2}H{sub 4}]choline, was synthesized and evaluated as a potential PET imaging probe. Methods: [{sup 18}F]Fluorocholine, [{sup 18}F]fluoro-[1-{sup 2}H{sub 2}]choline and [{sup 18}F]fluoro-[1,2-{sup 2}H{sub 4}]choline were synthesized by alkylation of the relevant precursor with [{sup 18}F]fluorobromomethane or [{sup 18}F]fluoromethyl tosylate. Radiosynthesis of [{sup 18}F]fluoromethyl tosylate required extensive modification of the existing method. [{sup 18}F]Fluorocholine and [{sup 18}F]fluoro-[1,2-{sup 2}H{sub 4}]choline were then subjected to in vitro oxidative stability analysis in a chemical oxidation model using potassium permanganate and an enzymatic model using choline oxidase. The two radiotracers, together with the corresponding di-deuterated compound, [{sup 18}F]fluoro-[1-{sup 2}H{sub 2}]choline, were then evaluated in vivo in a time-course biodistribution study in HCT-116 tumor-bearing mice. Results: Alkylation with [{sup 18}F]fluoromethyl tosylate proved to be the most reliable radiosynthetic route. Stability models indicate that [{sup 18}F]fluoro-[1,2-{sup 2}H{sub 4}]choline possesses increased chemical and enzymatic (choline oxidase) oxidative stability relative to [{sup 18}F]fluorocholine. The distribution of the three radiotracers, [{sup 18}F]fluorocholine, [{sup 18}F]fluoro-[1-{sup 2}H{sub 2}]choline and [{sup 18}F]fluoro-[1,2-{sup 2}H{sub 4}]choline, showed a similar uptake profile in most organs. Crucially, tumor uptake of [{sup 18}F

Studies on the relationship between Pitzer's equation and medium effect: the system of HCl + H{sub 2}SO{sub 4} in {l_brace}0.06455C{sub 2}H{sub 5}OH + 0.93545H{sub 2}O{r_brace}

Energy Technology Data Exchange (ETDEWEB)

Lu Xingmei E-mail: lxmqt@sohu.com; Xu Weiguo; Chang Xiaohong; Lu Dianzhen; Yang Jiazhen

2004-03-01

The second ionization constant of sulfuric acid in mixed solvent, K{sub 2}, was determined by e.m.f. of cell without liquid junction: (Pt,H{sub 2}(101.325 kPa) vertical bar HCl(m{sub 1}),H{sub 2}SO{sub 4}(m{sub 2}),{l_brace}ethanol(x=0.06455)+water(x=0.93545){r_brace} vertical bar AgCl-Ag))over the temperatures (278.15 to 318.15) K, where x is mole fraction. Combining Owen's definition of medium effect with Pitzer's equations, the values of combination parameters: ({lambda}{sub nHS}+{lambda}{sub nCl}-{lambda}{sub nS})+(3/2)m{sub n}({mu}{sub nnHS}+{mu}{sub nnC=} l-{mu}{sub nnS}),(1/2)({xi}{sub nHHS}+{xi}{sub nHCl}-{xi}{sub nHS}), that represent the interactions between ions and ethanol were obtained at 298.15 K.

Thermal decomposition of (UO{sub 2})O{sub 2}(H{sub 2}O){sub 2}·2H{sub 2}O: Influence on structure, microstructure and hydrofluorination

Energy Technology Data Exchange (ETDEWEB)

Thomas, R. [Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille (France); Hall de Recherche de Pierrelatte, AREVA NC, BP 16, 26701 Pierrelatte (France); Rivenet, M., E-mail: murielle.rivenet@ensc-lille.fr [Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille (France); Berrier, E. [Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille (France); Waele, I. de [Université de Lille, CNRS, UMR 8516 – LASIR - Laboratoire de Spectrochimie Infrarouge et Raman, F-59000 Lille (France); Arab, M.; Amaraggi, D.; Morel, B. [Hall de Recherche de Pierrelatte, AREVA NC, BP 16, 26701 Pierrelatte (France); Abraham, F. [Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-59000 Lille (France)

2017-01-15

The thermal decomposition of uranyl peroxide tetrahydrate, (UO{sub 2})O{sub 2}(H{sub 2}O){sub 2}.2H{sub 2}O, was studied by combining high temperature powder X-ray diffraction, scanning electron microscopy, thermal analyses and spectroscopic techniques (Raman, IR and {sup 1}H NMR). In situ analyses reveal that intermediates and final uranium oxides obtained upon heating are different from that obtained after cooling at room temperature and that the uranyl precursor used to synthesize (UO{sub 2})O{sub 2}(H{sub 2}O){sub 2}·2H{sub 2}O, sulfate or nitrate, has a strong influence on the peroxide thermal behavior and morphology. The decomposition of (UO{sub 2})O{sub 2}(H{sub 2}O){sub 2}·2H{sub 2}O ex sulfate is pseudomorphic and leads to needle-like shaped particles of metastudtite, (UO{sub 2})O{sub 2}(H{sub 2}O){sub 2}, and UO{sub 3-x}(OH){sub 2x}·zH{sub 2}O, an amorphous phase found in air in the following of (UO{sub 2})O{sub 2}(H{sub 2}O){sub 2} dehydration. (UO{sub 2})O{sub 2}(H{sub 2}O){sub 2}·2H{sub 2}O and the compounds resulting from its thermal decomposition are very reactive towards hydrofluorination as long as their needle-like morphology is kept.

Hydrogenation of ethylene over PrCo5Hsub(2.4)

International Nuclear Information System (INIS)

Soga, Kazuo; Imamura, Hayao; Ikeda, Sakuji

1977-01-01

To elucidate the chemical reactivity of the hydrogen atom absorbed in the hydrogenated alloy PrCo 5 H sub(n), the hydrogenation of ethylene was carried out over PrCo 5 Hsub(2.4) in the absence (A) or presence (B) of hydrogen in gas phase. PrCo 5 Hsub(2.4) was prepared from PrCo 5 according to an ordinary procedure with repeated heating and cooling in hydrogen atmosphere. The hydrogenation of ethylene was conducted at about -70 0 C in a conventional gas circulation system in a pressure range of ethylene 5 -- 16 cmHg and hydrogen 0 -- 38.0 cmHg. The hydrogenation rate was followed by gas chromatography. In the case of (A), the total gas pressure in the gas phase remained constant during the reaction. The hydrogenation rate was independent of the partial pressure of ethylene and it increased in proportion to the concentration of the absorbed hydrogen atom. The rate of desorption of the absorbed hydrogen atom from PrCo 5 Hsub(2.4) also measured under a reduced pressure. The desorption rate was approximately the same as the hydrogenation rate under the similar conditions. From these results, it was concluded that the migration process of the absorbed hydrogen atom from the bulk of the alloy to its surface was rate-determining. In the case of (B), on the other hand, the hydrogenation rate was accelerated by the gaseous hydrogen; the rate increased almost linearly with increasing pressure of hydrogen. The hydrogenation of ethylene was also conducted over PrCo 5 under the similar conditions. (auth.)

Synthesis and photocatalytic activity of CuY{sub y}Fe{sub 2-y}O{sub 4}-CuCo{sub 2}O{sub 4} nanocomposites for H{sub 2} evolution under visible light irradiation

Energy Technology Data Exchange (ETDEWEB)

Yan, Jianhui; Yang, Haihua; Yao, Maohai; Han, Yong [Department of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Shuyuan Load, Yueyang, Hunan 414000 (China); College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083 (China); Tang, Yougen; Lu, Zhouguang [College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083 (China); Zheng, Shuqin [Department of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Shuyuan Load, Yueyang, Hunan 414000 (China)

2009-11-15

Spinel-type CuY{sub y}Fe{sub 2-y}O{sub 4}-CuCo{sub 2}O{sub 4} nanocomposites have been successfully synthesized via a facile citric acid (CA)-assisted sol-gel method. And the as-synthesized nanocomposites have been characterized by techniques of X-ray diffraction (XRD), nitrogen adsorption BET method, and transmission electron microscopy (TEM). The samples are composed of primary ultrafine nanoparticles with nearly spherical morphology and mean particle size of about 80 nm. Moreover, the photocatalytic H{sub 2} evolution activity of the as-obtained samples has been evaluated from aqueous oxalic acid solution under visible light irradiation. The influence of photocatalyst type, calcination temperature, Y{sup 3+} doping content, and the durability of the as-obtained photocatalyst have been investigated in detail. The best photocatalytic H{sub 2} evolution activity was obtained over the as-synthesized CuY{sub 0.08}Fe{sub 1.92}O{sub 4}-CuCo{sub 2}O{sub 4} nanocomposite. (author)

Low-temperature solid-state preparation of ternary CdS/g-C{sub 3}N{sub 4}/CuS nanocomposites for enhanced visible-light photocatalytic H{sub 2}-production activity

Energy Technology Data Exchange (ETDEWEB)

Cheng, Feiyue; Yin, Hui; Xiang, Quanjun, E-mail: xiangqj@mail.hzau.edu.cn

2017-01-01

Highlights: • CdS/g-C{sub 3}N{sub 4}/CuS composite were synthesized by low-temperature solid-state method. • CdS/g-C{sub 3}N{sub 4}/CuS show enhanced visible-light photocatalytic H{sub 2} evolution activity. • The enhanced photocatalytic H{sub 2} production activity is due to the heterojunction. • Heterojunction between the components promote charge separation/transfer property. - Abstract: Low-temperature solid-state method were gradually demonstrated as a high efficiency, energy saving and environmental protection strategy to fabricate composite semiconductor materials. CdS-based multiple composite photocatalytic materials have attracted increasing concern owning to the heterostructure constituents with tunable band gaps. In this study, the ternary CdS/g-C{sub 3}N{sub 4}/CuS composite photocatalysts were prepared by a facile and novel low-temperature solid-state strategy. The optimal ternary CdS/g-C{sub 3}N{sub 4}/CuS composite exhibits a high visible-light photocatalytic H{sub 2}-production rate of 57.56 μmol h{sup −1} with the corresponding apparent quantum efficiency reaches 16.5% at 420 nm with Na{sub 2}S/Na{sub 2}SO{sub 3} mixed aqueous solution as sacrificial agent. The ternary CdS/g-C{sub 3}N{sub 4}/CuS composites show the enhanced visible-light photocatalytic H{sub 2}-evolution activity comparing with the binary CdS-based composites or simplex CdS. The enhanced photocatalytic activity is ascribed to the heterojunctions and the synergistic effect of CuS and g-C{sub 3}N{sub 4} in promotion of the charge separation and charge mobility. This work shows that the low-temperature solid-state method is efficient and environmentally benign for the preparation of CdS-based multiple composite photocatalytic materials with enhanced visible-light photocatalytic H{sub 2}-production activity.

Bi[NC{sub 5}H{sub 3}(CO{sub 2}){sub 2}](OH{sub 2}){sub x}F (x=1 and 2): New one-dimensional Bi-coordination materials-Reversible hydration and topotactic decomposition to {alpha}-Bi{sub 2}O{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Jeon, Hye Rim [Department of Chemistry Education, Chung-Ang University, Seoul 156-756 (Korea, Republic of); Lee, Dong Woo [Department of Chemistry, Chung-Ang University, Seoul 156-756 (Korea, Republic of); Ok, Kang Min, E-mail: kmok@cau.ac.kr [Department of Chemistry, Chung-Ang University, Seoul 156-756 (Korea, Republic of)

2012-03-15

Two one-dimensional bismuth-coordination materials, Bi[NC{sub 5}H{sub 3}(CO{sub 2}){sub 2}](OH{sub 2}){sub x}F (x=1 and 2), have been synthesized by hydrothermal reactions using Bi{sub 2}O{sub 3}, 2,6-NC{sub 5}H{sub 3}(CO{sub 2}H){sub 2}, HF, and water at 180 Degree-Sign C. Structures of the two materials were determined by single-crystal X-ray diffraction. Although they have different crystal structures, both Bi-organic materials shared a common structural motif, a one-dimensional chain structure consisting of Bi{sup 3+} cations and pyridine dicarboxylate linkers. Detailed structural analyses include infrared spectroscopy, thermogravimetric analysis, and reversible hydration reactions for the coordinated water molecules were reported. Also, thermal decomposition of the rod-shaped Bi[NC{sub 5}H{sub 3}(CO{sub 2}){sub 2}](OH{sub 2})F single crystals at 800 Degree-Sign C led to {alpha}-Bi{sub 2}O{sub 3} that maintained the same morphology of the original crystals. - Graphical abstract: Calcination of the Bi[NC{sub 5}H{sub 3}(CO{sub 2}){sub 2}](OH{sub 2})F single crystals at 800 Degree-Sign C results in the {alpha}-Bi{sub 2}O{sub 3} rods that maintain the original morphology of the crystals. Highlights: Black-Right-Pointing-Pointer Synthesis of one-dimensional chain Bi-organic frameworks. Black-Right-Pointing-Pointer Reversible hydration reactions of Bi[NC{sub 5}H{sub 3}(CO{sub 2}){sub 2}](OH{sub 2})F. Black-Right-Pointing-Pointer Topotactic decomposition maintaining the same morphology of the original crystals.

SIMULTANEOUS OBSERVATIONS OF SiO AND H{sub 2}O MASERS TOWARD KNOWN STELLAR H{sub 2}O MASER SOURCES

Energy Technology Data Exchange (ETDEWEB)

Kim, Jaeheon [Yonsei University Observatory, Seongsan-ro 262, Seodaemun, Seoul 120-749 (Korea, Republic of); Cho, Se-Hyung [Korean VLBI Network Yonsei Radio Astronomy Observatory, Yonsei University, Seongsan-ro 262, Seodaemun, Seoul 120-749 (Korea, Republic of); Kim, Sang Joon, E-mail: jhkim@kasi.re.kr, E-mail: cho@kasi.re.kr, E-mail: sjkim1@khu.ac.kr [Department of Astronomy and Space Science, Kyung Hee University, Seocheon-Dong, Giheung-Gu, Yongin, Gyeonggi-Do 446-701 (Korea, Republic of)

2013-01-01

We present the results of simultaneous observations of SiO v = 1, 2, {sup 29}SiO v = 0, J = 1-0, and H{sub 2}O 6{sub 16}-5{sub 23} maser lines toward 152 known stellar H{sub 2}O maser sources using the Yonsei 21 m radio telescope of the Korean VLBI Network from 2009 June to 2011 January. Both SiO and H{sub 2}O masers were detected from 62 sources with a detection rate of 40.8%. The SiO-only maser emission without H{sub 2}O maser detection was detected from 27 sources, while the H{sub 2}O-only maser without SiO maser detection was detected from 22 sources. Therefore, the overall SiO maser emission was detected from 89 sources, resulting in a detection rate of 58.6%. We have identified 70 new detections of the SiO maser emission. For both H{sub 2}O and SiO maser detected sources, the peak and integrated antenna temperatures of SiO masers are stronger than those of H{sub 2}O masers in both Mira variables and OH/IR stars and the relative intensity ratios of H{sub 2}O to SiO masers in OH/IR stars are larger than those in Mira variables. In addition, distributions of 152 observed sources were investigated in the IRAS two-color diagram.

Crystallographic isomorphism in the structural type of α-HgI{sub 2} by example of KHgI{sub 3} · H{sub 2}O, β-Ag{sub 2}HgI{sub 4}, and β-Cu{sub 2}HgI{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Borisov, S. V., E-mail: borisov@niic.nsc.ru; Magarill, S. A.; Pervukhina, N. V. [Russian Academy of Sciences, Nikolaev Institute of Inorganic Chemistry, Siberian Branch (Russian Federation)

2017-03-15

The structure of KHgI{sub 3} · H{sub 2}O is assigned to the family of crystal structures having the three-layer cubic packing of iodine anions with cations in the tetrahedral voids (the structures of α-HgI{sub 2}, β-Ag{sub 2}HgI{sub 4}, and β-Cu{sub 2}HgI{sub 4} among them). Crystallographic analysis shows that the nodes of the three-layer close packing are populated by iodine anions and K cations in the ratio 3/4: 1/4. Transformation of the structure of α-HgI{sub 2} into the structure of KHgI{sub 3} · H{sub 2}O can be formally represented as the replacement of (HgI){sub n}{sup +} fragments by (KH{sub 2}O){sub n}{sup +} fragments: (Hg{sub 2}I{sub 4})–(HgI){sup +} + (KH{sub 2}O){sub n}{sup +} = KHgI{sub 3} · H{sub 2}O. Perforated layers of vertex-sharing HgI{sub 4} tetrahedra break down into parallel isolated chains. Channels formed in place of I–Hg–I–Hg–fragments are occupied by–H{sub 2}O–K–-H{sub 2}-O-K-H{sub 2}O-chains weakly bound to neighbors.

Potentiometric investigation into complexing of Pr,Eu,Yb with new. beta. -diketones containing oxygen atom in fluorinated radical

Energy Technology Data Exchange (ETDEWEB)

Gritsenko, T.V.; Lozinskij, M.O.; Panyushkin, V.T.; Fialkov, Yu.A.; Berenblit, V.V. (Kubanskij Gosudarstvennyj Univ., Krasnodar (USSR); AN Ukrainskoj SSR, Kiev. Inst. Organicheskoj Khimii)

1983-01-01

Potentiometric method in the aqueous-methanol media at 25 deg and ionic torce of 0.15 (NaCl) has been used to determine the constants of acidic dissociation of the next ..beta..-diketones; Rsub(F)-CO-CHsub(2)-CO-R, where R=-C/sub 6/H/sub 5/, Rsub(F) C/sub 3/F/sub 7/OCF(CF/sub 3/) - (1), CF/sub 3/O(CF/sub 2/)/sub 3/OCF(CF/sub 3/) - (2), CF/sub 3/O(CF/sub 2/O)/sub 4/CF/sub 2/ - (3), CF/sub 3/O(CF/sub 2/)/sub 2/ - (4) and R=-C/sub 4/H/sub 3/S, Rsub(F) CF/sub 3/O(CF/sub 2/)/sub 3/OCF(CF/sub 3/) - (5), CF/sub 3/O(CF/sub 2/O)/sub 4/CF/sub 2/ - (6). Synthesis of the 1-3, 5, 6 is described. Stability constants of Pr/sup 3 +/, Eu/sup 3 +/, Yb/sup 3 +/ with 1-6 are calculated. Stability of the complexes for the each ..beta..-diketone increases in Pr-Eu-Yb series. Correlation between stability of the chelates and acidic properties of the ..beta..-diketonates is traced for the complexes of one metal with different ligands. Thus, the acidic properties of the ..beta..-diketones increase in the 1, 6-4 series; stability of their complexes with rare earths decreases in such order.

Two actinide-organic frameworks constructed by a tripodal flexible ligand: Occurrence of infinite ((UO{sub 2})O{sub 2}(OH){sub 3}){sub 4n} and hexanuclear (Th{sub 6}O{sub 4}(OH){sub 4}) motifs

Energy Technology Data Exchange (ETDEWEB)

Liang, Lingling; Zhang, Ronglan [College of Chemistry and Materials, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of education, Northwest University, Xi’an 710069 (China); Zhao, Jianshe, E-mail: jszhao@nwu.edu.cn [College of Chemistry and Materials, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of education, Northwest University, Xi’an 710069 (China); Liu, Chiyang, E-mail: lcy@nwu.edu.cn [Department of Geology, Northwest University, Xi’an 710069 (China); Weng, Ng Seik [The University of Nottingham Malaysia Campus, 43500 Semenyih, Selangor Darul Ehsan (Malaysia)

2016-11-15

Two new actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H{sub 3}tci) under hydrothermal condition. The combination of H{sub 3}tci and uranyl nitrate hexahydrate in aqueous solution leads to the isolation of [(UO{sub 2}){sub 2}(H{sub 2}O){sub 4}]{sub 0.5}(tci){sub 2}(UO{sub 2}){sub 4}(OH){sub 4}·18H{sub 2}O (1), which contains two distinct UO{sub 2}{sup 2+} coordination environments. Four uranyl cations, linked through μ{sub 3}-OH respectively, result in the edge-sharing ribbons. Then, the layer structure is constructed by U-O clusters linked through other eight-coordinated uranyl unions, giving rise to a porous structure in the space. Topological analysis reveals that complex 1 belongs to a (4, 8)-connected net with a schläfli symbol of (3{sup 4.}2{sup 6.}3){sub 2}(3{sup 4.}4{sup 6.}5{sup 6.}6{sup 8.}7{sup 3.}8). Th{sub 3}(tci){sub 2}O{sub 2}(OH){sub 2}(H{sub 2}O){sub 3}·12H{sub 2}O (2) generated by the reaction of H{sub 3}tci and thorium nitrate tetrahydrate, possesses nine-fold coodinated Th(IV) centers with a monocapped square antiprismatic geometry. The hexamers “Th{sub 6}O{sub 4}(OH){sub 4}” motifs are connected together by the carboxylate groups, showing a three-dimensional structures. Complex 2 takes on an 8-connected architecture and the point symbol is (4{sup 24.}6{sup 4}). - Graphical abstract: Two new 3D actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H3tci) and their topological structures were displayed. The infinite ((UO{sub 2})O{sub 2}(OH){sub 3}){sub 4n} and hexanuclear (Th{sub 6}O{sub 4}(OH){sub 4}) motifs were found in the title actinides networks.

One-pot synthesis of porphyrin functionalized γ-Fe{sub 2}O{sub 3} nanocomposites as peroxidase mimics for H{sub 2}O{sub 2} and glucose detection

Energy Technology Data Exchange (ETDEWEB)

Liu, Qingyun, E-mail: qyliu@sdust.edu.cn; Zhang, Leyou; Li, Hui; Jia, Qingyan; Jiang, Yanling; Yang, Yanting; Zhu, Renren

2015-10-01

Meso-tetrakis(4-carboxyphenyl)-porphyrin-functionalized γ-Fe{sub 2}O{sub 3} nanoparticles (H{sub 2}TCPP-γ-Fe{sub 2}O{sub 3}) were successfully prepared by one-pot method under hydrothermal conditions and were found to possess intrinsic peroxidase-like activity. The H{sub 2}TCPP-γ-Fe{sub 2}O{sub 3} nanocomposites can catalytically oxidize peroxidase substrate 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of H{sub 2}O{sub 2} to produce a blue color reaction, which can be easily observed by the naked eye. Furthermore, kinetic studies indicate that the H{sub 2}TCPP-γ-Fe{sub 2}O{sub 3} nanocomposites have an even higher affinity to TMB than that of the natural enzyme, horseradish peroxidase (HRP). On the basis of the high activity, the reaction provides a simple, sensitive and selective method for colorimetric detection of H{sub 2}O{sub 2} over a range of 10–100 μM with a minimum detection limit of 1.73 μM. Moreover, H{sub 2}TCPP-γ-Fe{sub 2}O{sub 3}/glucose oxidase (GOx)/TMB system provides a novel colorimetric sensor for glucose and shows good response toward glucose detection over a range of 5–25 μM with a minimum detection limit of 2.54 μM. The results indicated that it is a simple, cheap, convenient, highly selective, sensitive and easy handling colorimetric assay. Results of a fluorescent probe suggest that the catalase-mimic activity of the H{sub 2}TCPP-γ-Fe{sub 2}O{sub 3} nanocomposites effectively catalyze the decomposition of H{sub 2}O{sub 2} into H{sub 2}O and O{sub 2}. - Graphical abstract: 5,10,15,20-Tetrakis(4-carboxyl phenyl)-porphyrin (H{sub 2}TCPP)-γ-Fe{sub 2}O{sub 3} nanocomposites were demonstrated to possess intrinsic peroxidase-like activity and showed a higher catalytic activity, compared to that of γ-Fe{sub 2}O{sub 3} nanoparticles alone. - Highlights: • Porphyrin-functionalized γ-Fe{sub 2}O{sub 3} nanoparticles were prepared by one-pot method. • The porphyrin-γ-Fe{sub 2}O{sub 3} nanocomposites were found to possess

The ‘sub’ metallide oxide hydrides Sr{sub 21}Si{sub 2}O{sub 5}H{sub 12+x} and Ba{sub 21}M{sub 2}O{sub 5}H{sub 12+x} (M = Zn, Cd, Hg, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi)

Energy Technology Data Exchange (ETDEWEB)

Jehle, Michael; Hoffmann, Anke [Institut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstr. 21, D-79104 Freiburg (Germany); Kohlmann, Holger [Institut für Anorganische Chemie, Universität Leipzig, Johannisallee 29, D-04103 Leipzig (Germany); Scherer, Harald [Institut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstr. 21, D-79104 Freiburg (Germany); Röhr, Caroline, E-mail: caroline@ruby.chemie.uni-freiburg.de [Institut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstr. 21, D-79104 Freiburg (Germany)

2015-02-25

interpenetrating diamond-like networks: Network A consists of suboxide-like clusters [O{sub 5}A{sub 18}] (4{sup ¯}3m, 8a) and icosahedra [MA{sub 12}], i.e. isolated M anions (3{sup ¯}m, 16c). Network B, within which the H/D ions are interspersed in octahedral and tetrahedral coordination by Sr/Ba, contains FK-16 polyhedra [A(1)A{sub 16}] (4{sup ¯}3m, 8b) and bicapped hexagonal prisms [A(2)A{sub 14}] (3{sup ¯}m, 16d). For the tetrelides, the observed hydrogen content of 14 H/f.u. is in best accordance with the presence of the suboxide cluster [O{sub 5}A{sub 18}], the results of the FP-LAPW band structure calculations, the physical and chemical properties as well as with the NMR chemical shifts and dipolar coupling motifs. The range of suitable elements M (encompassing transition metals and pentelides too) also support the derived model for the H atom distribution inside the network B. The distinct minima at 90 (Zn: 88) v.e./f.u. in the tDOS of all calculated model compounds Ba{sub 21}M{sub 2}O{sub 5}H{sub 12} suggest hydrogen contents of 12 H/f.u. for Zn, Cd, Hg and the triels and 16 H/f.u. for the pentels.

Unprecedented connection mode of [V{sub 16}Sb{sub 4}O{sub 42}(H{sub 2}O)]{sup 8-} cluster anions by Mn{sup 2+} centered complexes. Solvothermal synthesis and properties of {[Mn(teta)]_4V_1_6Sb_4O_4_2(H_2O)}{sub n}.[(H{sub 2}O){sub 12}]{sub n}

Energy Technology Data Exchange (ETDEWEB)

Rasmussen, Maren; Naether, Christian; Bensch, Wolfgang [Institute of Inorganic Chemistry, Christian-Albrechts-University of Kiel (Germany); Leusen, Jan van; Koegerler, Paul [Institute of Inorganic Chemistry, RWTH Aachen University, Aachen (Germany)

2017-11-17

The new compound {[Mn(teta)]_4V_1_6Sb_4O_4_2}{sub n}.[(H{sub 2}O){sub 12}]{sub n} (teta = triethylenetetraamine) was synthesized under solvothermal conditions. The crystal structure features the high nuclearity [V{sub 16}{sup IV}Sb{sub 4}{sup III}O{sub 42}(H{sub 2}O)]{sup 8-} cluster anion, which consists of two rings composed of 8 edge-sharing VO{sub 5} polyhedra. The rings are perpendicular to each other generating four niches, which are occupied by two VO{sub 5} pyramids and two handle-like Sb{sub 2}O{sub 5} units. The two unique anions are each surrounded by eight Mn{sup 2+} centered complexes via Mn-O{sub term}-V bonds. Such an expansion has never been observed in heterometal polyoxovanadate chemistry. The connection mode between cluster anions and complex cations generates two individual layers stacked onto each other. Between the layers weak Sb..O contacts are observed. The crystal water molecules are mainly located in the empty space between the layers. Upon heating H{sub 2}O molecules are removed, while the crystal structure remains intact. The magnetic behavior is dominated by strong antiferromagnetic exchange interactions between the central V{sup 4+} ions, while the interaction between the cluster anion and central Mn{sup 2+} ions is significantly less pronounced. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Emulsion-phase synthesis of honeycomb-like Mg{sub 5}(OH){sub 2}(CO{sub 3}){sub 4}.4H{sub 2}O micro-spheres and subsequent decomposition to MgO

Energy Technology Data Exchange (ETDEWEB)

Gao Guo, E-mail: gaogaoguoguo@yahoo.com.c [Department of Bio-Nano-Science and Engineering, National Key Laboratory of Nano/Micro Fabrication Technology, Key Laboratory for Thin Film and Microfabrication of Ministry of Education, Institute of Micro-Nano Science and Technology, Shanghai Jiao Tong University, Shanghai 200240 (China); Beijing Key Laboratory of Green Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084 (China); Xiang Lan, E-mail: xianglan@mail.tsinghua.edu.c [Beijing Key Laboratory of Green Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084 (China)

2010-04-09

Herein we report a simple emulsion-phase route for the synthesis of honeycomb-like basic magnesium carbonate (BMC, Mg{sub 5}(OH){sub 2}(CO{sub 3}){sub 4}.4H{sub 2}O) micro-spheres at 80 {sup o}C. Magnesium(II) salts in water are precipitated by sodium carbonate in the presence of cetyltrimethylammonium bromide (CTAB). Scanning electron microscopy shows the obtained BMC samples are composed of a lot of micro-spheres (diameter ranging from 8 to 10 {mu}m) which are interweaved by a lot of nano-sized thin sheets (thickness of 20-30 nm and length >1 {mu}m). The BMC micro-spheres prepared by this approach are porous and appear to be hollow structures. The size and shape of BMC are related to the CTAB concentration and temperature. The lower concentration of CTAB resulted in the decrease of the micro-spheres sizes. When the temperature was elevated to 110 {sup o}C, hexagonal tablets (thickness of 20 nm, length of each side varies from 400 to 600 nm) can be prepared. After the calcinations for BMC at 600 {sup o}C for 2 h, BMC are almost completely converted to MgO. Transmission electron microscopy indicates that the obtained MgO samples have a poly-crystalline feature. The possible formation mechanism of BMC micro-spheres has been discussed.

Photochemistry of U(BH/sub 4/)/sub 4/ and U(BD/sub 4/)/sub 4/

Energy Technology Data Exchange (ETDEWEB)

Paine, R T; Schonberg, P R; Light, R W [New Mexico Univ., Albuquerque (USA). Dept. of Chemistry; Danen, W C; Freund, S M

1979-01-01

U(BH/sub 4/)/sub 4/ and U(BD/sub 4/)/sub 4/ are observed to undergo complex degradation reactions promoted by broadband UV radiation. The primary products of these reactions appear to be U(BH/sub 4/)/sub 3/, B/sub 2/H/sub 6/, H/sub 2/, U(BD/sub 4/)/sub 3/, B/sub 2/D/sub 6/ and D/sub 2/. Further, U(BD/sub 4/)/sub 4/ undergoes a related decomposition reaction under the influence of CO/sub 2/ laser irradiation at 924.97 cm/sup -1/.

Preparation of {sup 35}SO{sub 4}H{sub 2} and of some other {sup 35}S labeled mineral compounds; Preparation de {sup 35}SO{sub 4}H{sub 2} et de quelques autres composes mineraux simples marques a {sup 35}S

Energy Technology Data Exchange (ETDEWEB)

De la Gueronniere, E; Henry, R [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1958-07-01

Methods of preparation, from pile irradiated KCI, of the following labeled molecules are described: - carrier free H{sub 2}SO{sub 4} - SCd (100 m curies/milli mole) - solution of SNa{sub 2} (100 m curies/milli mole) - solution of SK{sub 2} (100 m curies/milli mole) - S metalloid (100 m curies/milli mole) - SO{sub 3}Na{sub 2} (90 m curies/milli mole) - S{sub 2}C{sub 3}Na{sub 2} (50 m curies/mammalia). (author) [French] On decrit les methodes de preparation, a partir de KCl irradie dans les piles, des molecules suivantes marquees au {sup 35}S: - SO{sub 4}H{sub 2} (sans entraineur) - SCd (100 mcuries/millimole) - solution de SNa{sub 2} (100 mcuries/millimole) - solution de SK{sub 2} (100 mcuries/millimole) - S metalloide (100 mcuries/millimole) - Na{sub 2}SO{sub 3} (90 mcuries/millimole) - Na{sub 2}S{sub 2}C{sub 3} (50 mcuries/milIimole). (auteur)

Syntheses, crystal structures and solid-state properties of the lanthanoid-containing nanoclusters [(Ln{sub 2}PW{sub 10}O{sub 38}){sub 4}(W{sub 3}O{sub 8})(OH){sub 4}(H{sub 2}O){sub 2}]{sup 26-}

Energy Technology Data Exchange (ETDEWEB)

Gupta, Rakesh; Saini, Mukesh Kumar; Hussain, Firasat [Department of Chemistry, University of Delhi (India)

2014-12-15

A series of lanthanoid-substituted polyoxometalates have been synthesized by a self-assembly process in potassium chloride solution by the reaction of dilacunary [P{sub 2}W{sub 19}O{sub 69}(H{sub 2}O)]{sup 14-} with mid- and late-lanthanoid Ln(NO{sub 3}){sub 3}.nH{sub 2}O salts leading to the formation of the tetrameric tungstophosphates [(Ln{sub 2}PW{sub 10}O{sub 38}){sub 4}(W{sub 3}O{sub 8})(OH){sub 4}(H{sub 2}O){sub 2}]{sup 26-} [Ln = Y{sup 3+} (1), Sm{sup 3+} (2), Eu{sup 3+} (3), Gd{sup 3+} (4), Tb{sup 3+} (5), Dy{sup 3+} (6), Ho{sup 3+} (7), Er{sup 3+} (8), Tm{sup 3+} (9), Yb{sup 3+} (10)]. The polyanions were isolated as potassium or mixed-alkali salts. Most of the compounds were characterized by single-crystal X-ray diffraction and various analytical techniques, such as FTIR, UV/Vis, {sup 31}P NMR and photoluminescence spectroscopy, magnetism, as well as thermogravimetric analysis. The FTIR spectra suggest that all the compounds are isomorphous. The crystal structures of these complexes consist of four A-[α-PW{sub 10}O{sub 36}]{sup 7-} units, each incorporating two Ln{sup III} ions to create four Keggin-like anions that further assemble with three additional tungstate units to form a tetramer species with C{sub 2} symmetry. The photoluminescent properties of 3a and 6a were investigated following photoexcitation at room temperature. The magnetic properties of 3a, 4a, 5a and 6a were investigated at room temperature, the complexes exhibiting paramagnetic behaviour. (Copyright copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Ellipsometric investigation of nitrogen doped diamond thin films grown in microwave CH{sub 4}/H{sub 2}/N{sub 2} plasma enhanced chemical vapor deposition

Energy Technology Data Exchange (ETDEWEB)

Ficek, Mateusz, E-mail: rbogdan@eti.pg.gda.pl [Department of Metrology and Optoelectronics, Faculty of Electronics, Telecommunications and Informatics, Gdansk University of Technology, 11/12 G. Narutowicza St., 80-233 Gdansk (Poland); Institute for Materials Research (IMO), Hasselt University, Wetenschapspark 1, B-3590 Diepenbeek (Belgium); Sankaran, Kamatchi J.; Haenen, Ken [Institute for Materials Research (IMO), Hasselt University, Wetenschapspark 1, B-3590 Diepenbeek (Belgium); IMOMEC, IMEC vzw, Wetenschapspark 1, B-3590 Diepenbeek (Belgium); Ryl, Jacek; Darowicki, Kazimierz [Department of Electrochemistry, Corrosion and Material Engineering, Gdansk University of Technology, 11/12 Narutowicza St., 80-233 Gdansk (Poland); Bogdanowicz, Robert [Department of Metrology and Optoelectronics, Faculty of Electronics, Telecommunications and Informatics, Gdansk University of Technology, 11/12 G. Narutowicza St., 80-233 Gdansk (Poland); Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125 (United States); Lin, I-Nan [Department of Physics, Tamkang University, Tamsui 251, Taiwan (China)

2016-06-13

The influence of N{sub 2} concentration (1%–8%) in CH{sub 4}/H{sub 2}/N{sub 2} plasma on structure and optical properties of nitrogen doped diamond (NDD) films was investigated. Thickness, roughness, and optical properties of the NDD films in the VIS–NIR range were investigated on the silicon substrates using spectroscopic ellipsometry. The samples exhibited relatively high refractive index (2.6 ± 0.25 at 550 nm) and extinction coefficient (0.05 ± 0.02 at 550 nm) with a transmittance of 60%. The optical investigation was supported by the molecular and atomic data delivered by Raman studies, bright field transmission electron microscopy imaging, and X-ray photoelectron spectroscopy diagnostics. Those results revealed that while the films grown in CH{sub 4}/H{sub 2} plasma contained micron-sized diamond grains, the films grown using CH{sub 4}/H{sub 2}/(4%)N{sub 2} plasma exhibited ultranano-sized diamond grains along with n-diamond and i-carbon clusters, which were surrounded by amorphous carbon grain boundaries.

Synthesis, structure and electronic configuration of [Rh{sub 6}Te{sub 8}(PPh{sub 3}){sub 6}].4C{sub 6}H{sub 6}

Energy Technology Data Exchange (ETDEWEB)

Thiele, Guenther; Balmer, Markus [Marburg Univ. (Germany). Fachbereich Chemie; Dehnen, Stefanie [Marburg Univ. (Germany). Fachbereich Chemie and Wissenschaftliches Zentrum fuer Materialwissenschaften

2016-08-01

[Rh{sub 6}Te{sub 8}(PPh{sub 3}){sub 6}].4C{sub 6}H{sub 6}, the first compound with a molecular Chevrel-type [Rh{sub 6}Te{sub 8}] cluster core has been synthesized and structurally characterized. By means of quantum chemical calculation, the close relationship of its electronic configuration to that of the lighter homologue has been demonstrated. The different crystal solvent content prevents an isostructural crystallization.

Controllable solvothermal synthesis and photocatalytic properties of complex (oxy)fluorides K{sub 2}TiOF{sub 4}, K{sub 3}TiOF{sub 5}, K{sub 7}Ti{sub 4}O{sub 4}F{sub 7} and K{sub 2}TiF{sub 6}

Energy Technology Data Exchange (ETDEWEB)

Sheng Jie [Division of Nanomaterials and Nanochemistry, Hefei National Laboratory for Physical Sciences at Microscale, Hefei, Anhui 230026 (China); Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026 (China); Tang Kaibin, E-mail: kbtang@ustc.edu.cn [Division of Nanomaterials and Nanochemistry, Hefei National Laboratory for Physical Sciences at Microscale, Hefei, Anhui 230026 (China); Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026 (China); Cheng Wei; Wang Junli; Nie Yanxiang; Yang Qing [Division of Nanomaterials and Nanochemistry, Hefei National Laboratory for Physical Sciences at Microscale, Hefei, Anhui 230026 (China); Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026 (China)

2009-11-15

Complex (oxy)fluorides K{sub 2}TiF{sub 6}, K{sub 2}TiOF{sub 4}, K{sub 3}TiOF{sub 5} and K{sub 7}Ti{sub 4}O{sub 4}F{sub 7} have been successfully synthesized for the first time through a controllable solvothermal route involving different solvents, for example, methanol, methanol-H{sub 2}O and methanol-H{sub 2}O{sub 2}. The as-prepared products were characterized by X-ray powder diffraction, N{sub 2} surface area adsorption, scanning electron microscope, Fourier transform infrared spectroscopy, UV-vis absorption spectra and X-ray fluorescence. The influences of reaction conditions such as the ratio of methanol to H{sub 2}O{sub 2} or methanol to H{sub 2}O, reaction temperature on the phase, crystallizability and purity of the (oxy)fluorides products were discussed in detail. Meanwhile, the photocatalytic behaviors of the as-prepared K{sub 2}TiF{sub 6}, K{sub 2}TiOF{sub 4}, K{sub 3}TiOF{sub 5} and K{sub 7}Ti{sub 4}O{sub 4}F{sub 7} were evaluated by degradation of rhodamine B molecules, and the results showed that all of the products possessed photocatalytic activities in the order of K{sub 2}TiOF{sub 4} > K{sub 2}TiF{sub 6} > K{sub 7}Ti{sub 4}O{sub 4}F{sub 7} > K{sub 3}TiOF{sub 5} at room temperature under the UV light.

Estudio de la susceptibilidad de un acero inoxidable austenítico estabilizado con niobio al dañado por tensocorrosión en medio H>2sub>S (SSC y corrosión intergranular (IGC en otros medios agresivos

Directory of Open Access Journals (Sweden)

Gutiérrez de Saiz-Solabarría, S.

1998-05-01

Full Text Available Behavior to hydrogen damage caused by stress corrosion in a H>2sub>S medium (SSC and to intergranular corrosion (IGC in different mediums, such as oxalic acid (C2H>2sub>O>4sub>-2H>2sub>0, iron sulphate-50 % sulfuric acid [Fe<sub>2sub>(SO>4sub>>3sub>-50 % H>2sub>SO>4sub>], nitric acid (HNO<sub>3sub>, copper sulphate-16 % sulfuric acid (CuSO<sub>4sub>-5H>2sub>O-16 % H>2sub>SO>4sub> and cooper sulphate-50 % sulfuric acid (CuSO<sub>4sub>-5H>2sub>O-50 % H>2sub>SO>4sub>, is studied in an AISI 347 austenitic stainless steel stabilized with 0.61 mass % Nb and hot rolled to a seamless pipe with 273.1 mm in diameter and 18.2 mm in thickness.

Se estudia el comportamiento de un acero inoxidable austenítico del tipo AISI 347 estabilizado con un 0,61 % en masa de Nb, laminado en caliente para producir una tubería sin soldadura de 273,1 mm de diámetro y 18,2 mm de espesor, frente al dañado por hidrógeno generado por tensocorrosión en medio H>2sub>S (SSC y frente a la corrosión intergranular (IGC en diferentes medios agresivos tales como ácido oxálico (C<sub>2sub>H>2sub>O>4sub>∙2H>2sub>O, sulfato de hierro-50% ácido sulfúrico [Fe<sub>2sub> (SO<sub>4sub>>3sub>-50 % H>2sub>SO>4sub>], ácido nítrico (HNO<sub>3sub>, sulfato de cobre-16% ácido sulfúrico (CuSO<sub>4sub>-5H>2sub>O-16 % H>2sub>SO>4sub> y sulfato de cobre-50 % ácido sulfúrico (CuSO<sub>4sub>-5H>2sub>O-50 % H>2sub>SO>4sub>, respectivamente.

Tris(Cyclopentadienyl)Uranium-t-Butyl: Synthesis, reactions, and mechanisms

Energy Technology Data Exchange (ETDEWEB)

Weydert, Marc [Univ. of California, Berkeley, CA (United States)

1993-04-01

Compounds (RC>5sub>H>4sub>)>3sub>U(t-Bu) were prepared for R = H, Me, Et. Their decomposition products in aromatic solvents are consistent with a radical decomposition pathway induced by solvent-assisted U-C bond homolysis. NMR was used to study the reactions of (RC>5sub>H>4sub>)>3sub>UCl with t-BuLi (R = t-Bu, Me<sub>3sub>Si). Reactions of (MeC<sub>5sub>H>4sub>)>3sub>U(t-Bu) with Lewis bases and fluorocarbons were studied. Analogous reaction chemistry between (RC>5sub>H>4sub>)>3sub>ThX systems and t-BuLi was also studied, and reactivity differences between U and Th are discussed. Synthesis of sterically crowded (RC>5sub>H>4sub>)>4sub>U compounds is next considered. Reaction of the trivalent (RC>5sub>H>4sub>)>3sub>U with (RC>5sub>H>4sub>)>2sub>Hg results in formation of (RC>5sub>H>4sub>)>4sub>U. Steric congestion, cyclopentadienyl ligand exchange, and electron transfer are discussed. (DLC)

Synthesis, characterization and sorption properties of functionalized Cr-MIL-101-X (X=–F, –Cl, –Br, –CH{sub 3}, –C{sub 6}H{sub 4}, –F{sub 2}, –(CH{sub 3}){sub 2}) materials

Energy Technology Data Exchange (ETDEWEB)

Buragohain, Amlan [Department of Chemistry, Indian Institute of Technology Guwahati, 781039 Assam (India); Couck, Sarah [Department of Chemical Engineering, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Brussels (Belgium); Van Der Voort, Pascal [Department of Inorganic and Physical Chemistry, Ghent University, COMOC – Center for Ordered Materials, Organometallics and Catalysis, Krijgslaan 281-S3, 9000 Ghent (Belgium); Denayer, Joeri F.M. [Department of Chemical Engineering, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Brussels (Belgium); Biswas, Shyam, E-mail: sbiswas@iitg.ernet.in [Department of Chemistry, Indian Institute of Technology Guwahati, 781039 Assam (India)

2016-06-15

Four existing and three new functionalized chromium terephthalates having MIL-101 topology and denoted as Cr-MIL-101-X (existing ones with X=–F, 1-F; –Cl, 2-Cl; –Br, 3-Br; –CH{sub 3}, 4-CH{sub 3}; new ones with X=–C{sub 6}H{sub 4}, 5-C{sub 6}H{sub 4}; –F{sub 2}, 6-F{sub 2}, –(CH{sub 3}){sub 2}, 7-(CH{sub 3}){sub 2}) were synthesized under hydrothermal conditions. All the materials except 5-C{sub 6}H{sub 4} could be prepared by a general synthetic route, in which the mixtures of CrO{sub 3}, H{sub 2}BDC-X (BDC=1,4-benzenedicarboxylate) linkers, conc. HCl and water with a molar ratio of 1:1:3.9:222.2 were reacted at 180 °C for 144 h. Compared to the 144 h of synthesis time, three of the compounds, namely 1-Cl, 2-Br and 5-C{sub 6}H{sub 4}, could be prepared in much shorter reaction times (12–18 h at 180–210 °C). The materials possess high thermal stability up to 270–300 °C in an air atmosphere. The activated compounds exhibit significant porosity (S{sub BET} range: 1273–2135 m{sup 2} g{sup −1}). At 0 °C and 1 bar, the CO{sub 2} adsorption capacities of the compounds fall in the 1.7–2.9 mmol g{sup −1} range. Compounds 1-F and 6-F{sub 2} showed enhanced CO{sub 2} uptake values compared to parent Cr-MIL-101. The benzene adsorption capacities of the compounds lie in the range of 66.2–139.5 molecules per unit cell at 50 °C and p/p{sub 0}=0.35. The increased benzene uptake value of 1-F compared to un-functionalized Cr-MIL-101 and 4-CH{sub 3} suggests that the fluorination has induced more hydrophobicity in Cr-MIL-101 as compared to the methylation. - Graphical abstract: Benzene adsorption by seven functionalized Cr-MIL-101-X metal-organic framework (MOF) materials Display Omitted - Highlights: • Seven functionalized Cr-MIL-101-X materials were synthesized solvothermally. • All Cr-MIL-101-X materials exhibited high thermal stability up to 270–300 °C in air. • All Cr-MIL-101-X compounds displayed considerable porosity towards N{sub 2

Two ternary mixed-anion chlorides with divalent europium: Eu{sub 2}H{sub 3}Cl and Eu{sub 7}F{sub 12}Cl{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Reckeweg, Olaf [Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301 (United States); Institut fuer Anorganische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany); DiSalvo, Francis J. [Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301 (United States); Wolf, Sarah; Schleid, Thomas [Institut fuer Anorganische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany)

2014-06-15

Dark ruby-red, transparent, triangular plate-shaped single crystals of Eu{sub 2}H{sub 3}Cl and colorless, transparent, needle-shaped single crystals of Eu{sub 7}F{sub 12}Cl{sub 2} were obtained by solid-state reactions of Eu, NaH, NaCl, and Na (2:4:1:2 molar ratio) or Eu, EuCl{sub 3}, and LiF (1:1:4 molar ratio), respectively, in silica-jacketed tantalum ampoules at 900 C for 13 h. Eu{sub 2}H{sub 3}Cl crystallizes isotypically to Ba{sub 2}H{sub 3}X (X = Cl, Br, I) in the trigonal space group P anti 3m1 (no. 164) with lattice parameters a = 409.67(4) and c = 696.18(7) pm, whereas Eu{sub 7}F{sub 12}Cl{sub 2} crystallizes isotypically to Ba{sub 7}F{sub 12}Cl{sub 2} or Sr{sub 7}H{sub 12}Cl{sub 2} in the hexagonal space group P anti 6 (no. 174) with lattice parameters a = 1002.31(5) and c = 392.54(2) pm. Both compounds contain Eu{sup 2+} cations with coordination numbers as high as nine (Eu{sub 7}F{sub 12}Cl{sub 2}) and ten (Eu{sub 2}H{sub 3}Cl) with respect to the halide anions (F{sup -} or H{sup -} and Cl{sup -}). The structural results are corroborated by EUTAX and MAPLE calculations on both ternary mixed-anion europium(II) chlorides in comparison to these for related binary and ternary compounds with divalent europium. (Copyright copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Study of UO{sub 2}F{sub 2} - H{sub 2}O - HF compounds; Etude des composes UO{sub 2}F{sub 2} - H{sub 2}O - HF

Energy Technology Data Exchange (ETDEWEB)

Neveu, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1961-07-01

We study various compounds resulting from the interaction of UO{sub 2}F{sub 2} with H{sub 2}O and HF (gas), and various triple compounds UO{sub 2}F{sub 2} - H{sub 2}O - HF; the conditions of decomposition and the thermodynamic limits of stability are specified. (author) [French] Nous etudions divers composes formes par reaction de UO{sub 2}F{sub 2} avec H{sub 2}O et HF (gaz) et divers composes triples UO{sub 2}F{sub 2} - H{sub 2}O - HF, en essayant de preciser les decompositions et domaines d'exisfence thermodynamiques de ces corps. (auteur)

Novel synthetic route to molybdenum hydrido-thiocarbamoyl and hydrosulfido-carbyne complexes by reactions of trans-Mo(N{sub 2}){sub 2}(R{sub 2}PC{sub 2}H{sub 4}PR{sub 2}){sub 2} with N,N-dimethylthioformamide

Energy Technology Data Exchange (ETDEWEB)

Luo, X.L.; Kubas, G.J.; Burns, C.J.; Butcher, R.J. [Los Alamos National Lab., NM (United States)

1995-07-01

The reactions of bis(dinitrogen)molybdenum complexes trans-Mo(N{sub 2}){sub 2}(R{sub 2}PC{sub 2}H{sub 4}PR{sub 2}){sub 2} (R = Ph, Et) with N,N-dimethylthioformamide (HC(S)NMe{sub 2}) in refluxing benzene under argon give the molybdenum hydrido-thiocarbamoyl complexes MoH({eta}{sup 2}-C(S)NMe{sub 2})(R{sub 2}PC{sub 2}H{sub 4}PR{sub 2}){sub 2} (R = Ph (1a), Et (1b)). On heating at 125{degree}C in toluene solutions, compounds 1a and 1b rearrange to form the molybdenum hydrosulfido-aminocarbyne complexes trans-Mo(SH)-(=CNMe{sub 2})(R{sub 2}PC{sub 2}H{sub 4}PR{sub 2}){sub 2} (R = Ph (2a), Et (2b)). A mechanism is proposed for this thermal rearrangement which involves migration of the hydride ligand from molybdenum to the sulfur atom of the thiocarbamoyl ligand to give the 16-electron Fischer carbene intermediate Mo-(=C(SH)NMe{sub 2})(R{sub 2}PC{sub 2}H{sub 4}PR{sub 2}){sub 2}, followed by migration of the hydrosulfido group from the carbene carbon to molybdenum. The molecular structures of compounds 1a and 2a have been determined by single-crystal X-ray diffraction studies. 30 refs., 4 figs., 4 tabs.

INFRARED ABSORPTION LINES TOWARD NGC 7538 IRS 1: ABUNDANCES OF H{sub 2}, H{sub 3}{sup +}, AND CO

Energy Technology Data Exchange (ETDEWEB)

Goto, Miwa [Universitäts-Sternwarte München, Scheinerstr. 1, D-81679 Munich (Germany); Geballe, T. R. [Gemini Observatory, 670 North A‘ohoku Place, Hilo, HI 96720 (United States); Usuda, Tomonori, E-mail: mgoto@usm.lmu.de, E-mail: tgeballe@gemini.edu, E-mail: usuda@naoj.org [Subaru Telescope, 650 North A‘ohoku Place, Hilo, HI 96720 (United States)

2015-06-10

We report high-resolution near-infrared absorption spectroscopy of H{sub 2}, H{sub 3}{sup +}, and CO toward the young high mass object NGC 7538 IRS 1. The v = 1–0 H{sub 2} S(0) line and lines in the CO v = 2–0 band were detected; the v = 1–0 H{sub 2} S(1) line and the v = 1–0 H{sub 3}{sup +} lines [R(1, 1){sup l}, R(1, 0), R(1, 1){sup u}] were not detected. The line of sight traverses two clouds, with temperatures 45 and 259 K and with roughly equal column densities of CO. Assuming that H{sub 2} is at the same temperature as CO and that the two species are uniformly mixed, [H{sub 2}]/[CO] = 3600 ± 1200. NGC 7538 is the most distant object from the Galactic center for which [H{sub 2}]/[CO] has been directly measured using infrared absorption spectroscopy.

Nano Fe{sub 2}O{sub 3,} clinoptilolite and H{sub 3}PW{sub 12}O{sub 40} as efficient catalysts for solvent-free synthesis of 5(4H)-isoxazolone under microwave irradiation conditions

Energy Technology Data Exchange (ETDEWEB)

Fozooni, Samieh, E-mail: samieh.fozooni@uk.ac.ir, E-mail: s_fozooni@yahoo.com [Shahid Bahonar University, Kerman (Iran, Islamic Republic of). Mining Engineering Department. Zarand High Education Center; Hosseinzadeh, Nasrin Gholam; Akhgar, Mohammad Reza [Islamic Azad University, Kerman (Iran, Islamic Republic of). Department of Chemistry; Hamidian, Hooshang [Payame Noor University (PNU), Tehran (Iran, Islamic Republic of). Department of Chemistry

2013-10-15

A quick and solvent-free approach involving the exposure of neat reactants to microwave irradiation in conjunction with the use of clinoptilolite, H{sub 3}PW{sub 12}O{sub 40} and Fe{sub 2}O{sub 3} nanoparticle catalysts is described. In this work, condensation of hydroxylamine hydrochloride, sodium acetate, acetoacetic or benzoyl acetic ethyl ester and appropriate aldehydes by employing catalysts gave 5(4H)-isoxazolone only in one step. Catalyst amount, temperature effects and catalysts reusability were monitored. Among the catalysts, Fe{sub 2}O{sub 3} nanoparticles had better performance than other catalysts from viewpoint of yield and reaction time. The present protocol offers several advantages, such as short reaction time, reasonable yield, mild reaction condition and recycling catalysts with a very easy workup. (author)

Investigation of the chemistry of liquid H{sub 2}S scavengers

Energy Technology Data Exchange (ETDEWEB)

Buhaug, Janne Bjoerntvedt

2002-07-01

The production of natural gas in the North Sea is facing a growing problem: contamination of the natural gas with dihydrogen sulfide, H{sub 2}S. As a gas reservoir is emptied, seawater containing sulfates is pumped into it, and the sulfates are reduced to dihydrogen sulfide by sulfate-reducing bacteria. Dihydrogen sulfide is then pumped up along with the oil, gas and water from the reservoir, causing severe corrosion of pipelines and contamination of the final natural gas product. Dihydrogen sulfide is extremely toxic, and in fields with especially large concentrations of H{sub 2}S this is a severe health risk for the platform workers. Hence, it is desirable to remove the dihydrogen sulfide at the earliest stage possible. There are four main methods for removing H{sub 2}S from natural gas: (1) Liquid scavengers, (2) Solid scavengers, (3) Liquid redox processes, (4) Amine / Claus catalyst. Liquid scavengers are widely used in the natural gas industry, especially at sites with relatively low concentrations of H{sub 2}S. As a rule of thumb, liquid scavengers are economically favourable at sites with a removal of less than 50 kg/day of H{sub 2}S. This thesis is concerned with the cyclic amine 1,3,5 -tris(2-hydroxyethyl)-1,3,5-triazinane, often referred to as Triazine. This is used in fields with relatively low concentration of H{sub 2}S and dominates the liquid scavenger market.

Electronic, magnetic and optical properties of reduced hybrid layered complex Ni(pyz)V{sub 4}O{sub 10} (pyz=C{sub 4}H{sub 4}N{sub 2}) by first-principles

Energy Technology Data Exchange (ETDEWEB)

Munir, Junaid; Mat Isa, Ahmad Radzi [Physics Department, Faculty of Science, Universiti Teknologi Malaysia, Skudai 81310, Johor (Malaysia); Yousaf, Masood [IBS Center for Multidimensional Carbon Materials, Ulsan National Institute of Science and Technology, Ulsan 689-798 (Korea, Republic of); Aliabad, H.A. Rahnamaye [Department of Physics, Hakim Sabzevari University (Iran, Islamic Republic of); Ain, Qurat-ul [Key Laboratory for Laser Plasamas (MOE) & Department of Physics and Astronomy, Shanghai Jiao Tong University, Shanghai 200240 (China); Saeed, M.A., E-mail: saeed@utm.my [Physics Department, Faculty of Science, Universiti Teknologi Malaysia, Skudai 81310, Johor (Malaysia)

2016-10-15

This article reports the electronic, structure, magnetic and optical properties of reduced hybrid layered complex Ni(pyz)V{sub 4}O{sub 10} (pyz=C{sub 4}H{sub 4}N{sub 2}) studied by employing density functional theory with local density approximation (LDA), generalized gradient approximation (GGA) of Perdew–Burke–Ernzerhof-96 (PBE) and modified Becke–Johnson (mBJ) exchange-correlation potential and energy. The band structure and density of states of these compounds are also presented. The total density of states (DOS) for up and down spin states clearly split, which means that the exchange interaction causes the ordered spin arrangement. PBE-mBJ calculation reveals a wider band gap in spin down state, which shows a half-metallic electronic character at the equilibrium state. The spin-polarized calculations indicate metallic nature in orthorhombic crystalline phase. It is also noted that the optical conductivity for PBE-mBJ is larger than that of LDA and PBE-GGA. Furthermore, the results show a half-metallic ferromagnetic ground state for Ni(pyz)V{sub 4}O{sub 10} in PBE-mBJ potential. The present results suggest Ni(pyz)V{sub 4}O{sub 10} compound as a potential candidate for the future optoelectronic and spintronic applications. - Highlights: • First study of the electronic, structure, magnetic and optical properties of reduced hybrid layered complex Ni(pyz)V{sub 4}O{sub 10} (pyz=C{sub 4}H{sub 4}N{sub 2}) by first principles. • PBE-mBJ calculation reveals a wider band gap in spin down state indicating its half-metallic electronic character. • The large spin magnetic moment on Ni and V cations indicates the ferromagnetic interaction which makes this compound suitable candidate for spintronics applications. • An optical band gap reveals that this compound is also useful for the application in optoelectronics.

Synthesis, vibrational and optical properties of a new three-layered organic-inorganic perovskite (C{sub 4}H{sub 9}NH{sub 3}){sub 4}Pb{sub 3}I{sub 4}Br{sub 6}

Energy Technology Data Exchange (ETDEWEB)

Dammak, T., E-mail: thameurlpa@yahoo.f [Laboratoire de Physique appliquee (LPA), Faculte des Sciences de Sfax, 3018, BP 802 (Tunisia); Elleuch, S. [Laboratoire de Physique appliquee (LPA), Faculte des Sciences de Sfax, 3018, BP 802 (Tunisia); Bougzhala, H. [Laboratoire de cristallochimie et des materiaux, Faculte des Sciences de Tunis (Tunisia); Mlayah, A. [Centre d' Elaboration de Materiaux et d' Etudes Structurales, CNRS-Universite Paul Sabatier, 29 rue Jeanne Marvig, 31055 Toulouse, Cedex 4 (France); Chtourou, R. [Centre de Recherche et des Technologies de l' Energie CRTEn BP. 95, Hammam-Lif 2050, Laboratoire de Photovoltaique et de Semiconducteur (Tunisia); Abid, Y. [Laboratoire de Physique appliquee (LPA), Faculte des Sciences de Sfax, 3018, BP 802 (Tunisia)

2009-09-15

An organic-inorganic hybrid perovskite (C{sub 4}H{sub 9}NH{sub 3}){sub 4}Pb{sub 3}I{sub 4}Br{sub 6} was synthesized and studied by X-ray diffraction, Raman and infrared spectroscopies, optical transmission and photoluminescence. The title compound, abbreviated (C{sub 4}){sub 4}Pb{sub 3}I{sub 4}Br{sub 6}, crystallises in a periodic two-dimensional multilayer structure with P2{sub 1}/a space group. The structure is built up from alternating inorganic and organic layers. Each inorganic layer consists of three sheets of PbX{sub 6} (X=I, Br) octahedra. Raman and infrared spectra of the title compound were recorded in the 100-3500 and 400-4000 cm{sup -1} frequency ranges, respectively. An assignment of the observed vibration modes is reported. Optical transmission measurements, performed on thin films of (C{sub 4}){sub 4}Pb{sub 3}I{sub 4}Br{sub 6}, revealed two absorption bands at 474 and 508 nm. Photoluminescence measurements have shown a green emission peak at 519 nm.

Effective Liquid-phase Nitration of Benzene Catalyzed by a Stable Solid Acid Catalyst: Silica Supported Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40}

Energy Technology Data Exchange (ETDEWEB)

Gong, Shu-wen; Liu, Li-jun; Zhang, Qian; Wang, Liang-yin [Liaocheng University, Liaocheng (China)

2012-04-15

Silica supported Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40} catalyst was prepared through sol-gel method with ethyl silicate-40 as silicon resource and characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, nitrogen adsorption-desorption and potentiometric titration methods. The Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40} particles with Keggin-type structure well dispersed on the surface of silica, and the catalyst exhibited high surface area and acidity. The catalytic performance of the catalysts for benzene liquid-phase nitration was examined with 65% nitric acid as nitrating agent, and the effects of various parameters were tested, which including temperature, time and amount of catalyst, reactants ratio, especially the recycle of catalyst was emphasized. Benzene was effectively nitrated to mononitro-benzene with high conversion (95%) in optimized conditions. Most importantly, the supported catalyst was proved has excellent stability in the nitration progress, and there were no any other organic solvent and sulfuric acid were used in the reaction system, so the liquid-phase nitration of benzene that we developed was an eco-friendly and attractive alternative for the commercial technology

Synthesis, structural approach and electronic properties of V{sub 18}O{sub 45}, (N{sub 2}C{sub 6}H{sub 14}){sub 6}: a new organically templated vanadium oxide exhibiting V{sub 2}O{sub 5} layer topology

Energy Technology Data Exchange (ETDEWEB)

Sicard, M.; Maignan, A. [Laboratoire Crismat-ISMRa UMR 6508, 14 - Caen (France); Riou, D. [Universite de Versailles St Quentin, Institut Lavoisier UMR CNRS 8637, 78 - Versailles (France)

2002-02-01

V{sub 18}O{sub 45}, (N{sub 2}C{sub 6}H{sub 14}){sub 6} was hydrothermally synthesized in the form of thin platelets. Its structural approach was investigated by single crystal X-ray diffraction (non-centrosymmetric P2{sub 1} (No 4) monoclinic space group with a 10.7713(3) Angstrom, b = 11.2697(3) Angstrom, c = 29.7630(9) Angstrom, {beta} = 93.924(1) deg., V = 3604.4(2) Angstrom{sup 3}, Z = 2). V{sub 18}O{sub 45}, (N{sub 2}C{sub 6}H{sub 14}){sub 6} exhibits a lamellar structure built up from the stacking of vanadium oxide slabs between which the di-protonated 1,4-di-aza-bi-cyclo[2.2.2]octane organic cations are intercalated. The oxide layers are topologically similar to those encountered in the parent vanadium penta-oxide V{sub 2}O{sub 5} but exhibiting here a mixed valence V{sup IV}/V{sup V} with a ratio equal to 2. The electronic conductivity measurements performed on the crystals show that the resistivity curves are described by an Arrhenius law with an activation energy of 0.16 eV. (authors)

“Plug-and-Play” potentials: Investigating quantum effects in (H{sub 2}){sub 2}–Li{sup +}–benzene

Energy Technology Data Exchange (ETDEWEB)

D’Arcy, Jordan H.; Kolmann, Stephen J.; Jordan, Meredith J. T. [School of Chemistry, The University of Sydney, Sydney (Australia)

2015-08-21

Quantum and anharmonic effects are investigated in (H{sub 2}){sub 2}–Li{sup +}–benzene, a model for hydrogen adsorption in metal-organic frameworks and carbon-based materials, using rigid-body diffusion Monte Carlo (RBDMC) simulations. The potential-energy surface (PES) is calculated as a modified Shepard interpolation of M05-2X/6-311+G(2df,p) electronic structure data. The RBDMC simulations yield zero-point energies (ZPE) and probability density histograms that describe the ground-state nuclear wavefunction. Binding a second H{sub 2} molecule to the H{sub 2}–Li{sup +}–benzene complex increases the ZPE of the system by 5.6 kJ mol{sup −1} to 17.6 kJ mol{sup −1}. This ZPE is 42% of the total electronic binding energy of (H{sub 2}){sub 2}–Li{sup +}–benzene and cannot be neglected. Our best estimate of the 0 K binding enthalpy of the second H{sub 2} to H{sub 2}–Li{sup +}–benzene is 7.7 kJ mol{sup −1}, compared to 12.4 kJ mol{sup −1} for the first H{sub 2} molecule. Anharmonicity is found to be even more important when a second (and subsequent) H{sub 2} molecule is adsorbed; use of harmonic ZPEs results in significant error in the 0 K binding enthalpy. Probability density histograms reveal that the two H{sub 2} molecules are found at larger distance from the Li{sup +} ion and are more confined in the θ coordinate than in H{sub 2}–Li{sup +}–benzene. They also show that both H{sub 2} molecules are delocalized in the azimuthal coordinate, ϕ. That is, adding a second H{sub 2} molecule is insufficient to localize the wavefunction in ϕ. Two fragment-based (H{sub 2}){sub 2}–Li{sup +}–benzene PESs are developed. These use a modified Shepard interpolation for the Li{sup +}–benzene and H{sub 2}–Li{sup +}–benzene fragments, and either modified Shepard interpolation or a cubic spline to model the H{sub 2}–H{sub 2} interaction. Because of the neglect of three-body H{sub 2}, H{sub 2}, Li{sup +} terms, both fragment PESs lead to overbinding

Quantum-chemical ab initio calculations on the three isomers of diborabenzene (C{sub 4}H{sub 4}B{sub 2})

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Singh, Jaswinder; Raabe, Gerhard [Inst. fuer Organische Chemie, RWTH Aachen Univ. (Germany); Wang Yuekui [Key Lab. of Chemical Biology and Molecular Engineering of the Education Ministry, Inst. of Molecular Science, Shanxi Univ., Taiyuan, SH (China)

2010-01-15

Quantum-chemical ab initio calculations up to the ZPE+CCSD(T)/aug-cc-pVTZ/MP2/6-311++G** level were performed on three possible structural isomers of diborabenzene (C{sub 4}H{sub 4}B{sub 2}). All three molecules were found to be local minima on the C{sub 4}H{sub 4}B{sub 2} energy surface and to have closed shell singlet ground states. While the ground states of the 1,3- and 1,4-isomer are planar and of C{sub 2v} and D{sub 2h} symmetry, respectively, 1,2-diborabenzene is non-planar with a C{sub 2} axis passing through the center of the BB bond and the middle of the opposite carbon-carbon bond as the only symmetry element. The energetically most favourable 1,3-diborabenzene was found to be about 19 and 36 kcal/mol lower in energy than the 1,2- and the 1,4-isomer. Planar 1,3- and 1,4-diborabenzene have three doubly occupied {pi} orbitals while non-planar 1,2-diborabenzene has also three doubly occupied orbitals which can be derived from the {pi} orbitals of its 3.7 kcal/mol energetically less favourable planar form (''{pi}=like'' orbitals). The lowest unoccupied orbitals of all three isomers have {sigma} symmetry with large coefficients at the two boron atoms. These orbitals are lower in energy than the lowest unoccupied molecular orbitals (LUMOs) of e. g. benzene and pyridine and might cause pronounced acceptor properties which could be one of the reasons for the elusiveness of the title compounds. The results of bond separation reactions show that cyclic conjugation stabilizes all three diborabenzenes relative to their isolated fragments. The most effective stabilization energy of about 24 kcal/mol was found for the energetically lowest 1,3-isomer. This value amounts to approximately one third of the experimental value for the bond separation energy of pyridine. In all cases the energetically lowest triplet states are significantly (16 - 24 kcal/mol) higher in energy than the singlet ground states. Also among the triplets the 1,3-isomer is the

Metal–organic frameworks assembled from lanthanide and 2,5-pyridinedicaboxylate with cubane-like [Ln{sub 4}(OH){sub 4}] building units

Energy Technology Data Exchange (ETDEWEB)

Abdelbaky, Mohammed S.M. [Departamentos de Química Física y Analítica y Química Orgánica e Inorgánica, University of Oviedo—CINN, Oviedo 33006 (Spain); Amghouz, Zakariae, E-mail: amghouz.uo@uniovi.es [Departamentos de Química Física y Analítica y Química Orgánica e Inorgánica, University of Oviedo—CINN, Oviedo 33006 (Spain); Servicios Científico-Técnicos, University of Oviedo—CINN, Oviedo 33006 (Spain); Fernández-Zapico, Eva; García-Granda, Santiago; García, José R. [Departamentos de Química Física y Analítica y Química Orgánica e Inorgánica, University of Oviedo—CINN, Oviedo 33006 (Spain)

2015-09-15

Lanthanide–organic frameworks based on 2,5-pyridinedicaboxylate (25p) ligand, formulated as [Yb{sub 4}(OH){sub 4}(25p){sub 4}(H{sub 2}O){sub 3}]·H{sub 2}O (25pYb), [Y{sub 4}(OH){sub 4}(25p){sub 4}(H{sub 2}O){sub 3}]·H{sub 2}O (25pY-1) and [Y{sub 6}(OH){sub 8}(25p){sub 5}(H{sub 2}O){sub 2}] (25pY-2), have been obtained as single phases under hydrothermal conditions. 25pYb and 25pY-1 are isostructural, and crystallize in the triclinic space group, P-1, with a=8.6075(5) Å, b=14.8478(7) Å, c=15.9164(9) Å, α=86.277(4)°, β=80.196(5)°, γ=81.785(4)°, and a=8.7166(6) Å, b=14.966(1) Å, c=15.966(1) Å, α=86.260(6)°, β=80.036(6)°, γ=81.599(6)°, respectively. 25pY-2 crystallizes in the monoclinic space group, P2{sub 1}/c, with a=24.9117(17) Å, b=13.7340(8) Å, c=14.3385(10) Å, β=100.551(7)°. 25pYb and 25pY-2 have been structurally characterized by single-crystal X-ray diffraction. The 25pYb structure is based on tetranuclear cubane-like [Yb{sub 4}(OH){sub 4}]{sup 8+} clusters, which are interconnected to eight neighbouring clusters through teen surrounding 25p ligands leading to neutral 3D framework, while the structure of 25pY-2 is based on two independent cuban-like [Y{sub 4}(OH){sub 4}]{sup 8+} clusters, which are joined together through Y1 cation leading to the formation of hexanuclear [Y{sub 6}(OH){sub 8}]{sup 10+} clusters, which in turn are joined via Y2 cation resulting in infinite inorganic chain extending along c-axis, and each chain is interconnected to six adjacent chains through 25p ligands leading finally to 3D framework. The luminescence properties of Eu{sup 3+} and Tb{sup 3+} doped 25pY-1 and 25pY-2 compounds have also been investigated. All materials has been characterized by powder X-ray diffraction, thermal analyses (TG–SDTA–MS), FTIR spectroscopy, C–H–N elemental analysis, scanning electron microscopy (SEM-EDX), and powder X-ray thermodiffraction. - Graphical abstract: Nowadays, lanthanide–organic frameworks (LOFs) attract

Early-transition-metal ketenimine complexes. Synthesis, reactivity, and structural characterization of complexes with. eta. sup 2 (C,N)-ketenimine groups bound to the halogenobis((trimethylsilyl)cyclopentadienyl)niobium unit. X-ray structure of Nb(. eta. sup 5 -C sub 5 H sub 4 SiMe sub 3 ) sub 2 Cl(. eta. sup 2 (C,N)-PhN double bond C double bond CPh sub 2 )

Energy Technology Data Exchange (ETDEWEB)

Antinolo, A.; Fajardo, M.; Lopez Mardomingo, C.; Otero, A. (Univ. de Alcala de Henares (Spain)); Mourad, Y.; Mugnier, Y. (Centre National de la Recherche Scientifique, Dijon (France)); Sanz-Aparicio, J.; Fonseca, I.; Florencio, F. (CSIC, Madrid (Spain))

1990-11-01

The reaction of Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}X (X = Cl, Br) with 1 equiv of various ketenimines, R{sup 1}N{double bond}C{double bond}CR{sup 2}R{sup 3}, leads to the niobium derivatives Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}X({eta}{sup 2}(C,N)-R{sup 1}N{double bond}C{double bond}CR{sup 2}R{sup 3}) (1, X = Cl, R{sup 1} = R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 2, X = Cl, R{sup 1} = p-CH{sub 3}-C{sub 6}H{sub 4}, R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 3, X = Br, R{sup 1} = R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 4, X = Br, R{sup 1} = p-CH{sub 3}-C{sub 6}H{sub 4}, R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 5, X = Cl, R{sup 1} = R{sup 2} = C{sub 6}H{sub 5}, R{sup 3} = CH{sub 3}; 6, X = Br, R{sup 1} = R{sup 2} = C{sub 6}H{sub 5}, R{sup 3} = CH{sub 3}) with the expected ketenimine C{double bond}N bonding mode. Reduction of 1 with 1 equiv of Na/Hg gives the complex Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}({eta}{sup 2}(C,N)-PhN{double bond}C{double bond}CPh{sub 2}) (9) as a paramagnetic compound. The reduction of 9 with 1 equiv of Na/Hg and the subsequent addition of a proton source (ethanol) leads to the iminoacyl compound Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}(CRNR{sup 1}) (10, R = CH(Ph{sub 2}), R{sup 1} = Ph). The one- and two-electron reductions of 1 have been studied by cyclic voltammetry experiments. The structure of 1 was determined by single-crystal X-ray diffractometry: a = 24.4904 (14) {angstrom}, b = 11.0435 (04) {angstrom}, c = 26.6130 (15) {angstrom}, {beta} = 109.890 (5){degree}, monoclinic, space group C2/c, Z = 8, V = 6,768.4 (5) {angstrom}{sup 3}, {rho}{sub calcd} = 1.3194 g/mL, R = 0.048, R{sub w} = 0.060 based on 4,806 observed reflections. The structure contains a niobium atom bonded to two cyclopentadienyl rings in a {eta}{sup 5} fashion; the coordination of the metal is completed by a Cl atom and a {eta}{sup 2}(C,N)-bonded ketenimine ligand.

Reaction of Tris(cyclopentadienyl)uranium compounds with amines, azides, and related ligands

Energy Technology Data Exchange (ETDEWEB)

Rosen, R.K.

1989-12-01

The trivalent uranium compound, (MeC{sub 5}H{sub 4}){sub 3}U(thf), serves as a one- or two-electron reducing agent towards azides, RN{sub 3}. These reactions produce either the uranium(IV) azide, (MeC{sub 5}H{sub 4}){sub 3}UN{sub 3}, or uranium(V) imides, (MeC{sub 5}H{sub 4}){sub 3}UNR. The role of steric and electronic effects upon this reaction has been investigated using several series of azides. For Me{sub 3}XN{sub 3}, the imides are produced when X = C or Si, both products are formed when X = Ge, and the azide is produced when X = Sn. For Ph{sub 3}XN{sub 3}, the azide is produced when X = C or Sn. For Ph{sub 3-x}CH{sub 3}N{sub 3}, the imide is produced when x = 2 and both compounds are produced when x = 1. For substituted phenylazides, RC{sub 6}H{sub 4}N{sub 3}, only the imides are produced. The magnetic properties of uranium diimides, ((MeC{sub 5}H{sub 4}){sub 3}U){sub 2}({mu}-NRN), were investigated. Several uranium(III) amines, (MeC{sub 5}H{sub 4}){sub 3}U(NH{sub 2}R), were produced from (MeC{sub 5}H{sub 4}){sub 3}U(thf) and RNH{sub 2}, and NH{sub 3} was found to be a better ligand towards (MeC{sub 5}H{sub 4}){sub 3}U than is PMe{sub 3}.

Structure and magnetic properties of Sm{sub 2}Rh{sub 3}Sn{sub 5}. An intergrowth of TiNiSi- and NdRh{sub 2}Sn{sub 4}-related slabs

Energy Technology Data Exchange (ETDEWEB)

Heying, Birgit; Koesters, Jutta; Hoffmann, Rolf-Dieter; Heletta, Lukas; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

2017-07-01

The stannide Sm{sub 2}Rh{sub 3}Sn{sub 5} was obtained by arc-melting of the elements and subsequent annealing at 1070 K in a silica tube. Sm{sub 2}Rh{sub 3}Sn{sub 5} crystallizes with the orthorhombic Y{sub 2}Rh{sub 3}Sn{sub 5} type structure, space group Cmc2{sub 1}, Z=4: a=444.46(8), b=2636.2(4), c=718.3(1) pm, wR=0.0711, 1761 F{sup 2} values and 61 variables. The three crystallographically independent rhodium atoms show tricapped trigonal prismatic coordination by samarium and tin atoms. Sm{sub 2}Rh{sub 3}Sn{sub 5} can be considered as a simple 1:1 intergrowth structure of TiNiSi- and NdRh{sub 2}Sn{sub 4}-related slabs of compositions SmRhSn and SmRh{sub 2}Sn{sub 4}. Temperature dependent magnetic susceptibility data revealed van Vleck type behavior caused by the proximity of the exited {sup 6}H{sub 7/2} state to the {sup 6}H{sub 5/2} ground state of Sm{sup 3+}, and an antiferromagnetic ordering occurs at T{sub N}=3.5(5) K.

Involvement of the histamine H{sub 4} receptor in clozapine-induced hematopoietic toxicity: Vulnerability under granulocytic differentiation of HL-60 cells

Energy Technology Data Exchange (ETDEWEB)

Goto, Aya; Mouri, Akihiro; Nagai, Tomoko; Yoshimi, Akira; Ukigai, Mako; Tsubai, Tomomi; Hida, Hirotake [Division of Clinical Sciences and Neuropsychopharmacology, Faculty and Graduate School of Pharmacy, Meijo University, 150 Yagotoyama, Tempaku-ku, Nagoya 468-8503 (Japan); Ozaki, Norio [Department of Psychiatry, Graduate School of Medicine, Nagoya University, 65 Tsurumai-cho, Showa-ku, Nagoya 466-8550 (Japan); Noda, Yukihiro, E-mail: ynoda@meijo-u.ac.jp [Division of Clinical Sciences and Neuropsychopharmacology, Faculty and Graduate School of Pharmacy, Meijo University, 150 Yagotoyama, Tempaku-ku, Nagoya 468-8503 (Japan)

2016-09-01

Clozapine is an effective antipsychotic for treatment-resistant schizophrenia, but can cause fatal hematopoietic toxicity as agranulocytosis. To elucidate the mechanism of hematopoietic toxicity induced by clozapine, we developed an in vitro assay system using HL-60 cells, and investigated the effect on hematopoiesis. HL-60 cells were differentiated by all-trans retinoic acid (ATRA) into three states according to the following hematopoietic process: undifferentiated HL-60 cells, those undergoing granulocytic ATRA-differentiation, and ATRA-differentiated granulocytic cells. Hematopoietic toxicity was evaluated by analyzing cell survival, cell proliferation, granulocytic differentiation, apoptosis, and necrosis. In undifferentiated HL-60 cells and ATRA-differentiated granulocytic cells, both clozapine (50 and 100 μM) and doxorubicin (0.2 µM) decreased the cell survival rate, but olanzapine (1–100 µM) did not. Under granulocytic differentiation for 5 days, clozapine, even at a concentration of 25 μM, decreased survival without affecting granulocytic differentiation, increased caspase activity, and caused apoptosis rather than necrosis. Histamine H{sub 4} receptor mRNA was expressed in HL-60 cells, whereas the expression decreased under granulocytic ATRA-differentiation little by little. Both thioperamide, a histamine H{sub 4} receptor antagonist, and DEVD-FMK, a caspase-3 inhibitor, exerted protection against clozapine-induced survival rate reduction, but not of live cell counts. 4-Methylhistamine, a histamine H{sub 4} receptor agonist, decreased the survival rate and live cell counts, as did clozapine. HL-60 cells under granulocytic differentiation are vulnerable under in vitro assay conditions to hematopoietic toxicity induced by clozapine. Histamine H{sub 4} receptor is involved in the development of clozapine-induced hematopoietic toxicity through apoptosis, and may be a potential target for preventing its occurrence through granulocytic differentiation

Synthesis and characterization of MoS{sub 2} cocatalysts for H{sub 2}-generation; Darstellung und Charakterisierung von MoS{sub 2} Cokatalysatoren fuer die H{sub 2}-Entwicklung

Energy Technology Data Exchange (ETDEWEB)

Djamil, John

2015-10-05

As a suitable alternative to fossil fuels and nuclear energy light induced generation of H{sub 2} represents a trend-setting research area in the field of regenerative energy. Therefore photocatalysts, which provide surface sites for light driven reduction of protons to H{sub 2}, are being investigated and developed. Enhancement of photocatalytic systems can be achieved by the usage of cocatalysts, which simplify charge separation and provide additional catalytic active sites as well. In the present work cocatalysts based on MoS{sub 2} were synthesized, characterized and investigated for photocatalytic H{sub 2} generation. MoS{sub 2} cocatalysts were synthesized by thermal decomposition of tetraalkyl ammonium thiomolybdates with varying carbon content in the organic cation and by mechanical treatment of bulk MoS{sub 2} respectively. Hence, samples with differing chemical composition as well as structural properties were obtained. Based on these findings relations between chemical composition, microstructural properties and photocatalytic activity were supposed to reveal. Nanoparticulate molybdenum sulfides resulted in both synthetic routes. Thermal decomposition of tetraalkyl ammonium thiomolybdates yielded in carbon containing molybdenum sulfide nanocomposites, in which carbon and sulfur content and the crystallite size as well varied with the carbon amount in the precursor. Additionally a composite with a significant enlarged interlayer distance between the MoS{sub 2} layers was obtained by thermal decomposition of (Ph{sub 4}P){sub 2}MoS{sub 4}. Such interlayer expansion could be explained by an insertion of in situ generated Ph{sub 3}PS- and (Ph{sub 4}P){sub 2}S-molecules between the MoS{sub 2} layers. While Ph{sub 3}PS-molecules were bonded through Mo-S-bonds to the MoS{sub 2} layers, (Ph{sub 4}P){sub 2}S-molecules remained free in rotation between MoS{sub 2} sheets. The mechanical treatment of bulk MoS{sub 2} resulted in different-sized MoS{sub 2

Comparison of field data with a thermodynamic model for the H/sub 2/SO/sub 4/ - HNO/sub 3/ - NH/sub 3/ system at high humidities and in fogs

Energy Technology Data Exchange (ETDEWEB)

Jacob, D.J.; Munger, J.W.; Waldman, J.M.; Hoffmann, M.R.

1986-04-01

A systematic characterization of the atmospheric H/sub 2/SO/sub 4/ - NH/sub 2/ system was conducted in the fogwater, the aerosol, and the gas phase at a network of sites in the San Joaquin Valley of California. Spatial patterns of concentrations were established that reflect the distribution of SO/sub 2/, NO/sub X/, and NH/sub 3/ emissions within the valley. The concept of atmospheric alkalinity was introduced to interpret these concentrations in terms of the buffering capacity of the atmosphere with respect to inputs of strong acids. Regions of predominantly acidic and alkaline fogwater were identified. Fogwater was found to be alkaline in most of the valley, but small changes in emission budgets could lead to widespread acid fog. An extended stagnation episode was studied in detail: progressive accumulation of H/sub 2/SO/sub 4/ - HNO/sub 3/ - NH/sub 3/ species was documented over the course of the episode, and interpreted in terms of production and removal mechanisms. Secondary production of strong acids H/sub 2/SO/sub 4/ and HNO/sub 3/ under stagnant conditions resulted in a complete titration of available alkalinity at sites furthest from NH/sub 3/ sources. A steady SO/sub 2/ conversion rate of 0.4 - 1.1% h/sup -1/ was estimated in the stagnant mixed layer of haze aerosol under overcast conditions, and was attributed to non-photochemical heterogeneous processes. Removal of SO/sub 2/ was enhanced in fog as compared to non-foggy conditions. Conversion of NO/sub X/ to HNO/sub 3/ slowed down during the stagnation episode because of reduced photochemical activity: fog did not appear to enhance conversion of NO/sub X/. Decreases in total HNO/sub 3/ concentrations were observed upon acidification of the atmosphere, and were attributed to displacement of NO/sub 3-/ by H/sub 2/SO/sub 4/ in the aerosol followed by rapid deposition of HNO/sub 3/(g). The occurrence of fog was associated with general decreases of aerosol concentrations due to enhanced removal by deposition.

Investigation of the Dynamics Of NH{sup +}{sub 4} and H{sub 2}O Molecular Groups in Crystals; Etude de la Dynamique des Groupes Moleculaires NH{sup +}{sub 4} et H{sub 2}O dans les Cristaux; 0418 0421 0421 041b 0415 0414 041e 0412 0410 041d 0418 0415 0414 0418 041d 0410 041c 0418 041a 0418 041c 041e 041b 0415 041a 0423 041b 042f 0420 041d 042b 0425 0413 0420 0423 041f 041f NH{sup +}{sub 4} H H{sub 2}O 0412 041a 0420 0418 0421 0422 0410 041b 041b 0410 0425 ; Estudio de la Dinamica de los Grupos Moleculares NH{sup +}{sub 4} Y H{sub 2}O en Cristales

Energy Technology Data Exchange (ETDEWEB)

Bajorek, A.; Machehina, T. A.; Parlin' Ski, K. [Ob' edinennyj Institut Jadernyh Issledovanij, Dubna, SSSR (Russian Federation)

1965-06-15

The authors give the results of thermal neutron scattering measurements in crystals containing ammonium ion (NH{sub 4}CI, NH{sub 4}Br, NH{sub 4}I, NH{sub 4}F, NH{sub 4}NO{sub 3}, NH{sub 4}CNS, (NH{sub 4}){sub 2}SO{sub 4}, (NH{sub 4}){sub 2}S{sub 2}O{sub 8}, (NH{sub 4}){sub 2}Cr{sub 2}O{sub 7}, (NH{sub 4}){sub 2}CO{sub 3}) and water of crystallization (BaCl{sub 2} * 2H{sub 2}O, SrCl{sub 2} * 6H{sub 2}O, CuSO{sub 4} * 5H{sub 2}O) . The investigations were made to study the influence of various crystal lattices on the dynamics of these groups and the connection between scattering processes and phase transitions. In spite of the structural differences of the substances examined, the spectra obtained at the temperature of liquid nitrogen proved to be similar. As a rule, there are two peaks, one in the 15-20 meV energy transfer range, and the other in the 35-70 meV range, associated with the torsional vibrations of.ammonium ions. The intensity of the peaks depends on the structure of the substances under examination and falls as the sample temperature rises. It was found that there is a jump in the elastic region of the spectrum at certain phase transitions (in the cases of NH{sub 4}I, NH{sub 4}NO{sub 3} and (NH{sub 4}){sub 2}SO{sub 4}). At increased temperatures an additional peak appears in NH{sub 4}Cl, NH{sub 4}Br and (NH{sub 4}){sub 2}(COO){sub 2} to the lower energy side of the rotational retardation peak. The spectra of neutrons scattered in crystals containing water of crystallization also resemble one another. Three groups of peaks are observed in the spectra, associated with optical vibrations and rotational retardation of the water molecules. (author) [French] Us auteurs indiquent les resultats qu'ils ont obtenus en mesurant la diffusion des neutrons thermiques par des cristaux contenant un ion ammonium (NH{sub 4}CI, NH{sub 4}Br, NH{sub 4}I, NH{sub 4}F, NH{sub 4}NO{sub 3}, NH{sub 4}CNS, (NH{sub 4}){sub 2}SO{sub 4}, (NH{sub 4}){sub 2}S{sub 2}O{sub 8}, (NH{sub 4

Straw - H{sub 2}O gasification kinetics. Determination and discussion

Energy Technology Data Exchange (ETDEWEB)

Holst Soerensen, L.; Tarp Poulsen, K. [ReaTech, Roskilde (Denmark); Henriksen, U. [The Technical Univ., Dept. of Energy Engineering, Lyngby (Denmark); Risnes, H. [NTNU, Dept. of Thermal Energy and Hydropower, Trondheim (Norway); Hansen, L.K. [FLS Miljoe A/S, Valby (Denmark); Olsen, A.; Rathmann, O. [Risoe National Lab., Roskilde (Denmark)

1999-11-01

Preliminary steam reactivity data is presented from an experimental study of reactivity for wheat and barley char. The parameters currently investigated ranges from 0.15-1.5 bar H{sub 2}O and 0-1.0 bar H{sub 2}. Kinetics of the Langmuir-Hinshelwood type is used to discuss the reactivity variations with steam partial pressure and also the effects of adding hydrogen. The reactivity of char from wheat and washed barley was low and significantly decreasing with conversion. A significant increasing reactivity with conversion was observed for the char derived from a barley sample and a barley sample six times enriched by the water-soluble parts from the straw sample. The six times enriched barley was roughly six times as reactive as the barley. For wheat significant inhibiting effect from hydrogen was found. Assuming Langmuir Hinshelwood kinetics with reverse oxygen exchange and structural profile invariance, kinetics for the inhibiting reaction by H{sub 2} were estimated. 0.5 and 1 bar H{sub 2} decreased the reactivity roughly by one order of magnitude in 1.5 bar H{sub 2}O. (au) EFP-96. 17 refs.

First time-dependent study of H{sub 2} and H{sub 3}{sup +} ortho-para chemistry in the diffuse interstellar medium: Observations meet theoretical predictions

Energy Technology Data Exchange (ETDEWEB)

Albertsson, T.; Semenov, D.; Henning, Th. [Max-Planck-Institut für Astronomie, Königstuhl 17, D-69117 Heidelberg (Germany); Indriolo, N. [Department of Physics and Astronomy, Johns Hopkins University, Baltimore, MD 21218 (United States); Kreckel, H. [Max-Planck-Institut für Kernphysik, D-69117 Heidelberg (Germany); Crabtree, K. N. [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States)

2014-05-20

The chemistry in the diffuse interstellar medium (ISM) initiates the gradual increase of molecular complexity during the life cycle of matter. A key molecule that enables build-up of new molecular bonds and new molecules via proton donation is H{sub 3}{sup +}. Its evolution is tightly related to molecular hydrogen and thought to be well understood. However, recent observations of ortho and para lines of H{sub 2} and H{sub 3}{sup +} in the diffuse ISM showed a puzzling discrepancy in nuclear spin excitation temperatures and populations between these two key species. H{sub 3}{sup +}, unlike H{sub 2}, seems to be out of thermal equilibrium, contrary to the predictions of modern astrochemical models. We conduct the first time-dependent modeling of the para-fractions of H{sub 2} and H{sub 3}{sup +} in the diffuse ISM and compare our results to a set of line-of-sight observations, including new measurements presented in this study. We isolate a set of key reactions for H{sub 3}{sup +} and find that the destruction of the lowest rotational states of H{sub 3}{sup +} by dissociative recombination largely controls its ortho/para ratio. A plausible agreement with observations cannot be achieved unless a ratio larger than 1:5 for the destruction of (1, 1)- and (1, 0)-states of H{sub 3}{sup +} is assumed. Additionally, an increased cosmic-ray ionization rate to 10{sup –15} s{sup –1} further improves the fit whereas variations of other individual physical parameters, such as density and chemical age, have only a minor effect on the predicted ortho/para ratios. Thus, our study calls for new laboratory measurements of the dissociative recombination rate and branching ratio of the key ion H{sub 3}{sup +} under interstellar conditions.

Experimental determination and modeling of the solubility phase diagram of the ternary system (Li{sub 2}SO{sub 4} + K{sub 2}SO{sub 4} + H{sub 2}O) at 288.15 K

Energy Technology Data Exchange (ETDEWEB)

Wang, Shiqiang, E-mail: wangshiqiang@tust.edu.cn [Tianjin Key Laboratory of Marine Resources and Chemistry, College of Marine Science and Engineering, Tianjin University of Science and Technology, Tianjin 300457 (China); Guo, Yafei [Tianjin Key Laboratory of Marine Resources and Chemistry, College of Marine Science and Engineering, Tianjin University of Science and Technology, Tianjin 300457 (China); Li, Dongchan [Engineering Research Center of Seawater Utilization Technology of Ministry of Education, Hebei University of Technology, Tianjin 300130 (China); Tang, Peng; Deng, Tianlong [Tianjin Key Laboratory of Marine Resources and Chemistry, College of Marine Science and Engineering, Tianjin University of Science and Technology, Tianjin 300457 (China)

2015-02-10

Highlights: • Solubility of the ternary system Li{sub 2}SO{sub 4} + K{sub 2}SO{sub 4} + H{sub 2}O at 288.15 K has been measured. • Phase diagram of this system was simulated and calculated by a thermodynamic model. • Li{sub 2}SO{sub 4}·K{sub 2}SO{sub 4} belongs to the incongruent double salt in this system. • Solution density was calculated using empirical equation. - Abstract: The solubility and density in the thermodynamic phase equilibria ternary system (Li{sub 2}SO{sub 4} + K{sub 2}SO{sub 4} + H{sub 2}O) at 288.15 K and 0.1 MPa were investigated experimentally with the method of isothermal dissolution equilibrium. This system at 288.15 K consists of two invariant points, three univariant isothermal dissolution curves; and three crystallization regions. The salt Li{sub 2}SO{sub 4}·K{sub 2}SO{sub 4} belongs to the incongruent double salt, and no solid solution was found. Based on the Pitzer model and its extended Harvie–Weare (HW) model, the mixing ion-interaction parameters of θ{sub Li,K}, ψ{sub Li,K,SO4} at 288.15 K and the solubility equilibrium constants K{sub sp} of solid phases Li{sub 2}SO{sub 4}·H{sub 2}O and Li{sub 2}SO{sub 4}·K{sub 2}SO{sub 4}, which are not reported in the literature were acquired. A comparison between the calculated and experimental results at 288.15 K for the ternary system shows that the calculated solubilities obtained with the extended HW model agree well with experimental data.

Inhibition of mild steel corrosion by 1,4,6-trimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile and synergistic effect of halide ion in 0.5 M H{sub 2}SO{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Mourya, Punita, E-mail: mouryapunita025@gmail.com [Department of Chemistry, Indian Institute of Technology (Banaras Hindu University), Varanasi 221005 (India); Singh, Praveen [Department of Chemistry, Banaras Hindu University, Varanasi 221005 (India); Rastogi, R.B.; Singh, M.M. [Department of Chemistry, Indian Institute of Technology (Banaras Hindu University), Varanasi 221005 (India)

2016-09-01

Highlights: • TODPCN is a good corrosion inhibitor for mild steel in 0.5 M H{sub 2}SO{sub 4} solution. • Addition of iodide ion increases the inhibition efficiency of the studied nitrile derivative. • Inhibition efficiency successively increases with concentration. • XPS study has revealed the chemical composition of the protective film. - Abstract: The effect of iodide ions on inhibitive performance of 1,4,6-trimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (TODPCN) on mild steel (MS) corrosion in 0.5 M H{sub 2}SO{sub 4} was studied using gravimetric and electrochemical measurements. TODPCN inhibits the corrosion of MS to the extent of 62.3% at its lowest concentration (0.5 mM) and its inhibition efficiency (η) further increases on increasing concentration at 298 K. The adsorption of TODPCN on MS was found to follow the Langmuir adsorption isotherm. The value of η increased on the addition of 2.0 mM KI. The value of synergism parameter being more than unity indicates that the enhanced η value in the presence of iodide ions is only due to synergism. Thus, a cooperative mechanism of inhibition exists between the iodide anion and TODPCN cations. The increase in surface coverage in the presence of KI indicates that iodide ions enhance the adsorption of TODPCN. The surface morphology of corroded/inhibited MS was studied by atomic force microscopy. X-ray photoelectron spectroscopy of inhibited MS surface was carried out to determine the composition of the adsorbed film. Some quantum chemical parameters and the Mulliken charge densities for TODPCN calculated by density functional theory provided further insight into the mechanism of inhibition.

Toluene and chlorobenzene dinitration over solid H{sub 3}PO{sub 4}/MoO{sub 3}/SiO{sub 2} catalyst

Energy Technology Data Exchange (ETDEWEB)

Adamiak, Joanna, E-mail: jadamiak@ch.pw.edu.pl [Warsaw University of Technology, Faculty of Chemistry, Division of High Energetic Materials, Noakowskiego 3, 00-664 Warsaw (Poland); Kalinowska-Alichnewicz, Dorota; Szadkowski, Michal; Skupinski, Wincenty [Warsaw University of Technology, Faculty of Chemistry, Division of High Energetic Materials, Noakowskiego 3, 00-664 Warsaw (Poland)

2011-11-15

Highlights: {yields} A novel catalyst H{sub 3}PO{sub 4}/MoO{sub 3}/SiO{sub 2} was characterized and used in nitration. {yields} On the surface domains of phosphomolybdic acid (HPM) are obtained. {yields} Dinitrotoluene is obtained with very high yield i.e. 96 wt.% in mild conditions. {yields} Dinitrochlorobenzene is obtained with only twelve-fold excess of nitric acid. {yields} It is sulfuric acid free and solvent free nitration of aromatic compounds. - Abstract: A new catalyst, H{sub 3}PO{sub 4}/MoO{sub 3}/SiO{sub 2}, was prepared by modification of MoO{sub 3}/SiO{sub 2} using phosphoric acid. The characterization of the catalyst was performed using Infrared and Raman Spectroscopy, potentiometric titration and nitrogen adsorption-desorption methods. Molybdenum oxides were identified along with phosphomolybdic acid and polymolybdates on the modified surface. The suitability of the catalysts for toluene and chlorobenzene nitration in continuous process was examined. Toluene is effectively nitrated to dinitrotoluene (DNT) in one-stage process (96 wt.% of DNT in the product) and in mild conditions i.e. at room temperature and only with ten-fold excess of nitric acid. In chlorobenzene nitration only twelve-fold excess of nitric acid is needed to obtain as high yield as 95 wt.%. Most importantly, the novel catalysts we have developed, provide the opportunity for sulfuric acid- free nitration of aromatic compounds.

Thermodynamic study of (alkyl esters + {alpha},{omega}-alkyl dihalides) VII. H{sub m}{sup E} and V{sub m}{sup E} for 20 binary mixtures {l_brace}xC{sub u-1}H{sub 2u-1}CO{sub 2}C{sub 3}H{sub 7} + (1 - x){alpha},{omega}-ClCH{sub 2}(CH{sub 2}){sub v-2}CH{sub 2}Cl{r_brace}, where u = 1 to 4, {alpha} = 1 and v = {omega} = 2 to 6. An analysis of behavior using the COSMO-RS methodology

Energy Technology Data Exchange (ETDEWEB)

Marrero, E. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos (www.thermo.ulpgc.es), Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071 Las Palmas de Gran Canaria, Canary Islands (Spain); Ortega, J. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos (www.thermo.ulpgc.es), Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071 Las Palmas de Gran Canaria, Canary Islands (Spain)], E-mail: jortega@dip.ulpgc.es; Palomar, J. [Seccion de Ingenieria Quimica, Dpto. de Quimica-Fisica Aplicada, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain)

2009-03-15

Summary: Excess enthalpies H{sub m}{sup E} and excess volumes V{sub m}{sup E} obtained at a temperature of 298.15 K and atmospheric pressure are presented for a set of 20 binary mixtures comprised of the first four propyl esters, C{sub u-1}H{sub 2u-1}COOC{sub 3}H{sub 7} (u = 1 to 4), and five {alpha},{omega}-dichloroalkanes, ClCH{sub 2}(CH{sub 2}){sub v-2}CH{sub 2}Cl (v = 2 to 6). All the mixtures are exothermic except for those corresponding to propyl methanoate with v {>=} 4. The V{sub m}{sup E} are positive in most mixtures except for those where v = 4, 5, 6, for V{sub m}{sup E}<0. There is a regular rise in H{sub m}{sup E} with v, while the increase in u produces a greater exothermicity in the mixing process, which becomes inverted for propyl butanoate. The variation in V{sub m}{sup E} with the chain length of the compounds of the mixtures studied is not regular since both the enthalpic and the volumetric effects are due to interactions of different nature, positive and negative. Interpretation of the behavior was assisted by applying the quantum-chemistry method COSMO-RS. This method describes qualitatively and quantitatively the contribution of the different types of interactions, electrostatic, van der Waals, and those due to the (Cl, Cl) bond in the dihalide, and the influence of the ester and dichloroalkane chains. This information was also useful to adequately modify the application of the UNIFAC group contribution model, proposing parameters for the Cl, Cl/carboxylate interaction that vary with the chain length of the compounds involved. With this modification, the results estimated by UNIFAC model can be considered good.

Electrocatalysts of platinum, cobalt and nickel prepared by mechanical alloying for the oxygen reduction reaction in H{sub 2}SO{sub 4} 0.5M; Electrocatalizadores de Platino, Cobalto y Niquel preparados por Aleado Mecanico para la reaccion de reduccion de oxigeno en H{sub 2}SO{sub 4} 0.5M

Energy Technology Data Exchange (ETDEWEB)

Garcia C, M.A.; Fernandez V, S.M.; Vargas G, J.R. [lNIN, Depto. de Quimica, 52750 La Marquesa, Estado de Mexico (Mexico)

2007-07-01

Metallic powders of Pt, Co and Nickel were processed by mechanical alloyed and electrocatalysts were synthesized for the oxygen reduction reaction, applicable in fuel cells. The structural and morphological characterization was carried out using X-ray Diffraction, scanning electron microscopy and transmission electron microscopy. It was found that the alloyed powders formed agglomerates that consist of crystalline particles of nano metric size. Its were obtained polarization curves by the Electrode of Rotational Disk technique in a solution of H{sub 2}SO{sub 4} 0.5 M, used as electrolyte, to evaluate the electrocatalytic activity of mechanically alloyed powders. Tafel graphics were built to determine the kinetic parameters of each electro catalyst. The PtCoNi alloy exhibited the biggest electrocatalytic activity, with the smallest over potential for the oxygen reduction reaction. (Author)

Mechanism of protodesorption—exchange of heavy metal cations for protons in a heterophase system of H{sub 2}O–H{sub 2}SO{sub 4}–MSO{sub 4}—cellulose sorbent

Energy Technology Data Exchange (ETDEWEB)

Kozlov, V.A.; Nikiforova, T.E., E-mail: tatianaenik@mail.ru; Loginova, V.A.; Koifman, O.I.

2015-12-15

Highlights: • Protodesorption takes place with participation of anions. • The interphase indicator MSO{sub 4} is used in ion exchange investigation. • In ion exchange process salt and acid participate in equivalent proportions. • In a protodesorption process proton acts in degree of ½. • M{sup 2+}/2Na{sup +} and M{sup 2+}/2H{sup +} exchanges take place in ion and molecular forms. - Abstract: The influence of pH on the distribution of metal cations [Cd(II), Cu(II), Fe(II), Ni(II), Zn(II)] in a four-component heterophase system (H{sub 2}O–H{sub 2}SO{sub 4}–MSO{sub 4}–cellulose sorbent) was studied. Protodesorption of metal cations was studied with indicator and constant quantities of [MSO{sub 4}] salts and constant solvent–sorbent ratio. Linear dependence lgK{sub DM2+} = f(pH) with tgα = 1/2 of the K{sub DM2+} metal ions distribution coefficients from the acidity of the aqueous phase is observed in logarithmic coordinates. Depression of the exponent corresponding to proton involvement in protodesorption from 2 (theory) to 0.5 (experiment) indicates that anions of the aqueous phase are involved in the process of exchange of metal cation for proton on the anionic centers of the sorbent, which corresponds to participation of the salt and acid components of the system in molecular non-dissociated form in an equivalent proportion H{sub 2}SO{sub 4}/MSO{sub 4} = 1/1. Different behavior of the salt and acid components in ion exchange of cations for cations and cations for protons is due to the differences in the constraint coefficients of their molecular and ionic forms which must be taken into consideration in equations describing thermodynamics of the interphase exchange.

Inelastic neutron scattering of H{sub 2} adsorbed in HKUST-1

Energy Technology Data Exchange (ETDEWEB)

Liu, Y. [Department of Materials and Engineering, University of Maryland, College Park, MD 20742 (United States); NIST Center for Neutron Research, 100 Bureau Drive, Gaithersburg, MD 20899-8562 (United States); Brown, C.M. [NIST Center for Neutron Research, 100 Bureau Drive, Gaithersburg, MD 20899-8562 (United States); Indiana University Cyclotron Facility, Indiana University, 2401 Milo B. Sampson Lane, Bloomington, IN 47408 (United States)], E-mail: craig.brown@nist.gov; Neumann, D.A. [NIST Center for Neutron Research, 100 Bureau Drive, Gaithersburg, MD 20899-8562 (United States); Peterson, V.K.; Kepert, C.J. [School of Chemistry, University of Sydney, NSW 2006 (Australia)

2007-10-31

A series of inelastic neutron scattering (INS) investigations of hydrogen adsorbed in activated HKUST-1 (Cu{sub 3}(1,3,5-benzenetricarboxylate){sub 2}) result in INS spectra with rich features, even at very low loading (<1.0 H{sub 2}:Cu). The distinct inelastic features in the spectra show that there are three binding sites that are progressively populated when the H{sub 2} loading is less than 2.0 H{sub 2}:Cu, which is consistent with the result obtained from previous neutron powder diffraction experiments. The temperature dependence of the INS spectra reveals the relative binding enthalpies for H{sub 2} at each site.

Synthesis, Characterization and Antimicrobial Activity of Zirconium (IV) Complexes

Energy Technology Data Exchange (ETDEWEB)

Sharma, Shobhana; Jain, Asha; Saxena, Sanjiv [Univ. of Rajasthan, Jaipur (India)

2012-08-15

Heteroleptic complexes of zirconium (IV) derived from bulky Schiff base ligands containing a sulphur atom and oximes of heterocyclic β-diketones of the general formula ZrLL' (where L'H{sub 2}=RCNH(C{sub 6}H{sub 4})SC : C(OH)N(C{sub 6}H{sub 5})N : CCH{sub 3}, R=-C{sub 6}H{sub 5}, -C{sub 6}H{sub 4}Cl(p) and L'H{sub 2}=R'C : (NOH)C : C(OH)N(C{sub 6}H{sub 5})N : CCH{sub 3}, R' = -CH{sub 2}CH{sub 3}, -C{sub 6}H{sub 5}, -C{sub 6}H{sub 4}Cl (p) were prepared by the reactions of zirconium tetrachloride with disodium salts of Schiff bases (L Na{sub 2}) and oximes of heterocyclic β-diketones (L' Na{sub 2}) in 1:1:1 molar ratio in dry refluxing THF. The structures of these monomeric zirconium (IV) complexes were elucidated with the help of elemental analysis, molecular weight measurements, spectroscopic (IR, NMR and mass) studies. A distorted trigonal bipyramidal geometry may be suggested for these heteroleptic zirconium (IV) complexes. The ligands (bulky Schiff base ligands containing a sulphur atom and oximes of heterocyclic β-diketones) and their heteroleptic complexes of zirconium (IV) were screened against A. flavus, P. aeruginesa and E. coli.

Treatment by (N H{sub 4}){sub 2} Si F{sub 6} of hydrothermally stabilized Y zeolite: NMR, infrared and atomic absorption monitoring; Tratamento por (NH4){sub 2} SiF{sub 6} de zeolito Y estabilizado hidrotermicamente: monitoramento por RMN, IV e A.A

Energy Technology Data Exchange (ETDEWEB)

Martins, Ruth L; Camorim, Vera L.D.D.; Menezes, Sonia M.C. de [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas

1992-12-31

The kinetics of NFA leaching of a hydrothermal treated Y zeolite was determined by using AAS, IR and NMR techniques. It was observed first order with respect to NFA onto intra crystalline volume. The transformation of octahedral Aluminium into mainly tetrahedral species was observed at the first contact with the fluorinated reagent,being leached as NM{sub 4} Al F{sub 4} and, in a less amount, as (N H{sub 4}){sub 3} Al F{sub 6}. (author) 4 refs., 5 figs., 1 tab.

Porous carbon derived via KOH activation of a hypercrosslinked porous organic polymer for efficient CO{sub 2}, CH{sub 4}, H{sub 2} adsorptions and high CO{sub 2}/N{sub 2} selectivity

Energy Technology Data Exchange (ETDEWEB)

Modak, Arindam; Bhaumik, Asim, E-mail: msab@iacs.res.in

2015-12-15

Microporous carbon having Brunauer-Emmett-Teller (BET) surface area of 2186 m{sup 2} g{sup −1} and micropore volume of 0.85 cm{sup 3} g{sup −1} has been synthesized via KOH induced high temperature carbonization of a non-conjugated hypercrosslinked organic polymer. Owing to the templating and activation by KOH, we have succeeded in making a microporous carbon from this porous polymer and the resultant carbon material showed high uptake for CO{sub 2} (7.6 mmol g{sup −1}) and CH{sub 4} (2.4 mmol g{sup −1}) at 1 atm, 273 K together with very good selectivity for the CO{sub 2}/N{sub 2} (30.2) separation. Furthermore, low pressure (1 atm) H{sub 2} (2.6 wt%, 77 K) and water uptake (57.4 wt%, 298 K) ability of this polymer derived porous activated carbon is noteworthy. - Graphical abstract: Microporous carbon with BET surface area of 2186 m{sup 2} g{sup −1} has been synthesized via KOH activation of a porous organic polymer and it showed high uptake for CO{sub 2} (7.6 mmol g{sup −1}), CH{sub 4} (2.4 mmol g{sup −1}) and H{sub 2} (2.6 wt%) at 1 atm together with very good selectivity for CO{sub 2}. - Highlights: • Porous carbon from hypercrosslinked organic polymer. • KOH activated carbon with BET surface area 2186 m{sup 2} g{sup −1}. • High CO2 uptake (7.6 mmol g{sup −1}) and CO{sub 2}/N{sub 2} selectivity (30.2). • Porous carbon also showed high H{sub 2} (2.6 wt%) and H{sub 2}O (57.4 wt%) uptakes.

Hydrothermal synthesis and study of an inorganic-organic hybrid vanadate of a nickel(II) coordination complex with pyrazine, Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23})

Energy Technology Data Exchange (ETDEWEB)

Larrea, Edurne S. [Dpto. de Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/Euskal Herriko Unibertsitatea, UPV/EHU, Apdo. 644, E-48080 Bilbao (Spain); Mesa, Jose L., E-mail: joseluis.mesa@ehu.es [Dpto. de Quimica Inorganica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/Euskal Herriko Unibertsitatea, UPV/EHU, Apdo. 644, E-48080 Bilbao (Spain); Arriortua, Maria I. [Dpto. de Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/Euskal Herriko Unibertsitatea, UPV/EHU, Apdo. 644, E-48080 Bilbao (Spain)

2011-06-15

Highlights: {yields} A novel inorganic-organic hybrid vanadate of nickel(II) coordination complex with pyrazine has been synthesized hydrothermally. {yields} The thermal and spectroscopic behavior has been studied. {yields} The compound shows AFM interactions which has been fitted to a magnetic model of lineal chains. -- Abstract: The three-dimensional hybrid compound Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23}) has been synthesized by mild hydrothermal methods under autogenous pressure at 170 {sup o}C. The structure of the phase is stable until 380 {sup o}C. The removal of the pyrazine molecules from the structure induces its collapse. The IR spectrum shows the vibration modes of the pyrazine molecule and those of the [VO{sub 4}]{sup 3-} groups. A UV-visible spectrum shows the characteristic bands of the Ni(II) d{sup 8}-high-spin cation in a slightly distorted octahedral coordination. Magnetic measurements indicate the existence of antiferromagnetic interactions that can be fitted with a chain model to give g = 2.31, J/k = -5.3, and zJ'/k = -5.5.

Disodium terephthalate (Na{sub 2}C{sub 8}H{sub 4}O{sub 4}) as high performance anode material for low-cost room-temperature sodium-ion battery

Energy Technology Data Exchange (ETDEWEB)

Zhao, Liang; Hu, Yong-Sheng; Li, Hong; Armand, Michel; Chen, Liquan [Key Laboratory for Renewable Energy, Beijing Key Laboratory for New, Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing (China); Zhao, Junmei [Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing (China); Zhou, Zhibin [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan (China)

2012-08-15

In this contribution, a cheap organic material, disodium terephthalate, Na{sub 2}C{sub 8}H{sub 4}O{sub 4}, has been firstly evaluated as a novel anode for room-temperature Na-ion batteries. The material exhibits a high reversible capacity of 250 mAh/g with excellent cycleability. The average Na storage voltage is approximately 0.43 V vs. Na{sup +}/Na. A thin layer of Al{sub 2}O{sub 3} coating on the electrode surface derived from the atomic layer deposition technique is effective in further enhancing Na storage performance. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Low-temperature heat capacity and thermodynamic properties of [Re{sub 2}(Ile){sub 4}(H{sub 2}O){sub 8}](ClO{sub 4}){sub 6} (Re=Nd, Er, Ile=isoleucine)

Energy Technology Data Exchange (ETDEWEB)

Lan Xiaozheng; Tan Zhicheng; Liu Beiping; Nan Zhaodong; Sun Lixian; Xu Fen

2003-06-03

The heat capacities of two kinds of rare-earth element solid complexes with isoleucine [Re{sub 2}(Ile){sub 4}(H{sub 2}O){sub 8}](ClO{sub 4}){sub 6} (where Re=Nd, Er, and Ile=isoleucine) have been measured by an automatic adiabatic calorimeter in the temperature range from 80 to 370 K. Two solid-solid phase transitions were found from the C{sub p} curve of Nd formed complex in the range of 165-175 K with a peak temperature of 167.88 K and in the range of 195-210 K with a peak temperature of 202.13 K. The corresponding molar enthalpies of these phase transitions were determined to be 404.61 J mol{sup -1} and 2.955 kJ mol{sup -1}, respectively. One solid-solid phase transition was found for the Er formed complex in the range of 190-205 K with a peak temperature of 193.42 K. The corresponding molar enthalpy of this transition was 14.11 kJ mol{sup -1}. Smooth heat capacities and thermodynamic functions relative to the standard state (298.15 K), H{sub T}-H{sub 298.15}, S{sub T}-S{sub 298.15} and -[G{sub T}-G{sub 298.15}], of the two compounds, were calculated on basis of experimental heat capacity data. Possible mechanisms of thermal decompositions for the pair of compounds were suggested according to the thermogravimetric (TG) analysis.

The first 3D malonate bridged copper [Cu(O{sub 2}C-CH{sub 2}-CO{sub 2}H){sub 2}{center_dot}2H{sub 2}O]: Structure, properties and electronic structure

Energy Technology Data Exchange (ETDEWEB)

Seguatni, A., E-mail: seguatni@gmail.com [LBPC-INSERM U 698, Institut Galilee, Universite Paris XIII, 99, avenue J. B. Clement 93430, Villetaneuse (France); Fakhfakh, M. [Unite de recherche UR 12-30, Synthese et Structure de Materiaux Inorganiques, Faculte des Sciences de Bizerte, 7021 Zarzouna (Tunisia); Departement de Chimie, Universite du Quebec a Montreal, C.P. 8888, Succ. Centre-ville, Montreal, Que., H3C 3P8 (Canada); Smiri, L.S. [Unite de recherche UR 12-30, Synthese et Structure de Materiaux Inorganiques, Faculte des Sciences de Bizerte, 7021 Zarzouna (Tunisia); Gressier, P.; Boucher, F. [Institut des Materiaux Jean Rouxel, Universite de Nantes, CNRS, 2 rue de la Houssiniere, BP 32229, 44322 Nantes Cedex 3 (France); Jouini, N. [Departement de Chimie, Universite du Quebec a Montreal, C.P. 8888, Succ. Centre-ville, Montreal, Que., H3C 3P8 (Canada)

2012-03-15

A new inorganic-organic compound [Cu(O{sub 2}C-CH{sub 2}-CO{sub 2}H){sub 2}{center_dot}2H{sub 2}O] ([Cumal]) was hydrothermally synthesized and characterized by IR spectroscopy, thermal analysis and single crystal X-ray diffraction. [Cumal] is the first three-dimensional compound existing in the system Cu(II)-malonic acid-H{sub 2}O. Its framework is built up through carboxyl bridged copper where CuO{sub 6} octahedra are elongated with an almost D{sub 4h} symmetry (4+2) due to the Jahn-Teller effect. The magnetic properties were studied by measuring its magnetic susceptibility in the temperature range of 2-300 K indicating the existence of weak ferromagnetic interactions. The electronic structure of [Cumal] was calculated within the density functional theory (DFT) framework. Structural features are well reproduced using DFT structural optimizations and the optical spectra, calculated within the dielectric formalism, explain very well the light blue colour of the compound. It is shown that a GGA+U approach with a U{sub eff} value of about 6 eV is necessary for a better correlation with the experiment. - Graphical abstract: [Cu(O{sub 2}C-CH{sub 2}-CO{sub 2}H){sub 2}{center_dot}2H{sub 2}O]: the first 3D hybrid organic-inorganic compound built up carboxyl groups. The network presents a diamond-like structure achieved via carboxyl. Highlights: Black-Right-Pointing-Pointer A new organic-inorganic material with an unprecedented topology is synthesized. Black-Right-Pointing-Pointer Crystallographic structure is determined using single crystal X-ray diffraction. Black-Right-Pointing-Pointer Electronic structure is obtained from DFT, GGA+U calculation. Black-Right-Pointing-Pointer Framework can be described as formed from CuC{sub 4} tetrahedron sharing four corners. Black-Right-Pointing-Pointer This structure can be classified as an extended diamond structure.

Evaluation of sintering effects on SiC-incorporated UO{sub 2} kernels under Ar and Ar–4%H{sub 2} environments

Energy Technology Data Exchange (ETDEWEB)

Silva, Chinthaka M., E-mail: silvagw@ornl.gov [Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, Tennessee TN 37831-6223 (United States); Materials Science and Engineering, The University of Tennessee Knoxville, TN 37996-2100, United States. (United States); Lindemer, Terrence B.; Hunt, Rodney D.; Collins, Jack L.; Terrani, Kurt A.; Snead, Lance L. [Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, Tennessee TN 37831-6223 (United States)

2013-11-15

Silicon carbide (SiC) is suggested as an oxygen getter in UO{sub 2} kernels used for tristructural isotropic (TRISO) particle fuels and to prevent kernel migration during irradiation. Scanning electron microscopy and X-ray diffractometry analyses performed on sintered kernels verified that an internal gelation process can be used to incorporate SiC in UO{sub 2} fuel kernels. Even though the presence of UC in either argon (Ar) or Ar–4%H{sub 2} sintered samples suggested a lowering of the SiC up to 3.5–1.4 mol%, respectively, the presence of other silicon-related chemical phases indicates the preservation of silicon in the kernels during sintering process. UC formation was presumed to occur by two reactions. The first was by the reaction of SiC with its protective SiO{sub 2} oxide layer on SiC grains to produce volatile SiO and free carbon that subsequently reacted with UO{sub 2} to form UC. The second process was direct UO{sub 2} reaction with SiC grains to form SiO, CO, and UC. A slightly higher density and UC content were observed in the sample sintered in Ar–4%H{sub 2}, but both atmospheres produced kernels with ∼95% of theoretical density. It is suggested that incorporating CO in the sintering gas could prevent UC formation and preserve the initial SiC content.

Strong red-emission of Eu{sup 3+}:Li{sub 4}Ti{sub 5}O{sub 12} powders for phosphor applications

Energy Technology Data Exchange (ETDEWEB)

Yang, Yan [Kazuo Inamori School of Engineering, New York State College of Ceramics, Alfred University, Alfred, NY 14802 (United States); Jiménez, José A. [Department of Chemistry, University of North Florida, Jacksonville, FL 32224 (United States); Wu, Yiquan, E-mail: wuy@alfred.edu [Kazuo Inamori School of Engineering, New York State College of Ceramics, Alfred University, Alfred, NY 14802 (United States)

2016-08-15

The synthesis and photoluminescence properties of trivalent europium doped lithium titanate (Eu{sup 3+}:Li{sub 4}Ti{sub 5}O{sub 12}) with different Eu{sup 3+} concentrations (0.1 mol%, 0.3 mol%, 1.0 mol%, 3.0 mol%) are reported and analyzed as a phosphor. Europium (III) nitrate (Eu(NO{sub 3}){sub 3}) was employed as Eu{sup 3+} source, while lithium acetate dihydrate (CH{sub 3}COOLi·2H{sub 2}O) and titanium n-butoxide (Ti(OC{sub 4}H{sub 9}){sub 4}) were adopted as raw materials to synthesize the host lithium titanate with a Li:Ti stoichiometry of 4.5:1. Phase identification was performed using X-ray diffraction (XRD), and morphology was examined using scanning electron microscopy (SEM). Eu{sup 3+}:Li{sub 4}Ti{sub 5}O{sub 12} powders showed strong red emission at 612 nm, corresponding to the {sup 5}D{sub 0}–{sup 7}F{sub 2} transition, with the strongest excitation peak observed in the blue light region at 464 nm. Decay time analyses revealed relatively short lifetimes accompanying typical exponential decay rates. The effect of Eu{sup 3+} concentration (0.1 mol%, 0.3 mol%, 1.0 mol%, 3.0 mol%) on photoluminescence intensity and decay time was explored, and is reported here. It was determined that the CIE color coordinates (0.66, 0.34) of the doped Li{sub 4}Ti{sub 5}O{sub 12} powders were independent of Eu{sup 3+} concentration, and that the coordinates are very similar to the ideal red chromaticity (0.67, 0.33) designated by the National Television Standard Committee (NTSC) system.

A [Mo{sub 2}O{sub 2}S{sub 2}]-based ring system incorporating tartrate as the bridging ligand. Synthesis, structure and catalytic activity of Cs{sub 4}[Mo{sub 2}O{sub 2}(μ-S){sub 2}]{sub 2}(μ{sub 4}-tart){sub 2} (tart=[C{sub 4}H{sub 2}O{sub 6}]{sup 4-})

Energy Technology Data Exchange (ETDEWEB)

Qian, Ting-Ting; Cui, Yu-Jie; Xin, Zhifeng; Jia, Ai-Quan; Zhang, Qian-Feng [Anhui Univ. of Technology, Anhui (China). Inst. of Molecular Engineering and Applied Chemistry and Anhui Province Key Lab. of Metallurgy Engineering and Resources Recycling

2017-08-01

Treatment of [Mo{sub 2}S{sub 2}O{sub 2}(H{sub 2}O){sub 6}]{sup 2+} with racemic tartaric acid (tartH{sub 4}) in the presence of sodium hydroxide and cesium chloride in aqueous solution led to the isolation of a new tetra-molybdenum ring cluster Cs{sub 4}[Mo{sub 2}O{sub 2}(μ-S){sub 2}]{sub 2}(μ{sub 4}-tart){sub 2}. The cyclic cluster polyanion consists of two dinuclear [Mo{sub 2}O{sub 2}(μ-S){sub 2}]{sup 2+} moieties and two bridging tart{sup 4-} ligands. The cyclic polyoxothiomolybdate cluster, supported on the mesoporous silica SBA-15, was tested for heterogenerous catalysis in thiophene hydrodesulfurization.

Synthesis of TiO{sub 2} sol in a neutral solution using TiCl{sub 4} as a precursor and H{sub 2}O{sub 2} as an oxidizing agent

Energy Technology Data Exchange (ETDEWEB)

Sasirekha, Natarajan; Rajesh, Baskaran [Department of Chemical Engineering, National Central University, Chung-Li 320, Taiwan (China); Chen, Yu-Wen, E-mail: ywchen@cc.ncu.edu.t [Department of Chemical Engineering, National Central University, Chung-Li 320, Taiwan (China)

2009-11-02

Nanosize TiO{sub 2} thin film on glass substrate was obtained through dip-coating method using TiO{sub 2} sol. Suspended nanosize TiO{sub 2} sols with anatase structure in aqueous solution were synthesized by sol-gel method using TiCl{sub 4} as a precursor. TiCl{sub 4} was reacted with an aqueous solution of NH{sub 4}OH to form Ti(OH){sub 4}, and H{sub 2}O{sub 2} was then added to form peroxo titanic acid. It was further heated in water and converted to TiO{sub 2}. The effects of the preparation parameters, viz., pH value of the Ti(OH){sub 4} gel, concentration of H{sub 2}O{sub 2}, and heating temperature and time, on the properties of the TiO{sub 2} sol were investigated. The materials were characterized by X-ray diffraction, Fourier transform-infrared spectroscopy, and transmission electron microscopy. The results showed that the primary TiO{sub 2} particles were rhombus with the major axis ca. 10 nm and minor axis ca. 4 nm, and were in anatase structure. The sol was excellent in dispersibility and was stable in neutral and even slight basic conditions for at least 2 years without causing agglomeration. The best preparation condition was optimized with the pH value of Ti(OH){sub 4} gel at 8, H{sub 2}O{sub 2}/TiO{sub 2} mole ratio of 2, and heating at 97 {sup o}C for 8 h. The transparent adherent TiO{sub 2} film on glass substrates exhibits strong hydrophilicity after illuminating with ultraviolet light and it can be used as an efficient photocatalyst.

Effect of calcination temperature on the H{sub 2}O{sub 2} decomposition activity of nano-crystalline Co{sub 3}O{sub 4} prepared by combustion method

Energy Technology Data Exchange (ETDEWEB)

Makhlouf, M.Th. [Chemistry Department, Faculty of Science, Assiut University, 71516 Assiut (Egypt); Abu-Zied, B.M., E-mail: babuzied@aun.edu.eg [Chemistry Department, Faculty of Science, Assiut University, 71516 Assiut (Egypt); Mansoure, T.H. [Chemistry Department, Faculty of Science, Assiut University, 71516 Assiut (Egypt)

2013-06-01

Cobalt oxide nano-particles were prepared by combustion method using urea as a combustion fuel. The effects of calcination temperature, 350–1000 °C, on the physicochemical, surface and catalytic properties of the prepared Co{sub 3}O{sub 4} nano-particles were studied. The products were characterized by thermal analyses (TGA and DTA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) techniques. Textural features of the obtained catalysts were investigated using nitrogen adsorption at −196 °C. X-ray diffraction confirmed that the resulting oxide was pure single-crystalline Co{sub 3}O{sub 4} nano-particles. Transmission electron microscopy indicating that, the crystallite size of Co{sub 3}O{sub 4} nano-crystals was in the range of 8–34 nm. The catalytic activities of prepared nano-crystalline Co{sub 3}O{sub 4} catalysts were tested for H{sub 2}O{sub 2} decomposition at 35–50 °C temperature range. Experimental results revealed that, the catalytic decomposition of H{sub 2}O{sub 2} decreases with increasing the calcination temperature. This was correlated with the observed particle size increase accompanying the calcination temperature rise.

NaBH{sub 4}/H{sub 2}O{sub 2} fuel cells for air independent power systems

Energy Technology Data Exchange (ETDEWEB)

Luo, Nie; Miley, G.H.; Kim, Kyu-Jung [Department of Nuclear Engineering, University of Illinois, 104 S. Wright, Urbana, IL 61801 (United States); Burton, Rodney [Department of Aerospace Engineering, University of Illinois, 104 S. Wright, Urbana, IL 61801 (United States); Huang, Xinyu [Florida Solar Energy Center, 1679 Clearlake Road, Cocoa, FL 32922 (United States)

2008-12-01

The performance and characteristics of direct sodium-borohydride/hydrogen-peroxide (NaBH{sub 4}/H{sub 2}O{sub 2}) fuel cells are studied in the context of potential applications for air independent propulsion for outer space and underwater. Due to the existence of ocean (sea) water as a natural heat sink, this new fuel cell technology is best suited for underwater propulsion/power systems for small scale high performance marine vehicles. The characteristics of such a power system are compared to other options, specifically for the underwater scenario. The potential of this fuel cell is demonstrated in laboratory experiments. Power density over 1.5 W cm{sup -2}, at 65 C and ambient pressure, have been achieved with the help of some unique treatments of the fuel cell. One such treatment is an in-situ electroplating technique, which results in electrodes with power density 20-40% higher, than that of the electrodes produced by the ordinary ex-situ electroplating method. This unique process also makes repair or reconditioning of the fuel cell possible and convenient. (author)

X-ray-induced dissociation of H.sub.2O and formation of an O.sub.2-H.sub.2 alloy at high pressure

Science.gov (United States)

Mao, Ho-kwang [Washington, DC; Mao, Wendy L [Washington, DC

2011-11-29

A novel molecular alloy of O.sub.2 and H.sub.2 and a method of producing such a molecular alloy are provided. When subjected to high pressure and extensive x-radiation, H.sub.2O molecules cleaved, forming O--O and H--H bonds. In the method of the present invention, the O and H framework in ice VII was converted into a molecular alloy of O.sub.2 and H.sub.2. X-ray diffraction, x-ray Raman scattering, and optical Raman spectroscopy demonstrate that this crystalline solid differs from previously known phases.

Probing cosmic-ray acceleration and propagation with H{sub 3}{sup +} observations

Energy Technology Data Exchange (ETDEWEB)

Indriolo, Nick; Fields, Brian D.; McCall, Benjamin J. [3D University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States)

2015-01-22

As cosmic rays traverse the interstellar medium (ISM) they interact with the ambient gas in various ways. These include ionization of atoms and molecules, spallation of nuclei, excitation of nuclear states, and production of pions among others. All of these interactions produce potential observables which may be used to trace the flux of cosmic rays. One such observable is the molecular ion H{sub 3}{sup +}-produced via the ionization of an H{sub 2} molecule and its subsequent collision with another H{sub 2}-which can be identified by absorption lines in the 3.5-4 μm spectral region. We have detected H{sub 3}{sup +} in several Galactic diffuse cloud sight lines and used the derived column densities to infer ζ{sub 2}, the cosmic-ray ionization rate of H{sub 2}. Ionization rates determined in this way vary from about 7×10{sup −17} s{sup −1} to about 8×10{sup −16} s{sup −1}, and suggest the possibility of discrete sources producing high local fluxes of low-energy cosmic rays. Theoretical calculations of the ionization rate from postulated cosmic-ray spectra also support this possibility. Our recent observations of H{sub 3}{sup +} near the supernova remnant IC 443 (a likely site of cosmic-ray acceleration) point to even higher ionization rates, on the order of 10{sup −15} s{sup −1}. Together, all of these results can further our understanding of the cosmic-ray spectrum both near the acceleration source and in the general Galactic ISM.

Thermally activated 3D to 2D structural transformation of [Ni{sub 2}(en){sub 2}(H{sub 2}O){sub 6}(pyr)]·4H{sub 2}O flexible coordination polymer

Energy Technology Data Exchange (ETDEWEB)

Begović, Nebojša N. [Faculty of Physical Chemistry, University of Belgrade (Serbia); Institute of General and Physical Chemistry, Belgrade (Serbia); Blagojević, Vladimir A. [Faculty of Physical Chemistry, University of Belgrade (Serbia); Ostojić, Sanja B.; Radulović, Aleksandra M. [Institute of General and Physical Chemistry, Belgrade (Serbia); Poleti, Dejan [Faculty of Technology and Metallurgy, University of Belgrade (Serbia); Minić, Dragica M., E-mail: dminic@ffh.bg.ac.rs [Faculty of Physical Chemistry, University of Belgrade (Serbia); Department of Biomedical Sciences, State University of Novi Pazar (Serbia)

2015-01-15

Thermally activated 3D to 2D structural transformation of the binuclear [Ni{sub 2}(en){sub 2}(H{sub 2}O){sub 6}(pyr)]·4H{sub 2}O complex was investigated using a combination of theoretical and experimental methods. Step-wise thermal degradation (dehydration followed by release of ethylene diamine) results in two layered flexible coordination polymer structures. Dehydration process around 365 K results in a conjugated 2D structure with weak interlayer connectivity. It was shown to be a reversible 3D to 2D framework transformation by a guest molecule, and rehydration of the dehydration product occurs at room temperature in saturated water vapor. Rehydrated complex exhibits lower dehydration temperature, due to decreased average crystalline size, with higher surface area resulting in easier release and diffusion of water during dehydration. Thermal degradation of dehydration around 570 K, results in loss of ethylene diamine, producing a related 2D layered polymer structure, without interconnectivity between individual polymer layers. - Highlights: • Reversible 3D to 2D framework topochemical transformation on dehydration around 365 K. • Resulting polymer exhibits 2D layered structure with weak interlayer connectivity. • Dehydration is fully reversible in saturated water vapor at room temperature. • Further degradation around 570 K yields 2D polymer without interlayer connectivity. • 2D polymer exhibits conjugated electronic system.

Structural disorder in Li{sub x}(C{sub 5}H{sub 5}N){sub y}Fe{sub 2−z}Se{sub 2} and Cs{sub x}Fe{sub 2−z}Se{sub 2} superconductors studied by Mössbauer spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Komędera, K.; Jasek, A.K.; Błachowski, A. [Mössbauer Spectroscopy Laboratory, Pedagogical University, ul. Podchorążych 2, PL-30-084 Kraków (Poland); Ruebenbauer, K., E-mail: sfrueben@cyf-kr.edu.pl [Mössbauer Spectroscopy Laboratory, Pedagogical University, ul. Podchorążych 2, PL-30-084 Kraków (Poland); Żukrowski, J. [AGH University of Science and Technology, Academic Center for Materials and Nanotechnology, Av. A. Mickiewicza 30, PL-30-059 Kraków (Poland); Krztoń-Maziopa, A. [Warsaw University of Technology, Faculty of Chemistry, ul. Noakowskiego 3, PL-00-664 Warsaw (Poland); Conder, K. [Laboratory for Developments and Methods, Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland)

2016-05-15

Two iron-chalcogenide superconductors Li{sub x}(C{sub 5}H{sub 5}N){sub y}Fe{sub 2−z}Se{sub 2} and Cs{sub x}Fe{sub 2–z}Se{sub 2} in the as-prepared and annealed state have been investigated by means of the Mössbauer spectroscopy versus temperature. Multi-component spectra are obtained. One can see a non-magnetic component due to iron located in the unperturbed Fe–Se sheets responsible for superconductivity. Remaining components are magnetically ordered even at room temperature. There is some magnetically ordered iron in Fe–Se sheets perturbed by presence of the iron vacancies. Additionally, one can see iron dispersed between sheets in the form of magnetically ordered high spin trivalent ions, some clusters of above ions, and in the case of pyridine intercalated compound in the form of α-Fe precipitates. Pyridine intercalated sample shows traces of superconductivity in the as-prepared state, while cesium intercalated sample in the as-prepared state does not show any superconductivity. Superconductors with transition temperatures being 40 K and 25 K, respectively, are obtained upon annealing. Annealing leads to removal/ordering of the iron vacancies within Fe–Se sheets, while clusters of α-Fe grow in the pyridine intercalated sample. - Highlights: • Secondary phases dispersed in single crystal of Cs{sub x}Fe{sub 2−z}Se{sub 2}. • α-Fe precipitates between Fe–Se layers in Li{sub x}(C{sub 5}H{sub 5}N){sub y}Fe{sub 2−z}Se{sub 2}. • Superconductivity is obtained by removing of the iron vacancies within Fe–Se sheets.

Treatment for GaSb surfaces using a sulphur blended (NH{sub 4}){sub 2}S/(NH{sub 4}){sub 2}SO{sub 4} solution

Energy Technology Data Exchange (ETDEWEB)

Murape, D.M., E-mail: Davison.Murape@nmmu.ac.za [Department of Physics, Nelson Mandela Metropolitan University, PO Box 77000, Port Elizabeth, 6031 (South Africa); Eassa, N.; Neethling, J.H. [Department of Physics, Nelson Mandela Metropolitan University, PO Box 77000, Port Elizabeth, 6031 (South Africa); Betz, R. [Department of Chemistry, Nelson Mandela Metropolitan University, PO Box 77000, Port Elizabeth, 6031 (South Africa); Coetsee, E.; Swart, H.C. [Department of Physics, University of the Free State, PO Box 339, Bloemfontein, 9300 (South Africa); Botha, J.R.; Venter, A. [Department of Physics, Nelson Mandela Metropolitan University, PO Box 77000, Port Elizabeth, 6031 (South Africa)

2012-07-01

A sulphur based chemical, [(NH{sub 4}){sub 2}S/(NH{sub 4}){sub 2}SO{sub 4}] to which S has been added, not previously reported for the treatment of (1 0 0) n-GaSb surfaces, is introduced and benchmarked against the commonly used passivants Na{sub 2}S{center_dot}9H{sub 2}O and (NH{sub 4}){sub 2}S. The surfaces of the treated material were studied by scanning electron microscopy (SEM), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). It has been found that the native oxides present on the GaSb surface are more effectively removed when treated with ([(NH{sub 4}){sub 2}S/(NH{sub 4}){sub 2}SO{sub 4}] + S) than with (NH{sub 4}){sub 2}S or Na{sub 2}S{center_dot}9H{sub 2}O, as evidenced by the ratio of the O{sub 506eV} to Sb{sub 457eV} AES peaks. XPS results reveal that Sb{sub 2}S{sub 3}/Sb{sub 2}S{sub 5} 'replaces' Sb{sub 2}O{sub 3}/Sb{sub 2}O{sub 5}, suggesting that sulphur atoms substitute oxygen atoms in Sb{sub 2}O{sub 3}/Sb{sub 2}O{sub 5} to form Sb-S. It seems sulphurization only partially removes Ga{sub 2}O{sub 3}. Treatment with ([(NH{sub 4}){sub 2}S/(NH{sub 4}){sub 2}SO{sub 4}] + S) also results in a noteworthy improvement in the current-voltage (I-V) characteristics of Au/n-GaSb Schottky contacts compared to those fabricated on as-received material.

The H{sub 60}Si{sub 6}C{sub 54} heterofullerene as high-capacity hydrogen storage medium

Energy Technology Data Exchange (ETDEWEB)

Yong, Yongliang, E-mail: ylyong@haust.edu.cn [College of Physics and Engineering, Henan University of Science and Technology, Luoyang 471003 (China); Department of Physics, Zhejiang University, Hangzhou 310027 (China); Zhou, Qingxiao; Li, Xiaohong; Lv, Shijie [College of Physics and Engineering, Henan University of Science and Technology, Luoyang 471003 (China)

2016-07-15

With the great success in Si atoms doped C{sub 60} fullerene and the well-established methods for synthesis of hydrogenated carbon fullerenes, this leads naturally to wonder whether Si-doped fullerenes are possible for special applications such as hydrogen storage. Here by using first-principles calculations, we design a novel high-capacity hydrogen storage material, H{sub 60}Si{sub 6}C{sub 54} heterofullerene, and confirm its geometric stability. It is found that the H{sub 60}Si{sub 6}C{sub 54} heterofullerene has a large HOMO-LUMO gap and a high symmetry, indicating it is high chemically stable. Further, our finite temperature simulations indicate that the H{sub 60}Si{sub 6}C{sub 54} heterofullerene is thermally stable at 300 K. H{sub 2} molecules would enter into the cage from the Si-hexagon ring because of lower energy barrier. Through our calculation, a maximum of 21 H{sub 2} molecules can be stored inside the H{sub 60}Si{sub 6}C{sub 54} cage in molecular form, leading to a gravimetric density of 11.11 wt% for 21H{sub 2}@H{sub 60}Si{sub 6}C{sub 54} system, which suggests that the hydrogenated Si{sub 6}C{sub 54} heterofullerene could be suitable as a high-capacity hydrogen storage material.

Reinvestigation of the crystal structure of kasolite, Pb[(UO{sub 2})(SiO{sub 4})](H{sub 2}O), an important alteration product of uraninite, UO{sub 2+x}

Energy Technology Data Exchange (ETDEWEB)

Fejfarová, Karla; Dušek, Michal [Institute of Physics ASCR, v.v.i., Na Slovance 2, 18221 Praha (Czech Republic); Plášil, Jakub, E-mail: jakub_plasil@nm.cz [Department of Mineralogy and Petrology, National Museum, Václavské nám. 68, Prague 1, 115 79-CZ (Czech Republic); Institute of Geological Science, Faculty of Science, Masaryk University, Kotlářská 2, CZ-611 37, Brno (Czech Republic); Čejka, Jiří; Sejkora, Jiří [Department of Mineralogy and Petrology, National Museum, Václavské nám. 68, Prague 1, 115 79-CZ (Czech Republic); Škoda, Radek [Institute of Geological Science, Faculty of Science, Masaryk University, Kotlářská 2, CZ-611 37, Brno (Czech Republic)

2013-03-15

The crystal structure of kasolite, Pb[(UO{sub 2})(SiO{sub 4})](H{sub 2}O), Z = 4, monoclinic, with a = 6.7050(3), b = 6.9257(2), c = 13.2857(5) Å, β = 105.064(4)°, V = 595.74(3) Å{sup 3}, the space group P2{sub 1}/c, has been solved by charge-flipping method and refined by the full-matrix least-squares techniques to an agreement factor (R{sub obs}) of 2.2% and, a goodness-of-fit (GOF) of 1.26 using 1243 unique observed diffraction maxima (I{sub obs} > 3σ(I)) collected with MoKα X-radiation and a 4 K CCD area detector. The crystal structure of kasolite contains 1 unique U{sup 6+} position that is part of a nearly linear uranyl ion (UO{sub 2}){sup 2+}, coordinated in the equatorial plane by five O ligands, forming pentagonal bipyramid. The uranyl pentagonal bipyramids share edges to form chains parallel to [0 1 0]. The additional edge of uranyl polyhedra is shared by silicate tetrahedra to form sheets parallel to (1 0 0). There is one unique position of Pb{sup 2+} in the interlayer. O ligands and 1 (H{sub 2}O) non-transformer group coordinate Pb{sup 2+} exhibiting [2 + 6] coordination. A network of H-bonds provides an additional linkage of an interlayer to the sheets besides Pb–O bonds. Chemical composition of the studied crystals, obtained by the electron microprobe, is reported and is in agreement with the crystal structure refinement.

Reaction of H{sub 2}S with MoRu(CO){sub 6}(dppm){sub 2} to give H{sub 2} and a bridged-sulfide product via hydrido-sulfhydryl intermediates (dppm equals Ph{sub 2}PCH{sub 2}PPh{sub 2})

Energy Technology Data Exchange (ETDEWEB)

Khorasani-Motlagh, M. [Sistan and Baluchestan Univ., Zahedan (Iran, Islamic Republic of). Dept. of Chemistry; Safari, N. [Shahid Beheshti Univ., Tehran (Iran, Islamic Republic of). Dept. of Chemistry; Pamplin, C.B.; Patrick, B.O.; James, B.R. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemistry

2006-02-15

The reactivity of hydrogen sulphide toward transition metal complexes was studied with particular focus on the reactions of hydrogen sulphide (H{sub 2}S) with solutions of bimetallic-dppm complexes. The complex MoRu(CO){sub 6}({mu}-dppm){sub 2} (1) (dppm equals Ph{sub 2}PCH{sub 2}PPh{sub 2}) reaction toward hydrogen sulphide was examined because of the fact that Ru is the second-row analogue of Fe and because of the key role of sulphur ligands in the Mo-Fe enzyme systems. This paper reported on the interaction of the Mo-Ru complex with hydrogen sulphide to form the bridged sulphide complex Mo(CO){sub 2}({mu}-CO)({mu}-S)(dppm){sub 2}Ru(CO) which can be synthesized with elemental sulphur. Oxidative addition of H{sub 2}S to MoRu(CO){sub 6}({mu}-dppm){sub 2} (1) at 20 degrees C in toluene yields an isolable complex formulated as Mo(CO){sub 3}({mu}-SH)({mu}-CO)({mu}-dppm){sub 2}RuH(CO) (2) via the possible intermediate Mo(CO){sub 3}({mu}-H)({mu}-CO)({mu}-dppm){sub 2}Ru(SH)(CO) (4) (dppm equals Ph{sub 2}PCH{sub 2}PPh{sub 2}) that is detectable at lower temperatures. Over 2 days, species 2 in toluene lost H{sub 2} (and CO) to yield the bridged-sulfide product, Mo(CO){sub 2}({mu}-CO)({mu}-S)({mu}-dppm){sub 2}Ru(CO) (5) that is also formed directly from the reaction of 1 with elemental sulfur. The solid-state molecular structure of 5 was determined by X-ray crystallography. A further hydrido-sulfhydryl species was found to be in equilibrium with 2 at ambient temperature. It was concluded that it is not impossible that hydrogen sulphide can react in a concerted manner with dimetallic precursors, without prior formation of an adduct. 24 refs., 2 tabs., 3 figs.