Sample records for complex mg-ni-la-co-h phases

  1. Hydrogen atom distribution and hydrogen induced site depopulation for the La{sub 2-x}Mg{sub x}Ni{sub 7}-H system

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Guzik, Matylda N., E-mail: Matylda.Guzik@ife.no; Physics Department, Institute for Energy Technology, P.O. Box 40, NO-2027 Kjeller; Hauback, Bjorn C.

    2012-02-15

    sites as opposed to nine proposed for La{sub 1.5}Mg{sub 0.5}Ni{sub 7}D{sub 8.9(9.1)}. The reported four remaining deuterium atom positions in La{sub 1.5}Mg{sub 0.5}Ni{sub 7}D{sub 8.9(9.1)} were not found in the investigated La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 8.8}. The five Ni atoms have deuterium among their nearest neighbors, which surround them in a way similar to configurations observed in some complex transition metal hydrides and already reported for metallic hydrides. In the presented deuterium-rich phase, deformed tetrahedron, rigid trigonal pyramids as well as disordered and deformed saddle-like configuration are observed. Highlights: Black-Right-Pointing-Pointer Alpha- and beta-phase for La{sub 2-x}Mg{sub x}Ni{sub 7}-H system have been characterized. Black-Right-Pointing-Pointer Five different interstitial sites are occupied by deuterium/hydrogen atoms in the beta-phase. Black-Right-Pointing-Pointer One D/H site has been determined in the alpha-phase. Black-Right-Pointing-Pointer Deuterium/hydrogen induced site depopulation during phase transformation is observed. Black-Right-Pointing-Pointer Ni atoms tend to have tetrahedral-like D/H atom coordination.« less

  2. Hydrogen in La2MgNi9D13: the role of magnesium.

    PubMed

    Denys, Roman V; Yartys, Volodymyr A; Webb, Colin J

    2012-04-02

    Reversible hydrogen storage capacity of the La(3-x)Mg(x)Ni(9) alloys, charged by gaseous hydrogen or by electrochemical methods, reaches its maximum at composition La(2)MgNi(9). As (La,Mg)Ni(3-3.5) alloys are the materials used in advanced metal hydride electrodes in Ni-MH batteries, this raises interest in the study of the structure-properties interrelation in the system La(2)MgNi(9)-H(2) (D(2)). In the present work, this system has been investigated by use of in situ synchrotron X-ray and neutron powder diffraction in H(2)/D(2) gas and by performing pressure-composition-temperature measurements. The saturated La(2)MgNi(9)D(13.1) hydride forms via an isotropic expansion and crystallizes with a trigonal unit cell (space group R3m (No.166); a = 5.4151(1) Å; c = 26.584(2) Å; V = 675.10(6) Å(3)). The studied hybrid structure is composed of a stacking of two layers resembling existing intermetallic compounds LaNi(5) (CaCu(5) type) and LaMgNi(4) (Laves type). These are occupied by D to form LaNi(5)D(5.2) and LaMgNi(4)D(7.9). The LaNi(5)D(5.2) slab has a typical structure observed for all reported LaNi(5)-containing hybrid structures of the AB(5) + Laves phase types. However, the Laves type slab LaMgNi(4)D(7.9) is different from the characterized individual LaMgNi(4)D(4.85) hydride. This results from the filling of a greater variety of interstitial sites in the La(2)MgNi(9)D(13)/LaMgNi(4)D(7.9), including MgNi(2), Ni(4), (La/Mg)(2)Ni(2), and (La/Mg)Ni(3), in contrast with individual LaMgNi(4)D(4.85) where only La(2)MgNi(2) and Ni(4) interstitials are occupied. Despite a random distribution of La and Mg in the structure, a local hydrogen ordering takes place with H atoms favoring occupation of two Mg-surrounded sites, triangles MgNi(2) and tetrahedra LaMgNi(2). A directional bonding between Ni, Mg, and hydrogen is observed and is manifested by a formation of the NiH(4) tetrahedra and MgH(6) octahedra, which are connected to each other by sharing H vertexes to form a

  3. Thermodynamical properties of La-Ni-T (T = Mg, Bi and Sb) hydrogen storage systems

    NASA Astrophysics Data System (ADS)

    Giza, K.; Iwasieczko, W.; Pavlyuk, V. V.; Bala, H.; Drulis, H.

    The hydrogen absorption properties of LaNi 4.8T 0.2 (T = Mg, Bi and Sb) alloys are reported. The effects of the substitution of Ni in the LaNi 5 compound with Mg, Bi and Sb are investigated. The ability of alloys to absorb hydrogen is characterized by the pressure-composition (p- c) isotherms. The p- c isotherms allow the determining thermodynamic parameters enthalpy (Δ H des) and entropy (Δ S des) of the dehydrogenation processes. The calculated Δ H des and Δ S des data helps to explain the decrease of hydrogen equilibrium pressure in alloys doped with Al, Mg and Bi and its increase in the Sb-doped LaNi 5 compound. Generally, partial substitution of Ni in LaNi 5 compound with Mg, Bi and Sb cause insignificant changes of hydrogen storage capacity compared to the hydrogen content in the initial LaNi 5H 6 hydride phase. However, it is worth to stress that, in the case of LaNi 4.8Bi 0.2, a small increase of H/f.u. up to 6.8 is observed. The obtained results in these investigations indicate that the LaNi 4.8T 0.2 (T = Al, Mg and Bi) alloys can be very attractive materials dedicated for negative electrodes in Ni/MH batteries.

  4. Effect of stoichiometry and Cu-substitution on the phase structure and hydrogen storage properties of Ml-Mg-Ni-based alloys

    NASA Astrophysics Data System (ADS)

    Li, Yuan; Tao, Yang; Huo, Quan

    2015-01-01

    To improve the electrochemical properties of rare-earth-Mg-Ni-based hydrogen storage alloys, the effects of stoichiometry and Cu-substitution on the phase structure and thermodynamic properties of the alloys were studied. Nonsubstituted Ml0.80Mg0.20(Ni2.90Co0.50-Mn0.30Al0.30) x ( x = 0.68, 0.70, 0.72, 0.74, 0.76) alloys and Cu-substituted Ml0.80Mg0.20(Ni2.90Co0.50- y Cu y Mn0.30Al0.30)0.70 ( y = 0, 0.10, 0.30, 0.50) alloys were prepared by induction melting. Phase structure analysis shows that the nonsubstituted alloys consist of a LaNi5 phase, a LaNi3 phase, and a minor La2Ni7 phase; in addition, in the case of Cu-substitution, the Nd2Ni7 phase appears and the LaNi3 phase vanishes. Thermodynamic tests show that the enthalpy change in the dehydriding process decreases, indicating that hydride stability decreases with increasing stoichiometry and increasing Cu content. The maximum discharge capacity, kinetic properties, and cycling stability of the alloy electrodes all increase and then decrease with increasing stoichiometry or increasing Cu content. Furthermore, Cu substitution for Co ameliorates the discharge capacity, kinetics, and cycling stability of the alloy electrodes.

  5. Enhanced hydrogen storage properties of MgH2 co-catalyzed with K2NiF6 and CNTs.

    PubMed

    Sulaiman, N N; Ismail, M

    2016-12-06

    The composite of MgH 2 /K 2 NiF 6 /carbon nanotubes (CNTs) is prepared by ball milling, and its hydrogenation properties are studied for the first time. MgH 2 co-catalyzed with K 2 NiF 6 and CNTs exhibited an improvement in the onset dehydrogenation temperature and isothermal de/rehydrogenation kinetics compared with the MgH 2 -K 2 NiF 6 composite. The onset dehydrogenation temperature of MgH 2 doped with 10 wt% K 2 NiF 6 and 5 wt% CNTs is 245 °C, which demonstrated a reduction of 25 °C compared with the MgH 2 + 10 wt% K 2 NiF 6 composite. In terms of rehydrogenation kinetics, MgH 2 doped with 10 wt% K 2 NiF 6 and 5 wt% CNTs samples absorbed 3.4 wt% of hydrogen in 1 min at 320 °C, whereas the MgH 2 + 10 wt% K 2 NiF 6 sample absorbed 2.6 wt% of hydrogen under the same conditions. For dehydrogenation kinetics at 320 °C, the MgH 2 + 10 wt% K 2 NiF 6 + 5 wt% CNTs sample released 3.3 wt% hydrogen after 5 min of dehydrogenation. By contrast, MgH 2 doped with 10 wt% K 2 NiF 6 released 3.0 wt% hydrogen in the same time period. The apparent activation energy, E a , for the dehydrogenation of MgH 2 doped with 10 wt% K 2 NiF 6 reduced from 100.0 kJ mol -1 to 70.0 kJ mol -1 after MgH 2 was co-doped with 10 wt% K 2 NiF 6 and 5 wt% CNTs. Based on the experimental results, the hydrogen storage properties of the MgH 2 /K 2 NiF 6 /CNTs composite is enhanced because of the catalytic effects of the active species of KF, KH and Mg 2 Ni that are formed in situ during dehydrogenation, as well as the unique structure of CNTs.

  6. Primary fragmentation pathways of gas phase [M(uracil-H)(uracil)]+ complexes (M=Zn, Cu, Ni, Co, Fe, Mn, Cd, Pd , Mg, Ca, Sr, Ba, and Pb): loss of uracil versus HNCO.

    PubMed

    Ali, Osama Y; Randell, Nicholas M; Fridgen, Travis D

    2012-04-23

    Complexes formed between metal dications, the conjugate base of uracil, and uracil are investigated by sustained off-resonance irradiation collision-induced dissociation (SORI-CID) in a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. Positive-ion electrospray spectra show that [M(Ura-H)(Ura)](+) (M=Zn, Cu, Ni, Co, Fe, Mn, Cd, Pd, Mg, Ca, Sr, Ba, or Pb) is the most abundant ion even at low concentrations of uracil. SORI-CID experiments show that the main primary decomposition pathway for all [M(Ura-H)(Ura)](+) , except where M=Ca, Sr, Ba, or Pb, is the loss of HNCO. Under the same SORI-CID conditions, when M is Ca, Sr, Ba, or Pb, [M(Ura-H)(Ura)](+) are shown to lose a molecule of uracil. Similar results were observed under infrared multiple-photon dissociation excitation conditions, except that [Ca(Ura-H)(Ura)](+) was found to lose HNCO as the primary fragmentation product. The binding energies between neutral uracil and [M(Ura-H)](+) (M=Zn, Cu, Ni, Fe, Cd, Pd ,Mg, Ca, Sr Ba, or Pb) are calculated by means of electronic-structure calculations. The differences in the uracil binding energies between complexes which lose uracil and those which lose HNCO are consistent with the experimentally observed differences in fragmentation pathways. A size dependence in the binding energies suggests that the interaction between uracil and [M(Ura-H)](+) is ion-dipole complexation and the experimental evidence presented supports this. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Structures and Electrochemical Hydrogen Storage Properties of the As-Spun RE-Mg-Ni-Co-Al-Based AB2-Type Alloys Applied to Ni-MH Battery

    NASA Astrophysics Data System (ADS)

    Zhang, Yanghuan; Yuan, Zeming; Shang, Hongwei; Li, Yaqin; Qi, Yan; Zhao, Dongliang

    2017-05-01

    In this paper, the La0.8- x Ce0.2Y x MgNi3.5Co0.4Al0.1 ( x = 0, 0.05, 0.1, 0.15, 0.2) alloys were synthesized via smelting and melt spinning. The effect of Y content on the structure and electrochemical hydrogen storage characteristics of the as-cast and spun alloys was investigated. The identifications of XRD and SEM demonstrate that the experimental alloys possess a major phase LaMgNi4 and a minor phase LaNi5. The variation of Y content results in an obvious transformation of the phase abundance rather than phase composition in the alloys, namely LaMgNi4 phase increases while LaNi5 phase decreases with Y content growing. Furthermore, the replacement of Y for La causes the lattice constants and cell volume to clearly decrease and markedly refines the alloy grains. The electrochemical tests reveal that these alloys can obtain the maximum values of discharge capacity at the first cycling without any activation needed. With Y content growing, the discharge capacity of the alloys obviously declines, but its cycle stability remarkably improves. Moreover, the electrochemical dynamics of the alloys, involving the high-rate discharge ability, hydrogen diffusion coefficient ( D), limiting current density ( I L), and charge transfer rate, initially augment and then decrease with rising Y content.

  8. Self-discharge characteristic and mechanism of single-phase PuNi3-, Gd2Co7-, and Pr5Co19-type Nd-Mg-Ni-based alloys

    NASA Astrophysics Data System (ADS)

    Jia, Zeru; Zhang, Lu; Zhao, Yumeng; Cao, Juan; Li, Yuan; Dong, Zhentao; Wang, Wenfeng; Han, Shumin

    2017-12-01

    To decrease the self-discharge rate of the nickel metal hydride batteries, the self-discharge characteristic and mechanism of single-phase PuNi3-, Gd2Co7-, and Pr5Co19-type Nd-Mg-Ni-based alloys are studied from the perspective of structure in this work. It is found that the self-discharge rate of the alloy electrodes gradually increases with a rising [NdNi5]/[NdMgNi4] subunit ratio. The factors resulting in reversible and irreversible self-discharge are analyzed by electrochemical pressure-composition isotherms, Tafel and SEM measurements. Electrochemical P-C isotherms show that with the increasing [NdNi5]/[NdMgNi4] subunit ratio, the hydrogen desorption plateau pressure sharply elevates, leading to less stability of the corresponding hydride and more reversible self-discharge of the alloys; whereas, corrosion current density of the three alloy electrodes gradually decreases and SEM shows that the amount of hydroxide accumulating on the alloy surface diminishes, indicating the oxidation/corrosion degree alleviates and less irreversible self-discharge with the higher [NdNi5]/[NdMgNi4] ratio. By calculating the proportion of reversible and irreversible self-discharge in total capacity loss, we find that the reversible self-discharge is nearly more than 90% for the three single-phase alloys, while irreversible self-discharge is less than 10%, which illustrates that reversible self-discharge is the dominate factor in self-discharge of Nd-Mg-Ni-based alloys in this study.

  9. Highly destabilized Mg-Ti-Ni-H system investigated by density functional theory and hydrogenography

    NASA Astrophysics Data System (ADS)

    Broedersz, C. P.; Gremaud, R.; Dam, B.; Griessen, R.; Løvvik, O. M.

    2008-01-01

    Using hydrogenography, we recently mapped the thermodynamic properties of a large range of compositions in the quaternary Mg-Ti-Ni-H system. The enthalpy of hydride formation of Mg-Ni alloys is significantly altered upon Ti doping. For a small range of compositions, we find a hydrogenation enthalpy ΔH=-40kJ (molH2)-1 , which is the desired enthalpy for hydrogen storage at moderate temperature and pressure. This enthalpy value is surprising since it is significantly less negative than the ΔH of the Mg-Ni and Mg-Ti hydrides. The nanostructure of the Mg-Ti-Ni-H films hinders a direct determination of the hydride phases involved by x-ray diffraction. Using density functional theory calculations for various hydrogenation reaction paths, we establish that the destabilization of the Mg-Ni-H system by Ti doping is due to the formation of Mg2Ni and Ti-Ni intermetallics in the as-deposited state, which transform into a metastable Ti-doped Mg2NiH4 phase upon hydrogenation. The Ti-doped Mg2NiH4 phase can be considered as a heavily doped semiconductor.

  10. Pyrolysis and gasification of landfilled plastic wastes with Ni-Mg-La/Al2O3 catalyst.

    PubMed

    Kaewpengkrow, Prangtip; Atong, Duangduen; Sricharoenchaikul, Viboon

    2012-12-01

    Pyrolysis and gasification processes were utilized to study the feasibility of producing fuels from landfilled plastic wastes. These wastes were converted in a gasifier at 700-900 degrees C. The equivalence ratio (ER) was varied from 0.4-0.6 with or without addition ofa Ni-Mg-La/Al2O3 catalyst. The pyrolysis and gasification of plastic wastes without catalyst resulted in relatively low H2, CO and other fuel gas products with methane as the major gaseous species. The highest lower heating value (LHV) was obtained at 800 degrees C and for an ER of 0.4, while the maximum cold gas efficiency occurred at 700 degrees C and for an ER of 0.4. The presence of the Ni-Mg-La/Al2O3 catalyst significantly enhanced H2 and CO production as well as increasing the gas energy content to 15.76-19.26 MJ/m3, which is suitable for further usage as quality fuel gas. A higher temperature resulted in more H2 and CO and other product gas yields, while char and liquid (tars) decreased. The maximum gas yield, gas calorific value and cold gas efficiency were achieved when the Ni-Mg-La/Al2O3 catalyst was used at 900 degrees C. In general, addition of prepared catalyst resulted in greater H2, CO and other light hydrocarbon yields from superior conversion of wastes to these gases. Thus, thermochemical treatment of these problematic wastes using pyrolysis and gasification processes is a very attractive alternative for sustainable waste management.

  11. In operando neutron diffraction study of LaNdMgNi9H13 as a metal hydride battery anode

    NASA Astrophysics Data System (ADS)

    Nazer, N. S.; Denys, R. V.; Yartys, V. A.; Hu, Wei-Kang; Latroche, M.; Cuevas, F.; Hauback, B. C.; Henry, P. F.; Arnberg, L.

    2017-03-01

    La2MgNi9-related alloys are superior metal hydride battery anodes as compared to the commercial AB5 alloys. Nd-substituted La2-yNdyMgNi9 intermetallics are of particular interest because of increased diffusion rate of hydrogen and thus improved performance at high discharge currents. The present work presents in operando characterization of the LaNdMgNi9 intermetallic as anode for the nickel metal hydride (Ni-MH) battery. We have studied the structural evolution of LaNdMgNi9 during its charge and discharge using in situ neutron powder diffraction. The work included experiments using deuterium gas and electrochemical charge-discharge measurements. The alloy exhibited a high electrochemical discharge capacity (373 mAh/g) which is 20% higher than the AB5 type alloys. A saturated β-deuteride synthesized by solid-gas reaction at PD2 = 1.6 MPa contained 12.9 deuterium atoms per formula unit (D/f.u.) which resulted in a volume expansion of 26.1%. During the electrochemical charging, the volume expansion (23.4%) and D-contents were found to be slightly reduced. The reversible electrochemical cycling is performed through the formation of a two-phase mixture of the α-solid solution and β-hydride phases. Nd substitution contributes to the high-rate dischargeability, while maintaining a good cyclic stability. Electrochemical Impedance Spectroscopy (EIS) was used to characterize the anode electrode on cycling. A mathematical model for the impedance response of a porous electrode was utilized. The EIS showed a decreased hydrogen transport rate during the long-term cycling, which indicated a corresponding slowing down of the electrochemical processes at the surface of the metal hydride anode.

  12. Nano-Ni induced surface modification relevant to the hydrogenation performances in La-Mg based alloys

    NASA Astrophysics Data System (ADS)

    Zhang, Huaiwei; Fu, Li; Xuan, Weidong; Li, Xingguo

    2018-05-01

    Nano-Ni drived modification in LaMg3/Ni composite is investigated. The new phases of LaMg2 and MgNi2 can be formed on the sample surface during the milling process. There is almost no electric charge transfer process between Ni and La element through XPS analyses. The amorphization structure can be found on the alloy surface with the increasing of reaction duration, and the capacity and cycle stability are also greatly promoted. On the other hand, the milled alloys show the lower charge transfer resistance, better anti-corrosion ability and higher oxidation current density.

  13. [Ni III(OMe)]-mediated reductive activation of CO 2 affording a Ni(κ 1-OCO) complex

    DOE PAGES

    Chiou, Tzung -Wen; Tseng, Yen -Ming; Lu, Tsai -Te; ...

    2016-02-24

    Here, carbon dioxide is expected to be employed as an inexpensive and potential feedstock of C 1 sources for the mass production of valuable chemicals and fuel. Versatile chemical transformations of CO 2, i.e. insertion of CO 2 producing bicarbonate/acetate/formate, cleavage of CO 2 yielding μ-CO/μ-oxo transition-metal complexes, and electrocatalytic reduction of CO 2 affording CO/HCOOH/CH 3OH/CH 4/C 2H 4/oxalate were well documented. Herein, we report a novel pathway for the reductive activation of CO 2 by the [Ni III(OMe)(P(C 6H 3-3-SiMe 3-2-S) 3)] – complex, yielding the [Ni III(κ 1-OCO˙ –)(P(C 6H 3-3-SiMe 3-2-S) 3)] – complex. The formationmore » of this unusual Ni III(κ 1-OCO ˙–) complex was characterized by single-crystal X-ray diffraction, EPR, IR, SQUID, Ni/S K-edge X-ray absorption spectroscopy, and Ni valence-to-core X-ray emission spectroscopy. The inertness of the analogous complexes [Ni III(SPh)], [Ni II(CO)], and [Ni II(N 2H 4)] toward CO 2, in contrast, demonstrates that the ionic [Ni III(OMe)] core attracts the binding of weak σ-donor CO 2 and triggers the subsequent reduction of CO 2 by the nucleophilic [OMe] – in the immediate vicinity. This metal–ligand cooperative activation of CO 2 may open a novel pathway promoting the subsequent incorporation of CO 2 in the buildup of functionalized products.« less

  14. Formation of Multiple-Phase Catalysts for the Hydrogen Storage of Mg Nanoparticles by Adding Flowerlike NiS.

    PubMed

    Xie, Xiubo; Ma, Xiujuan; Liu, Peng; Shang, Jiaxiang; Li, Xingguo; Liu, Tong

    2017-02-22

    In order to enhance the hydrogen storage properties of Mg, flowerlike NiS particles have been successfully prepared by solvothermal reaction method, and are subsequently ball milled with Mg nanoparticles (NPs) to fabricate Mg-5 wt % NiS nanocomposite. The nanocomposite displays Mg/NiS core/shell structure. The NiS shell decomposes into Ni, MgS and Mg 2 Ni multiple-phases, decorating on the surface of the Mg NPs after the first hydrogen absorption and desorption cycle at 673 K. The Mg-MgS-Mg 2 Ni-Ni nanocomposite shows enhanced hydrogenation and dehydrogenation rates: it can quickly uptake 3.5 wt % H 2 within 10 min at 423 K and release 3.1 wt % H 2 within 10 min at 573 K. The apparent hydrogen absorption and desorption activation energies are decreased to 45.45 and 64.71 kJ mol -1 . The enhanced sorption kinetics of the nanocomposite is attributed to the synergistic catalytic effects of the in situ formed MgS, Ni and Mg 2 Ni multiple-phase catalysts during the hydrogenation/dehydrogenation process, the porthole effects for the volume expansion and microstrain of the phase transformation of Mg 2 Ni and Mg 2 NiH 4 and the reduced hydrogen diffusion distance caused by nanosized Mg. This novel method of in situ producing multiple-phase catalysts gives a new horizon for designing high performance hydrogen storage material.

  15. Evidence of Intermediate Hydrogen States in the Formation of a Complex Hydride

    DOE PAGES

    Sato, Toyoto; Ramirez-Cuesta, Anibal J.; Daemen, Luke L.; ...

    2017-12-26

    A complex hydride (LaMg 2NiH 7) composed of La 3+, two Mg 2+, [NiH 4] 4– with a covalently bonded hydrogen, and three H – was formed from an intermetallic LaMg 2Ni via an intermediate phase (LaMg 2NiH 4.6) composed of La, Mg, NiH 2, NiH 3 units, and H atoms at tetrahedral sites. The NiH 2 and NiH 3 units in LaMg 2NiH 4.6 were reported as precursors for [NiH 4] 4– in LaMg 2NiH 7 [Miwa et al. J. Phys. Chem. C 2016, 120, 5926–5931]. To further understand the hydrogen states in the precursors (the NiH 2 andmore » NiH 3 units) and H atoms at the tetrahedral sites in the intermediate phase, LaMg 2NiH 4.6, we observed the hydrogen vibrations in LaMg 2NiH 4.6 and LaMg 2NiH 7 by using inelastic neutron scattering. A comparison of the hydrogen vibrations of the NiH 2 and NiH 3 units with that of [NiH 4] 4– shows that the librational modes of the NiH 2 and NiH 3 units were nonexistent; librational modes are characteristic modes for complex anions, such as [NiH 4] 4–. Furthermore, the hydrogen vibrations for the H atoms in the tetrahedral sites showed a narrower wavenumber range than that for H – and a wider range than that for typical interstitial hydrogen. The results indicated the presence of intermediate hydrogen states before the formation of [NiH 4] 4– and H –.« less

  16. Evidence of Intermediate Hydrogen States in the Formation of a Complex Hydride

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sato, Toyoto; Ramirez-Cuesta, Anibal J.; Daemen, Luke L.

    A complex hydride (LaMg 2NiH 7) composed of La 3+, two Mg 2+, [NiH 4] 4– with a covalently bonded hydrogen, and three H – was formed from an intermetallic LaMg 2Ni via an intermediate phase (LaMg 2NiH 4.6) composed of La, Mg, NiH 2, NiH 3 units, and H atoms at tetrahedral sites. The NiH 2 and NiH 3 units in LaMg 2NiH 4.6 were reported as precursors for [NiH 4] 4– in LaMg 2NiH 7 [Miwa et al. J. Phys. Chem. C 2016, 120, 5926–5931]. To further understand the hydrogen states in the precursors (the NiH 2 andmore » NiH 3 units) and H atoms at the tetrahedral sites in the intermediate phase, LaMg 2NiH 4.6, we observed the hydrogen vibrations in LaMg 2NiH 4.6 and LaMg 2NiH 7 by using inelastic neutron scattering. A comparison of the hydrogen vibrations of the NiH 2 and NiH 3 units with that of [NiH 4] 4– shows that the librational modes of the NiH 2 and NiH 3 units were nonexistent; librational modes are characteristic modes for complex anions, such as [NiH 4] 4–. Furthermore, the hydrogen vibrations for the H atoms in the tetrahedral sites showed a narrower wavenumber range than that for H – and a wider range than that for typical interstitial hydrogen. The results indicated the presence of intermediate hydrogen states before the formation of [NiH 4] 4– and H –.« less

  17. Pressure-induced effects and phase relations in Mg2NiH4

    NASA Astrophysics Data System (ADS)

    Gavra, Z.; Kimmel, G.; Gefen, Y.; Mintz, Moshe H.

    1985-05-01

    The low-temperature (<210 °C) crystallographic structure, electrical conductivity, and thermal stability of Mg2NiH4 powders compacted under isostatic pressures of up to 10 kbar were studied. A comparison is made with the corresponding properties of the noncompressed material. It has been concluded that under stress-free hydriding conditions performed below 210 °C, a two-phase hydride mixture is formed. Each of the hydride particles consists of an inner core composed of an hydrogen-deficient monoclinic phase coated by a layer of a stoichiometric orthorhombic phase. The monoclinic phase has a metalliclike electrical conductivity while the orthorhombic phase is insulating. High compaction pressures cause the transformation of the orthorhombic structure into the monoclinic one, thereby resulting in a pressure-induced insulator-to-conductor transition. Reduced decomposition temperatures are obtained for the compressed hydrides. This reduction is attributed to kinetic factors rather than to a reduced thermodynamic stability.

  18. Phase Equilibria, Crystal Structure and Hydriding/Dehydriding Mechanism of Nd4Mg80Ni8 Compound

    PubMed Central

    Luo, Qun; Gu, Qin-Fen; Zhang, Jie-Yu; Chen, Shuang-Lin; Chou, Kuo-Chih; Li, Qian

    2015-01-01

    In order to find out the optimal composition of novel Nd-Mg-Ni alloys for hydrogen storage, the isothermal section of Nd-Mg-Ni system at 400 °C is established by examining the equilibrated alloys. A new ternary compound Nd4Mg80Ni8 is discovered in the Mg-rich corner. It has the crystal structure of space group I41/amd with lattice parameters of a = b = 11.2743(1) Å and c = 15.9170(2) Å, characterized by the synchrotron powder X-ray diffraction (SR-PXRD). High-resolution transmission electron microscopy (HR-TEM) is used to investigate the microstructure of Nd4Mg80Ni8 and its hydrogen-induced microstructure evolution. The hydrogenation leads to Nd4Mg80Ni8 decomposing into NdH2.61-MgH2-Mg2NiH0.3 nanocomposites, where the high density phase boundaries provide a great deal of hydrogen atoms diffusion channels and nucleation sites of hydrides, which greatly enhances the hydriding/dehydriding (H/D) properties. The Nd4Mg80Ni8 exhibits a good cycle ability. The kinetic mechanisms of H/D reactions are studied by Real Physical Picture (RPP) model. The rate controlling steps are diffusion for hydriding reaction in the temperature range of 100 ~ 350 °C and surface penetration for dehydriding reaction at 291 ~ 347 °C. In-situ SR-PXRD results reveal the phase transformations of Mg to MgH2 and Mg2Ni to Mg2NiH4 as functions of hydrogen pressure and hydriding time. PMID:26471964

  19. Effect of Mg substitution on crystal structure and hydrogenation of Ce{sub 2}Ni{sub 7}-type Pr{sub 2}Ni{sub 7}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Iwase, Kenji, E-mail: fbiwase@mx.ibaraki.ac.jp; Mori, Kazuhiro; Terashita, Naoyoshi

    2017-03-15

    The effect of Pr being substituted by Mg in Pr{sub 2}Ni{sub 7} with a Ce{sub 2}Ni{sub 7}-type structure was investigated by X-ray diffraction (XRD) and pressure−composition (P−C) isotherm measurements. The maximum hydrogen capacity of Pr{sub 2}Ni{sub 7} reached 1.24 H/M in the first absorption process. However, 0.61 H/M hydrogen remained in the sample after the first desorption and the reversible hydrogen capacity decreased to 0.63 H/M. Severe peak broadening was observed in the XRD profile of Pr{sub 2}Ni{sub 7}H{sub 5.4} after the first P−C isotherm cycle. The metal sublattice of Pr{sub 2}Ni{sub 7}H{sub 5.4} is deformed and changes from themore » Ce{sub 2}Ni{sub 7}-type structure to a lower symmetry during hydrogenation, with no detection of an amorphous phase. Pr{sub 1.5}Mg{sub 0.5}Ni{sub 7} consists of two phases: 80% Gd{sub 2}Co{sub 7}-type and 20% PuNi{sub 3}-type phases. Mg substitution leads to the relative stability of the Gd{sub 2}Co{sub 7}-type and PuNi{sub 3}-type structures. The Gd{sub 2}Co{sub 7}-type and PuNi{sub 3}-type structures are retained after the P-C isotherm. The reversible hydrogen capacity reached 1.05 H/M. The structural change during the hydrogen absorption−desorption cycle and the hydrogenation characteristics are changed by Mg atoms replacing Pr in the MgZn{sub 2}-type cell. - Graphical abstract: The maximum hydrogen capacity is 1.2 H/M in the first absorption process and the reversible capacity is 0.63 H/M.« less

  20. New LaMAsH(x) (M = Co, Ni, or Cu) arsenides with covalent M-H chains.

    PubMed

    Mizoguchi, Hiroshi; Park, SangWon; Hiraka, Haruhiro; Ikeda, Kazutaka; Otomo, Toshiya; Hosono, Hideo

    2014-12-17

    A new series of tetragonal LaPtSi-type mixed-anion arsenides, LaMAsH(x) (M = Co, Ni, or Cu), has been synthesized using high-temperature and high-pressure techniques. The crystal structure of these intermetallic compounds determined via powder neutron diffraction is composed of a 3D framework of three connected planes with the La ions filling the cavities in the structure. Each late transition-metal ion M, all of which have relatively large electronegativities, behaves like a main group element and forms a planar coordination configuration with three As ions. The trigonal-bipyramidal coordination adopted by the H in the cavity, HM2La3, is compressed along the C3 axis, and unusual M-H chains run along the x and y directions, reinforcing the covalent framework. These chains, which are unique in solids, are stabilized by covalent interactions between the M 4s and H 1s orbitals.

  1. Preparation and characterization of mechanically alloyed AB3-type based material LaMg2Ni5Al4 and its solid-gaz hydrogen storage reaction

    NASA Astrophysics Data System (ADS)

    Jaafar, Hassen; Aymard, Luc; Dachraoui, Walid; Demortière, Arnaud; Abdellaoui, Mohieddine

    2018-04-01

    We developed in the present paper the synthesis of a new AB3-type compound LaMg2Ni5Al4 by mechanical alloying (MA) process. ​​X-ray diffraction analysis (XRD) was used to determine the structural properties and the phase evolution of the powder mixtures. Two different synthesis pathways have been investigated. The first starting from elemental metals and the second from a mixture of two binary compounds LaNi5 (CaCu5-type structure, P6/mmm space group) and Al(Mg) solid solution (cubic Fm-3 m space group). The results show multiphase alloys which contain LaMg2Ni5Al4 main phase with hexagonal PuNi3-type structure (R-3 m space group). Rietveld analysis shows that using a planetary ball mill, we obtain a good yield of LaMg2Ni5Al4 compound after 5 h of mechanical alloying for both synthesis pathways. TEM analysis confirmed XRD results. SEM-EDX analysis of the final product was in agreement with the nominal chemical formula. A setup of possible solid-gaz hydrogenation reaction will be described so far at the end of this work. Electrochemical results demonstrate evidence on hydrogen absorption in the AB3 material and the discharge capacity was equal to 5.9 H/f.u.

  2. Material properties of perovskites in the quasi-ternary system LaFeO3-LaCoO3-LaNiO3

    NASA Astrophysics Data System (ADS)

    Tietz, F.; Arul Raj, I.; Ma, Q.; Baumann, S.; Mahmoud, A.; Hermann, R. P.

    2016-05-01

    An overview is presented on the variation of electrical conductivity, oxygen permeation, and thermal expansion coefficient as a function of the composition of perovskites in the quasi-ternary system LaFeO3-LaCoO3-LaNiO3. Powders of thirteen nominal perovskite compositions were synthesized under identical conditions by the Pechini method. The powder X-ray diffraction data of two series, namely La(Ni0.5Fe0.5)1-xCoxO3 and LaNi0.5-xFexCo0.5O3, are presented after the powders had been sintered at 1100 °C for 6 h in air. The measurements revealed a rhombohedral structure for all compositions except LaNi0.5Fe0.5O3 for which 60% rhombohedral and 40% orthorhombic phase was found. The maximum DC electrical conductivity value of the perovskites at 800 °C was 1229 S cm-1 for the composition LaCoO3 and the minimum was 91 S cm-1 for the composition LaCo0.5Fe0.5O3. The oxygen permeation of samples with promising conductivities at 800 °C was one order of magnitude lower than that of La0.6Sr0.4Co0.8Fe0.2O3 (LSCF). The highest value of 0.017 ml cm-2 min-1 at 950 °C was obtained with LaNi0.5Co0.5O3. The coefficients of thermal expansion varied in the range of 13.2×10-6 K-1 and 21.9×10-6 K-1 for LaNi0.5Fe0.5O3 and LaCoO3, respectively. 57Fe Mössbauer spectroscopy was used as probe for the oxidation states, local environment and magnetic properties of iron ions as a function of chemical composition. The substitution had a great influence on the chemical properties of the materials.

  3. On the decrepitation mechanism of MgNi and LaNi 5-based electrodes studied by in situ acoustic emission

    NASA Astrophysics Data System (ADS)

    Etiemble, A.; Idrissi, H.; Roué, L.

    In situ monitoring of the pulverization of amorphous MgNi and crystalline LaNi 5-based alloys has been studied during their hydrogen charge by combining acoustic emission and electrochemical measurements. In both alloys, two classes of acoustic signals with specific temporal and energetic characteristics were detected during their charge: a P1 class related to the particle cracking and a P2 class due to the release of H 2 bubbles. By comparing the P1 activity on both materials as a function of the charge input, it was shown that the pulverization phenomenon becomes significant at a much lower charge input for the LaNi 5-based electrode (∼5-25 mAh g -1) than for the MgNi electrode (∼365 mAh g -1), reflecting the fact that the mechanism responsible of their decrepitation is not similar. Indeed, it was demonstrated that the cracking of the amorphous and porous MgNi material is mainly induced by the hydrogen evolution reaction whereas for the crystalline and denser LaNi 5-based material, the α-β lattice expansion is responsible of its decrepitation. It was also shown that the particle size and the charge current density have a major impact on the MgNi decrepitation. The correlation between the MgNi particle cracking and the discharge capacity decay with cycling was established.

  4. Stabilization of Reactive MgO Surfaces by Ni Doping

    NASA Astrophysics Data System (ADS)

    Mazheika, Aliaksei; Levchenko, Sergey V.

    Ni-MgO solid solutions are promising materials for catalytic reduction of CO2 and dry reforming of CH4. To explain the catalytic activity, an ab initio study of Ni-substitutional defects in MgO (NiMg) has been performed. At first, the validation of the theory level was done. We compared results of CCSD(T) embedded-cluster calculations of NiMg formation energies and adsorption energies of CO, CO2 and H2 on them to the HSE(α) hybrid DFT functional with the fraction of the exact exchange α varied between 0 and 1. HSE(0.3) was found to be the best compromise in this study. Our periodic HSE(0.3) calculations show that NiMg defects are most stable at corner sites, followed by steps, and are least stable at (001) terraces. Thus, Ni-doping stabilizes stepped MgO surfaces. The dissociative adsorption of H2 on the terrace is found to be endothermic (+ 1 . 1 eV), whereas on (110) surface with NiMg it is highly exothermic (- 1 . 6 eV). Adsorbed CO2 is also significantly stabilized (- 0 . 6 vs. - 2 . 2 eV). These findings explain recent microcalorimetry measurements of H2 and CO2 adsorption at doped Ni-MgO samples. partially supported by UniCat (Deutsche Forschungsgemeinschaft).

  5. Crystal structures of the new ternary stannides La3Mg4-xSn2+x and LaMg3-xSn2

    NASA Astrophysics Data System (ADS)

    Solokha, P.; De Negri, S.; Minetti, R.; Proserpio, D. M.; Saccone, A.

    2016-01-01

    Synthesis and structural characterization of the two new lanthanum-magnesium-stannides La3Mg4-xSn2+x (0.12≤x≤0.40) and LaMg3-xSn2 (0.33≤x≤0.78) are reported. The crystal structures of these intermetallics were determined by single crystal X-ray diffraction analysis and confirmed by Rietveld refinement of powder X-ray diffraction patterns of the corresponding samples. The La3Mg4-xSn2+x phase crystallizes in the hexagonal Zr3Cu4Si2 structure type (P6bar2m, hP9, Z=3, x=0.12(1), a=7.7974(7), c=4.8384(4) Å), which represents an ordered derivative of the hP9-ZrNiAl prototype, ubiquitous among equiatomic intermetallics. The LaMg3-xSn2 phase is the second representative of the trigonal LaMg3-xGe2 type, which is a superstructure of the LaLi3Sb2 structure type (P3bar1c, hP34-0.12, Z=6, x=0.35(1), a=8.3222(9), c=14.9546(16) Å). The scheme describing the symmetry reduction/coloring with respect to the parent type is reported here with the purpose to discuss the LaMg3-xSn2 off-stoichiometry from the geometrical point of view. Structural relationships between the La-Mg-Sn ternary phases, including the already known equiatomic LaMgSn compound (oP12-TiNiSi), are presented in the framework of the AlB2-related compounds family and discussed with the aid of group-subgroup relations in the Bärnighausen formalism.

  6. Material properties of perovskites in the quasi-ternary system LaFeO 3–LaCoO 3–LaNiO 3

    DOE PAGES

    Tietz, F.; Arul Raj, I.; Ma, Q.; ...

    2016-02-02

    We present an overview on the variation of electrical conductivity, oxygen permeation, oxygen surface exchange and thermal expansion coefficient as a function of the composition of perovskites in the quasi-ternary system LaFeO 3–LaCoO 3–LaNiO 3. Powders of thirteen nominal perovskite compositions were synthesized under identical conditions by the Pechini method. The powder X-ray diffraction data of two series, namely La(Ni 0.5Fe 0.5) 1-xCo xO 3 and LaNi 0.5- xFe xCo 0.5O 3, are presented after the powders had been sintered at 1100 C for 6 h in air. The measurements revealed a rhombohedral structure for all compositions except LaNi 0.5Femore » 0.5O 3 for which 60% rhombohedral and 40% orthorhombic phase was found. Moreover, the maximum DC electrical conductivity value of the perovskites at 800 C was 1229 S cm-1 for the composition LaCoO 3 and the minimum was 91 S cm-1 for the composition LaCo 0.5Fe 0.5O 3. The oxygen permeation of samples with promising conductivities at 800 C was one order of magnitude lower than that of La 0.6Sr 0.4Co 0.8Fe 0.2O 3 (LSCF). The highest value of 0.017 ml cm -2 min-1 at 950 C was obtained with LaNi 0.5Co 0.5O 3. The coefficients of thermal expansion varied in the range of 13.2 x 10 -6 K -1 and 21.9 x 10 -6 K -1 for LaNi 0.5Fe 0.5O 3 and LaCoO 3, respectively. 57Fe M ssbauer spectroscopy was used as probe for the oxidation states, local environment and magnetic properties of iron ions as a function of chemical composition. Ultimately, the substitution had a great influence on the chemical properties of the materials.« less

  7. Cu(II), Co(II) and Ni(II) complexes of new Schiff base ligand: Synthesis, thermal and spectroscopic characterizations

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Sayed, Mohamed Y.; Adam, Abdel Majid A.

    2013-04-01

    Cu(II), Co(II), and Ni(II) complexes were synthesized from 2-[(5-o-chlorophenylazo-2-hydroxybenzylidin)amino]-phenol Schiff base (H2L). Metal ions coordinate in a tetradentate or hexadentate features with these O2N donor ligand, which are characterized by elemental analyses, magnetic moments, infrared, Raman laser, electronic, and 1H NMR spectral studies. The elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). Reactions with Cu(II), Co(II) and Ni(II), resulted [Cu(H2L)(H2O)2(Cl)]Cl, [Co(H2L)(H2O)3]Cl2ṡ3H2O and [Ni(H2L)(H2O)2]Cl2ṡ6H2O. The thermal decomposition behavior of H2L complexes has been investigated by thermogravimetric analysis (TG/DTG) at a heating rate of 10 °C min-1 under nitrogen atmosphere. The brightness side in this study is to take advantage for the preparation and characterizations of single phases of CuO, CoO and NiO nanoparticles using H2L complexes as precursors via a solid-state decomposition procedure. The crystalline structures of products using X-ray diffractometer (XRD), morphology of particles by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) were investigated.

  8. Effects of Mg substitution on the structural and magnetic properties of Co0.5Ni0.5-x Mg x Fe2O4 nanoparticle ferrites

    NASA Astrophysics Data System (ADS)

    R, M. Rosnan; Z, Othaman; R, Hussin; Ali, A. Ati; Alireza, Samavati; Shadab, Dabagh; Samad, Zare

    2016-04-01

    In this study, nanocrystalline Co-Ni-Mg ferrite powders with composition Co0.5Ni0.5-x Mg x Fe2O4 are successfully synthesized by the co-precipitation method. A systematic investigation on the structural, morphological and magnetic properties of un-doped and Mg-doped Co-Ni ferrite nanoparticles is carried out. The prepared samples are characterized using x-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), and vibrating sample magnetometry (VSM). The XRD analyses of the synthesized samples confirm the formation of single-phase cubic spinel structures with crystallite sizes in a range of ˜ 32 nm to ˜ 36 nm. The lattice constant increases with increasing Mg content. FESEM images show that the synthesized samples are homogeneous with a uniformly distributed grain. The results of IR spectroscopy analysis indicate the formation of functional groups of spinel ferrite in the co-precipitation process. By increasing Mg2+ substitution, room temperature magnetic measurement shows that maximum magnetization and coercivity increase from ˜ 57.35 emu/g to ˜ 61.49 emu/g and ˜ 603.26 Oe to ˜ 684.11 Oe (1 Oe = 79.5775 A·m-1), respectively. The higher values of magnetization M s and M r suggest that the optimum composition is Co0.5Ni0.4Mg0.1Fe2O4 that can be applied to high-density recording media and microwave devices. Project supported by the Ibnu Sina Institute for Scientific and Industrial Research, Physics Department of Universiti Teknologi Malaysia and the Ministry of Education Malaysia (Grant Nos. Q.J130000.2526.04H65).

  9. Local electronic structure and ferromagnetic interaction in La(Co,Ni)O3

    NASA Astrophysics Data System (ADS)

    Schuppler, S.; Nagel, P.; Fuchs, D.; Löhneysen, H. V.; Merz, M.; Huang, M.-J.

    Perovskite-related transition-metal oxides exhibit properties ranging from insulating to superconducting as well as unusual magnetic phases, and cobaltates, in particular, have been known for their propensity for spin-state transitions. Nonmagnetic LaCoO3 and paramagnetic LaNiO3 are parent compounds for the La(Co1-xNix) O3 (LCNO) family, which, for intermediate Ni content x, exhibits ferromagnetism. The local electronic structure and the ferromagnetic interaction in LCNO have been studied by x-ray absorption (XAS) and x-ray magnetic circular dichroism (XMCD). XAS indicates a mixed-valence state for both Co and Ni, with both valences changing systematically with increasing x. Simultaneously, a spin-state redistribution towards HS (Co site) and LS (Ni site) occurs, and temperature-dependent spin-state transitions are increasingly suppressed. XMCD identifies the element-specific contributions to the magnetic moment and interactions. A simple model based on a double-exchange-like mechanism between Co3+ HS and Ni3+HS can qualitatively account for the evolution of ferromagnetism in the LCNO series.

  10. Effect of a CoFeB layer on the anisotropic magnetoresistance of Ta/CoFeB/MgO/NiFe/MgO/CoFeB/Ta films

    NASA Astrophysics Data System (ADS)

    Li, Minghua; Shi, Hui; Dong, Yuegang; Ding, Lei; Han, Gang; Zhang, Yao; Liu, Ye; Yu, Guanghua

    2017-10-01

    The anisotropic magnetoresistance (AMR) and magnetic properties of NiFe films can be remarkably enhanced via CoFeB layer. In the case of an ultrathin NiFe film having a Ta/CoFeB/MgO/NiFe/MgO/CoFeB/Ta structure, the CoFeB/MgO layers suppressed the formation of magnetic dead layers and the interdiffusions and interface reactions between the NiFe and Ta layers. The AMR reached a maximum value of 3.56% at 450 °C. More importantly, a single NiFe (1 1 1) peak can be formed resulting in higher AMR values for films having CoFeB layer. This enhanced AMR also originated from the significant specular reflection of electrons owing to the crystalline MgO layer, together with the sharp interfaces with the NiFe layer. These factors together resulted in higher AMR and improved magnetic properties.

  11. Improved electrochemical properties of amorphous Mg 65Ni 27La 8 electrodes: Surface modification using graphite

    NASA Astrophysics Data System (ADS)

    Wu, D. C.; Li, Lu; Liang, G. Y.; Guo, Y. L.; Wu, H. B.

    Amorphous Mg 65Ni 27La 8 alloy is prepared by melt-spinning. The alloy surface is modified using different contents of graphite to improve the performances of the Mg 65Ni 27La 8 electrodes. In detail, the electrochemical properties of (Mg 65Ni 27La 8) + xC (x = 0-0.4) electrodes are studied systematically, where x is the mass ratio of graphite to alloy. Experimental results reveal that the discharge capacity, cycle life, discharge potential characteristics and electrochemical kinetics of the electrodes are all improved. The surface modification enhances the electrocatalytic activity of the alloy, reduces the contact resistance of the electrodes and obstructs the formation of Mg(OH) 2 on the alloy surface. An optimal content of graphite has been obtained. The (Mg 65Ni 27La 8) + 0.25 C electrode has the largest discharge capacity of 827 mA h g -1, which is 1.47 times as large as that of the electrode without graphite, and the best electrochemical kinetics. Further increasing of graphite content will lead to the increase of contact resistance and activation energy for charge-transfer reaction of the electrode, resulting in the degradation of electrode performance.

  12. Investigation of magnetic and structural properties of Ni-Zr co-doped M-type Sr-La hexaferrites

    NASA Astrophysics Data System (ADS)

    Yang, Yujie; Wang, Fanhou; Shao, Juxiang; Huang, Duohui; Tang, Jin; Rehman, Khalid Mehmood Ur

    2018-02-01

    In this research, Ni2+ and Zr4+ co-doped Sr-La hexaferrites Sr0.7La0.3Fe12.0-2 x (NiZr) x O19 (0.0 ≤ x ≤ 0.5) were synthesized by the standard ceramic method. The phase identification of the hexaferrites was confirmed by X-ray diffraction analysis. X-ray diffraction analysis showed that all the samples were in single phase M-type hexagonal structure and no impurity phase was observed. Lattice parameters ( c and a) increased with increasing NiZr content ( x) from 0.0 to 0.5. The morphology of the hexaferrites was analyzed by a field emission scanning electron microscopy (FE-SEM). FE-SEM micrographs showed that the grains exhibited hexagonal shape in a plate-like structure with clear grain boundaries. Magnetization properties of the hexaferrites were carried out at room temperature using a physical property measurement system-vibrating sample magnetometer. The values of saturation magnetization ( M s), remanent magnetization ( M r) and coercivity ( H c) were calculated from magnetic hysteresis ( M- H) loops. M s and H c decreased with increasing NiZr content ( x) from 0.0 to 0.5. M r and M r/ M s ratio first increased with increasing NiZr content ( x) from 0.0 to 0.1, and then decreased when NiZr content ( x) ≥ 0.1.

  13. Novel reactions of homodinuclear Ni2 complexes [Ni(RNPyS4)]2 with Fe3(CO)12 to give heterotrinuclear NiFe2 and mononuclear Fe complexes relevant to [NiFe]- and [Fe]-hydrogenases.

    PubMed

    Song, Li-Cheng; Cao, Meng; Wang, Yong-Xiang

    2015-04-21

    The homodinuclear complexes [Ni(RNPyS4)]2 (; RNPyS4 = 2,6-bis(2-mercaptophenylthiomethyl)-4-R-pyridine; R = H, MeO, Cl, Br, i-Pr) were found to be prepared by reactions of the in situ generated Li2[Ni(1,2-S2C6H4)2] with 2,6-bis[(tosyloxy)methyl]pyridine and its substituted derivatives 2,6-bis[(tosyloxy)methyl]-4-R-pyridine. Further reactions of with Fe3(CO)12 gave both heterotrinuclear complexes NiFe2(RNPyS4)(CO)5 () and mononuclear complexes Fe(RNPyS4)(CO) (), unexpectedly. Interestingly, complexes and could be regarded as models for the active sites of [NiFe]- and [Fe]-hydrogenases, respectively. All the prepared complexes were characterized by elemental analysis, spectroscopy, and particularly for some of them, by X-ray crystallography. In addition, the electrochemical properties of and as well as the electrocatalytic H2 production catalyzed by and were investigated by CV techniques.

  14. Synthesis and structural characterization of transition metal doped MgO: Mg0.95Mn0.01TM0.04O (TM = Co, Ni, Cu)

    NASA Astrophysics Data System (ADS)

    Islam, Ishtihadah; Khandy, Shakeel Ahmad; Hafiz, Aurangzeb Khurram

    2018-05-01

    In the present work, preparation and characterization of transition metal doped MgO: Zn0.94Mn0.01TM0.05O (TM = Co, Ni and Cu) nano-particles have been reported. Transition metal doped samples of MgO were synthesized by Sol gel auto combustion method. Structural characterisation from XRD and SEM show the formation of single-phase primary particles, nearly of spherical shaped nano-crystallites. The crystallite size was found to be 78.2, 67.02, 78.11 and 64 nm for pure, Co, Cu and Ni doped MgMnO nano-particles, respectively. Hence, the average crystallite size increases monotonously from Co to Cu doping.

  15. La-Sr-Ni-Co-O based perovskite-type solid solutions as catalyst precursors in the CO 2 reforming of methane

    NASA Astrophysics Data System (ADS)

    Valderrama, Gustavo; Kiennemann, Alain; Goldwasser, Mireya R.

    La 1- xSr xNi 0.4Co 0.6O 3 and La 0.8Sr 0.2Ni 1- yCo yO 3 solid solutions with perovskite-type structure were synthesized by the sol-gel resin method and used as catalytic precursors in the dry reforming of methane with CO 2 to syngas, between 873 and 1073 K at atmospheric pressure under continuous flow of reactant gases with CH 4/CO 2 = 1 ratio. These quaternary oxides were characterized by X-ray diffraction (XRD), BET specific surface area and temperature-programmed reduction (TPR) techniques. XRD analyses of the more intense diffraction peaks and cell parameter measurements showed formation of La-Sr-Ni-Co-O solid solutions with La 0.9Sr 0.1CoO 3 and/or La 0.9Sr 0.1NiO 3 as the main crystallographic phases present on the solids depending on the degree of substitution. TPR analyses showed that Sr doping decreases the temperature of reduction via formation of intermediary species producing Ni 0, Co 0 with particle sizes in the range of nanometers over the SrO and La 2O 3 phases. These metallic nano particles highly dispersed in the solid matrix are responsible for the high activity shown during the reaction and avoid carbon formation. The presence of Sr in doping quantities also promotes the secondary reactions of carbon formation and water-gas shift in a very small extension during the dry reforming reaction.

  16. Hydrogen storage and hydrolysis properties of core-shell structured Mg-MFx (M=V, Ni, La and Ce) nano-composites prepared by arc plasma method

    NASA Astrophysics Data System (ADS)

    Mao, Jianfeng; Zou, Jianxin; Lu, Chong; Zeng, Xiaoqin; Ding, Wenjiang

    2017-10-01

    In this work, core-shell structured Mg-MFx (M = V, Ni, La and Ce) nano-composites are prepared by using arc plasma method. The particle size distribution, phase components, microstructures, hydrogen sorption properties of these composites and hydrolysis properties of their corresponding hydrogenated powders are carefully investigated. It is shown that the addition of MFx through arc plasma method can improve both the hydrogen absorption kinetics of Mg and the hydrolysis properties of corresponding hydrogenated powders. Among them, the Mg-NiF2 composite shows the best hydrogen absorption properties at relatively low temperatures, which can absorb 3.26 wt% of H2 at 373 K in 2 h. Such rapid hydrogen absorption rate is mainly due to the formation of Mg2Ni and MgF2 on Mg particles during arc evaporation and condensation. In contrast, measurements also show that the hydrogenated Mg-VF3 composite has the lowest peak desorption temperature and the fastest hydrolysis rate among all the hydrogenated Mg-MFx composites. The less agglomeration tendency of Mg particles and VO2 covered on MgH2 particles account for the reduced hydrogen desorption temperature and enhanced hydrolysis rate.

  17. Activation mechanism and dehydrogenation behavior in bulk hypo/hyper-eutectic Mg-Ni alloy

    NASA Astrophysics Data System (ADS)

    Ding, Xin; Chen, Ruirun; Jin, Yinling; Chen, Xiaoyu; Guo, Jingjie; Su, Yanqing; Ding, Hongsheng; Fu, Hengzhi

    2018-01-01

    To investigate the effect of microstructure on the better de-/hydrogenation property of Mg-based alloy, hypo-eutectic Mg-8Ni (at. %) alloy and hyper-eutectic Mg-15Ni alloy are prepared by metallurgy method. The phase constitutions and microstructures are characterized by XRD and SEM/EDS. Mg-8/15Ni alloy is composed of primary Mg/Mg2Ni and eutectic Mg-Mg2Ni. In isothermal sorption test, Mg-15Ni alloy shows preferable activation performance and faster de-/hydrogenation rates than Mg-8Ni alloy. The respective hydrogen uptake capacity in 165min is 5.62 wt% and 5.76 wt% H2 at 300 °C 3 MPa. Intersections of Mg-Mg2Ni eutectic phase boundaries with particle surface provide excellent sites and paths for the dissociation and permeation of hydrogen. The de-/hydrogenation enthalpy and entropy values are determined by PCI measurement. Based on the DSC curves at different heating rates, the desorption behavior of Mg-8/15Ni hydride is revealed and the respective activation energy is calculated to be 134.67 kJ mol-1 and 88.34 kJ mol-1 H2 by Kissinger method. Synergic dehydrogenation occurs in eutectic MgH2-Mg2NiH4, which facilitates the primary MgH2 in Mg-8Ni hydride to decompose at a lower temperature. The rapid H diffusion and synergic effect in eutectic MgH2-Mg2NiH4 collectively contribute to the lower dehydrogenation energy barrier of Mg-15Ni hydride.

  18. Thermodynamic Modeling of Poorly Complexing Metals in Concentrated Electrolyte Solutions: An X-Ray Absorption and UV-Vis Spectroscopic Study of Ni(II) in the NiCl2-MgCl2-H2O System

    PubMed Central

    Zhang, Ning; Brugger, Joël; Etschmann, Barbara; Ngothai, Yung; Zeng, Dewen

    2015-01-01

    Knowledge of the structure and speciation of aqueous Ni(II)-chloride complexes is important for understanding Ni behavior in hydrometallurgical extraction. The effect of concentration on the first-shell structure of Ni(II) in aqueous NiCl2 and NiCl2-MgCl2 solutions was investigated by Ni K edge X-ray absorption (XAS) and UV-Vis spectroscopy at ambient conditions. Both techniques show that no large structural change (e.g., transition from octahedral to tetrahedral-like configuration) occurs. Both methods confirm that the Ni(II) aqua ion (with six coordinated water molecules at R Ni-O = 2.07(2) Å) is the dominant species over the whole NiCl2 concentration range. However, XANES, EXAFS and UV-Vis data show subtle changes at high salinity (> 2 mol∙kg-1 NiCl2), which are consistent with the formation of small amounts of the NiCl+ complex (up to 0.44(23) Cl at a Ni-Cl distance of 2.35(2) Å in 5.05 mol∙kg-1 NiCl2) in the pure NiCl2 solutions. At high Cl:Ni ratio in the NiCl2-MgCl2-H2O solutions, small amounts of [NiCl2]0 are also present. We developed a speciation-based mixed-solvent electrolyte (MSE) model to describe activity-composition relationships in NiCl2-MgCl2-H2O solutions, and at the same time predict Ni(II) speciation that is consistent with our XAS and UV-Vis data and with existing literature data up to the solubility limit, resolving a long-standing uncertainty about the role of chloride complexing in this system. PMID:25885410

  19. Kinetics of CO/CO2 and H2/H2O reactions at Ni-based and ceria-based solid-oxide-cell electrodes.

    PubMed

    Graves, Christopher; Chatzichristodoulou, Christodoulos; Mogensen, Mogens B

    2015-01-01

    The solid oxide electrochemical cell (SOC) is an energy conversion technology that can be operated reversibly, to efficiently convert chemical fuels to electricity (fuel cell mode) as well as to store electricity as chemical fuels (electrolysis mode). The SOC fuel-electrode carries out the electrochemical reactions CO2 + 2e(-) ↔ CO + O(2-) and H2O + 2e(-) ↔ H2 + O(2-), for which the electrocatalytic activities of different electrodes differ considerably. The relative activities in CO/CO2 and H2/H2O and the nature of the differences are not well studied, even for the most common fuel-electrode material, a composite of nickel and yttria/scandia stabilized zirconia (Ni-SZ). Ni-SZ is known to be more active for H2/H2O than for CO/CO2 reactions, but the reported relative activity varies widely. Here we compare AC impedance and DC current-overpotential data measured in the two gas environments for several different electrodes comprised of Ni-SZ, Gd-doped CeO2 (CGO), and CGO nanoparticles coating Nb-doped SrTiO3 backbones (CGOn/STN). 2D model and 3D porous electrode geometries are employed to investigate the influence of microstructure, gas diffusion and impurities.Comparing model and porous Ni-SZ electrodes, the ratio of electrode polarization resistance in CO/CO2vs. H2/H2O decreases from 33 to 2. Experiments and modelling suggest that the ratio decreases due to a lower concentration of impurities blocking the three phase boundary and due to the nature of the reaction zone extension into the porous electrode thickness. Besides showing higher activity for H2/H2O reactions than CO/CO2 reactions, the Ni/SZ interface is more active for oxidation than reduction. On the other hand, we find the opposite behaviour in both cases for CGOn/STN model electrodes, reporting for the first time a higher electrocatalytic activity of CGO nanoparticles for CO/CO2 than for H2/H2O reactions in the absence of gas diffusion limitations. We propose that enhanced surface reduction at the

  20. Theoretical Prediction on [5]Radialene Sandwich Complexes (CpM)2(C10H10) (Cp = η5-C5H5; M = Fe, Co, Ni): Geometry, Spin States, and Bonding.

    PubMed

    Liu, Nan-Nan; Xue, Ying-Ying; Ding, Yi-Hong

    2017-02-09

    [5]Radialene, the missing link for synthesis of radialene family, has been finally obtained via the preparation and decomplexation of the [5]radialene-bis-Fe(CO) 3 complex. The stability of [5]radialene complex benefits from the coordination with Fe(CO) 3 by losing free 1,3-butadiene structures to avoid polymerization. In light of the similar coordination ability of half-sandwiches CpM(Cp = η 5 -C 5 H 5 ; M = Fe, Co, Ni), there is a great possibility that the sandwiched complexes of [5]radialene with CpM are available. Herein, we present the first theoretical prediction on the geometry, spin states and bonding of (CpM)(C 10 H 10 ) and (CpM) 2 (C 10 H 10 ). For M = Fe, Co, Ni, the ground states of (CpM)(C 10 H 10 ) and (CpM) 2 (C 10 H 10 ) are doublet and triplet, singlet and singlet, and doublet and triplet states, where each Fe, Co, and Ni adopts 17, 18, and 19 electron-configuration, respectively. In particular, (CpFe) 2 (C 10 H 10 ) and (CpNi) 2 (C 10 H 10 ) have considerable open-shell singlet features. Generally the trans isomers of (CpM) 2 (C 10 H 10 ) with two CpM fragments on the opposite sides of the [5]radialene plane are apparently more stable than the cis ones with CpM fragments on the same side. However, for the singlet and triplet isomers of (CpNi) 2 (C 10 H 10 ) (both cis and trans isomers), the energy differences are relatively small, indicating that these isomers all have the opportunity to exist. Besides, the easy Diels-Alder (DA) dimerization between the [3]dendralene-like fragments of (CpM)(C 10 H 10 ) suggests the great difficulty in isolating the (CpM)(C 10 H 10 ) monomer.

  1. Structural discrimination via density functional theory and lattice dynamics: Monoclinic Mg2NiH4

    NASA Astrophysics Data System (ADS)

    Herbst, J. F.; Hector, L. G., Jr.

    2009-04-01

    Two distinct crystal structures for the monoclinic, low-temperature phase of Mg2NiH4 , which we designate as LTI and LTII, are available in the published literature. We demonstrate that density functional theory and lattice dynamics can easily identify LTII as the preferable structure at two levels of inquiry. First, enthalpies of formation ΔH calculated using three different forms for the exchange-correlation energy functional are in better agreement with experiment for LTII. Second, the phonon spectrum calculated for LTII contains no anomalies while that for LTI exhibits a variety of soft modes. By analyzing the soft modes in LTI as well as those we find for the known CaMgNiH4 structure with Ca replaced by Mg we derive a crystal structure that closely approximates LTII.

  2. Study on glass-forming ability and hydrogen storage properties of amorphous Mg{sub 60}Ni{sub 30}La{sub 10−x}Co{sub x} (x = 0, 4) alloys

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lv, Peng; Wang, Zhong-min, E-mail: zmwang@guet.edu.cn; Zhang, Huai-gang

    2013-12-15

    Mg{sub 60}Ni{sub 30}La{sub 10−x}Co{sub x} (x = 0, 4) amorphous alloys were prepared by rapid solidification, using a melt-spinning technique. X-ray diffraction and differential scanning calorimetry analysis were employed to measure their microstructure, thermal stability and glass-forming ability, and hydrogen storage properties were studied by means of PCTPro2000. Based on differential scanning calorimetry results, their glass-forming ability and thermal stability were investigated by Kissinger method, Lasocka curves and atomic cluster model, respectively. The results indicate that glass-forming ability, thermal properties and hydrogen storage properties in the Mg-rich corner of Mg–Ni–La–Co system alloys were enhanced by Co substitution for La. Itmore » can be found that the smaller activation energy (ΔΕ) and frequency factor (υ{sub 0}), the bigger value of B (glass transition point in Lasocka curves), and higher glass-forming ability of Mg–Ni–La–Co alloys would be followed. In addition, atomic structure parameter (λ), deduced from atomic cluster model is valuable in the design of Mg–Ni–La–Co system alloys with good glass-forming ability. With an increase of Co content from 0 to 4, the hydrogen desorption capacity within 4000 s rises from 2.25 to 2.85 wt.% at 573 K. - Highlights: • Amorphous Mg{sub 60}Ni{sub 30}La{sub 10−x}Co{sub x} (x = 0 and 4) alloys were produced by melt spinning. • The GFA and hydrogen storage properties were enhanced by Co substitution for La. • With an increase of Co content, the hydrogen desorption capacity rises at 573 K.« less

  3. Co(II) and Ni(II) complexes based on anthraquinone-1,4,5,8-tetracarboxylic acid (H4AQTC): canted antiferromagnetism and slow magnetization relaxation in {[Co2(AQTC)(H2O)6]·6H2O}.

    PubMed

    Yan, Wei-Hong; Bao, Song-Song; Huang, Jian; Ren, Min; Sheng, Xiao-Li; Cai, Zhong-Sheng; Lu, Chang-Sheng; Meng, Qing-Jin; Zheng, Li-Min

    2013-06-21

    Three coordination polymers {[Co2(AQTC)(H2O)6]·6H2O}n (1), {[M2(AQTC)(bpym)(H2O)6]·6H2O}n (M = Co(2), Ni(3)) have been synthesized and structurally characterized, where H4AQTC is anthraquinone-1,4,5,8-tetracarboxylic acid and bpym is 2,2'-bipyrimidine. Complex 1 features a 3-D structure, where layers of Co2(AQTC) are cross-linked by Co-H2O chains. Complexes 2 and 3 are isostructural and display 1-D chain structures. The chains are connected through hydrogen-bonding interactions to form 3-D supramolecular structures. Magnetic properties of these complexes are investigated. Compound 1 shows canted antiferromagnetism and slow relaxation below 4.0 K. For complexes 2 and 3, dominant antiferromagnetic interactions are observed. The luminescent properties of the three complexes are investigated as well.

  4. A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO)3Fe(μ-StBu)3Ni{SC6H3-2,6-(mesityl)2} and reversible CO addition at the Ni site

    PubMed Central

    Ohki, Yasuhiro; Yasumura, Kazunari; Ando, Masaru; Shimokata, Satoko; Tatsumi, Kazuyuki

    2010-01-01

    A [NiFe] hydrogenase model compound having a distorted trigonal-pyramidal nickel center, (CO)3Fe(μ-StBu)3Ni(SDmp), 1 (Dmp = C6H3-2,6-(mesityl)2), was synthesized from the reaction of the tetranuclear Fe-Ni-Ni-Fe complex [(CO)3Fe(μ-StBu)3Ni]2(μ-Br)2, 2 with NaSDmp at -40 °C. The nickel site of complex 1 was found to add CO or CNtBu at -40 °C to give (CO)3Fe(StBu)(μ-StBu)2Ni(CO)(SDmp), 3, or (CO)3Fe(StBu)(μ-StBu)2Ni(CNtBu)(SDmp), 4, respectively. One of the CO bands of 3, appearing at 2055 cm-1 in the infrared spectrum, was assigned as the Ni-CO band, and this frequency is comparable to those observed for the CO-inhibited forms of [NiFe] hydrogenase. Like the CO-inhibited forms of [NiFe] hydrogenase, the coordination of CO at the nickel site of 1 is reversible, while the CNtBu adduct 4 is more robust. PMID:20147622

  5. Crystal structures of the new ternary stannides La{sub 3}Mg{sub 4−x}Sn{sub 2+x} and LaMg{sub 3−x}Sn{sub 2}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Solokha, P., E-mail: pavlo.solokha@unige.it; De Negri, S.; Minetti, R.

    2016-01-15

    Synthesis and structural characterization of the two new lanthanum–magnesium–stannides La{sub 3}Mg{sub 4−x}Sn{sub 2+x} (0.12≤x≤0.40) and LaMg{sub 3−x}Sn{sub 2} (0.33≤x≤0.78) are reported. The crystal structures of these intermetallics were determined by single crystal X-ray diffraction analysis and confirmed by Rietveld refinement of powder X-ray diffraction patterns of the corresponding samples. The La{sub 3}Mg{sub 4−x}Sn{sub 2+x} phase crystallizes in the hexagonal Zr{sub 3}Cu{sub 4}Si{sub 2} structure type (P6¯2m, hP9, Z=3, x=0.12(1), a=7.7974(7), c=4.8384(4) Å), which represents an ordered derivative of the hP9-ZrNiAl prototype, ubiquitous among equiatomic intermetallics. The LaMg{sub 3–x}Sn{sub 2} phase is the second representative of the trigonal LaMg{sub 3−x}Ge{sub 2}more » type, which is a superstructure of the LaLi{sub 3}Sb{sub 2} structure type (P3¯1c, hP34-0.12, Z=6, x=0.35(1), a=8.3222(9), c=14.9546(16) Å). The scheme describing the symmetry reduction/coloring with respect to the parent type is reported here with the purpose to discuss the LaMg{sub 3−x}Sn{sub 2} off-stoichiometry from the geometrical point of view. Structural relationships between the La–Mg–Sn ternary phases, including the already known equiatomic LaMgSn compound (oP12-TiNiSi), are presented in the framework of the AlB{sub 2}-related compounds family and discussed with the aid of group-subgroup relations in the Bärnighausen formalism. - Graphical abstract: Crystal structure of LaMg{sub 3−x}Sn{sub 2} viewed along the (001) direction together with the puckered layer of Mg and Sn atoms hosting Mg2, Mg3 and vacancy □. - Highlights: • Crystal structures of the new La{sub 3}Mg{sub 4−x}Sn{sub 2+x} and LaMg{sub 3−x}Sn{sub 2} phases were determined. • The off-stoichiometry of LaMg{sub 3−x}Sn{sub 2} was discussed from geometrical point of view. • Structural relations between the known La–Mg–Sn phases were established. • The studied

  6. Preparation and characterization of polyol assisted ultrafine Cu-Ni-Mg-Ca mixed ferrite via co-precipitation method

    NASA Astrophysics Data System (ADS)

    Boobalan, T.; Pavithradevi, S.; Suriyanarayanan, N.; Manivel Raja, M.; Ranjith Kumar, E.

    2017-04-01

    Nanocrystalline spinel ferrite of composition Cu0.2Ni0.2Mg0.2Ca0.4Fe2O4 is synthesized by wet hydroxyl co-precipitation method in ethylene glycol as chelating agent and sodium hydroxide as precipitator at pH 8. Ethylene glycol is utilized as the medium which serves as the dissolvable and in addition a complexing specialist. The synthesized particles are annealed at various temperatures. Thermogravimetric investigation affirms that at 280 °C ethylene glycol is dissipated totally and stable phase arrangement happens over 680 °C. FTIR spectra of as synthesized and annealed at 1050 °C recorded between 400 cm-1 and 4000 cm-1. Structural characterizations of all the samples are carried out by X-ray diffraction (XRD) technique. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) affirm that the particles are spherical and cubic shape with the crystallite size of 12 nm to 32 nm. Magnetic measurements are performed utilizing vibrating sample magnetometer at room temperature.

  7. Monte Carlo and Ab-initio calculation of TM (Ti, V, Cr, Mn, Fe, Co, Ni) doped MgH2 hydride: GGA and SIC approximation

    NASA Astrophysics Data System (ADS)

    Salmani, E.; Laghrissi, A.; Laamouri, R.; Benchafia, E.; Ez-Zahraouy, H.; Benyoussef, A.

    2017-02-01

    MgH2: TM (TM: V, Cr, Mn, Fe, Co, Ni) based dilute magnetic semiconductors (DMS) are investigated using first principle calculations. Our results show that the ferromagnetic state is stable when TM introduces magnetic moments as well as intrinsic carriers in TM: Co, V, Cr, Ti; Mg0.95TM0.05H2. Some of the DMS Ferro magnets under study exhibit a half-metallic behavior, which make them suitable for spintronic applications. The double exchange is shown to be the underlying mechanism responsible for the magnetism of such materials. The exchange interactions obtained from first principle calculations and used in a classical Ising model by a Monte Carlo approach resulted in ferromagnetic states with Curie temperatures within the ambient conditions.

  8. Microstructures and hydrogen absorption/desorption properties of La-Ni alloys in the composition range of La-77.8--83.2 at.% Ni

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yamamoto, T.; Inui, H.; Yamaguchi, M.

    1997-12-01

    Alloys based on the intermetallic phase, LaNi{sub 5} have been used as negative electrode materials of rechargeable nickel-metal hydride (Ni-MH) batteries because of their fast activation, high storage-capacity, long cycle-life and excellent electrochemical charge/discharge kinetics. Here, microstructure and hydrogen absorption/desorption properties of La-Ni alloys have been investigated as a function of alloy composition in the range of La-77.8 {approximately} 83.2 at.% Ni, which corresponds to compositions between two intermetallic phases, La{sub 2}Ni{sub 7} and LaNi{sub 5}. The intermetallic phase, La{sub 5}Ni{sub 19} of the Ce{sub 5}Co{sub 19}-type is found for the first time to exist as an equilibrium phase atmore » a composition between La{sub 2}Ni{sub 7} and LaNi{sub 5}. This phase is stable at high temperatures around 1,000 C but decomposes into La{sub 2}Ni{sub 7} and LaNi{sub 5} below 900 C. Hydrogen absorption/desorption properties described in terms of pressure-composition isotherms decline with decreasing Ni content (i.e. with increasing volume fraction of intermetallic phases other than LaNi{sub 5}). In particular, the plateau at the equilibrium pressure corresponding to the hydrogen absorption in the LaNi{sub 5} phase is narrowed with decreasing Ni content and additional plateaus with higher equilibrium pressures come into existence. The degradation becomes more pronounced in the presence of La{sub 2}Ni{sub 7} than La{sub 5}Ni{sub 19}. This can be understood in terms of the ratio of the number of LaNi{sub 2} (Laves) unit layers to that of LaNi{sub 5} unit layers in the unit cell of the two intermetallic phases.« less

  9. MgCoAl and NiCoAl LDHs synthesized by the hydrothermal urea hydrolysis method: Structural characterization and thermal decomposition

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chagas, L.H., E-mail: lhchagas-prometro@inmetro.gov.br; Instituto Nacional de Metrologia Qualidade e Tecnologia, Divisão de Metrologia de Materiais, 25250-020 Duque de Caxias, RJ; De Carvalho, G.S.G.

    Highlights: • We synthesized MgCoAl and NiCoAl LDHs by the urea hydrolysis method. • Aluminum rich and crystalline materials have been formed. • The calcination of the LDHs generated mixed oxides with high surface areas. - Abstract: Layered double hydroxides (LDHs) with Mg/Co/Al and Ni/Co/Al were synthesized for the first time by the urea hydrolysis method. The experimental conditions promoted aluminum rich and crystalline materials. The formation of LDHs was investigated by powder X-ray diffraction (XRD), chemical analysis, solid state nuclear magnetic resonance with magic angle spinning ({sup 27}Al-MAS-NMR), simultaneous thermogravimetric/differential thermal analysis (TGA/DTA), FTIR spectroscopy, scanning electron microscopy (SEM),more » and N{sub 2} adsorption–desorption experiments. A single phase corresponding to LDH could be obtained in all the investigated compositions. Thermal calcination of these LDHs at 500 °C resulted in the formation of solid solutions in which Al{sup 3+} was dissolved. All the calcined materials have rock-salt like structures and high surface areas.« less

  10. Coupled Electronic and Magnetic Phase Transition in the Infinite-Layer Phase LaSrNiRuO4.

    PubMed

    Patino, Midori Amano; Zeng, Dihao; Bower, Ryan; McGrady, John E; Hayward, Michael A

    2016-09-06

    Topochemical reduction of the ordered double perovskite LaSrNiRuO6 with CaH2 yields LaSrNiRuO4, an extended oxide phase containing infinite sheets of apex-linked, square-planar Ni(1+)O4 and Ru(2+)O4 units ordered in a checkerboard arrangement. At room temperature the localized Ni(1+) (d(9), S = (1)/2) and Ru(2+) (d(6), S = 1) centers behave paramagnetically. However, on cooling below 250 K the system undergoes a cooperative phase transition in which the nickel spins align ferromagnetically, while the ruthenium cations appear to undergo a change in spin configuration to a diamagnetic spin state. Features of the low-temperature crystal structure suggest a symmetry lowering Jahn-Teller distortion could be responsible for the observed diamagnetism of the ruthenium centers.

  11. Steam reforming of fast pyrolysis-derived aqueous phase oxygenates over Co, Ni, and Rh metals supported on MgAl 2O 4

    DOE PAGES

    Xing, Rong; Dagle, Vanessa Lebarbier; Flake, Matthew; ...

    2016-02-03

    In this paper we examine the feasibility of steam reforming the mixed oxygenate aqueous fraction derived from fast pyrolysis bio-oils. Catalysts selective towards hydrogen formation and resistant to carbon formation utilizing feeds with relatively low steam-to-carbon (S/C) ratios are desired. Rh (5 wt%), Pt (5 wt%), Ru (5 wt%), Ir (5 wt%), Ni (15 wt%), and Co (15 wt%) metals supported on MgAl2O4 were evaluated for catalytic performance at 500 °C and 1 atm using a complex feed mixture comprising acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active and resistant to carbonmore » formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir).« less

  12. Neutron diffraction studies of magnetic ordering in Ni-doped LaCoO3

    NASA Astrophysics Data System (ADS)

    Rajeevan, N. E.; Kumar, Vinod; Kumar, Rajesh; Kumar, Ravi; Kaushik, S. D.

    2015-11-01

    Research in rare earth cobaltite has recently been intensified due to its fascinating magnetic properties. LaCoO3, an important cobaltite, exhibits two prominent susceptibility features at 90 K and 500 K in low field measurement. The magnetic behavior below 100 K is predominantly antiferromagnetic (AFM), but absence of pure AFM ordering and emergence of ferromagnetic coupling on further decreasing temperature made situation more intricate. The present work of studying the effect of Ni substitution at Co site in polycrystalline LaCo1-xNixO3 (0≤x≤0.3) is motivated by the interesting changes in magnetic and electronic properties. For lucid understanding, temperature dependent neutron diffraction (ND) study was carried out. ND patterns fitted with rhombohedral structure in perovskite form with R-3c space group, elucidated information on phase purity. Further temperature dependent cell parameter, Co-O bond-length and Co-O-Co bond angle were calculated for the series of Ni doped LaCoO3. The results are explained in terms of decrease in the crystal field energy which led to the transition of cobalt from low Spin (LS) state to intermediate spin state (IS).

  13. In-situ catalyzation approach for enhancing the hydrogenation/dehydrogenation kinetics of MgH2 powders with Ni particles

    PubMed Central

    El-Eskandarany, M. Sherif; Shaban, Ehab; Ali, Naser; Aldakheel, Fahad; Alkandary, Abdullah

    2016-01-01

    One practical solution for utilizing hydrogen in vehicles with proton-exchange fuel cells membranes is storing hydrogen in metal hydrides nanocrystalline powders. According to its high hydrogen capacity and low cost of production, magnesium hydride (MgH2) is a desired hydrogen storage system. Its slow hydrogenation/dehydrogenation kinetics and high thermal stability are the major barriers restricting its usage in real applications. Amongst the several methods used for enhancing the kinetics behaviors of MgH2 powders, mechanically milling the powders with one or more catalyst species has shown obvious advantages. Here we are proposing a new approach for gradual doping MgH2 powders with Ni particles upon ball milling the powders with Ni-balls milling media. This proposed is-situ method showed mutually beneficial for overcoming the agglomeration of catalysts and the formation of undesired Mg2NiH4 phase. Moreover, the decomposition temperature and the corresponding activation energy showed low values of 218 °C and 75 kJ/mol, respectively. The hydrogenation/dehydrogenation kinetics examined at 275 °C of the powders milled for 25 h took place within 2.5 min and 8 min, respectively. These powders containing 5.5 wt.% Ni performed 100-continuous cycle-life time of hydrogen charging/discharging at 275 °C within 56 h without failure or degradation. PMID:27849033

  14. In-situ catalyzation approach for enhancing the hydrogenation/dehydrogenation kinetics of MgH2 powders with Ni particles

    NASA Astrophysics Data System (ADS)

    El-Eskandarany, M. Sherif; Shaban, Ehab; Ali, Naser; Aldakheel, Fahad; Alkandary, Abdullah

    2016-11-01

    One practical solution for utilizing hydrogen in vehicles with proton-exchange fuel cells membranes is storing hydrogen in metal hydrides nanocrystalline powders. According to its high hydrogen capacity and low cost of production, magnesium hydride (MgH2) is a desired hydrogen storage system. Its slow hydrogenation/dehydrogenation kinetics and high thermal stability are the major barriers restricting its usage in real applications. Amongst the several methods used for enhancing the kinetics behaviors of MgH2 powders, mechanically milling the powders with one or more catalyst species has shown obvious advantages. Here we are proposing a new approach for gradual doping MgH2 powders with Ni particles upon ball milling the powders with Ni-balls milling media. This proposed is-situ method showed mutually beneficial for overcoming the agglomeration of catalysts and the formation of undesired Mg2NiH4 phase. Moreover, the decomposition temperature and the corresponding activation energy showed low values of 218 °C and 75 kJ/mol, respectively. The hydrogenation/dehydrogenation kinetics examined at 275 °C of the powders milled for 25 h took place within 2.5 min and 8 min, respectively. These powders containing 5.5 wt.% Ni performed 100-continuous cycle-life time of hydrogen charging/discharging at 275 °C within 56 h without failure or degradation.

  15. Enhancing hydrogen storage performances of MgH2 by Ni nano-particles over mesoporous carbon CMK-3

    NASA Astrophysics Data System (ADS)

    Chen, Gang; Zhang, Yao; Chen, Jian; Guo, Xinli; Zhu, Yunfeng; Li, Liquan

    2018-06-01

    Nano-dispersed Ni particles over mesoporous carbon material CMK-3 (Ni/CMK-3) was fabricated by means of impregnation-reduction strategy using precursor NiCl2 · 6H2O, which is beneficial to improving the de/rehydrogenation performances of MgH2. The dehydrogenation onset temperature of MgH2–Ni/CMK-3 is significantly lowered by 170 K from that of pristine MgH2 (around 603 K). Totally 5.9 wt% of hydrogen absorption capacity is liberated within 1 h at a temperature of 423 K under a pressure of 3 MPa. This composite can absorb 3.9 wt% hydrogen even at a temperature of 328 K under 3 MPa H2. Activation energy values of both dehydrogenation (43.4 kJ mol‑1) and rehydrogenation (37.4 kJ mol‑1) for MgH2–Ni/CMK-3 are greatly enhanced from those of as-milled MgH2. Ni/CMK-3 also slightly destabilizes the dehydrogenation of MgH2 by 1.5 kJ mol {{{{H}}}2}-1. The enhanced performances can be attributed to the synergistic effects of both destabilization and activation from nano-dispersed Ni particles.

  16. Enhancing hydrogen storage performances of MgH2 by Ni nano-particles over mesoporous carbon CMK-3.

    PubMed

    Chen, Gang; Zhang, Yao; Chen, Jian; Guo, Xinli; Zhu, Yunfeng; Li, Liquan

    2018-06-29

    Nano-dispersed Ni particles over mesoporous carbon material CMK-3 (Ni/CMK-3) was fabricated by means of impregnation-reduction strategy using precursor NiCl 2  · 6H 2 O, which is beneficial to improving the de/rehydrogenation performances of MgH 2 . The dehydrogenation onset temperature of MgH 2 -Ni/CMK-3 is significantly lowered by 170 K from that of pristine MgH 2 (around 603 K). Totally 5.9 wt% of hydrogen absorption capacity is liberated within 1 h at a temperature of 423 K under a pressure of 3 MPa. This composite can absorb 3.9 wt% hydrogen even at a temperature of 328 K under 3 MPa H 2 . Activation energy values of both dehydrogenation (43.4 kJ mol -1 ) and rehydrogenation (37.4 kJ mol -1 ) for MgH 2 -Ni/CMK-3 are greatly enhanced from those of as-milled MgH 2 . Ni/CMK-3 also slightly destabilizes the dehydrogenation of MgH 2 by 1.5 kJ mol [Formula: see text] The enhanced performances can be attributed to the synergistic effects of both destabilization and activation from nano-dispersed Ni particles.

  17. Effect of MgO spacer and annealing on interface and magnetic properties of ion beam sputtered NiFe/Mg/MgO/CoFe layer structures

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bhusan Singh, Braj; Chaudhary, Sujeet

    2012-09-15

    The effect of variation in the thickness of ion assisted ion beam sputtered MgO spacer layer deposited at oxygen ion assisted energy of 50 eV on the extent of magnetic coupling of NiFe and CoFe layers in Si/NiFe(10 nm)/Mg(1 nm)/MgO(2,4,6 nm)/CoFe(10 nm) sandwich structure is investigated. At MgO spacer layer thickness of 4 nm, the separate reversal of magnetizations of the two ferromagnetic layers is observed in the hystresis loop recorded along easy direction. This results in a 3.5 Oe wide plateau like region during magnetization reversal, which became 4.5 Oe at 6 nm thin MgO. At 2 nm thinmore » MgO, the absence of plateau during magnetization reversal region revealed ferromagnetic coupling between the two ferromagnetic layers, which is understood to arise due to the growth of very thin and low density (1.22 gm/cc) MgO spacer layer, indicating the presence of pinholes as revealed by x-ray reflectometry. After vaccum annealing (200 Degree-Sign C/1 h), the plateau region for 4 and 6 nm thin MgO case decreased to 1.5 Oe and 2.0 Oe, respectively, due to enhanced interface roughness/mixing. In addition, an enhancement of the in-plane magnetic anisotropy is also observed.« less

  18. Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O.

    PubMed

    Antonova, Elena; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

    2012-02-20

    Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) Å, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) Å(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) Å, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) Å(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not

  19. Structural, elastic and electronic properties of typical NdMgT4 (T = Co, Ni, Cu) alloys from ab initio calculation

    NASA Astrophysics Data System (ADS)

    Wang, Na; Zhang, Wei-bing; Tang, Bi-yu; Gao, Hai-Tao; He, En-jie; Wang, Lei

    2018-07-01

    The crystal structure, elastic and magnetic properties of important ternary Mg-based alloys NdMgT4 (T = Co, Ni, Cu) have been studied using reliable ab initio calculations. Both cohesive energy and charge density difference suggest that three alloys have good structural stability with the order: NdMgCo4 > NdMgNi4 > NdMgCu4. It shows that NdMgCo4 alloy has magnetic moments with the Co atoms being the main contribution, which is also in agreement with the calculated electronic structures. We find that NdMgT4 (T = Co, Ni, Cu) alloys are all ductile materials with bulk-to-shear modulus (B/G) values higher than 1.75. The trends of calculated values for the shear moduli Cs and C44 are consistent with that of shear modulus G and young's modulus E, proving that NdMgT4 (T = Co, Ni, Cu) alloys exhibit good plasticity with the trend: NdMgNi4 > NdMgCu4 > NdMgCo4. These calculated results give the basis guidance for the design of rare earth-magnesium-transition metal (R-Mg-T) alloys with improved mechanical properties.

  20. Phase change of hydromagnesite, Mg5(CO3)4(OH)2 4H2O by thermal decomposition

    NASA Astrophysics Data System (ADS)

    Yamamoto, G. I.; Kyono, A.; Tamura, T.

    2017-12-01

    In recent years, the global warming is the most important environment problem, and thus attempts of CO2 geological storage have been made to remove carbon dioxide from the atmosphere all over the world (XUE and Nakao 2008). Regarding mineral CO2 sequestration, CO2 is chemically stored in solid carbonates by carbonation of minerals. Magnesium and calcium carbonates have long been known as a good CO2 storage. Hydrous magnesium carbonates can be, however, considered as much better candidates for CO2 storage because they precipitate easily from aqueous solutions. The typical hydrous magnesium carbonates are nesquehonite, MgCO3 3H2O and hydromagnesite, Mg5(CO3)4(OH)2 4H2O. Concerning their thermal properties, the former has been studied in detail, whereas, the latter is not enough. In this study, we performed in-site high-temperature X-ray diffraction (XRD) and thermogravimetric and differential thermal (TG-DTA) analyses to reveal the phase change of hydromagnesite at high temperature. The high-temperature XRD and TG-DTA were measured up to 320 oC and 550 oC, respectively. The results of in-site high-temperature XRD showed that, no significant change was observed up to 170 oC. With increasing temperature, the intensities of started to decrease at 200 oC, and all peaks disappeared at 290 oC. Above the temperature of the decomposition a few peaks corresponding to periclase appeared. The results of TG-DTA clearly showed that there were two weight loss steps in the temperature range of 200 to 340 oC and 340 to 500 oC, which correspond to the dehydration and decarbonation of hydromagnesite, respectively. These weight losses were accompanied by the endothermic maxima in the DTA. The dihydroxylation of hydromagnesite is spread over the two steps. Therefore, hydromagnesite decomposes into periclase, carbon dioxide, and water without passing through magnesite around 300 oC as following reaction: Mg5(CO3)4(OH)2 4H2O → 5MgO + 4CO2 + 5H2O.

  1. In situ preparation of MgCo2O4 nanosheets on Ni-foam as a binder-free electrode for high performance hybrid supercapacitors.

    PubMed

    Vijayakumar, Subbukalai; Nagamuthu, Sadayappan; Ryu, Kwang-Sun

    2018-05-15

    A binder-free, MgCo2O4 nanosheet-like architecture was prepared on Ni-foam using a hydrothermal method. MgCo2O4/Ni-foam was characterized by X-ray diffraction, field emission scanning electron microscopy (FESEM), and transmission electron microscopy techniques. The FESEM image revealed a nanosheet array-like architecture. The MgCo2O4 nanosheets grown on Ni-foam exhibited the maximum specific capacity of 947 C g-1 at a specific current of 2 A g-1. Approximately 96% of the specific capacity was retained from the maximum specific capacity after 5000 continuous charge-discharge cycles. This hybrid device exhibited a maximum specific capacity of 52 C g-1 at a specific current of 0.5 A g-1, and also exhibited a maximum specific energy of 12.99 W h kg-1 at a specific power of 448.7 W kg-1. These results confirmed that the binder-free MgCo2O4 nanosheets grown on Ni-foam are a suitable positive electrode material for hybrid supercapacitors.

  2. C-H Activation of Benzene by a Photoactivated Ni(II)(azide): Formation of a Transient Nickel Nitrido Complex.

    PubMed

    Vreeken, Vincent; Siegler, Maxime A; de Bruin, Bas; Reek, Joost N H; Lutz, Martin; van der Vlugt, Jarl Ivar

    2015-06-08

    Photochemical activation of nickel-azido complex 2 [Ni(N3)(PNP)] (PN(H)P=2,2'-di(isopropylphosphino)-4,4'-ditolylamine) in neat benzene produces diamagnetic complex 3 [Ni(Ph)(PN(P)N(H))], which is crystallographically characterized. DFT calculations support photoinitiated N2-loss of the azido complex to generate a rare, transient Ni(IV) nitrido species, which bears significant nitridyl radical character. Subsequent trapping of this nitrido through insertion into the Ni-P bond generates a coordinatively unsaturated Ni(II) imidophosphorane P=N donor. This species shows unprecedented reactivity toward 1,2-addition of a C-H bond of benzene to form 3. The structurally characterized chlorido complex 4 [Ni(Cl)(PN(P)N(H))] is generated by reaction of 3 with HCl or by direct photolysis of 2 in chlorobenzene. This is the first report of aromatic C-H bond activation by a trapped transient nitrido species of a late transition metal. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Synthesis, characterization, and biological activity of some novel Schiff bases and their Co(II) and Ni(II) complexes: A new route for Co3O4 and NiO nanoparticles for photocatalytic degradation of methylene blue dye

    NASA Astrophysics Data System (ADS)

    Nassar, Mostafa Y.; Aly, Hisham M.; Abdelrahman, Ehab A.; Moustafa, Moustafa E.

    2017-09-01

    Six novel Co(II) and Ni(II)-triazole Schiff base complexes have been successfully synthesized by refluxing the prepared triazole Schiff bases with CoCl2·6H2O or NiCl2·6H2O. The Schiff base ligands were prepared through condensation of 3-R-4-amino-5-hydrazino-1,2,4-triazole with dibenzoylmethane [Rdbnd H, CH3, and CH2CH3; namely, L1, L2, and L3, respectively]. The prepared Co(II) and Ni(II) complexes have been identified using elemental analysis, FT-IR, UV-Vis, magnetic moment, conductivity, and thermal analysis. On the basis of the conductance results, it was concluded that all the prepared complexes are nonelectrolytes. Interestingly, the prepared Co(II) and Ni(II) complexes were employed as precursors for producing of Co3O4 and NiO nanoparticles, respectively. The produced nanostructures have been identified by XRD, HR-TEM, FT-IR and UV-Vis spectra. The produced nanoparticles revealed good photocatalytic activity for the degradation of methylene blue dye under UV illumination in presence of hydrogen peroxide. The percent of degradation was estimated to be 55.71% in 420.0 min and 90.43% in 360.0 min for Co3O4 and NiO, respectively. Moreover, the synthesized complexes, nano-sized Co3O4, and NiO products have been examined, employing modified Bauer- Kirby method, for antifungal (Candida albicans and Aspergillus flavus) and antibacterial (Staphylococcus aureus and Escherichia coli) activities.

  4. Poisoning of Ni-Based anode for proton conducting SOFC by H2S, CO2, and H2O as fuel contaminants

    NASA Astrophysics Data System (ADS)

    Sun, Shichen; Awadallah, Osama; Cheng, Zhe

    2018-02-01

    It is well known that conventional solid oxide fuel cells (SOFCs) based on oxide ion conducting electrolyte (e.g., yttria-stabilized zirconia, YSZ) and nickel (Ni) - ceramic cermet anodes are susceptible to poisoning by trace amount of hydrogen sulfide (H2S) while not significantly impacted by the presence of carbon dioxide (CO2) and moisture (H2O) in the fuel stream unless under extreme operating conditions. In comparison, the impacts of H2S, CO2, and H2O on proton-conducting SOFCs remain largely unexplored. This study aims at revealing the poisoning behaviors caused by H2S, CO2, and H2O for proton-conducting SOFCs. Anode-supported proton-conducting SOFCs with BaZe0.1Ce0.7Y0.1Yb0.1O3 (BZCYYb) electrolyte and Ni-BZCYYb anode and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) cathode as well as Ni-BZCYYb/BZCYYb/Ni-BZCYYb anode symmetrical cells were subjected to low ppm-level H2S or low percentage-level CO2 or H2O in the hydrogen fuel, and the responses in cell electrochemical behaviors were recorded. The results suggest that, contrary to conventional SOFCs that show sulfur poisoning and CO2 and H2O tolerance, such proton-conducting SOFCs with Ni-BZCYYb cermet anode seem to be poisoned by all three types of "contaminants". Beyond that, the implications of the experimental observations on understanding the fundamental mechanism of anode hydrogen electrochemical oxidation reaction in proton conducting SOFCs are also discussed.

  5. The Co(II), Ni(II) and Cu(II) complexes with herbicide 2,4-dichlorophenoxyacetic acid - Synthesis and structural studies

    NASA Astrophysics Data System (ADS)

    Drzewiecka-Antonik, Aleksandra; Ferenc, Wiesława; Wolska, Anna; Klepka, Marcin T.; Cristóvão, Beata; Sarzyński, Jan; Rejmak, Paweł; Osypiuk, Dariusz

    2017-01-01

    The Co(II), Ni(II) and Cu(II) complexes with herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) were synthesized and structurally characterized. The geometry of metal-ligand interaction was refined using XAFS and DFT studies. The Co(2,4-D)2·6H2O and Ni(2,4-D)2·4H2O complexes have octahedral geometry with two carboxylate groups of 2,4-D anions and four water molecules in the coordination sphere. The square planar geometry around metal cations formed by the carboxylate groups from two monodentate ligands and two water molecules, is observed for Cu(2,4-D)2·4H2O complex. In the recrystallized Ni(II) complex dinuclear 'Chinese lantern' structures with bridging carboxylate groups of 2,4-D were observed.

  6. Steam reforming of simulated bio-oil on K-Ni-Cu-Mg-Ce-O/Al 2O 3: The effect of K

    DOE PAGES

    Yu, Ning; Rahman, Muhammad Mahfuzur; Chen, Jixiang; ...

    2018-04-10

    Steam reforming of simulated bio-oil (ethanol, acetone, phenol, and acetic acid) and phenol has been studied on K-Ni-Cu-Mg-Ce-O/Al 2O 3 composite catalysts. Complementary characterization techniques, such as nitrogen sorption, XRD, H 2-TPR, H 2-TPD, CO-TPD, CO-DRIFTS, and in situ XPS, were used to correlate surface structure and functionality to catalytic performance of potassium (K) doped catalysts. K doping of the Ni-Cu-Mg-Ce-O/Al 2O 3 catalyst created a Ni°/Ni 2+ mixed active phase, which not only enhanced steam reforming activity, but also suppressed the methanation reaction. In addition, K doping changed the surface acid-basic properties of the catalyst, which instead favor themore » gasifcation and water-gas shift reactions. In conclusion, with the combination of these effects, K doping of Ni-Cu-Mg-Ce-O/Al 2O 3 catalysts led to higher C1 yield and much lower methane formation, favoring hydrogen production in steam reforming of both phenol and simulated bio-oil.« less

  7. Steam reforming of simulated bio-oil on K-Ni-Cu-Mg-Ce-O/Al 2O 3: The effect of K

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yu, Ning; Rahman, Muhammad Mahfuzur; Chen, Jixiang

    Steam reforming of simulated bio-oil (ethanol, acetone, phenol, and acetic acid) and phenol has been studied on K-Ni-Cu-Mg-Ce-O/Al 2O 3 composite catalysts. Complementary characterization techniques, such as nitrogen sorption, XRD, H 2-TPR, H 2-TPD, CO-TPD, CO-DRIFTS, and in situ XPS, were used to correlate surface structure and functionality to catalytic performance of potassium (K) doped catalysts. K doping of the Ni-Cu-Mg-Ce-O/Al 2O 3 catalyst created a Ni°/Ni 2+ mixed active phase, which not only enhanced steam reforming activity, but also suppressed the methanation reaction. In addition, K doping changed the surface acid-basic properties of the catalyst, which instead favor themore » gasifcation and water-gas shift reactions. In conclusion, with the combination of these effects, K doping of Ni-Cu-Mg-Ce-O/Al 2O 3 catalysts led to higher C1 yield and much lower methane formation, favoring hydrogen production in steam reforming of both phenol and simulated bio-oil.« less

  8. Influence of H 2O and H 2S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl 2O 4 for hydrodeoxygenation of ethylene glycol

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dabros, Trine Marie Hartmann; Gaur, Abhijeet; Pintos, Delfina Garcia

    Here in this work, density functional theory (DFT), catalytic activity tests, and in-situ X-ray absorption spectroscopy (XAS) was performed to gain detailed insights into the activity and stability of MoS 2, Ni-MoS 2, and Co-MoS 2 catalysts used for hydrodeoxygenation (HDO) of ethylene glycol upon variation of the partial pressures of H 2O and H 2S. The results show high water tolerance of the catalysts and highlight the importance of promotion and H 2S level during HDO. DFT calculations unraveled that the active edge of MoS 2 could be stabilized against SO exchanges by increasing the partial pressure of Hmore » 2S or by promotion with either Ni or Co. The Mo, NiMo, and CoMo catalysts of the present study were all active and fairly selective for ethylene glycol HDO at 400 °C, 27 bar H 2, and 550–2200 ppm H 2S, and conversions of ≈50–100%. The unpromoted Mo/MgAl 2O 4 catalyst had a lower stability and activity per gram catalyst than the promoted analogues. The NiMo and CoMo catalysts produced ethane, ethylene, and C1 cracking products with a C 2/C 1 ratio of 1.5–2.0 at 550 ppm H 2S. This ratio of HDO to cracking could be increased to ≈2 at 2200 ppm H 2S which also stabilized the activity. Removing H 2S from the feed caused severe catalyst deactivation. Both DFT and catalytic activity tests indicated that increasing the H 2S concentration increased the concentration of SH groups on the catalyst, which correspondingly activated and stabilized the catalytic HDO performance. In-situ XAS further supported that the catalysts were tolerant towards water when exposed to increasing water concentration with H2O/H2S ratios up to 300 at 400–450 °C. Raman spectroscopy and XAS showed that MoS2 was present in the prepared catalysts as small and highly dispersed particles, probably owing to a strong interaction with the support. Linear combination fitting (LCF) analysis of the X-ray absorption near edge structure (XANES) spectra obtained during in-situ sulfidation

  9. Influence of H 2O and H 2S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl 2O 4 for hydrodeoxygenation of ethylene glycol

    DOE PAGES

    Dabros, Trine Marie Hartmann; Gaur, Abhijeet; Pintos, Delfina Garcia; ...

    2017-12-10

    Here in this work, density functional theory (DFT), catalytic activity tests, and in-situ X-ray absorption spectroscopy (XAS) was performed to gain detailed insights into the activity and stability of MoS 2, Ni-MoS 2, and Co-MoS 2 catalysts used for hydrodeoxygenation (HDO) of ethylene glycol upon variation of the partial pressures of H 2O and H 2S. The results show high water tolerance of the catalysts and highlight the importance of promotion and H 2S level during HDO. DFT calculations unraveled that the active edge of MoS 2 could be stabilized against SO exchanges by increasing the partial pressure of Hmore » 2S or by promotion with either Ni or Co. The Mo, NiMo, and CoMo catalysts of the present study were all active and fairly selective for ethylene glycol HDO at 400 °C, 27 bar H 2, and 550–2200 ppm H 2S, and conversions of ≈50–100%. The unpromoted Mo/MgAl 2O 4 catalyst had a lower stability and activity per gram catalyst than the promoted analogues. The NiMo and CoMo catalysts produced ethane, ethylene, and C1 cracking products with a C 2/C 1 ratio of 1.5–2.0 at 550 ppm H 2S. This ratio of HDO to cracking could be increased to ≈2 at 2200 ppm H 2S which also stabilized the activity. Removing H 2S from the feed caused severe catalyst deactivation. Both DFT and catalytic activity tests indicated that increasing the H 2S concentration increased the concentration of SH groups on the catalyst, which correspondingly activated and stabilized the catalytic HDO performance. In-situ XAS further supported that the catalysts were tolerant towards water when exposed to increasing water concentration with H2O/H2S ratios up to 300 at 400–450 °C. Raman spectroscopy and XAS showed that MoS2 was present in the prepared catalysts as small and highly dispersed particles, probably owing to a strong interaction with the support. Linear combination fitting (LCF) analysis of the X-ray absorption near edge structure (XANES) spectra obtained during in-situ sulfidation

  10. La0.8Sr0.2Co0.8Ni0.2O3-δ impregnated oxygen electrode for H2O/CO2 co-electrolysis in solid oxide electrolysis cells

    NASA Astrophysics Data System (ADS)

    Zheng, Haoyu; Tian, Yunfeng; Zhang, Lingling; Chi, Bo; Pu, Jian; Jian, Li

    2018-04-01

    High-temperature H2O/CO2 co-electrolysis through reversible solid oxide electrolysis cell (SOEC) provides potentially a feasible and eco-friendly way to convert electrical energy into chemicals stored in syngas. In this work, La0.8Sr0.2Co0.8Ni0.2O3-δ (LSCN) impregnated Gd0.1Ce0.9O1.95 (GDC)-(La0.8Sr0.2)0.95MnO3-δ (LSM) composite oxygen electrode is studied as high-performance electrode for H2O/CO2 co-electrolysis. The LSCN impregnated cell exhibits competitive performance with the peak power density of 1057 mW cm-2 at 800 °C in solid oxide fuel cell (SOFC) mode; in co-electrolysis mode, the current density can reach 1.60 A cm-2 at 1.5 V at 800 °C with H2O/CO2 ratio of 2/1. With LSCN nanoparticles dispersed on the surface of GDC-LSM to maximize the reaction active sites, the LSCN impregnated cell shows significant enhanced electrochemical performance at both SOEC and SOFC modes. The influence of feed gas composition (H2O-H2-CO2) and operating voltages on the performance of co-electrolysis are discussed in detail. The cell shows a very stable performance without obvious degradation for more than 100 h. Post-test characterization is analyzed in detail by multiple measurements.

  11. Comparative study of synthesis, structural and magnetic properties of Cu2+ substituted Co-Ni, Co-Zn and Co-Mg nano ferrites

    NASA Astrophysics Data System (ADS)

    Ramakrishna, A.; Murali, N.; Margarette, S. J.; Samatha, K.; Veeraiah, V.

    2018-02-01

    Mixed ferrites of the form Co0.5M0.1Cu0.4Fe2O4 (M = Ni, Zn and Mg) have been synthesized using the sol-gel auto combustion technique. Structural analyses are carried out using powder X-ray diffraction to idntify pure ferrite phases. SEM analysis revealed clear crystal morphology with relatively uniform grain sizes with polygonal structures. The FT-IR studies also confirm the bond formation and cation vibrations at low (365-392 cm-1) and high (579-587 cm-1) bands that correspond to the tetrahedral and octahedral sites, respectively. The magnetic properties studied through vibrating sample magnetometer showed that the Ni substituted sample has more magnetic character by exhibiting the highest saturation magnetization.

  12. Strain and Ni substitution induced ferromagnetism in LaCoO3 thin films

    NASA Astrophysics Data System (ADS)

    Kumar, Ashok; Kumar, Vinod; Kumar, Rajesh; Kumar, Ravi

    2018-05-01

    We have grown epitaxial strained films of LaCoO3 and LaCo0.7Ni0.3O3 on LaAlO3 (100) substrate via pulsed laser deposition. Superconducting quantum interference device magnetization measurements show that, unlike its bulk counterpart, the ground state of the strained LaCoO3 on LAO is ferromagnetic. The saturation magnetization has been found increase strongly from a value of 118 emu/cm3 to 350 emu/ cm3 for Ni substituted thin film. Present study reveals that strain can stabilize FM order in these thin films down to low temperature, which can further be tuned to higher saturation magnetization with the Ni substitution.

  13. Phase, microstructure and hydrogen storage properties of Mg-Ni materials synthesized from metal nanoparticles.

    PubMed

    Shao, Huaiyu; Chen, Chunguang; Liu, Tong; Li, Xingguo

    2014-04-04

    After Mg and Ni nanoparticles were fabricated by hydrogen plasma metal reaction, Mg-rich MgxNi₁₀₀₋x(75 < x < 90) materials were synthesized from these metal nanoparticles to study the synergistic effects for hydrogen storage in these samples to show both good kinetics and high capacity. These MgxNi₁₀₀₋x materials may absorb hydrogen with a capacity of around 3.3-5.1 wt% in 1 min at 573 K. The Mg₉₀Ni₁₀ sample shows a hydrogen capacity of 6.1 wt%. The significant kinetic enhancement is thought to be due to the unique nanostructure from the special synthesis route, the catalytic effect of the Mg₂Ni nano phase, and the synergistic effects between the Mg₂Ni and Mg phases in the materials. An interesting phenomenon which has never been reported before was observed during pressure composition isotherm (PCT) measurements. One steep step in the absorption process and two obviously separated steps in the desorption process during PCT measurements of Mg₈₀Ni₂₀ and Mg₉₀Ni₁₀ samples were observed and a possible reason from the kinetic performance of the Mg₂Ni and Mg phases in absorption and desorption processes was explained. These MgxNi₁₀₀₋x materials synthesized from Mg and Ni nanoparticles show high capacity and good kinetics, which makes these materials very promising candidates for thermal storage or energy storage and utilization for renewable power.

  14. Vibrational and elastic properties of silicate spinels A2SiO4 (A = Mg, Fe, Ni, and Co)

    NASA Astrophysics Data System (ADS)

    Kushwaha, A. K.; Ma, C.-G.; Brik, M. G.; Akbudak, S.

    2018-06-01

    A six-parameter bond-bending force constant model is used to calculate the zone-center (Γ = 0) Raman and infrared phonon mode frequencies, elastic constants and related properties, the Debye temperatures, and sound velocities along high-symmetry directions for A2SiO4 (A = Mg, Fe, Ni, and Co) spinels. The main outcomes of the calculations are that the interactions between Si and O atoms (first-neighbor interaction) are stronger than those between A and Oatoms (A = Mg, Fe, Ni, and Co) (second-neighbor interaction). The elastic constants C11, C12, and C44 decrease in the order Mg > Fe > Ni > Co. The calculated bulk modulus, Poisson's ratio, and anisotropy decrease in the sequence Fe2SiO4 → Ni2SiO4 → Co2SiO4 → Mg2SiO4. On comparison, we find overall good agreement with the available experimental and previously calculated data.

  15. Hierarchical NiCo2 S4 Nanotube@NiCo2 S4 Nanosheet Arrays on Ni Foam for High-Performance Supercapacitors.

    PubMed

    Chen, Haichao; Chen, Si; Shao, Hongyan; Li, Chao; Fan, Meiqiang; Chen, Da; Tian, Guanglei; Shu, Kangying

    2016-01-01

    Hierarchical NiCo2 S4 nanotube@NiCo2 S4 nanosheet arrays on Ni foam have been successfully synthesized. Owing to the unique hierarchical structure, enhanced capacitive performance can be attained. A specific capacitance up to 4.38 F cm(-2) is attained at 5 mA cm(-2) , which is much higher than the specific capacitance values of NiCo2 O4 nanosheet arrays, NiCo2 S4 nanosheet arrays and NiCo2 S4 nanotube arrays on Ni foam. The hierarchical NiCo2 S4 nanostructure shows superior cycling stability; after 5000 cycles, the specific capacitance still maintains 3.5 F cm(-2) . In addition, through the morphology and crystal structure measurement after cycling stability test, it is found that the NiCo2 S4 electroactive materials are gradually corroded; however, the NiCo2 S4 phase can still be well-maintained. Our results show that hierarchical NiCo2 S4 nanostructures are suitable electroactive materials for high performance supercapacitors. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Identification of a new pseudo-binary hydroxide during calendar corrosion of (La, Mg)2Ni7-type hydrogen storage alloys for Nickel-Metal Hydride batteries

    NASA Astrophysics Data System (ADS)

    Monnier, J.; Chen, H.; Joiret, S.; Bourgon, J.; Latroche, M.

    2014-11-01

    To improve the performances of Nickel-Metal Hydride batteries, an important step is the understanding of the corrosion processes that take place in the electrode material. In particular, the present study focuses for the first time on the model (La, Mg)2Ni7 system. The calendar corrosion in 8.7 M KOH medium was investigated from 6 h to 16 weeks immersion. By a unique combination of structural and elemental characterisations, the corrosion products are evidenced in those systems. In particular, we demonstrate that Ni and Mg combine in a pseudo-binary hydroxide Mg1-xNix(OH)2 whereas La corrodes into nanoporous La(OH)3 needles with inner hollow nanochannels.

  17. Understanding phase stability of Al-Co-Cr-Fe-Ni high entropy alloys

    DOE PAGES

    Zhang, Chuan; Zhang, Fan; Diao, Haoyan; ...

    2016-07-19

    The concept of high entropy alloy (HEA) opens a vast unexplored composition range for alloy design. As a well-studied system, Al-Co-Cr-Fe-Ni has attracted tremendous amount of attention to develop new-generation low-density structural materials for automobile and aerospace applications. In spite of intensive investigations in the past few years, the phase stability within this HEA system is still poorly understood and needs to be clarified, which poses obstacles to the discovery of promising Al-Co-Cr-Fe-Ni HEAs. In the present work, the CALPHAD approach is employed to understand the phase stability and explore the phase transformation within the Al-Co-Cr-Fe-Ni system. As a result,more » the phase-stability mapping coupled with density contours is then constructed within the composition - temperature space, which provides useful guidelines for the design of low-density Al-Co-Cr-Fe-Ni HEAs with desirable properties.« less

  18. Understanding phase stability of Al-Co-Cr-Fe-Ni high entropy alloys

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhang, Chuan; Zhang, Fan; Diao, Haoyan

    The concept of high entropy alloy (HEA) opens a vast unexplored composition range for alloy design. As a well-studied system, Al-Co-Cr-Fe-Ni has attracted tremendous amount of attention to develop new-generation low-density structural materials for automobile and aerospace applications. In spite of intensive investigations in the past few years, the phase stability within this HEA system is still poorly understood and needs to be clarified, which poses obstacles to the discovery of promising Al-Co-Cr-Fe-Ni HEAs. In the present work, the CALPHAD approach is employed to understand the phase stability and explore the phase transformation within the Al-Co-Cr-Fe-Ni system. As a result,more » the phase-stability mapping coupled with density contours is then constructed within the composition - temperature space, which provides useful guidelines for the design of low-density Al-Co-Cr-Fe-Ni HEAs with desirable properties.« less

  19. Kinetic and thermodynamic studies of the Co(II) and Ni(II) ions removal from aqueous solutions by Ca-Mg phosphates.

    PubMed

    Ivanets, A I; Srivastava, V; Kitikova, N V; Shashkova, I L; Sillanpää, M

    2017-03-01

    The aim of this work was to study the sorption kinetics and thermodynamics of Co(II) and Ni(II) from aqueous solutions by sorbents on the basis of hydrogen (PD-1) and tertiary (PD-2) Ca-Mg phosphates depending on the solution temperature and sorbents chemical composition. Kinetic studies of adsorption of Co(II) and Ni(II) ions onto samples of phosphate sorbents were performed in batch experiment at the temperatures 288, 303, 318 and 333 K. The sorbent dose was fixed at 10 g L -1 , initial pH value 2.6, and contact time varied from 5 to 600 min. The kinetics of Co(II) and Ni(II) adsorption were analyzed by using pseudo-first order, pseudo-second order and intraparticle diffusion models. Thermodynamic parameters (ΔG°, ΔH° and ΔS°) for the sorption of Co(II) and Ni(II) were determined using the Gibbs-Helmholtz equation. The calculated kinetic parameters and corresponding correlation coefficients revealed that Co(II) and Ni(II) uptake process followed the pseudo-second order rate expression. Thermodynamic studies confirmed the spontaneous and endothermic nature of removal process which indicate that sorption of Co(II) and Ni(II) ions onto both phosphate sorbents is favoured at higher temperatures and has the chemisorptive mechanism. The data thus obtained would be useful for practical application of the low cost and highly effective Ca-Mg phosphate sorbents. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. A dithiolate-bridged (CN)2(CO)Fe-Ni complex reproducing the IR bands of [NiFe] hydrogenase.

    PubMed

    Tanino, Soichiro; Li, Zilong; Ohki, Yasuhiro; Tatsumi, Kazuyuki

    2009-03-16

    A dithiolate-bridged dinuclear Fe-Ni complex, which has the desired fac-(CN)(2)(CO) ligand set at iron, has been synthesized. Its CN/CO bands in the IR spectrum reproduce those of the Ni-A, Ni-B, and Ni-SU states, which indicate that these octahedral Fe(II) centers have similar electronic properties. This result verifies the assignment of a (CN)(2)(CO)Fe(II) moiety in the active site of [NiFe] hydrogenase.

  1. Different Effect of Co on the Formation of Topologically Close-Packed Phases in Ni-Cr-Mo and Ni-Cr-Re Alloys

    NASA Astrophysics Data System (ADS)

    Shi, Qianying; An, Ning; Huo, Jiajie; Ding, Xianfei; Zheng, Yunrong; Feng, Qiang

    2017-11-01

    In current study, two sets of Ni-based alloys (Ni-Cr-Mo and Ni-Cr-Re series) containing 0 to 15 at. pct of Co addition were investigated to understand the formation behavior of TCP phases. Significant difference on the formation behavior of TCP phases and corresponding Co effect was found in two series alloys. TCP precipitates ( P and µ phase) were observed in both grain interiors and boundaries in Ni-Cr-Mo series alloys. Higher levels of Co addition increased the supersaturation of Mo in the γ matrix, which explained that Co addition promoted µ phase formation. In contrast, the TCP precipitates ( σ phase) formed by the manner of discontinuous precipitation transformation in the grain boundaries in Ni-Cr-Re series alloys. More Co additions suppressed the formation of σ phase, which was mainly attributed to the decreased supersaturation of Re in thermodynamically metastable γ matrix. The information obtained from simplified alloy systems in this study is helpful for the design of multicomponent Ni-based superalloys.

  2. Laser photoelectron spectroscopy of CrH - , CoH - , and NiH - : Periodic trends in the electronic structure of the transition-metal hydrides

    NASA Astrophysics Data System (ADS)

    Stevens Miller, Amy E.; Feigerle, C. S.; Lineberger, W. C.

    1987-08-01

    The laser photoelectron spectra of CrH-, CoH-, and NiH- and the analogous deuterides are reported. The spectra are interpreted using a qualitative description of the electronic structure for the hydrides. This model is used to assign off-diagonal transitions in the photodetachment to low-spin states of the neutrals, and diagonal transitions to high-spin states of the neutrals. These data are used to identify the high-spin states of CoH and NiH; several other states of CrH, CoH, and NiH are also identified. Periodic trends in the bond lengths, vibrational frequencies, and electronic excitation energies for the MnH through NiH molecules are examined. Electron affinities are reported for CrH (0.563±0.010 eV), CoH (0.671±0.010 eV), and NiH (0.481±0.007 eV), and the corresponding deuterides.

  3. Basin-scale contributions of Cr, Ni and Co from Ortegal Complex to the surrounding coastal environment (SW Europe).

    PubMed

    Prego, Ricardo; Caetano, Miguel; Ospina-Alvarez, Natalia; Raimundo, Joana; Vale, Carlos

    2014-01-15

    The enrichment of Cr and Ni in the coastal zones is usually associated with anthropogenic sources such as the tanning, galvanization, ceramic, and cement industries. However, geological complexes of specific lithologic composition located near shorelines may act as natural sources of metals to the continental shelf. Cape Ortegal (SW Europe) is an ultramafic complex that has Cr, Ni and Co enriched in rocks due to the minerals chromite, chromospinel, gersdorfite and pentlandite. Thus, the hypothesis that this geological complex contributes to metal enrichment in Ortigueira and Barqueiro Rias and the adjacent continental shelf was tested. Chromium, Ni, and Co were determined in water and in suspended particulate matter of ria tributaries, rainfall, surface sediments, mussels, and algae. High contents of Cr (max. 1670mg·kg(-1)) and Ni (max. 1360 mg · kg(-1)) were found in the sediments surrounding Cape Ortegal and the Ortigueira Ria as a result of erosion of exposed cliffs. Dissolved Cr and Ni concentrations in fluvial waters were significantly higher in the rivers that crosses the Ortegal Complex, i.e. Lourido (0.47 μg Cr · L(-1); 9.4 μg Ni · L(-1)) and Landoi (0.37 μg Cr · L(-1); 4.3 μg Ni · L(-1)), in comparison with the nearby basin out of the complex influence (Sor River: <0.01 μg Cr · L(-1); 0.57 μg Ni · L(-1)). The annual fluvial contributions of Cr and Ni to the Ortigueira Ria were higher than fluxes into the Barqueiro Ria. Moreover, the increase in Cr and Ni in the rainfall in summer demonstrated the importance of the atmosphere pathway for introducing these elements into the aquatic environment. As a consequence, the contents of these metals in soft tissues and shell of mussels and algae from the Ortigueira Ria were higher than the organisms from Barqueiro Ria. Thus, geological complexes, such as the Cape Ortegal, located in an uncontaminated area, can increase the land-sea exchange of trace metals. © 2013.

  4. Syngas Production from CO2 Reforming and CO2-steam Reforming of Methane over Ni/Ce-SBA-15 Catalyst

    NASA Astrophysics Data System (ADS)

    Tan, J. S.; Danh, H. T.; Singh, S.; Truong, Q. D.; Setiabudi, H. D.; Vo, D.-V. N.

    2017-06-01

    This study compares the catalytic performance of mesoporous 10 Ni/Ce-SBA-15 catalyst for CO2 reforming and CO2-steam reforming of methane reactions in syngas production. The catalytic performance of 10 Ni/Ce-SBA-15 catalyst for CO2 reforming and CO2-steam reforming of methane was evaluated in a temperature-controlled tubular fixed-bed reactor at stoichiometric feed composition, 1023 K and atmospheric pressure for 12 h on-stream with gas hourly space velocity (GHSV) of 36 L gcat -1 h-1. The 10 Ni/Ce-SBA-15 catalyst possessed a high specific BET surface area and average pore volume of 595.04 m2 g-1. The XRD measurement revealed the presence of NiO phase with crystallite dimension of about 13.60 nm whilst H2-TPR result indicates that NiO phase was completely reduced to metallic Ni0 phase at temperature beyond 800 K and the reduction temperature relied on different degrees of metal-support interaction associated with the location and size of NiO particles. The catalytic reactivity was significantly enhanced with increasing H2O/CO2 feed ratio. Interestingly, the H2/CO ratio for CO2-steam reforming of methane varied between 1 and 3 indicated the occurrence of parallel reactions, i.e., CH4 steam reforming giving a H2/CO of 3 whilst reverse water-gas shift (RWGS) reaction consuming H2 to produce CO gaseous product.

  5. Characterization and biological studies on Co(II), Ni(II) and Cu(II) complexes of carbohydrazones ending by pyridyl ring.

    PubMed

    Abu El-Reash, G M; El-Gammal, O A; Ghazy, S E; Radwan, A H

    2013-03-01

    The chelating behavior of ligands based on carbohydrazone core modified with pyridine end towards Co(II), Ni(II) and Cu(II) ions have been examined. The ligands derived from the condensation of carbohydrazide with 2-acetylpyridine (H(2)APC) and 4-acetylpyridine (H(2)APEC). The (1)H NMR, IR data and the binding energy calculations of H(2)APC revealed the presence of two stereoisomers syn and anti in the solid state and in the solution. The (1)H NMR, IR data and the binding energy calculations confirmed the presence of H(2)APEC in one keto form only in the solid state and in the solution. The spectroscopic data confirmed that H(2)APC behaves as a monobasic pentadentate in Co(II) and Cu(II) complexes and as mononegative tetradentate in Ni(II) complex. On the other hand, H(2)APEC acts as a mononegative tridentate in Co(II) complex, neutral tridentate in Ni(II) complex and neutral bidentate in Cu(II) complex. The electronic spectra and the magnetic measurements of complexes as well as the ESR of the copper complexes suggested the octahedral geometry. The bond length and bond angles were evaluated by DFT method using material studio program. The thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. The antioxidant (DDPH and ABTS methods), anti-hemolytic and in vitro Ehrlich ascites of the compounds have been screened. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. Structural study of Ni- or Mg-based complexes incorporated within UiO-66-NH{sub 2} framework and their impact on hydrogen sorption properties

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Žunkovič, E.; Mazaj, M.; Mali, G.

    2015-05-15

    Nickel and magnesium acetylacetonate molecular complexes were post-synthetically incorporated into microporous zirconium-based MOF (UiO-66-NH{sub 2}) in order to introduce active open-metal sites for hydrogen sorption. Elemental analysis, nitrogen physisorption and DFT calculations revealed that 5 molecules of Ni(acac){sub 2} or 2 molecules of Mg(acac){sub 2} were incorporated into one unit cell of UiO-66-NH{sub 2}. {sup 1}H–{sup 13}C CPMAS and {sup 1}H MAS NMR spectroscopy showed that, although embedded within the pores, both Ni- and Mg-complexes interacted with the UiO-66-NH{sub 2} framework only through weak van der Waals bonds. Inclusion of metal complexes led to the decrease of hydrogen sorption capacitiesmore » in Ni-modified as well as in Mg-modified samples in comparison with the parent UiO-66-NH{sub 2}. The isosteric hydrogen adsorption enthalpy slightly increased in the case of Ni-modified material, but not in the case of Mg-modified analogue. - Graphical abstract: A post-synthesis impregnation of Mg- and Ni-acetylacetonate complexes performed on zirconium-based MOF UiO-66-NH{sub 2} does influence the hydrogen sorption performance with respect to the parent matrix. The structural study revealed that Mg- and Ni-acetylacetonate molecules interact with zirconium-terephthalate framework only by weak interactions and they are not covalently bonded to aminoterephthalate ligand. Still, they remain confined into the pores even after hydrogen sorption experiments. - Highlights: • Mg- and Ni-acetylacetonate molecules embedded in the pores of UiO-66-NH{sub 2} by PSM. • Molecules of complexes interact with framework only by van der Waals interactions. • Type/structure of deposited metal-complex impact hydrogen enthalpy of adsorption.« less

  7. Dual shell-like magnetic clusters containing Ni(II) and Ln(III) (Ln = La, Pr, and Nd) ions.

    PubMed

    Kong, Xiang-Jian; Ren, Yan-Ping; Long, La-Sheng; Zheng, Zhiping; Nichol, Gary; Huang, Rong-Bin; Zheng, Lan-Sun

    2008-04-07

    Dual shell-like nanoscopic magnetic clusters featuring a polynuclear nickel(II) framework encapsulating that of lanthanide ions (Ln = La, Pr, and Nd) were synthesized using Ni(NO3)(2).6H2O, Ln(NO3)(3).6H2O, and iminodiacetic acid (IDA) under hydrothermal conditions. Structurally established by crystallographic studies, these clusters are [La20Ni30(IDA)30(CO3)6(NO3)6(OH)30(H2O)12](CO3)(6).72H2O (1), [Ln20Ni21(C4H5NO4)21(OH)24(C2H2O3)6(C2O4)3(NO3)9(H2O)12](NO3)9.nH2O [C2H2O3 is the alkoxide form of glycolate; Ln = Pr (2), n = 42; Nd (3), n = 50], and {[La4Ni5Na(IDA)5(CO3)(NO3)4(OH)5(H2O)5][CO3].10H2O} infinity (4). Carbonate, oxalate, and glycolate are products of hydrothermal decomposition of IDA. Compositions of these compounds were confirmed by satisfactory elemental analyses. It has been found that the cluster structure is dependent on the identity of the lanthanide ion as well as the starting Ln/Ni/IDA ratio. The cationic cluster of 1 features a core of the Keplerate type with an outer icosidodecahedron of Ni(II) ions encaging a dodecahedral kernel of La(III). Clusters 2 and 3, distinctly different from 1, are isostructural, possessing a core of an outer shell of 21 Ni(II) ions encapsulating an inner shell of 20 Ln(III) ions. Complex 4 is a three-dimensional assembly of cluster building blocks connected by units of Na(NO3)/La(NO3)3; the structure of the building block resembles closely that of 1, with a hydrated La(III) ion internalized in the decanuclear cage being an extra feature. Magnetic studies indicated ferromagnetic interactions in 1, while overall antiferromagnetic interactions were revealed for 2 and 3. The polymeric, three-dimensional cluster network 4 displayed interesting ferrimagnetic interactions.

  8. Phase-specific Geochemistry of Ni: a Tracer of Geosphere-Biosphere Co-evolution?

    NASA Astrophysics Data System (ADS)

    Ciscato, E. R.; Vance, D.; Bontognali, T. R. R.; Poulton, S.

    2016-12-01

    Metalloproteome analyses and culturing studies have suggested that trace metals, such as Cu, Fe, Mo, Ni, and Zn, were selectively utilized by different organisms and specific metabolisms throughout the evolution of the biosphere. Methanogens have a particular requirement for Ni and culturing studies have shown that they fractionate Ni isotopes upon uptake. It is not clear, however, whether a resulting Ni isotopic signal can be preserved in the geological record. We have developed a new approach that enables us to analyze phase-specific authigenic trace metal enrichments, and their respective isotopic signatures, in (predominantly organic-rich) sediments from the geological record. An acid digestion step followed by high-pressure ashing allows us to separate an `organic matter + Pyrite' phase from an `HF-extractable' phase. We have applied this approach to investigate the distribution of Ni isotopes in a variety of modern sediments, including organic-rich sediments from upwelling margins and a hypersaline lagoonal setting where methanogenesis is likely to be an active process. Preliminary results on geological record samples show a δ60Ni for the `HF-extractable' phases that agrees with the average continental crust, whereas the `organic matter + Pyrite' phases are heavier and shifted in the direction of modern seawater. By combining this data with our δ60Ni dataset from modern sediments, we investigate the dynamics of Ni cycling in environments with different O2 and H2S availabilities both in the modern and throughout the past 3.2 billion years. Our phase-specific δ60Ni record is of instrumental importance in determining whether a biologically induced fractionation imparted by methanogens is indeed observable, and if it can be used as a biosignature for tracing the predominance of methanogenic pathways throughout the co-evolution of the geosphere and biosphere.

  9. Model forecasting of phase composition of electrolytic alloys Co-Ni-Mn (part 1)

    NASA Astrophysics Data System (ADS)

    Schmidt, V. V.; Zhikhareva, I. G.

    2018-03-01

    With the help of four criteria for phase formation, a model forecasting of the phase composition of electrolytic alloy Co-Ni-Mn was carried out; the expected phases were calculated. The boundaries of the chemical content of the metal-solvent (Co) in these phases are determined, depending on the ratio of metal ions in the electrolyte of deposition. Model forecasting of the phase composition of Co-Ni-Mn alloys makes it possible to predict the type and number of Co phases (hexagonal close-packed - HCP-α-Co, face-centered cubic - FCC-β-Co) depending on the mole fraction of the solvent metal (Co). In the first approximation, the forecast allows one to determine the phase and chemical composition of the coating, which corresponds to the specified operational properties.

  10. Polymorphism of the bivalent metal vanadates MeV 2O 6 ( Me = Mg, Ca, Mn, Co, Ni, Cu, Zn, Cd)

    NASA Astrophysics Data System (ADS)

    Mocała, Krzysztof; Ziółkowski, Jacek

    1987-08-01

    Based on the literature data, our former findings and additional DTA and high-temperature X-ray studies performed for CdV 2O 6, MgV 2O 6, and MnV 2O 6, a consistent scheme of the phase transformations of the MeV 2O 6 ( Me = Mg, Ca, Mn, Co, Ni, Cu, Zn, Cd) metavanadates is constructed at normal pressure between room temperature and melting points. Three types of structures exist for the considered compounds: brannerite type (B), pseudobrannerite type (P), and NiV 2O 6 type (N). The following phase transformations have been observed: Me = Mg, B → P at 535°C; Me = Mn, B → P at 540°C; Me = Co, N → B at 660°C; Me = Cu, B (with triclinic distortion) → B at 625°C (secondary order); and Me = Cd, B → P at 170°. CaV 2O 6P, NiV 2O 6N, and ZnV 2O 6B exist in unique form in the entire temperature range. P-form seems to be favored by Me of larger ionic radii. N-form seems to appear at a peculiar d-shell structure and small Me size. Preliminary explanation of the dependence of the structure type on Me size is offered. New X-ray data are given for CdV 2O 6B, CdV 2O 6P, MgV 2O 6B, MgV 2O 6P, and MnV 2O 6P.

  11. Magnetic properties of intermetallic compounds La(Ni,Co,Cu)3

    NASA Astrophysics Data System (ADS)

    Tazuke, Y.; Tanikawa, H.; Okano, A.; Miyaji, T.

    2006-09-01

    LaNi3 exhibited a metallic antiferromagnetic property with T N = 30 K. La(Ni1-x Cox )3 with x = 0.01, 0.03 and 0.05 exhibited ferromagnetic properties, T C increasing linearly with increasing x . La(Ni1-2z Coz Cuz )3 with z = 0.015 exhibited a ferromagnetic property with a small T C. A La(Ni1-y Cuy )3 sample with y = 0.01 exhibited a Pauli-paramagnetic property; those with y = 0.02, 0.03 and 0.04 exhibited gradual metamagnetic behavior and that with y = 0.05 exhibited a ferromagnetic property. The gradual metamagnetic M -H variations are numerically simulated by using Landau-type free energies. The results suggest that the gradual metamagnetic behavior occurs from an antiferromagnetic state to a ferromagnetic one.

  12. Super-high-affinity binding site for [3H]diazepam in the presence of Co2+, Ni2+, Cu2+, or Zn2+.

    PubMed

    Mizuno, S; Ogawa, N; Mori, A

    1982-12-01

    Chloride salts of Li+, Na+, K+, Mg2+, Ca2+, Cr3+, Mn2+, Fe2+, and Fe3+ had no effect on [3H]diazepam binding. Chloride salts of Co2+, Ni2+, Cu2+, and Zn2+ increased [3H]diazepam binding by 34 to 68% in a concentration-dependent fashion. Since these divalent cations potentiated the GABA-enhanced [3H]diazepam binding and the effect of each divalent cation was nearly additive with GABA, these cations probably act at a site different from the GABA recognition site in the benzodiazepine-receptor complex. Scatchard plots of [3H]diazepam binding without an effective divalent cation showed a single class of binding, with a Kd value of 5.3 nM. In the presence of 1 mM Co2+, Ni2+, Cu2+, or Zn2+, two distinct binding sites were evident with apparent Kd values of 1.0 nM and 5.7 nM. The higher-affinity binding was not detected in the absence of an effective divalent cation and is probably a novel, super-high-affinity binding site.

  13. Steam Reforming of Ethylene Glycol over MgAl₂O₄ Supported Rh, Ni, and Co Catalysts

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mei, Donghai; Lebarbier, Vanessa M.; Xing, Rong

    Steam reforming of ethylene glycol (EG) over MgAl₂O₄ supported metal (15 wt.% Ni, 5 wt.% Rh, and 15 wt.% Co) catalysts were investigated using combined experimental and theoretical methods. Compared to highly active Rh and Ni catalysts with 100% conversion, the steam reforming activity of EG over the Co catalyst is comparatively lower with only 42% conversion under the same reaction conditions (500°C, 1 atm, 119,000 h⁻¹, S/C=3.3 mol). However, CH₄ selectivity over the Co catalyst is remarkably lower. For example, by varying the gas hour space velocity (GHSV) such that complete conversion is achieved for all the catalysts, CH₄more » selectivity for the Co catalyst is only 8%, which is much lower than the equilibrium CH₄ selectivity of ~ 24% obtained for both the Rh and Ni catalysts. Further studies show that varying H₂O concentration over the Co catalyst has a negligible effect on activity, thus indicating zero-order dependence on H₂O. These experimental results suggest that the supported Co catalyst is a promising EG steam reforming catalyst for high hydrogen production. To gain mechanistic insight for rationalizing the lower CH₃ selectivity observed for the Co catalyst, the initial decomposition reaction steps of ethylene glycol via C-O, O-H, C-H, and C-C bond scissions on the Rh(111), Ni(111) and Co(0001) surfaces were investigated using density functional theory (DFT) calculations. Despite the fact that the bond scission sequence in the EG decomposition on the three metal surfaces varies, which leads to different reaction intermediates, the lower CH₄ selectivity over the Co catalyst, as compared to the Rh and Ni catalysts, is primarily due to the higher barrier for CH₄ formation. The higher S/C ratio enhances the Co catalyst stability, which can be elucidated by the facile water dissociation and an alternative reaction path to remove the CH species as a coking precursor via the HCOH formation. This work was financially supported by the

  14. Crystallization Experiments in the MgO-CO2-H2O system: Role of Amorphous Magnesium Carbonate Precursors in Magnesium Carbonate Hydrated Phases and Morphologies in Low Temperature Hydrothermal Fluids

    NASA Astrophysics Data System (ADS)

    Giampouras, Manolis; Garcia-Ruiz, Juan Manuel; Garrido, Carlos J.

    2017-04-01

    Numerous forms of hydrated or basic magnesium carbonates occur in the complex MgO-CO2-H2O system. Mineral saturation states from low temperature hydrothermal fluids in Semail Ophiolite (Oman), Prony Bay (New Caledonia) and Lost City hydrothermal field (mid-Atlantic ridge) strongly indicate the presence of magnesium hydroxy-carbonate hydrates (e.g. hydromagnesite) and magnesium hydroxides (brucite). Study of formation mechanisms and morphological features of minerals forming in the MgO-CO2-H2O system could give insights into serpentinization-driven, hydrothermal, alkaline environments, which are related to early Earth conditions. Temperature, hydration degree, pH and fluid composition are crucial factors regarding the formation, coexistence and transformation of such mineral phases. The rate of supersaturation, on the other hand, is a fundamental parameter to understand nucleation and crystal growth processes. All these parameters can be examined in a solution using different crystallization techniques. In the present study, we applied different crystallization techniques to synthesize and monitor the crystallization of Mg-bearing carbonates and hydroxides under abiotic conditions. Various crystallization techniques (counter-diffusion, vapor diffusion and unseeded solution mixing) were used to screen the formation conditions of each phase, transformation processes and structural development. Mineral and textural characterization of the different synthesized phases were carried out by X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy coupled to dispersive energy spectroscopy (FE-SEM-EDS). Experimental investigation of the effect of pH level and silica content under variable reactant concentrations revealed the importance of Amorphous Magnesium Carbonate (AMC) in the formation of hydroxy-carbonate phases (hydromagnesite and dypingite). Micro-structural resemblance between AMC precursors and later stage crystalline phases highlights the

  15. Synthesis, characterization and some properties of mononuclear Ni and trinuclear NiFe2 complexes related to the active site of [NiFe]-hydrogenases.

    PubMed

    Song, Li-Cheng; Sun, Xiao-Jing; Zhao, Pei-Hua; Li, Jia-Peng; Song, Hai-Bin

    2012-08-07

    The [N(2)S(2)]-type ligand 1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4) (L) is prepared in 84% yield by a new method and its structure has been confirmed by X-ray crystallography. The new synthetic method involves sequential reaction of 1,2-phenylenedithiol with EtONa followed by treatment of the resulting disodium salt of 1,2-phenylenedithiol with in situ generated 2-(chloromethyl)pyridine from its HCl salt. Further treatment of ligand L with NiCl(2)·6H(2)O or NiI(2) affords the expected new mononuclear Ni complexes Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]Cl(2) (1) and Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]I(2) (3) in 87-88% yields, whereas reaction of L with NiBr(2) under similar conditions results in formation of the expected new mononuclear complex Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]Br(2) (2) and one unexpected new mononuclear complex Ni[1-(2-C(5)H(4)NCH(2)S)-2-(2-C(5)H(4)NCH(2)SC(6)H(4)S)C(6)H(4)]Br(2) (2*) in 82% and 5% yields, respectively. More interestingly, the ligand L-containing novel trinuclear NiFe(2) complex Ni{[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)}Fe(2)(CO)(6)(μ(3)-S)(2) (4) is found to be prepared by sequential reaction of (μ-S(2))Fe(2)(CO)(6) with Et(3)BHLi, followed by treatment of the resulting (μ-LiS)(2)Fe(2)(CO)(6) with mononuclear complex 1, 2, or 3 in 12-20% yields. The new complexes 1-4 and 2* are fully characterized by elemental analysis and various spectroscopies, and the crystal structures of 1, 2* and 3 as well as some electrochemical properties of 1-4 are also reported.

  16. Structural and magnetic properties of yttrium and lanthanum-doped Ni-Co and Ni-Co-Zn spinel ferrites

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Stergiou, Charalampos, E-mail: stergiou@cperi.certh.gr; Litsardakis, George, E-mail: lits@eng.auth.gr

    2014-11-05

    Rare earth doping of Co-rich spinel ferrites is investigated through the preparation of two groups of polycrystalline Ni-Co and Ni-Co-Zn ferrites, where Fe is partly substituted by Y and La. The characterization of the sintered ferrites by means of X-ray powder diffraction and Rietveld profile analysis, indicates the subtle expansion of the spinel unit cell and the cation redistribution in the doped ferrites in order to accommodate the incorporation of Y and La in the lattice. The impurity traces, detected only in the Ni-Co-Zn group, is ascribed to the Zn population in the tetrahedral A-sites impeding the cation transfer. Moreover,more » the examined microstructure of the doped Ni-Co samples comprises enlarged and more homogeneous grains, whereas grain growth is moderated in the doped Ni-Co-Zn ferrites. The discussed characteristics of the crystal and magnetic structure along with the morphological aspects define the impact of Y and La doping on the static magnetic properties of Ni-Co and Ni-Co-Zn ferrites, saturation magnetization MS and coercivity HC, which were extracted from the respective hysteresis loops.« less

  17. Function and CO binding properties of the NiFe complex in carbon monoxide dehydrogenase from Clostridium thermoaceticum.

    PubMed

    Shin, W; Lindahl, P A

    1992-12-29

    Adding 1,10-phenanthroline to carbon monoxide dehydrogenase from Clostridium thermoaceticum results in the complete loss of the NiFeC EPR signal and the CO/acetyl-CoA exchange activity. Other EPR signals characteristic of the enzyme (the gav = 1.94 and gav = 1.86 signals) and the CO oxidation activity are completely unaffected by the 1,10-phenanthroline treatment. This indicates that there are two catalytic sites on the enzyme; the NiFe complex is required for catalyzing the exchange and acetyl-CoA synthase reactions, while some other site is responsible for CO oxidation. The strength of CO binding to the NiFe complex was examined by titrating dithionite-reduced enzyme with CO. During the titration, the NiFeC EPR signal developed to a final spin intensity of 0.23 spin/alpha beta. The resulting CO titration curve (NiFeC spins/alpha beta vs CO pha beta) was fitted using two reactions: binding of CO to the oxidized NiFe complex, and reduction of the CO-bound species to a form that exhibits the NiFeC signal. Best fits yielded apparent binding constants between 6000 and 14,000 M-1 (Kd = 70-165 microM). This sizable range is due to uncertainty whether CO binds to all or only a small fraction (approximately 23%) of the NiFe complexes. Reduction of the CO-bound NiFe complex is apparently required to activate it for catalysis. The electron used for this reduction originates from the CO oxidation site, suggesting that delivery of a low-potential electron to the CO-bound NiFe complex is the physiological function of the CO oxidation reaction catalyzed by this enzyme.

  18. Crystal structures and high-temperature phase-transitions in SrNdMRuO{sub 6} (M=Zn,Co,Mg,Ni) new double perovskites studied by symmetry-mode analysis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Iturbe-Zabalo, E., E-mail: iturbe@ill.fr; Fisika Aplikatua II Saila, Zientzia eta Teknologia Fakultatea, UPV/EHU, P.O. Box 644, 48080 Bilbao; Igartua, J.M.

    2013-02-15

    Crystal structures of SrNdZnRuO{sub 6}, SrNdCoRuO{sub 6}, SrNdMgRuO{sub 6} and SrNdNiRuO{sub 6} double perovskites have been studied by X-ray, synchrotron radiation and neutron powder diffraction method, at different temperatures, and using the symmetry-mode analysis. All compounds adopt the monoclinic space group P2{sub 1}/n at room-temperature, and contain a completely ordered array of the tilted MO{sub 6} and RuO{sub 6} octahedra, whereas Sr/Nd cations are completely disordered. The analysis of the structures in terms of symmetry-adapted modes of the parent phase allows the identification of the modes responsible for the phase-transition. The high-temperature study (300-1250 K) has shown that the compoundsmore » present a temperature induced structural phase-transition: P2{sub 1}/n{yields}P4{sub 2}/n{yields}Fm3{sup Macron }m. - Graphical abstract: Representation of the dominant distortion modes of the symmetry mode decomposition of the room-temperature (P2{sub 1}/n), intermediate (P4{sub 2}/n) and cubic (Fm-3m) phase SrNdMRuO{sub 6} (M=Zn,Co,Mg,Ni), with respect to the parent phase Fm-3m. The dominant distortion modes are: in the monoclinic phase-GM{sub 4}{sup +} (blue arrow), X{sub 3}{sup +} (green arrow) and X{sub 5}{sup +} acting on A-site cations (red arrow); in the tetragonal phase-GM{sub 4}{sup +} (pink arrow), X{sub 3}{sup +} (light blue arrow) and X{sub 5}{sup +} acting on A-site cations (brown arrow). Highlights: Black-Right-Pointing-Pointer Structural study of four ruthenate double perovskites. Black-Right-Pointing-Pointer Room-temperature structural determination using symmetry-mode procedure. Black-Right-Pointing-Pointer Determination of temperature induced structural phase-transitions. Black-Right-Pointing-Pointer Symmetry adapted-mode analysis.« less

  19. Phase equilibria in the Tb-Mg-Co system at 500 °C, crystal structure and hydrogenation properties of selected compounds

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shtender, V.V.; Denys, R.V.; Zavaliy, I.Yu., E-mail: zavaliy@ipm.lviv.ua

    2015-12-15

    The isothermal section of the Tb–Mg–Co phase diagram at 500 °C has been built on the basis of XRD analysis of forty samples prepared by powder metallurgy. The existence of two ternary compounds Tb{sub 4}Mg{sub 3}Co{sub 2} and Tb{sub 4}MgCo was confirmed. The formation of two solid solutions, Tb{sub 1−x}Mg{sub x}Co{sub 3} (0≤x≤0.4) and Tb{sub 1-−x}Mg{sub x}Co{sub 2} (0≤x≤0.6), was found for the first time. It is shown that Tb{sub 5}Mg{sub 24} also dissolves a small amount of Co. Other binary compounds do not dissolve the third component. The Tb{sub 4}MgCo and TbMgCo{sub 4} compounds form hydrides (12.7 and 5.3more » at.H/f.u. capacity, respectively) that retain the original structure of metallic matrices. Upon thermal desorption the Tb{sub 4}MgCoH{sub 12.7} hydride was stable up to 300 °C and disproportionated at higher temperature. Two other hydrides, Tb{sub 4}Mg{sub 3}Co{sub 2}H{sub ∼4} and Tb{sub 2}MgCo{sub 9}H{sub 12}, are unstable in air and decompose into the initial compounds. - Highlights: • The phase equilibria at 500 °°C in the Tb–Mg–Co system has been studied. • The existence of two ternary compounds, Tb{sub 4}Mg{sub 3}Co{sub 2} and Tb{sub 4}MgCo, was confirmed. • The formation of two solid solutions, Tb{sub 1−x}Mg{sub x}Co{sub 3} and Tb{sub 1−x}Mg{sub x}Co{sub 2}, was found. • Hydrogen sorption–desorption properties have been studied for the selected alloys.« less

  20. Magnetic properties of Mg12O12 nanocage doped with transition metal atoms (Mn, Fe, Co and Ni): DFT study

    NASA Astrophysics Data System (ADS)

    Javan, Masoud Bezi

    2015-07-01

    Binding energy of the Mg12O12 nanocage doped with transition metals (TM=Mn, Fe, Co and Ni) in endohedrally, exohedrally and substitutionally forms were studied using density functional theory with the generalized gradient approximation exchange-correlation functional along 6 different paths inside and outside of the Mg12O12 nanocage. The most stable structures were determined with full geometry optimization near the minimum of the binding energy curves of all the examined paths inside and outside of the Mg12O12 nanocage. The results reveal that for all stable structures, the Ni atom has a larger binding energy than the other TM atoms. It is also found that for all complexes additional peaks contributed by TM-3d, 4s and 4p states appear in the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) gap of the host MgO cluster. The mid-gap states are mainly due to the hybridization between TM-3d, 4s and 4p orbitals and the cage π orbitals. The magnetic moment of the endohedrally doped TM atoms in the Mg12O12 are preserved to some extent due to the interaction between the TM and Mg12O12 nanocage, in contrast to the completely quenched magnetic moment of the Fe and Ni atoms in the Mg11(TM)O12 complexes. Furthermore, charge population analysis shows that charge transfer occurs from TM atom to the cage for endohedrally and substitutionally doping.

  1. pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases.

    PubMed

    Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

    2008-09-21

    The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds.

  2. Dithiolato- and halogenido-bridged nickel-iron complexes related to the active site of [NiFe]-H2ases: preparation, structures, and electrocatalytic H2 production.

    PubMed

    Song, Li-Cheng; Han, Xiao-Feng; Chen, Wei; Li, Jia-Peng; Wang, Xu-Yong

    2017-08-14

    A new series of the structural and functional models for the active site of [NiFe]-H 2 ases has been prepared by a simple and convenient synthetic route. Thus, treatment of diphosphines RN(PPh 2 ) 2 (1a, R = p-MeC 6 H 4 CH 2 ; 1b, R = EtO 2 CCH 2 ) with an equimolar NiCl 2 ·6H 2 O, NiBr 2 ·3H 2 O, and NiI 2 in refluxing CH 2 Cl 2 /MeOH or EtOH gave the mononuclear Ni complexes RN(PPh 2 ) 2 NiX 2 (2a, R = p-MeC 6 H 4 CH 2 , X = Cl; 2b, R = EtO 2 CCH 2 , X = Cl; 3a, R = p-MeC 6 H 4 CH 2 , X = Br; 3b, R = EtO 2 CCH 2 , X = Br; 4a, R = p-MeC 6 H 4 CH 2 , X = I; 4b, R = EtO 2 CCH 2 , X = I) in 67-97% yields. Further treatment of complexes 2a,b-4a,b with an equimolar mononuclear Fe complex (dppv)(CO) 2 Fe(pdt) and NaBF 4 resulted in formation of the targeted model complexes [RN(PPh 2 ) 2 Ni(μ-pdt)(μ-X)Fe(CO)(dppv)](BF 4 ) (5a, R = p-MeC 6 H 4 CH 2 , X = Cl; 5b, R = EtO 2 CCH 2 , X = Cl; 6a, R = p-MeC 6 H 4 CH 2 , X = Br; 6b, R = EtO 2 CCH 2 , X = Br; 7a, R = p-MeC 6 H 4 CH 2 , X = I; 7b, R = EtO 2 CCH 2 , X = I) in 60-96% yields. All the new complexes 3a,b-4a,b and 5a,b-7a,b have been characterized by elemental analysis and spectroscopy, and particularly for some of them (3a,b/4a,b and 5b/6b) by X-ray crystallography. More interestingly, the electrochemical and electrocatalytic properties of such halogenido-bridged model complexes are first studied systematically and particularly they have been found to be pre-catalysts for proton reduction to H 2 under CV conditions.

  3. Phase Constitution in Sr and Mg doped LaGaO3 System

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zheng, F; Bordia, Rajendra K.; Pederson, Larry R.

    Sr and Mg doped lanthanum gallate perovskites (La1-xSrxGa1-yMgyO3-delta, shortened as LSGM-XY where X and Y are the doping levels in mole percentage (mol%) at the La- or A-site and the Ga- or B-site, respectively) are promising electrolyte materials for intermediate temperature solid oxide fuel cells (SOFCs). In this study, we have investigated the primary perovskites as well as the secondary phases formed in terms of doping content changes and A/B ratio variations in these materials. Fifteen powder compositions (three doping levels, X = Y = 0, 0.1, and 0.2 mol; and five A/B ratios 0.95, 0.98, 1.00, 1.02, and 1.05)more » were synthesized by the glycine-nitrate combustion process (GNP). These powders were equilibrated by calcining at 1500 degreesC for 9 h prior to crystalline phase characterization by X-ray powder diffraction (XRD). From the results of this study and the available phase diagrams in the literature on constituent binary oxide systems, we propose a crystalline phase diagram of the La2O3-SrO-Ga2O3-MgO quaternary system at elevated temperature (1500 degreesC). (C) 2003 Elsevier Ltd. All rights reserved« less

  4. Carbonato-bridged Ni(II)2Ln(III)2 (Ln(III) = Gd(III), Tb(III), Dy(III)) complexes generated by atmospheric CO2 fixation and their single-molecule-magnet behavior: [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH or H2O)Ln(III)(NO3)}2]·solvent [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato].

    PubMed

    Sakamoto, Soichiro; Fujinami, Takeshi; Nishi, Koshiro; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Re, Nazzareno

    2013-06-17

    Atmospheric CO2 fixation of [Ni(II)(3-MeOsaltn)(H2O)2]·2.5H2O [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato], Ln(III)(NO3)3·6H2O, and triethylamine occurred in methanol/acetone, giving a first series of carbonato-bridged Ni(II)2Ln(III)2 complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH)Ln(III)(NO3)}2] (1Gd, 1Tb, and 1Dy). When the reaction was carried out in acetonitrile/water, it gave a second series of complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(H2O)Ln(III)(NO3)}2]·2CH3CN·2H2O (2Gd, 2Tb, and 2Dy). For both series, each Ni(II)2Ln(III)2 structure can be described as two di-μ-phenoxo-bridged Ni(II)Ln(III) binuclear units bridged by two carbonato CO3(2-) units to form a carbonato-bridged (μ4-CO3)2{Ni(II)2Ln(III)2} structure. The high-spin Ni(II) ion has octahedral coordination geometry, and the Ln(III) ion is coordinated by O9 donor atoms from Ni(II)(3-MeOsaltn), bidentate NO3(-), and one and two oxygen atoms of two CO3(2-) ions. The NO3(-) ion for the first series roughly lie on Ln-O(methoxy) bonds and are tilted toward the outside, while for the second series, the two oxygen atoms roughly lie on one of the Ln-O(phenoxy) bonds due to the intramolecular hydrogen bond. The temperature-dependent magnetic susceptibilities indicated a ferromagnetic interaction between the Ni(II) and Ln(III) ions (Ln(III) = Gd(III), Tb(III), Dy(III)) for all of the complexes, with a distinctly different magnetic behavior between the two series in the lowest-temperature region due to the Ln(III)-Ln(III) magnetic interaction and/or different magnetic anisotropies of the Tb(III) or Dy(III) ion. Alternating-current susceptibility measurements under the 0 and 1000 Oe direct-current (dc) bias fields showed no magnetic relaxation for the Ni(II)2Gd(III)2 complexes but exhibited an out-of-phase signal for Ni(II)2Tb(III)2 and Ni(II)2Dy(III)2, indicative of slow relaxation of magnetization. The energy barriers, Δ/kB, for the spin flipping were estimated from the Arrhenius

  5. Toward understanding the roaming mechanism in H + MgHMg + HH reaction

    DOE PAGES

    Mauguiere, Frederic A. L.; Collins, Peter; Stamatiadis, Stamatis; ...

    2016-02-26

    The roaming mechanism in the reaction H + MgHMg + HH is investigated by classical and quantum dynamics employing an accurate ab initio threedimensional ground electronic state potential energy surface. The reaction dynamics are explored by running trajectories initialized on a four-dimensional dividing surface anchored on three-dimensional normally hyperbolic invariant manifold associated with a family of unstable orbiting periodic orbits in the entrance channel of the reaction (H + MgH). By locating periodic orbits localized in the HMgH well or involving H orbiting around the MgH diatom, and following their continuation with the total energy, regions in phase spacemore » where reactive or nonreactive trajectories may be trapped are found. In this way roaming reaction pathways are deduced in phase space. Patterns similar to periodic orbits projected into configuration space are found for the quantum bound and resonance eigenstates. Roaming is attributed to the capture of the trajectories in the neighborhood of certain periodic orbits. As a result, the complex forming trajectories in the HMgH well can either return to the radical channel or “roam” to the MgHH minimum from where the molecule may react.« less

  6. Phase constitution in Sr and Mg doped LaGaO{sub 3} system

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zheng Feng; Bordia, Rajendra K.; Pederson, Larry R

    2004-01-03

    Sr and Mg doped lanthanum gallate perovskites (La{sub 1-x}Sr{sub x}Ga{sub 1-y}Mg{sub y}O{sub 3-{delta}}, shortened as LSGM-XY where X and Y are the doping levels in mole percentage (mol%) at the La- or A-site and the Ga- or B-site, respectively) are promising electrolyte materials for intermediate temperature solid oxide fuel cells (SOFCs). In this study, we have investigated the primary perovskites as well as the secondary phases formed in terms of doping content changes and A/B ratio variations in these materials. Fifteen powder compositions (three doping levels, X=Y=0, 0.1, and 0.2 mol; and five A/B ratios 0.95, 0.98, 1.00, 1.02, andmore » 1.05) were synthesized by the glycine-nitrate combustion process (GNP). These powders were equilibrated by calcining at 1500 deg. C for 9 h prior to crystalline phase characterization by X-ray powder diffraction (XRD). From the results of this study and the available phase diagrams in the literature on constituent binary oxide systems, we propose a crystalline phase diagram of the La{sub 2}O{sub 3}-SrO-Ga{sub 2}O{sub 3}-MgO quaternary system at elevated temperature (1500 deg. C)« less

  7. Effect of strontium substitution on the structural and magnetic properties of La1.8Sr0.2MMnO6 (M = Ni, Co)-layered manganites

    NASA Astrophysics Data System (ADS)

    Karimunnesa, Syeda; Ahmmad, Bashir; Basith, M. A.

    2017-07-01

    Sr-substituted perovskites, La1.8Sr0.2MMnO6 (M = Ni, Co), were synthesized using the solid-state reaction technique to present a systematic study on their morphological, structural and magnetic properties. The average grain size of the as-prepared La1.8Sr0.2NiMnO6 samples are in the range of 0.2-0.7 µm and those for La1.8Sr0.2CoMnO6 manganites are 0.1-2.8 μm, which is significantly less than that of unsubstituted La2NiMnO6 (LNMO) and La2CoMnO6 (LCMO) manganites. The XPS analysis enlightened about phase purity, binding energy and oxygen vacancy of La1.8Sr0.2MMnO6 manganites. The Sr-substituted LNMO has revealed a sharp ferromagnetic to paramagnetic phase transition at 160 ± 2 K, which is about 120 K less than that of parent LNMO. The Sr-substituted LCMO exhibited such a transition at 220 ± 2 K, which is 8 K less than that of parent LCMO. The temperature-dependent magnetization measurements suggest that the effect of Sr on the transition temperature in LNMO is more significant than that of LCMO.

  8. Heterobimetallic [NiFe] Complexes Containing Mixed CO/CN- Ligands: Analogs of the Active Site of the [NiFe] Hydrogenases.

    PubMed

    Perotto, Carlo U; Sodipo, Charlene L; Jones, Graham J; Tidey, Jeremiah P; Blake, Alexander J; Lewis, William; Davies, E Stephen; McMaster, Jonathan; Schröder, Martin

    2018-03-05

    The development of synthetic analogs of the active sites of [NiFe] hydrogenases remains challenging, and, in spite of the number of complexes featuring a [NiFe] center, those featuring CO and CN - ligands at the Fe center are under-represented. We report herein the synthesis of three bimetallic [NiFe] complexes [Ni( N 2 S 2 )Fe(CO) 2 (CN) 2 ], [Ni( S 4 )Fe(CO) 2 (CN) 2 ], and [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] that each contain a Ni center that bridges through two thiolato S donors to a {Fe(CO) 2 (CN) 2 } unit. X-ray crystallographic studies on [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ], supported by DFT calculations, are consistent with a solid-state structure containing distinct molecules in the singlet ( S = 0) and triplet ( S = 1) states. Each cluster exhibits irreversible reduction processes between -1.45 and -1.67 V vs Fc + /Fc and [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] possesses a reversible oxidation process at 0.17 V vs Fc + /Fc. Spectroelectrochemical infrared (IR) and electron paramagnetic resonance (EPR) studies, supported by density functional theory (DFT) calculations, are consistent with a Ni III Fe II formulation for [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] + . The singly occupied molecular orbital (SOMO) in [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] + is based on Ni 3d z 2 and 3p S with the S contributions deriving principally from the apical S-donor. The nature of the SOMO corresponds to that proposed for the Ni-C state of the [NiFe] hydrogenases for which a Ni III Fe II formulation has also been proposed. A comparison of the experimental structures, and the electrochemical and spectroscopic properties of [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] and its [Ni( N 2 S 3 )] precursor, together with calculations on the oxidized [Ni( N 2 S 3 )Fe(CO) 2 (CN) 2 ] + and [Ni( N 2 S 3 )] + forms suggests that the binding of the {Fe(CO)(CN) 2 } unit to the {Ni(CysS) 4 } center at the active site of the [NiFe] hydrogenases suppresses thiolate-based oxidative chemistry involving the bridging thiolate S donors

  9. Effects of cerium on the hydrogen absorption-desorption properties of rare earth-Mg-Ni hydrogen-absorbing alloys

    NASA Astrophysics Data System (ADS)

    Yasuoka, Shigekazu; Ishida, Jun; Kishida, Kyosuke; Inui, Haruyuki

    2017-04-01

    The influence of Ce addition on the phase constitution, microstructure, hydrogen absorption/desorption properties and battery performances of newly developed rare earth (RE)-Mg-Ni hydrogen-absorbing superlattice alloys for negative electrode materials in Ni-metal hydride (MH) batteries were investigated. The partial substitution of RE (La and Nd) with Ce results in a higher discharge performance and a lower cycle life in the battery. The Ce addition greatly affects the phase constitution, which is mainly characterized by increased formation of the AB2 phase (A = RE or Mg and B = Ni or Al). The existence of the AB2 phase is found to accelerate alloy pulverization and oxidation when the alloys are used as negative electrode materials in Ni-MH model cells. The accelerated pulverization and oxidation are considered to be responsible for the observed higher discharge performance and lower cycle life in the batteries, respectively.

  10. Electrochemical performances of co-substituted (La and Li) LiLa{sub x−y}Li{sub y}Ni{sub 1−x}O{sub 2} cathode materials for rechargeable lithium-ion batteries

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mohan, P.; Paruthimal Kalaignan, G., E-mail: pkalaignan@yahoo.com

    2013-09-01

    Graphical abstract: - Highlights: • LiLa{sub x−y}Li{sub x}Ni{sub 1−x}O{sub 2} powders were prepared by a sol–gel method at 600 °C for 10 h. • LiLa{sub x−y}Li{sub x}Ni{sub 1−x}O{sub 2} powder materials had well defined layer structure, and no impurities. • LiLa{sub 0.10}Li{sub 0.10}Ni{sub 0.80}O{sub 2} crystallite size was reduced compared with those of LiNiO{sub 2}. • Li/LiPF{sub 6}/LiLa{sub x−y}Li{sub x}Ni{sub 1−x}O{sub 2} cells were of high charge/discharge capacity, with columbic efficiency at 25 °C and 45 °C. • LiLa{sub 0.10}Li{sub 0.10}Ni{sub 0.80}O{sub 2} good cyclic stability, rate capability and better 45 °C. - Abstract: Co-substituted LiLa{sub x−y}Li{sub y}Ni{sub 1−x}O{sub 2}more » cathode materials were synthesized by sol–gel method using aqueous solutions of metal nitrates and tartaric acid as chelating agent at 600 °C for 10 h. The structure and electrochemical properties of the synthesized materials were characterized by using XRD, SEM, EDAX, TEM, cyclic voltammetry, charge/discharge and electrochemical impedance spectroscopy. XRD studies revealed a well defined layer structure and a linear variation of lattice parameters with the addition of lanthanum and lithium confirmed phase pure compounds in a rhombohedral structure. TEM and SEM analysis shows that LiLa{sub 0.10}Li{sub 0.10}Ni{sub 0.80}O{sub 2} has smaller particle size and regular morphological structure with narrow size distribution than those of LiNiO{sub 2}. Variations of dual mixing and hexagonal ordering with the substituted elements have enhanced the charge/discharge capacities at both room (25 °C) and elevated temperatures (45 °C), respectively. LiLa{sub 0.10}Li{sub 0.10}Ni{sub 0.80}O{sub 2} had high charge/discharge capacity, low irreversible capacity and better elevated temperature performance.« less

  11. Hydrogenation of CO 2 in Water Using a Bis(diphosphine) Ni–H Complex

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Burgess, Samantha A.; Kendall, Alexander J.; Tyler, David R.

    2017-03-17

    The water soluble Ni bis(diphosphine) complex [NiL2](BF4)2 (L = 1,2- bis(di(methoxypropyl)phosphino)ethane) and the corresponding hydride, [HNiL2]BF4, were synthesized and characterized. For HNiL2+, the hydricity was determined to be 23.2(3) kcal/mol in aqueous solution. Based on the hydricity of formate of 24.1 kcal/mol, the transfer of a hydride from HNiL2 + to CO2 to produce formate is favorable by 1 kcal/mol. Starting from either NiL2 2+ or HNiL2 + in water, catalytic hydrogenation of CO2 was observed with NaHCO3 (0.8 M) as the only additive. A maximum turnover frequency of 3.6(8) h–1 was observed at 80 °C and 51 atm ofmore » a 1:1 mixture of CO2 and H2.« less

  12. El Niño Southern Oscillation (ENSO) Enhances CO2 Exchange Rates in Freshwater Marsh Ecosystems in the Florida Everglades

    PubMed Central

    Malone, Sparkle L.; Staudhammer, Christina L.; Oberbauer, Steven F.; Olivas, Paulo; Ryan, Michael G.; Schedlbauer, Jessica L.; Loescher, Henry W.; Starr, Gregory

    2014-01-01

    This research examines the relationships between El Niño Southern Oscillation (ENSO), water level, precipitation patterns and carbon dioxide (CO2) exchange rates in the freshwater wetland ecosystems of the Florida Everglades. Data was obtained over a 5-year study period (2009–2013) from two freshwater marsh sites located in Everglades National Park that differ in hydrology. At the short-hydroperiod site (Taylor Slough; TS) and the long-hydroperiod site (Shark River Slough; SRS) fluctuations in precipitation patterns occurred with changes in ENSO phase, suggesting that extreme ENSO phases alter Everglades hydrology which is known to have a substantial influence on ecosystem carbon dynamics. Variations in both ENSO phase and annual net CO2 exchange rates co-occurred with changes in wet and dry season length and intensity. Combined with site-specific seasonality in CO2 exchanges rates, El Niño and La Niña phases magnified season intensity and CO2 exchange rates at both sites. At TS, net CO2 uptake rates were higher in the dry season, whereas SRS had greater rates of carbon sequestration during the wet season. As La Niña phases were concurrent with drought years and extended dry seasons, TS became a greater sink for CO2 on an annual basis (−11 to −110 g CO2 m−2 yr−1) compared to El Niño and neutral years (−5 to −43.5 g CO2 m−2 yr−1). SRS was a small source for CO2 annually (1.81 to 80 g CO2 m−2 yr−1) except in one exceptionally wet year that was associated with an El Niño phase (−16 g CO2 m−2 yr−1). Considering that future climate predictions suggest a higher frequency and intensity in El Niño and La Niña phases, these results indicate that changes in extreme ENSO phases will significantly alter CO2 dynamics in the Florida Everglades. PMID:25521299

  13. 3D Computer Models of T- x- y Diagrams, Forming the Fe-Ni-Co-FeS-NiS-CoS Subsystem

    NASA Astrophysics Data System (ADS)

    Lutsyk, V. I.; Vorob'eva, V. P.

    2017-12-01

    3D computer models of Fe-Ni-Co, Fe-Ni-FeS-NiS, Fe-Co-FeS-CoS, Ni-Co-NiS-CoS T- x- y diagrams have been designed. The geometric structure (35 surfaces, two-phase surface of the reaction type change, 17 phase regions) of the Fe-Ni-FeS-NiS T- x- y diagram is investigated in detail. The liquidus hypersurfaces prediction of the Fe-Ni-Co-FeS-NiS-CoS subsystem is represented.

  14. Synthesis, structural characterization, and electrochemical properties of dinuclear Ni/Mn model complexes for the active site of [NiFe]-hydrogenases.

    PubMed

    Song, Li-Cheng; Li, Jia-Peng; Xie, Zhao-Jun; Song, Hai-Bin

    2013-10-07

    Four new dinuclear Ni/Mn model complexes RN(PPh2)2Ni(μ-SEt)2(μ-Cl)Mn(CO)3 (7, R = p-MeC6H4CH2; 8, R = EtO2CCH2) and RN(PPh2)2Ni(μ-SEt)2(μ-Br)Mn(CO)3 (9, R = p-MeC6H4CH2; 10, R = EtO2CCH2) have been prepared via the four separated step-reactions involving six new precursors RN(PPh2)2 (1, R = p-MeC6H4CH2; 2, R = EtO2CCH2), RN(PPh2)2NiCl2 (3, R = p-MeC6H4CH2; 4, R = EtO2CCH2), and RN(PPh2)2Ni(SEt)2 (5, R = p-MeC6H4CH2; 6, R = EtO2CCH2). The Et3N-assisted aminolysis of Ph2PCl with p-MeC6H4CH2NH2 or EtO2CCH2NH2·HCl in CH2Cl2 gave the azadiphosphine ligands 1 and 2 in 38% and 53% yields, whereas the coordination reaction of 1 or 2 with NiCl2·6H2O in CH2Cl2/MeOH afforded the mononuclear Ni dichloride complexes 3 and 4 in 59% and 78% yields, respectively. While thiolysis of 3 or 4 with EtSH under the assistance of Et3N in CH2Cl2 produced the mononuclear Ni dithiolate complexes 5 and 6 in 64% and 68% yields, further treatment of 5 and 6 with Mn(CO)5Cl or Mn(CO)5Br resulted in formation of the dinuclear Ni/Mn model complexes 7-10 in 31-73% yields. All the new compounds 1-10 have been structurally characterized, while model complexes 7 and 9 have been found to be catalysts for HOAc proton reduction to hydrogen under CV conditions.

  15. Glucose- and cellulose-derived Ni/C-SO3H catalysts for liquid phase phenol hydrodeoxygenation.

    PubMed

    Kasakov, Stanislav; Zhao, Chen; Baráth, Eszter; Chase, Zizwe A; Fulton, John L; Camaioni, Donald M; Vjunov, Aleksei; Shi, Hui; Lercher, Johannes A

    2015-01-19

    Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalysed the reduction of phenol to cyclohexanol in water. The state of 3-5 nm grafted Ni particles was analysed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in the presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt % C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Phase transitions in the (Ni,Zn)TiF 6 · 6H 2O system

    NASA Astrophysics Data System (ADS)

    Lichti, R. L.; Jan, I.-Yuan; Casey, K. G.

    1989-02-01

    Measurements of the transformation rates and the characteristic temperatures of the trigonal ≡ monoclinic structural change in (Ni 1- xZn x)TiF 6 · 6H 2O show a double transition up to x = 0.5. The relationships between the phase changes generally observed in the ABF 6 · 6H 2O system and the internal motions of the octahedral ionic complexes are discussed, and a phase diagram for the mixed nickel/zinc fluorotitanate is established.

  17. Supramolecular complexes of Co(II), Ni(II) and Zn(II) p-hydroxybenzoates with caffeine: Synthesis, spectral characterization and crystal structure

    NASA Astrophysics Data System (ADS)

    Taşdemir, Erdal; Özbek, Füreya Elif; Sertçelik, Mustafa; Hökelek, Tuncer; Çelik, Raziye Çatak; Necefoğlu, Hacali

    2016-09-01

    Three novel complexes Co(II), Ni(II) and Zn(II) containing p-hydroxybenzoates and caffeine ligands were synthesized and characterized by elemental analysis, FT-IR and UV-vis Spectroscopy, molar conductivity and single crystal X-ray diffraction methods. The thermal properties of the synthesized complexes were investigated by TGA/DTA. The general formula of the complexes is [M(HOC6H4COO)2(H2O)4]·2(C8H10N4O2)·8H2O (where: M: Co, Ni and Zn). The IR studies showed that carboxylate groups of p-hydroxybenzoate ligands have monodentate coordination mode. The M2+ ions are octahedrally coordinated by two p-hydroxybenzoate ligands, four water molecules leading to an overall MO6 coordination environment. The medium-strength hydrogen bondings involving the uncoordinated caffeine ligands and water molecules, coordinated and uncoordinated water molecules and p-hydroxybenzoate ligands lead to three-dimensional supramolecular networks in the crystal structures.

  18. Self-organized layered hydrogenation in black Mg2NiHx switchable mirrors.

    PubMed

    Lohstroh, W; Westerwaal, R J; Noheda, B; Enache, S; Giebels, I A M E; Dam, B; Griessen, R

    2004-11-05

    In addition to a mirrorlike (Mg2Ni) and a transparent (Mg2NiH4) state, thin films of Mg2NiHx exhibit a remarkable black state with low reflection over the entire visible spectrum, essentially zero transmission and a low electrical resistivity. Such a black state is not explicable for a homogeneous layer since a large absorption coefficient always yields substantial reflection. We show that it results from a self-organized and reversible double layering of metallic Mg2NiH0.3 and semiconducting Mg2NiH4.

  19. Citrate, in collaboration with a guanidinium ion, as a generator of cubane-like complexes with a range of metal cations: synthesis, structures, and magnetic properties of [C(NH2)3]8[(M(II))4(cit)4].8H2O (M = Mg, Mn, Fe, Co, Ni, and Zn; cit = Citrate).

    PubMed

    Hudson, Timothy A; Berry, Kevin J; Moubaraki, Boujemaa; Murray, Keith S; Robson, Richard

    2006-05-01

    Aqueous reaction mixtures containing citric acid, guanidinium carbonate, and a range of metal cations (Mg2+, Mn2+, Fe2+, Co2+, Ni2+, and Zn2+) at room temperature give crystalline products of composition [C(NH2)3]8[(M(II))4(cit)4].8H2O (cit = citrate). In all cases, the crystals are suitable for single-crystal X-ray diffraction studies, which reveal that the compounds are isostructural (space group P4(2)/n; a approximately 16.2 A, and c approximately 11.5 A). As was intended, cubane-like [M4(cit)4]8- complex anions are present. The individual citrate units are chiral, but each cubane unit contains two of one hand and two of the other, related around an S4 axis. The cubane units are involved in no less than 40 H-bonding interactions with guanidinium cations and lattice water molecules. Detailed susceptibility and magnetization studies show that the intracluster magnetic coupling within the Mn(II), Fe(II), Co(II), and Ni(II) cubanes is very weak in all cases with J values of -0.82, -0.43, and -0.09 cm(-1) for the Mn, Fe, and Co species, respectively. A two-J model gave the best agreement with the susceptibility and high-field magnetization data for the Ni(II) case, over the whole temperature range studied, and the sign of the parameters, J12 = -0.3 cm(-1) and J13 = +2.97 cm(-1), correlated with the two Ni-(mu3-O)-Ni angles observed in the cluster structure. All members of the 3d-block [M4(cit)4]8- family have spin ground states, ST, of zero, with the higher ST levels just a few reciprocal centimeters away in energy.

  20. Evaluation and comparision of dc resistivity of NiZr x Co x Fe2-2x O4, Ni0.5Sn0.5Co x Mn x Fe2-2x O4, Mg1-x Ca x Ni y Fe2-y O4 and Mg1-x Ni x Co y Fe2-y O4 nanocrytalline materials

    NASA Astrophysics Data System (ADS)

    Ali, Rajjab; Gilani, Zaheer Abbas; Shahzad Shifa, Muhammad; Asghar, H. M. Noor Ul Huda Khan; Azhar Khan, Muhammad; Naeem Anjum, Muhammad; Nauman Usmani, Muhammad; Farooq Warsi, Muhammad; Khawaja, Imtiaz U.

    2017-11-01

    Four series nanocrystalline ferrites with nominal composition, NiZr x Co x Fe2-2x O4 (x  =  0.0, 0.2, 0.4, 0.6, 0.8) Ni0.5Sn0.5Co x Mn x Fe2-2x O4 (x  =  0.0, 0.2, 0.4, 0.6, 0.8), Mg1-x Ca x Ni y Fe2-y O4 (x  =  0.0, 0.2, 0.4, 0.6, 0.8; y  =  0, 04, 0.8, 1.2, 1.6) and Mg1-x Ni x Co y Fe2-y O4 (x,y  =  0.0, 0.2, 0.4, 0.6, 0.8) have been fabricated using the microemulsion synthesis route. The synthesized materials are investigated for dc electrical resistivity measurements. The variation of dc electrical resistivity of these materials has been explainedon the basis of hopping mechanism of both holes and electrons.

  1. Building robust architectures of carbon-wrapped transition metal nanoparticles for high catalytic enhancement of the 2LiBH4-MgH2 system for hydrogen storage cycling performance

    NASA Astrophysics Data System (ADS)

    Huang, Xu; Xiao, Xuezhang; Shao, Jie; Zhai, Bing; Fan, Xiulin; Cheng, Changjun; Li, Shouquan; Ge, Hongwei; Wang, Qidong; Chen, Lixin

    2016-08-01

    catalysis on the RHCs, provides a new inspiration to practical hydrogen storage application for high performance complex hydrides.Nanoscale catalyst doping is regarded as one of the most effective strategies to improve the kinetics performance of hydrogen storage materials, but the agglomeration of nanoparticles is usually unavoidable during the repeated de/rehydrogenation processes. Herein, hierarchically structured catalysts (Fe/C, Co/C and Ni/C) were designed and fabricated to overcome the agglomeration issue of nanocatalysts applied to the 2LiBH4-MgH2 system for the first time. Uniform transition metal (TM) nanoparticles (~10 nm) wrapped by few layers of carbon are synthesized by pyrolysis of the corresponding metal-organic frameworks (MOFs), and introduced into the 2LiBH4-MgH2 reactive hydride composites (RHCs) by ball milling. The particular features of the carbon-wrapped architecture effectively avoid the agglomeration of the TM nanoparticles during hydrogen storage cycling, and high catalysis is maintained during the subsequent de/rehydrogenation processes. After de/rehydrogenation cycling, FeB, CoB and MgNi3B2 can be formed as the catalytically active components with a particle size of 5-15 nm, which show a homogeneous distribution in the hydride matrix. Among the three catalysts, in situ-formed MgNi3B2 shows the best catalytic efficiency. The incubation period of the Fe/C, Co/C and Ni/C-doped 2LiBH4-MgH2 system between the two dehydrogenation steps was reduced to about 8 h, 4 h and 2 h, respectively, which is about 8 h, 12 h and 14 h shorter than that of the undoped 2LiBH4-MgH2 sample. In addition, the two-step dehydrogenation peak temperatures of the Ni/C-doped 2LiBH4-MgH2 system drop to 323.4 °C and 410.6 °C, meanwhile, the apparent activation energies of dehydrogenated MgH2 and LiBH4 decrease by 58 kJ mol-1 and 71 kJ mol-1, respectively. In particular, the cycling hydrogen desorption of the Ni/C-doped 2LiBH4-MgH2 sample exhibits very good stability compared

  2. Phase stability and magnetic behavior of FeCrCoNiGe high-entropy alloy

    NASA Astrophysics Data System (ADS)

    Huang, Shuo; Vida, Ádám; Molnár, Dávid; Kádas, Krisztina; Varga, Lajos Károly; Holmström, Erik; Vitos, Levente

    2015-12-01

    We report an alternative FeCrCoNiGe magnetic material based on FeCrCoNi high-entropy alloy with Curie point far below the room temperature. Investigations are done using first-principles calculations and key experimental measurements. Results show that the equimolar FeCrCoNiGe system is decomposed into a mixture of face-centered cubic and body-centered cubic solid solution phases. The increased stability of the ferromagnetic order in the as-cast FeCrCoNiGe composite, with measured Curie temperature of 640 K, is explained using the exchange interactions.

  3. Sorption Properties of Iron-Magnesium and Nickel-Magnesium Mg2FeH6 and Mg2NiH4 Hydrides

    NASA Astrophysics Data System (ADS)

    Matysina, Z. A.; Zaginaichenko, S. Yu.; Shchur, D. V.; Gabdullin, M. T.

    2016-06-01

    Based on molecular-kinetic representations, theory of hydrogen absorption-desorption processes in binary Mg-Fe and Mg-Ni alloys is developed. Free energies of hydrides of these alloys are calculated. Equations of their thermodynamically equilibrium state determining the P-T-c diagrams are derived. A temperature dependence of the desorbed hydrogen concentration is established. A maximal desorption temperature is estimated. The state diagrams determining the concentration dependence of the maximal desorption temperature are constructed. Isopleths and isotherms of hydrogen solubility in the alloys are calculated. The possibility of manifestation of the hysteresis effect in hydrogen solubility isotherms is revealed and the decrease of the width and length of a hysteresis loop with increasing temperature is demonstrated together with the influence of the magnesium hydrate MgH2 in Mg2FeH6 samples and running of chemical reactions on the behavior of the isotherms and the occurrence of bends and jumps in them. All established functional dependences of the sorption properties of the examined alloys are compared with experimental data available from the literature.

  4. Heterogeneous Two-Phase Pillars in Epitaxial NiFe 2 O 4 -LaFeO 3 Nanocomposites

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Comes, Ryan B.; Perea, Daniel E.; Spurgeon, Steven R.

    2017-07-10

    Self-assembled epitaxial oxide nanocomposites have been explored for a wide range of applications, including multiferroic and magnetoelectric properties, plasmonics, and catalysis. These so-called “vertically aligned nanocomposites” form spontaneously during the deposition process when segregation into two phases is energetically favorable as compared to a solid solution. However, there has been surprisingly little work understanding the driving forces that govern the synthesis of these materials, which can include point defect energetics, surface diffusion, and interfacial energies. To explore these factors, La-Ni-Fe-O films have been synthesized by molecular beam epitaxy and it is shown that these phase segregate into spinel-perovskite nanocomposites. Usingmore » complementary scanning transmission electron microscopy and atom-probe tomography, the elemental composition of each phase is examined and found that Ni ions are exclusively found in the spinel phase. From correlative analysis, a model for the relative favorability of the Ni2+ and Ni3+ valences under the growth conditions is developed. It is shown that multidimensional characterization techniques provide previously unobserved insight into the growth process and complex driving forces for phase segregation.« less

  5. Electrocatalytic performances of LaNi1-xMgxO3 perovskite oxides as bi-functional catalysts for lithium air batteries

    NASA Astrophysics Data System (ADS)

    Du, Zhenzhen; Yang, Peng; Wang, Long; Lu, Yuhao; Goodenough, J. B.; Zhang, Jian; Zhang, Dawei

    2014-11-01

    Mg-doped perovskite oxides LaNi1-xMgxO3 (x = 0, 0.08, 0.15) electrocatalysts are synthesized by a sol-gel method using citric acid as complex agent and ethylene glycol as thickening agent. The intrinsic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity of as-prepared perovskite oxides in aqueous electrolyte are examined on a rotating disk electrode (RDE) set up. Li-air primary batteries on the basis of Mg-doped perovskite oxides LaNi1-xMgxO3 (x = 0, 0.08, 0.15) and nonaqueous electrolyte are also fabricated and tested. In terms of the ORR current densities and OER current densities, the performance is enhanced in the order of LaNiO3, LaNi0.92Mg0.08O3 and LaNi0.85Mg0.15O3. Most notably, partially substituting nickel with magnesium suppresses formation of Ni2+ and ensures high concentration of both OER and ORR reaction energy favorable Ni3+ (eg = 1) on the surface of perovskite catalysts. Nonaqueous Li-air primary battery using LaNi0.92Mg0.08O3 and LaNi0.85Mg0.15O3 as the cathode catalysts exhibit improved performances compared with LaNiO3 catalyst, which are consistent with the ORR current densities.

  6. Investigations of mechanical, electronic, and magnetic properties of non-magnetic MgTe and ferro-magnetic Mg0.75 TM 0.25Te (TM = Fe, Co, Ni): An ab-initio calculation

    NASA Astrophysics Data System (ADS)

    Q, Mahmood; S, M. Alay-e.-Abbas; I, Mahmood; Mahmood, Asif; N, A. Noor

    2016-04-01

    The mechanical, electronic and magnetic properties of non-magnetic MgTe and ferro-magnetic (FM) Mg0.75 TM 0.25Te (TM = Fe, Co, Ni) in the zinc-blende phase are studied by ab-initio calculations for the first time. We use the generalized gradient approximation functional for computing the structural stability, and mechanical properties, while the modified Becke and Johnson local (spin) density approximation (mBJLDA) is utilized for determining the electronic and magnetic properties. By comparing the energies of non-magnetic and FM calculations, we find that the compounds are stable in the FM phase, which is confirmed by their structural stabilities in terms of enthalpy of formation. Detailed descriptions of elastic properties of Mg0.75 TM 0.25Te alloys in the FM phase are also presented. For electronic properties, the spin-polarized electronic band structures and density of states are computed, showing that these compounds are direct bandgap materials with strong hybridizations of TM 3d states and Te p states. Further, the ferromagnetism is discussed in terms of the Zener free electron model, RKKY model and double exchange model. The charge density contours in the (110) plane are calculated to study bonding properties. The spin exchange splitting and crystal field splitting energies are also calculated. The distribution of electron spin density is employed in computing the magnetic moments appearing at the magnetic sites (Fe, Co, Ni), as well as at the non-magnetic sites (Mg, Te). It is found that the p-d hybridization causes not only magnetic moments on the magnetic sites but also induces negligibly small magnetic moments at the non-magnetic sites.

  7. Study of Structural and Magnetic Properties of Silica and Polyethylene Glycol (PEG-4000)-Encapsulated Magnesium Nickel Ferrite (Mg0.5Ni0.5Fe2O4) Nanoparticles

    NASA Astrophysics Data System (ADS)

    Deswardani, F.; Maulia, R.; Suharyadi, E.

    2017-05-01

    Mg0.5Ni0.5Fe2O4 has been successfully synthesized by using co-precipitation method. Two series of Mg0.5Ni0.5Fe2O4 silica encapsulated have been prepared by varying the concentration of silica and variation of PEG-4000 concentration. Analysis of X-Ray Diffraction (XRD) pattern showed that nanoparticles contained Mg0.5Ni0.5Fe2O4 spinel phase and γ-Fe2O3 phase with a particle size of 5.1 nm. The various of silica encapsulation give rise to produce a new phase of SiO2 and increase the particle size to 16.1 nm. PEG-4000 encapsulation affected to create a new phase of γ-FeO(OH), and reduce the particle size down to 4.5 nm. Fourier Transform Infra Red (FTIR) for Mg0.5Ni0.5Fe2O4 showed absorption peaks around 300-600 cm-1 which are M-O bond vibration. After silica encapsulation, there was new bond vibration typical of silica such as Si-O-Si (1049.28 cm-1), Si-OH (779.24 cm-1), and Si-O-Fe (570.93 cm-1). The PEG-4000 encapsulation creates a new vibration for typical of PEG-like of C-O (1103.28 cm-1) and C-H (925.83, 1481.33, and 2924.09 cm-1). Both of encapsulations series have M-O bond vibration indicating the presence of Mg0.5Ni0.5Fe2O4. After silica encapsulation, the coercivity of Mg0.5Ni0.5Fe2O4 decreased from 47 Oe to 10 Oe due to the decrease of particle size. Even though, the discrepancy of particle size as the effect of PEG-4000 encapsulation, the coercivity just slightly reduced to 46 Oe. The saturation magnetization of Mg0.5Ni0.5Fe2O4 decreased from 4.7 emu/g to 1 emu/g after silica encapsulation because diamagnetic SiO2. Otherwise, the saturation magnetization increased to 7.7 emu/g after PEG-4000 encapsulation because of domination of Mg0.5Ni0.5Fe2O4 phase ratio.

  8. Terminal NiII-OH/-OH2 complexes in trigonal bipyramidal geometries derived from H2O.

    PubMed

    Lau, Nathanael; Sano, Yohei; Ziller, Joseph W; Borovik, A S

    2017-03-29

    The preparation and characterization of two Ni II complexes are described, a terminal Ni II -OH complex with the tripodal ligand tris[(N)-tertbutylureaylato)-N-ethyl)]aminato ([H 3 buea] 3- ) and a terminal Ni II -OH 2 complex with the tripodal ligand N , N ', N ″-[2,2',2″-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido) ([MST] 3- ). For both complexes, the source of the -OH and -OH 2 ligand is water. The salts K 2 [Ni II H 3 buea(OH)] and NMe 4 [Ni II MST(OH 2 )] were characterized using perpendicular-mode X-band electronic paramagnetic resonance, Fourier transform infrared, UV-visible spectroscopies, and its electrochemical properties were evaluated using cyclic voltammetry. The solid state structures of these complexes determined by X-ray diffraction methods reveal that they adopt a distorted trigonal bipyramidal geometry, an unusual structure for 5-coordinate Ni II complexes. Moreover, the Ni II -OH and Ni II -OH 2 units form intramolecular hydrogen bonding networks with the [H 3 buea] 3- and [MST] 3- ligands. The oxidation chemistry of these complexes was explored by treating the high-spin Ni II compounds with one-electron oxidants. Species were formed with S = 1/2 spin ground states that are consistent with formation of monomeric Ni III species. While the formation of Ni III -OH complexes cannot be ruled out, the lack of observable O-H vibrations from the putative Ni-OH units suggest the possibility that other high valent Ni species are formed.

  9. Influence of Mg and Ni substitution on structural, microstructural and magnetic properties of Sr2Co2-xMgx/2Nix/2Fe12O22 (Co2Y) hexaferrite

    NASA Astrophysics Data System (ADS)

    Alizad Farzin, Y.; Mirzaee, O.; Ghasemi, A.

    2014-12-01

    In this study, Mg and Ni substituted Y-type hexaferrite particles with narrow size distribution have been prepared by using a sol-gel auto combustion method. The effects on structural, microstructure and magnetic properties have been investigated by substituting Mg2+ and Ni2+ at Co2+ sites. XRD patterns showed that Y-type hexaferrite phase formation has not been affected by substituting magnesium and nickel with cobalt in the range of 0.0≤x≤0.75. Various parameters such as lattice constants, cell volume and crystallite size have been calculated based on XRD data. The morphology and size distribution of the particles have been studied using high resolution field emission scanning electron microscopy (FESEM). It was also understood that the average crystallite size of particles increased from 45 to 63 nm with an increase of x content at Co2Y compound. Magnetic properties were determined using a vibrating sample magnetometer (VSM). The magnetic results revealed that by increasing the Mg and Ni in octahedral and tetrahedral sites, the coercivity was also increased from 949 to 1066 Oe, whereas saturation magnetization and Remnant magnetization were decreased from 47.98 to 40.78 emu/g and 23.05 to 20.99 emu/g, respectively.

  10. H-Phase Precipitation and Martensitic Transformation in Ni-rich Ni-Ti-Hf and Ni-Ti-Zr High-Temperature Shape Memory Alloys

    NASA Astrophysics Data System (ADS)

    Evirgen, A.; Pons, J.; Karaman, I.; Santamarta, R.; Noebe, R. D.

    2018-03-01

    The distributions of H-phase precipitates in Ni50.3Ti29.7Hf20 and Ni50.3Ti29.7Zr20 alloys formed by aging treatments at 500 and 550 °C or slow furnace cooling and their effects on the thermal martensitic transformation have been investigated by TEM and calorimetry. The comparative study clearly reveals faster precipitate-coarsening kinetics in the NiTiZr alloy than in NiTiHf. For precipitates of a similar size of 10-20 nm in both alloys, the martensite plates in Ni50.3Ti29.7Zr20 have larger widths and span a higher number of precipitates compared with the Ni50.3Ti29.7Hf20 alloy. However, for large H-phase particles with hundreds of nm in length, no significant differences in the martensitic microstructures of both alloy systems have been observed. The martensitic transformation temperatures of Ni50.3Ti29.7Hf20 are 80-90 °C higher than those of Ni50.3Ti29.7Zr20 in the precipitate-free state and in the presence of large particles of hundreds on nm in length, but this difference is reduced to only 10-20 °C in samples with small H-phase precipitates. The changes in the transformation temperatures are consistent with the differences in the precipitate distributions between the two alloy systems observed by TEM.

  11. Role of stable and metastable Mg-H complexes in p-type GaN for cw blue laser diodes

    NASA Astrophysics Data System (ADS)

    Castiglia, A.; Carlin, J.-F.; Grandjean, N.

    2011-05-01

    Secondary ion mass spectroscopy (SIMS) and capacitance-voltage measurements were combined to thoroughly study Mg doping in GaN layers grown by metal organic vapor phase epitaxy. First we found that the Mg steady-state incorporation regime occurs for a surface coverage of 0.3 monolayer. Additionally SIMS indicates that H incorporates proportionally with Mg until a certain [Mg] where [H] saturates. After thermal activation, [H] while being much lower still scales with [Mg]. These results suggest that H combines with Mg to form two different types of Mg-H complexes: a metastable one leading to the Mg acceptor after annealing, the other one (dominating at high [Mg]) being stable and electrically inactive. The obtained results allowed us optimizing doping conditions for blue laser diodes.

  12. NiMg/Ceria-Zirconia Cylindrical Pellet Catalysts for Tri-reforming of Surrogate Biogas

    DOE PAGES

    Zhao, Xianhui; Walker, Devin; Maiti, Debtanu; ...

    2017-12-22

    Cylindrical NiMg/Ce 0.6Zr 0.4O 2 pellet catalysts with two different sizes (large: radius = 1.59 mm; and small: radius = 0.75 mm) were produced by extrusion of powder catalysts. The small catalyst pellets had a higher specific surface area, pore volume, average pore size, radial crush strength, and resistance to breakage than the large ones. Tri-reforming tests with surrogate biogas were conducted at 3 bar and 882 °C, with the feed molar ratios of CH 4: CO 2: air fixed at 1.0: 0.7: 0.95 and the H 2O/CH 4 molar feed ratio (0.35 – 1.16) varied. The small catalyst pelletsmore » exhibited lower internal mass transfer resistance and higher coking resistance, compared to the large ones. CO 2 conversion decreased and H 2/CO molar ratio increased with the increase of H 2O/CH 4 molar feed ratio, which are consistent with the trends predicted by thermodynamic equilibrium calculations. Finally, the results indicate that the NiMg/Ce 0.6Zr 0.4O 2 catalyst pellets are promising for commercial scale applications.« less

  13. Constructing CrIII-centered heterometallic complexes: [NiCrIII] and [CoCrIII] wheels.

    PubMed

    Kakaroni, Foteini E; Collet, Alexandra; Sakellari, Eirini; Tzimopoulos, Demetrios I; Siczek, Milosz; Lis, Tadeusz; Murrie, Mark; Milios, Constantinos J

    2017-12-19

    The solvothermal reaction between Cr(acac) 3 , MCl 2 ·6H 2 O (M = Ni, Co) and 2-hydroxy-4-methyl-6-phenyl-pyridine-3-amidoxime (H 2 L), under basic conditions, led to the synthesis of the heterometallic heptanuclear clusters [MCr(HL zw ) 6 (HL) 6 ]·3Cl (M = Ni, 1; Co, 2), with the nickel analogue displaying an S = 9/2 spin ground-state.

  14. Microstructure of hydrogenated Mg2Ni studied by SANS

    NASA Astrophysics Data System (ADS)

    Mori, K.; Sugiyama, M.; Iwase, K.; Kawabe, S.; Onodera, Y.; Itoh, K.; Otomo, T.; Fukunaga, T.

    2010-10-01

    X-ray powder diffraction (XRD) and small-angle neutron scattering (SANS) experiments were carried out for the hydrogenated and duterated Mg2Ni, respectively. According to the results of XRD experiments, both of them coexisted with unhydrogenated (or undeuterated) Mg2Ni in the hydrogen absorbing cycle. Furthermore, in the SANS experiments, a slope of SANS curve, I(Q), was roughly evaluated by using the following power law: I(Q) propto Q-m, where Q is the magnitude of the scattering vector, and m can be equated with a fractal dimensionality, DS (= 6 - m). In conclusion, the hydrogenated and duterated Mg2Ni showed DS~ 3 and ~ 2, respectively. The significant difference between DS's can be understood by considering the scattering length densities, ρ, of Mg2Ni, Mg2NiH4, and Mg2NiD4.

  15. Density functional theory study of small X-doped Mg(n) (X = Fe, Co, Ni, n = 1-9) bimetallic clusters: equilibrium structures, stabilities, electronic and magnetic properties.

    PubMed

    Kong, Fanjie; Hu, Yanfei

    2014-03-01

    The geometries, stabilities, and electronic and magnetic properties of Mg(n) X (X = Fe, Co, Ni, n = 1-9) clusters were investigated systematically within the framework of the gradient-corrected density functional theory. The results show that the Mg(n)Fe, Mg(n)Co, and Mg(n)Ni clusters have similar geometric structures and that the X atom in Mg(n)X clusters prefers to be endohedrally doped. The average atomic binding energies, fragmentation energies, second-order differences in energy, and HOMO-LUMO gaps show that Mg₄X (X = Fe, Co, Ni) clusters possess relatively high stability. Natural population analysis was performed and the results showed that the 3s and 4s electrons always transfer to the 3d and 4p orbitals in the bonding atoms, and that electrons also transfer from the Mg atoms to the doped atoms (Fe, Co, Ni). In addition, the spin magnetic moments were analyzed and compared. Several clusters, such as Mg₁,₂,₃,₄,₅,₆,₈,₉Fe, Mg₁,₂,₄,₅,₆,₈,₉Co, and Mg₁,₂,₅,₆,₇,₉Ni, present high magnetic moments (4 μ(B), 3 μ(B), and 2 μ(B), respectively).

  16. Development of B2 Shape Memory Intermetallics Beyond NiAl, CoNiAl and CoNiGa

    NASA Astrophysics Data System (ADS)

    Gerstein, G.; Firstov, G. S.; Kosorukova, T. A.; Koval, Yu. N.; Maier, H. J.

    2018-06-01

    The present study describes the development of shape memory alloys based on NiAl. Initially, this system was considered a promising but unsuccessful neighbour of NiTi. Later, however, shape memory alloys like CoNiAl or CoNiGa were developed that can be considered as NiAl derivatives and already demonstrated good mechanical properties. Yet, these alloys were still inferior to NiTi in most respects. Lately, using a multi-component approach, a CoNiCuAlGaIn high entropy intermetallic compound was developed from the NiAl prototype. This new alloy featured a B2 phase and a martensitic transformation along with a remarkable strength in the as-cast state. In the long-term, this new approach might led to a breakthrough for shape memory alloys in general.

  17. Mixed oxides of sodium, antimony (5+) and divalent metals (Ni, Co, Zn or Mg)

    NASA Astrophysics Data System (ADS)

    Politaev, V. V.; Nalbandyan, V. B.; Petrenko, A. A.; Shukaev, I. L.; Volotchaev, V. A.; Medvedev, B. S.

    2010-03-01

    A family of α-NaFeO 2-type oxides Na xM (1+x)/3Sb (2-x)/3O 2 ( M=Ni, Co, Zn, Mg; x≈0.8 or 0.9) has been prepared by solid state reactions and characterized by powder XRD. At x=1, ordering occurs with tripling the unit cells and formula units. The powder patterns for Na 3M2SbO 6 ( M=Ni, Co) comply with both trigonal P3 112 cell and monoclinic C2/ m cell. The Ni compound exhibits also a series of extremely weak reflections ( I<0.3%) that need doubling of the c axis, and the final cell is C2/ c, a=5.3048(3), b=9.1879(4), c=10.8356(7), β=99.390(5). These ambiguities are explained by stacking faults. The compounds absorb atmospheric moisture with c-axis expansion up to 29%. A delafossite-related superlattice Ag 3Co 2SbO 6 has been prepared by ion exchange and refined: P3 112, a=5.3842(2), c=18.6613(10). Ionic conductivity of the Na 0.8Ni 0.6Sb 0.4O 2 ceramics, 0.4 S/m at 300 °C, is greater than reported previously, presumably owing to the grain orientation produced by hot pressing.

  18. Investigation into the dehydration of selenate doped Na2M(SO4)2·2H2O (M = Mn, Fe, Co and Ni): Stabilisation of the high Na content alluaudite phases Na3M1.5(SO4)3-1.5x(SeO4)1.5x (M = Mn, Co and Ni) through selenate incorporation

    NASA Astrophysics Data System (ADS)

    Driscoll, L. L.; Kendrick, E.; Knight, K. S.; Wright, A. J.; Slater, P. R.

    2018-02-01

    In this paper we report an investigation into the phases formed on dehydration of Na2M(SO4)2-x(SeO4)x·2H2O (0 ≤ x ≤ 1; M = Mn, Fe, Co and Ni). For the Fe series, all attempts to dehydrate the samples doped with selenate resulted in amorphous products, and it is suspected that a side redox reaction involving the Fe and selenate may be occurring leading to phase decomposition and hence the lack of a crystalline product on dehydration. For M = Mn, Co, Ni, the structure observed was shown to depend upon the transition metal cation and level of selenate doping. An alluaudite phase, Na3M1.5(SO4)3-1.5x(SeO4)1.5x, was observed for the selenate doped compositions, with this phase forming as a single phase for x ≥ 0.5 M = Co, and x = 1.0 M = Ni. For M = Mn, the alluaudite structure is obtained across the series, albeit with small impurities for lower selenate content samples. Although the alluaudite-type phases Na2+2y(Mn/Co)2-y(SO4)3 have recently been reported [1,2], doping with selenate appears to increase the maximum sodium content within the structure. Moreover, the selenate doped Ni based samples reported here are the first examples of a Ni sulfate/selenate containing system exhibiting the alluaudite structure.

  19. Vibrational investigations of CO2-H2O, CO2-(H2O)2, and (CO2)2-H2O complexes isolated in solid neon.

    PubMed

    Soulard, P; Tremblay, B

    2015-12-14

    The van der Waals complex of H2O with CO2 has attracted considerable theoretical interest as a typical example of a weak binding complex with a dissociation energy less than 3 kcal/mol. Up to now, experimental vibrational data are sparse. We have studied by FTIR the complexes involving CO2 and water molecules in solid neon. Many new absorption bands close to the well known monomers fundamentals give evidence for at least three (CO2)n-(H2O)m complexes, noted n:m. Concentration effects combined with a detailed vibrational analysis allow for the identification of sixteen, twelve, and five transitions for the 1:1, 1:2, and 2:1 complexes, respectively. Careful examination of the far infrared spectral region allows the assignment of several 1:1 and 1:2 intermolecular modes, confirmed by the observation of combinations of intra + intermolecular transitions, and anharmonic coupling constants have been derived. Our results demonstrate the high sensibility of the solid neon isolation to investigate the hydrogen-bonded complexes in contrast with the gas phase experiments for which two quanta transitions cannot be easily observed.

  20. A First Principles Study of H2 Adsorption on LaNiO3(001) Surfaces

    PubMed Central

    Pan, Changchang; Chen, Yuhong; Wu, Na; Zhang, Meiling; Yuan, Lihua; Zhang, Cairong

    2017-01-01

    The adsorption of H2 on LaNiO3 was investigated using density functional theory (DFT) calculations. The adsorption sites, adsorption energy, and electronic structure of LaNiO3(001)/H2 systems were calculated and indicated through the calculated surface energy that the (001) surface was the most stable surface. By looking at optimized structure, adsorption energy and dissociation energy, we found that there were three types of adsorption on the surface. First, H2 molecules completely dissociate and then tend to bind with the O atoms, forming two –OH bonds. Second, H2 molecules partially dissociate with the H atoms bonding to the same O atom to form one H2O molecule. These two types are chemical adsorption modes; however, the physical adsorption of H2 molecules can also occur. When analyzing the electron structure of the H2O molecule formed by the partial dissociation of the H2 molecule and the surface O atom, we found that the interaction between H2O and the (001) surface was weaker, thus, H2O was easier to separate from the surface to create an O vacancy. On the (001) surface, a supercell was constructed to accurately study the most stable adsorption site. The results from analyses of the charge population; electron localization function; and density of the states indicated that the dissociated H and O atoms form a typical covalent bond and that the interaction between the H2 molecule and surface is mainly due to the overlap-hybridization among the H 1s, O 2s, and O 2p states. Therefore, the conductivity of LaNiO3(001)/H2 is stronger after adsorption and furthermore, the conductivity of the LaNiO3 surface is better than that of the LaFeO3 surface. PMID:28772396

  1. Preferential diffusion in concentrated solid solution alloys: NiFe, NiCo and NiCoCr

    DOE PAGES

    Zhao, Shijun; Osetsky, Yuri; Zhang, Yanwen

    2017-02-13

    In single-phase concentrated solid-solution alloys (CSAs), including high entropy alloys (HEAs), remarkable mechanical properties are exhibited, as well as extraordinary corrosion and radiation resistance compared to pure metals and dilute alloys. But, the mechanisms responsible for these properties are unknown in many cases. In this work, we employ ab initio molecular dynamics based on density functional theory to study the diffusion of interstitial atoms in Ni and Ni-based face-centered cubic CSAs including NiFe, NiCo and NiCoCr. We model the defect trajectories over >100 ps and estimate tracer diffusion coefficients, correlation factors and activation energies. Furthermore, we found that the diffusionmore » mass transport in CSAs is not only slower than that in pure components, i.e. sluggish diffusion, but also chemically non-homogeneous. The results obtained here can be used in understanding and predicting the atomic segregation and phase separation in CSAs under irradiation conditions.« less

  2. Building robust architectures of carbon-wrapped transition metal nanoparticles for high catalytic enhancement of the 2LiBH4-MgH2 system for hydrogen storage cycling performance.

    PubMed

    Huang, Xu; Xiao, Xuezhang; Shao, Jie; Zhai, Bing; Fan, Xiulin; Cheng, Changjun; Li, Shouquan; Ge, Hongwei; Wang, Qidong; Chen, Lixin

    2016-08-21

    Nanoscale catalyst doping is regarded as one of the most effective strategies to improve the kinetics performance of hydrogen storage materials, but the agglomeration of nanoparticles is usually unavoidable during the repeated de/rehydrogenation processes. Herein, hierarchically structured catalysts (Fe/C, Co/C and Ni/C) were designed and fabricated to overcome the agglomeration issue of nanocatalysts applied to the 2LiBH4-MgH2 system for the first time. Uniform transition metal (TM) nanoparticles (∼10 nm) wrapped by few layers of carbon are synthesized by pyrolysis of the corresponding metal-organic frameworks (MOFs), and introduced into the 2LiBH4-MgH2 reactive hydride composites (RHCs) by ball milling. The particular features of the carbon-wrapped architecture effectively avoid the agglomeration of the TM nanoparticles during hydrogen storage cycling, and high catalysis is maintained during the subsequent de/rehydrogenation processes. After de/rehydrogenation cycling, FeB, CoB and MgNi3B2 can be formed as the catalytically active components with a particle size of 5-15 nm, which show a homogeneous distribution in the hydride matrix. Among the three catalysts, in situ-formed MgNi3B2 shows the best catalytic efficiency. The incubation period of the Fe/C, Co/C and Ni/C-doped 2LiBH4-MgH2 system between the two dehydrogenation steps was reduced to about 8 h, 4 h and 2 h, respectively, which is about 8 h, 12 h and 14 h shorter than that of the undoped 2LiBH4-MgH2 sample. In addition, the two-step dehydrogenation peak temperatures of the Ni/C-doped 2LiBH4-MgH2 system drop to 323.4 °C and 410.6 °C, meanwhile, the apparent activation energies of dehydrogenated MgH2 and LiBH4 decrease by 58 kJ mol(-1) and 71 kJ mol(-1), respectively. In particular, the cycling hydrogen desorption of the Ni/C-doped 2LiBH4-MgH2 sample exhibits very good stability compared with the undoped sample. The present approach, which ideally addresses the agglomeration of nanoparticles with

  3. Effect of the Sm content on the structure and electrochemical properties of La 1.3 - xSm xCaMg 0.7Ni 9 ( x = 0-0.3) hydrogen storage alloys

    NASA Astrophysics Data System (ADS)

    Tang, Rui; Wei, Xuedong; Liu, Yongning; Zhu, Changchun; Zhu, Jiewu; Yu, Guang

    La 1.3 - xSm xCaMg 0.7Ni 9 (x = 0-0.3) hydrogen storage alloys were prepared by inductive melting and the effect of the Sm content on the structure and electrochemical properties was investigated in the paper. The Sm substitution for La in La 1.3 - xSm xCaMg 0.7Ni 9 (x = 0-0.3) alloys does not change the main phase structure (the rhombohedral PuNi 3-type structure), but leads to a shrinkage of unit cell and a decrease of hydrogen storage capacity. With the increase of the Sm content in the alloys, the maximum discharge capacity of electrode decreases from 400.2 (x = 0) to 346.6 mAh g -1 (x = 0.3), but the high-rate dischargeability and cycling stability is improved. After 100 cycles, the capacity retention rate increases from 75 (x = 0) to 85% (x = 0.3).

  4. Na, Mg, Ni and Cs distribution and speciation after long-term alteration of a simulated nuclear waste glass: A micro-XAS/XRF/XRD and wet chemical study

    NASA Astrophysics Data System (ADS)

    Curti, Enzo; Dähn, Rainer; Farges, François; Vespa, Marika

    2009-04-01

    trioctahedral Mg-clay minerals. Alternative models assuming other elements (Ni, Al, Fe) in addition to Mg in the second shell could not be fitted successfully. Aqueous concentration data were used to calculate the speciation of the leaching solutions. Saturation index (SI) calculations indicate undersaturation with respect to NiCO 3 and NiSO 4·7H 2O, but oversaturation with respect to β-Ni(OH) 2. The latter result is probably due to the omission of Ni borate and Ni silicate complexes in the speciation calculations, for which formation constants are not available. With the help of estimation techniques, we could infer that such complexes would dominate the Ni speciation and consequently reduce the SI below the saturation of β-Ni(OH) 2. The μ-XRF maps show that Cs is uniformly distributed in the MW glass, since no region with high Cs concentration could be detected. The Cs L III-edge μ-XAS spectra were all very similar independently of the degree of alteration, indicating similar coordination environments of Cs in the core regions of the glass as well as in the secondary clays. These spectra largely differ from that measured for pollucite (a potential secondary Cs-phase in altered glasses) implying that the coordination environments of Cs in the MW glass and in pollucite are fundamentally different. The present study shows that μ-XRF and μ-XAS are essential tools in determining the fate and the retention mechanisms of radionuclides released from nuclear waste during aqueous alteration. Our spectroscopic analyses allowed us to exclude formation of specific Ni and Cs secondary solids (e.g. nepouite, β-Ni(OH) 2, pollucite) during the aqueous alteration. Ni and Cs are instead distributed as trace elements in the alteration phases formed by major elements during the leaching process. Our results imply that solid solution and/or adsorption equilibria, rather than pure phase solubility equilibria, are the adequate chemical models to determine Ni and Cs aqueous concentrations in

  5. Controlled precipitation of nesquehonite (MgCO 3·3H 2O) by the reaction of MgCl 2 with (NH 4) 2CO 3

    NASA Astrophysics Data System (ADS)

    Wang, Yong; Li, Zhibao; Demopoulos, George P.

    2008-03-01

    In this study, homogeneous (unseeded) precipitation of nesquehonite (MgCO 3·3H 2O) by the reaction of MgCl 2 with (NH 4) 2CO 3 in supersaturated solutions was investigated. Factors that influence the precipitation of MgCO 3·3H 2O, such as reaction temperature, initial concentration, stirring speed, titration speed, equilibration time, have been studied. SEM images and particle size distribution show that the temperature, initial concentration and titration speed have significant effect on nesquehonite's crystal morphology and particle size. In addition, stirring speed and equilibration time also have some influence on its properties. X-ray powder diffraction (XRD) results show that the obtained crystals compositions are greatly affected by the reaction temperature. With the morphological transformation, their corresponding composition also change from MgCO 3· xH 2O to Mg 5(CO 3) 4(OH) 2·4H 2O in the interval of 288-333 K. With the optimization of operating conditions, the crystals can grow up to a length of about 40 μm and a width of 5 μm, indicating good filtration properties. High-purity nesquehonite obtained in this study was calcined to produce highly pure MgO at 1073 K as shown by XRD results.

  6. Influence of Sn-Mg co-substitution on the microstructural and magnetic characteristics of M-type SrCaLa hexagonal ferrites

    NASA Astrophysics Data System (ADS)

    Yang, Yujie; Wang, Fanhou; Huang, Duohui; Shao, Juxiang; Tang, Jin; Ur Rehman, Khalid Mehmood; Wu, Zhen

    2018-04-01

    Sn-Mg co-substituted M-type SrCaLa hexaferrites Sr0.5Ca0.2La0.3Fe12.0-2x(SnMg)xO19 (0.0 ≤ x ≤ 0.5) have been synthesized by ball milling and calcining. The results of X-ray diffraction show that a single magnetoplumbite phase is exhibited in all the samples and no impurity phase is observed in the structure. Lattice constants (c and a) increase with increasing Sn-Mg content (x) from 0.0 to 0.5. Platelet like structure exhibited by FE-SEM micrographs confirms the hexagonal structure of the synthesized samples. The saturation magnetization (Ms) first increases with increasing SnMg content (x) from 0.0 to 0.1, and then decreases when Sn-Mg content (x) ≥ 0.1. The remanent magnetization (Mr), Mr/Ms ratio, coercivity (Hc), magnetic anisotropy field (Ha) and first anisotropy constant (K1) decrease with increasing Sn-Mg content (x) from 0.0 to 0.5.

  7. Response of CO2 and H2O fluxes of a mountainous tropical rain forest in equatorial Indonesia to El Niño events

    NASA Astrophysics Data System (ADS)

    Olchev, A.; Ibrom, A.; Panferov, O.; Gushchina, D.; Propastin, P.; Kreilein, H.; June, T.; Rauf, A.; Gravenhorst, G.; Knohl, A.

    2015-03-01

    The possible impact of El Niño-Southern Oscillation (ENSO) events on the main components of CO2 and H2O fluxes in a pristine mountainous tropical rainforest growing in Central Sulawesi in Indonesia is described. The fluxes were continuously measured using the eddy covariance method for the period from January 2004 to June 2008. During this period, two episodes of El Niño and one episode of La Niña were observed. All these ENSO episodes had moderate intensity and were of Central Pacific type. The temporal variability analysis of the main meteorological parameters and components of CO2 and H2O exchange showed a very high sensitivity of Evapotranspiration (ET) and Gross Primary Production (GPP) of the tropical rain forest to meteorological variations caused by both El Niño and La Niña episodes. Incoming solar radiation is the main governing factor that is responsible for ET and GPP variability. Ecosystem Respiration (RE) dynamics depend mainly on the air temperature changes and are almost insensitive to ENSO. Changes of precipitation due to moderate ENSO events did not cause any notable effect on ET and GPP, mainly because of sufficient soil moisture conditions even in periods of anomalous reduction of precipitation in the region.

  8. Structurally characterized 1,1,3,3-tetramethylguanidine solvated magnesium aryloxide complexes: [Mg(mu-OEt)(DBP)(H-TMG)]2, [Mg(mu-OBc)(DBP)(H-TMG)]2, [Mg(mu-TMBA)(DBP)(H-TMG)]2, [Mg(mu-DPP)(DBP)(H-TMG)]2, [Mg(BMP)2(H-TMG)2], [Mg(O-2,6-Ph2C6H3)2 (H-TMG)2].

    PubMed

    Monegan, Jessie D; Bunge, Scott D

    2009-04-06

    The synthesis and structural characterization of several 1,1,3,3-tetramethylguanidine (H-TMG) solvated magnesium aryloxide complexes are reported. Bu(2)Mg was successfully reacted with H-TMG, HOC(6)H(3)(CMe(3))(2)-2,6 (H-DBP), and either ethanol, a carboxylic acid, or diphenyl phosphate in a 1:1 ratio to yield the corresponding [Mg(mu-L)(DBP)(H-TMG)](2) where L = OCH(2)CH(3) (OEt, 1), O(2)CC(CH(3))(3) (OBc, 2), O(2)C(C(6)H(2)-2,4,6-(CH(3))(3)) (TMBA, 3), or O(2)P(OC(6)H(5))(2) (DPP, 4). Bu(2)Mg was also reacted with two equivalents of H-TMG and HOC(6)H(3)(CMe(3))-2-(CH(3))-6 (BMP) or HO-2,6-Ph(2)C(6)H(3) to yield [Mg(BMP)(2)(H-TMG)(2)] (5) and [Mg(O-2,6-Ph(2)C(6)H(3))(2)(H-TMG)(2)] (6). Compounds 1-6 were characterized by single-crystal X-ray diffraction. Polymerization of l- and rac-lactide with 1 was found to generate polylactide (PLA). A discussion concerning the relevance of compounds 2 - 4 to the structure of Mg-activated phosphatase enzymes is also provided. The bulk powders for all complexes were found to be in agreement with the crystal structures based on elemental analyses, FT-IR spectroscopy, and (1)H, (13)C and (31)P NMR studies.

  9. Structural and optical properties of Mg2 Ni Hx switchable mirrors upon hydrogen loading

    NASA Astrophysics Data System (ADS)

    Lohstroh, W.; Westerwaal, R. J.; van Mechelen, J. L. M.; Chacon, C.; Johansson, E.; Dam, B.; Griessen, R.

    2004-10-01

    The structural, thermodynamic and optical properties of Mg2Ni thin films covered with Pd are investigated upon exposure to hydrogen. Similar to bulk, thin films of metallic Mg2Ni take up 4 hydrogen per formula unit and semiconducting transparent Mg2NiH4-δ is formed. The dielectric function γ˜ of Mg2Ni and fully loaded Mg2NiH4-δ is determined from reflection and transmission measurements using a Drude-Lorentz parametrization. Besides the two “normal” optical states of a switchable mirror—metallic reflecting and semiconducting transparent— Mg2NiHx exhibit a third “black” state at intermediate hydrogen concentrations with low reflection and essentially zero transmission. This state originates from a subtle interplay of the optical properties of the constituent materials and a self-organized double layering of the film during loading. Mg2NiH4-δ preferentially nucleates at the film/substrate interface and not—as intuitively expected—close to the catalytic Pd capping layer. Using γ˜Mg2Ni and γ˜Mg2NiH4 and this loading sequence, the optical response at all hydrogen concentrations can be described quantitatively. The uncommon hydrogen loading sequence is confirmed by x-ray diffraction and hydrogen profiling using the resonant nuclear reaction H1(N15,αγ)C12 . Pressure-composition isotherms suggest that the formation of Mg2NiH4-δ at the film/substrate interface is mainly due to locally enhanced kinetics.

  10. Magnetism and phase transitions in LaCoO3

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Belanger, David P; Durand, Alice M; Booth, C

    2013-01-01

    Neutron scattering and magnetometry measurements have been used to study phase transitions in LaCoO3 (LCO). For H 100 Oe, evidence for a ferromagnetic (FM) transition is observed at Tc 87 K. For 1 kOe H 60 kOe, no transition is apparent. For all H, Curie Weiss analysis shows predominantly antiferromagnetic (AFM) interactions for T > Tc, but the lack of long-range AFM order indicates magnetic frustration. We argue that the weak ferromagnetism in bulk LCO is induced by lattice strain, as is the case with thin films and nanoparticles. The lattice strain is present at the bulk surfaces and atmore » the interfaces between the LCO and a trace cobalt oxide phase. The ferromagnetic ordering in the LCO bulk is strongly affected by the Co O Co angle ( ), in agreement with recent band calculations which predict that ferromagnetic long-range order can only take place above a critical value, C. Consistent with recent thin film estimations, we find C D 162:8. For > C, we observe power-law behavior in the structural parameters. decreases with T until the critical temperature, To 37 K; below To the rate of change becomes very small. For T < To, FM order appears to be confined to regions close to the surfaces, likely due to the lattice strain keeping the local Co O Co angle above C.« less

  11. Properties of highly (100) oriented Pb(Mg1/3,Nb2/3)O3-PbTiO3 films on LaNiO3 bottom electrodes

    NASA Astrophysics Data System (ADS)

    Li, Y. W.; Hu, Z. G.; Yue, F. Y.; Yang, G. Y.; Shi, W. Z.; Meng, X. J.; Sun, J. L.; Chu, J. H.

    2007-12-01

    The 70%Pb(Mg1/3,Nb2/3)O3-30%PbTiO3 (PMNT) films have been fabricated on LaNiO3 (LNO) coated silicon substrate. The conductive LNO films act as a seed layer for the growth of PMNT films, which depresses the formation of pyrochlore phase and induces the high (100) preferred orientation of perovskite PMNT films. Compared with the PMNT films grown on platinum bottom electrode, the ferroelectric properties of PMNT films grown on LNO are enhanced. The frequency dependence of complex permittivity from PMNT films on LNO is the conjunct result of polarization relaxation and movement of oxygen vacancy, which can be fitted by the function containing Debye and universal dielectric response models, respectively.

  12. Investigation of collision-induced dissociation products and structures of gas-phase [ M·GlyGlyHis-H]+ ( M = Fe, Ni, Cu, and Zn) complexes.

    PubMed

    Gannamani, Bharathi; Shin, Joong-Won

    2017-02-01

    Collision-induced dissociation is carried out for electrosprayed [Fe·GlyGlyHis-H] + , [Ni·GlyGlyHis-H] + , [Cu·GlyGlyHis-H] + , and [Zn·GlyGlyHis-H] + complexes. [Fe·GlyGlyHis-H] + , [Ni·GlyGlyHis-H] + , and [Zn·GlyGlyHis-H] + yield metal-bound peptide sequence ions and dehydrated ions as primary products, whereas [Cu·GlyGlyHis-H] + generates a more extensive series of metal-bound sequence ions and a product arising from the unusual loss of a formaldehyde moiety; dehydration is significantly suppressed for this complex. Density functional theory calculations show that the copper ion-deprotonated peptide binding energy is substantially higher than those in other complexes, suggesting that there is a correlation between ion-ligand binding energy and their fragmentation behavior.

  13. Terpyridine complexes of first row transition metals and electrochemical reduction of CO₂ to CO.

    PubMed

    Elgrishi, Noémie; Chambers, Matthew B; Artero, Vincent; Fontecave, Marc

    2014-07-21

    Homoleptic terpyridine complexes of first row transition metals are evaluated as catalysts for the electrocatalytic reduction of CO2. Ni and Co-based catalytic systems are shown to reduce CO2 to CO under the conditions tested. The Ni complex was found to exhibit selectivity for CO2 over proton reduction while the Co-based system generates mixtures of CO and H2 with CO : H2 ratios being tuneable through variation of the applied potential.

  14. Photodissociation spectroscopy of the Mg + -CO2 complex and its isotopic analogs

    NASA Astrophysics Data System (ADS)

    Yeh, C. S.; Willey, K. F.; Robbins, D. L.; Pilgrim, J. S.; Duncan, M. A.

    1993-02-01

    Mg+-CO2 ion-molecule cluster complexes are produced by laser vaporization in a pulsed nozzle cluster source. The vibronic spectroscopy in these complexes is studied with mass-selected photodissociation spectroscopy in a reflectron time-of-flight mass spectrometer. Two excited electronic states are observed (2) 2Σ+ and 2Π. The 2Π state has a vibrational progression in the metal-CO2 stretching mode (ωe'=381.8 cm-1). The complexes are linear (Mg+-OCO) and are bound by the charge-quadrupole interaction. The dissociation energy (D0`) is 14.7 kcal/mol. Corresponding spectra are measured for each of the 24, 25, and 26 isotopes of magnesium. These results are compared to theoretical predictions made by Bauschlicher and co-workers.

  15. Low-temperature solvothermal approach to the synthesis of La4Ni3O8 by topotactic oxygen deintercalation.

    PubMed

    Blakely, Colin K; Bruno, Shaun R; Poltavets, Viktor V

    2011-07-18

    A chimie douce solvothermal reduction method is proposed for topotactic oxygen deintercalation of complex metal oxides. Four different reduction techniques were employed to qualitatively identify the relative reduction activity of each including reduction with H(2) and NaH, solution-based reduction using metal hydrides at ambient pressure, and reduction under solvothermal conditions. The reduction of the Ruddlesden-Popper nickelate La(4)Ni(3)O(10) was used as a test case to prove the validity of the method. The completely reduced phase La(4)Ni(3)O(8) was produced via the solvothermal technique at 150 °C--a lower temperature than by other more conventional solid state oxygen deintercalation methods.

  16. Porous framework of T{sub 2}[Fe(CN){sub 6}].xH{sub 2}O with T=Co, Ni, Cu, Zn, and H{sub 2} storage

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Avila, M.; Reguera, L.; Rodriguez-Hernandez, J.

    2008-11-15

    The materials under study were prepared from aqueous solutions of ferrocyanic acid and salts of the involved transition metals and their crystal structure solved and refined from X-ray powder diffraction data. Complementary information from thermogravimetric, infrared and Moessbauer data was also used for the structural study. Three different crystal structures were found: hexagonal (P-3) for Zn with the zinc atom coordinated to three N ends of CN groups plus a water molecule, cubic (Pm-3m) for Ni and Cu, and monoclinic (P2{sub 1}/m) for Co. For Ni and Cu the obtained solids have an open channel framework related to 50% ofmore » vacancies for the building unit, [Fe(CN){sub 6}]. In the as-synthesized material the framework free volume is occupied by coordinated and hydrogen-bonded water molecules. These of hexacyanoferrates (II) have received certain attention as prototype of materials for the hydrogen storage. In the anhydrous phase of Ni and Cu, 50% of the metal (T) coordination sites, located at the cavities surface, will be available to interact with the hydrogen molecule. However, when the crystal waters are removed the porous frameworks collapse as it is suggested by H{sub 2} and CO{sub 2} adsorption data. For Co, a structure of stacked layers was found where the cobalt atoms have both tetrahedral and octahedral coordination. The layers remain together through a network of hydrogen-bonding interactions between coordinated and weakly bonded water molecules. No H{sub 2} adsorption was observed in the anhydrous phase of Co. For Zn, the porous framework remains stable on the water removal but with a system of narrow channels and a small available volume, also inaccessible to H{sub 2}. - Graphical abstract: Structure of stacked layers for CO{sub 2}[Fe(CN){sub 6}].xH{sub 2}O.« less

  17. The Ni-rich part of the Al–Ge–Ni phase diagram

    PubMed Central

    Jandl, Isabella; Reichmann, Thomas L.; Richter, Klaus W.

    2013-01-01

    The Ni-rich part of the ternary system Al–Ge–Ni (xNi > 50 at.%) was investigated by means of optical microscopy, powder X-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM). The two isothermal sections at 550 °C and 700 °C were determined. Within these two sections a new ternary phase, designated as τ4, AlyGe9−yNi13±x (hP66, Ga3Ge6Ni13-type) was detected and investigated by single crystal X-ray diffraction. Another ternary low temperature phase, τ5, was found only in the isothermal section at 550 °C around the composition AlGeNi4. This compound was found to crystallise in the Co2Si type structure (oP12, Pnma). The structure was identified by Rietveld refinement of powder data. The NiAs type (B8) phase based on binary Ge3Ni5 revealed an extended solid solubility of Al and the two isotypic compounds AlNi3 and GeNi3 form a complete solid solution. Based on DTA results, six vertical sections at 55, 60, 70, 75 and 80 at.% Ni and at a constant Al:Ni ratio of 1:3 were constructed. Furthermore, the liquidus surface projection and the reaction scheme (Scheil diagram) were completed by combining our results with previous results from the Ni-poor part of the phase diagram. Six invariant ternary reactions were identified in the Ni-rich part of the system. PMID:27087754

  18. Electronic Structure and Reactivity of TM-Doped La1-xSrxCoO3 (TM = Ni, Fe) Catalysts

    NASA Astrophysics Data System (ADS)

    Grice, S. C.; Flavell, W. R.; Thomas, A. G.; Warren, S.; Marr, P. G.; Jewitt, D. E.; Khan, N.; Dunwoody, P. M.; Jones, S. A.

    The catalytic properties of LaCoO3 in the oxidation of organic molecules in aqueous solution are explored as a function of doping with both Sr substitution for La and Fe and Ni substitution for Co. VUV photoemission is used to explore the surface reactivity of the ceramic catalysts in aqueous solution, using H2O as a probe molecule. These measurements are complemented by EXAFS and XANES measurements designed to probe the local defect structure and by GC measurements of catalytic activity in the aqueous epoxidation of crotyl alcohol. We relate the observed catalytic activity to the defect structure of the doped materials. In Ni-doped materials, oxygen vacancies appear to be the predominant defect, whereas in Fe-doped samples, electron holes are stabilised on Fe, leading to very different behaviour in oxidation. The surface reactivity to water is also influenced by the TM d electron count, with water binding more strongly to Fe-doped materials than to those containing Ni. The influence of these factors on the rate of the unwanted hydrogen peroxide decomposition reaction and hence on activity in epoxidation is discussed.

  19. DNA cleavage, antibacterial, antifungal and anthelmintic studies of Co(II), Ni(II) and Cu(II) complexes of coumarin Schiff bases: Synthesis and spectral approach

    NASA Astrophysics Data System (ADS)

    Patil, Sangamesh A.; Prabhakara, Chetan T.; Halasangi, Bhimashankar M.; Toragalmath, Shivakumar S.; Badami, Prema S.

    2015-02-01

    The metal complexes of Co(II), Ni(II) and Cu(II) have been synthesized from 6-formyl-7,8-dihydroxy-4-methylcoumarin with o-toluidine/3-aminobenzotrifluoride. The synthesized Schiff bases and their metal complexes were structurally characterized based on IR, 1H NMR, 13C NMR, UV-visible, ESR, magnetic, thermal, fluorescence, mass and ESI-MS studies. The molar conductance values indicate that complexes are non-electrolytic in nature. Elemental analysis reveals ML2·2H2O [M = Co(II), Ni(II) and Cu(II)] stoichiometry, where 'L' stands for a singly deprotonated ligand. The presence of co-ordinated water molecules were confirmed by thermal studies. The spectroscopic studies suggest the octahedral geometry. Redox behavior of the complexes were confirmed by cyclic voltammetry. All the synthesized compounds were screened for their antibacterial (Escherichia coli, Pseudomonas auregenosa, klebsiella, Proteus, Staphylococcus aureus and salmonella) antifungal (Candida, Aspergillus niger and Rhizopus), anthelmintic (Pheretima posthuma) and DNA cleavage (Calf Thymus DNA) activity.

  20. Microstructure, thermal shock resistance and thermal emissivity of plasma sprayed LaMAl11O19 (M = Mg, Fe) coatings for metallic thermal protection systems

    NASA Astrophysics Data System (ADS)

    Liu, Hong-Zhi; Ouyang, Jia-Hu; Liu, Zhan-Guo; Wang, Ya-Ming

    2013-04-01

    LaMAl11O19 (M = Mg, Fe) ceramic coatings were plasma-sprayed on nickel-based superalloy with NiCoCrAlYTa as the bond coat. The microstructure, thermal shock resistance and thermal emissivity of these two ceramic coatings were investigated. LaMAl11O19 coatings exhibit a characteristic of stacked lamellae, and consist mainly of a magnetoplumbite-type hexaaluminate phase and an amorphous phase. During thermal cycling, the amorphous phase disappears and a LaAlO3 phase is formed at temperatures of both 1000 and 1200 °C. The thermal cycling numbers of LaMgAl11O19 coating are 102 at 1000 °C and 42 at 1200 °C; LaFeAl11O19 has a thermal cycling lifetime of 87 at 1000 °C and 30 at 1200 °C, respectively. Normal spectral emissivity of nickel-based superalloy is about 0.2 over the whole wavelength range of 3-14 μm. However, the emissivity of LaFeAl11O19 coating is about 0.7 at short wavelengths and above 0.9 in the wavelength range of 7-14 μm.

  1. 2-(hydroxymethyl)-1H-benzo[d]imidazole-5-carboxylic acid as linker for Co(II)/Ni(II)/Cu(II) coordination polymers: Synthesis, structures and properties

    NASA Astrophysics Data System (ADS)

    Wang, Duo-Zhi; Wang, Xin-Fang; Du, Jia-Qiang; Dong, Jun-Liang; Xie, Fei

    2018-02-01

    We report the synthesis and characterization of five transition metal coordination polymers (CPs) based on M(II) (M: Co, Ni and Cu), 2-(hydroxymethyl)-1H-benzo[d]imidazole-5-carboxylic acid (H2L) ligand. They are formulated as {[Co2(HL)2(H2O)3(SO4)]·H2O}n (1), {[Co2(HL)2(H2O)2]·SiF6}n (2), {[Ni2(HL)2(H2O)3(SO4)]·2H2O}n (3), {[Ni2(HL)2(H2O)4]·H2O·SiF6}n (4), {[Cu2(HL)2(H2O)2]·SiF6}n (5). The complexes 1-5 structure were characterized by single-crystal X-ray diffraction, elemental analyses, infrared spectroscopy (IR), powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). Complexes 1-5 are two-dimensional (2D) network type coordination polymers that 1-3, 5 crystallize in monoclinic system within the centrosymmetric space group P2(1)/c, and 4 in triclinic system P-1 space group, they show the same coordination modes (κ1-κ1)-(κ1)-(κ1)-μ3 in coordination polymers. Complexes 1 and 3 expand to three-dimensional framework by means of hydrogen bond interactions, and can be rationalized to be three-connected {63} topological network, while 2, 4, 5 exhibit the topological network with a four-connected {44·62} topological sql network. The luminescent properties (for complexes 1, 2) and UV diffuse reflectance (for complexes 1-5) in the solid state at room temperature were also investigated and discussed. Complexes 1-5 act as effective heterogeneous catalysts, under mild conditions, for the homocoupling reaction of 4-substituted aryl iodides bearing electron-donating groups (-CH3, -OCH3).

  2. Comparative study on the structure and electrochemical hydriding properties of MgTi, Mg 0.5Ni 0.5Ti and MgTi 0.5Ni 0.5 alloys prepared by high energy ball milling

    NASA Astrophysics Data System (ADS)

    Rousselot, Steeve; Guay, Daniel; Roué, Lionel

    MgTi, Mg 0.5Ni 0.5Ti and MgTi 0.5Ni 0.5 alloys doped with 10 wt.% Pd were prepared by high energy ball milling and evaluated as hydrogen storage electrodes for Ni-MH batteries. X-ray diffraction analyses indicated that the Mg 0.5Ni 0.5Ti and MgTi 0.5Ni 0.5 alloys could be monophased or composed of a nanoscale mixture of MgTi + NiTi and MgTi + MgNi phases, respectively. Their hydrogen storage characteristics were investigated electrochemically in KOH electrolyte. No activation step was observed during the cycling of the Mg-Ti-Ni electrodes in contrast to that observed with the MgTi electrode. The highest hydrogen discharge capacity was obtained with the MgTi 0.5Ni 0.5 electrode (536 mAh g -1) compared to 401 and 475 mAh g -1 for the Mg 0.5Ni 0.5Ti and MgTi electrodes, respectively. The ternary Mg-Ti-Ni alloys showed a better cycle life with an average capacity decay rate per cycle lower than 1.5% compared to ∼7% for the binary MgTi electrode. The Mg-Ni-Ti electrodes also displayed a much higher discharge rate capability than the binary MgTi electrode, especially with the Mg 0.5Ni 0.5Ti electrode. The origin of this was established on the basis of the anodic polarization curves, where a substantial decrease of the concentration overpotential (reflecting a higher hydrogen diffusivity) was observed for the Mg 0.5Ni 0.5Ti electrode.

  3. Ni-MH spent batteries: a raw material to produce Ni-Co alloys.

    PubMed

    Lupi, Carla; Pilone, Daniela

    2002-01-01

    Ni-MH spent batteries are heterogeneous and complex materials, so any kind of metallurgical recovery process needs a mechanical pre-treatment at least to separate irony materials and recyclable plastic materials (like ABS) respectively, in order to get additional profit from this saleable scrap, as well as minimize waste arising from the braking separation process. Pyrometallurgical processing is not suitable to treat Ni-MH batteries mainly because of Rare Earths losses in the slag. On the other hand, the hydrometallurgical method, that offers better opportunities in terms of recovery yield and higher purity of Ni, Co, and RE, requires several process steps as shown in technical literature. The main problems during leach liquor purification are the removal of elements such as Mn, Zn, Cd, dissolved during the leaching step, and the separation of Ni from Co. In the present work, the latter problem is overcome by co-deposition of a Ni-35/40%w Co alloy of good quality. The experiments carried out in a laboratory scale pilot-plant show that a current efficiency higher than 91% can be reached in long duration electrowinning tests performed at 50 degrees C and 4.3 catholyte pH.

  4. Phase purity of NiCo2O4, a catalyst candidate for electrolysis of water

    NASA Technical Reports Server (NTRS)

    Singer, J.; Fielder, W. L.; Garlick, R. G.; Negas, T.

    1987-01-01

    NiCo2O4 is shown to be difficult to obtain as a pure phase, and may never have been so obtained. High resolution x-ray diffractometry is required for its precise characterization. Film XRD is not likely to show the asymmetry in the spinel diffraction lines, caused by poorly crystallized NiO, as seen in diffractometer traces. The Co3O4 which is expected to accompany NiO as an impurity in NiCo2O4 syntheses has the same diffraction pattern as the binary oxide. Firings of the co-precipitated hydroxides at 300, 350, and 400 C, including one in pure O2, failed to produce single phase cobaltate. Scanning electron microscopy showed all the sintered products to range over several orders of magnitude in agglomerate/particle size. Surface areas by BET were all in the range 40 to 110 m sq/g, equivalent to particles of 200 to 100 Angstrom diameter. The spinel diffraction line breadths were compatible with those approximate dimensions.

  5. Releasing metal catalysts via phase transition: (NiO)0.05-(SrTi0.8Nb0.2O3)0.95 as a redox stable anode material for solid oxide fuel cells.

    PubMed

    Xiao, Guoliang; Wang, Siwei; Lin, Ye; Zhang, Yanxiang; An, Ke; Chen, Fanglin

    2014-11-26

    Donor-doped perovskite-type SrTiO3 experiences stoichiometric changes at high temperatures in different Po2 involving the formation of Sr or Ti-rich impurities. NiO is incorporated into the stoichiometric strontium titanate, SrTi0.8Nb0.2O3-δ (STN), to form an A-site deficient perovskite material, (NiO)0.05-(SrTi0.8Nb0.2O3)0.95 (Ni-STN), for balancing the phase transition. Metallic Ni nanoparticles can be released upon reduction instead of forming undesired secondary phases. This material design introduces a simple catalytic modification method with good compositional control of the ceramic backbones, by which transport property and durability of solid oxide fuel cell anodes are largely determined. Using Ni-STN as anodes for solid oxide fuel cells, enhanced catalytic activity and remarkable stability in redox cycling have been achieved. Electrolyte-supported cells with the cell configuration of Ni-STN-SDC anode, La0.8Sr0.2Ga0.87Mg0.13O3 (LSGM) electrolyte, and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) cathode produce peak power densities of 612, 794, and 922 mW cm(-2) at 800, 850, and 900 °C, respectively, using H2 as the fuel and air as the oxidant. Minor degradation in fuel cell performance resulted from redox cycling can be recovered upon operating the fuel cells in H2. Such property makes Ni-STN a promising regenerative anode candidate for solid oxide fuel cells.

  6. Phase transition in lithium garnet oxide ionic conductors Li7La3Zr2O12: The role of Ta substitution and H2O/CO2 exposure

    NASA Astrophysics Data System (ADS)

    Wang, Yuxing; Lai, Wei

    2015-02-01

    High Li-content lithium garnet oxides are promising solid electrolyte materials for lithium batteries. Being the highest Li-content lithium garnet oxides, Li7La3Zr2O12 has been reported to crystallize in either the tetragonal or cubic phase with no consensus on the exact conditions under which these two phases are formed, which may be due to unintentional Al contamination and air exposure. In this work, the effects of Ta substitution and H2O/CO2 exposure have been studied under Al-contamination free conditions with minimal air exposure. We showed that 1) the Ta-substitution induced phase transition occurred through a two-phase mechanism and a minimum 0.6 mol of Ta substitution to Zr is needed to stabilize the cubic phase; 2) H2O and CO2 can individually induce the tetragonal-cubic phase transition in Li7La3Zr2O12 through proton exchange and Li extraction, respectively, which can have great influence on the transport properties of Li7La3Zr2O12.

  7. Synthesis, spectroscopic and DNA binding ability of CoII, NiII, CuII and ZnII complexes of Schiff base ligand (E)-1-(((1H-benzo[d]imidazol-2-yl)methylimino)methyl)naphthalen-2-ol. X-ray crystal structure determination of cobalt (II) complex.

    PubMed

    Yarkandi, Naeema H; El-Ghamry, Hoda A; Gaber, Mohamed

    2017-06-01

    A novel Schiff base ligand, (E)-1-(((1H-benzo[d]imidazol-2-yl)methylimino)methyl)naphthalen-2-ol (HL), has been designed and synthesized in addition to its metal chelates [Co(L) 2 ]·l2H 2 O, [Ni(L)Cl·(H 2 O) 2 ].5H 2 O, [Cu(L)Cl] and [Zn(L)(CH 3 COO)]. The structures of the isolated compounds have been confirmed and identified by means of different spectral and physicochemical techniques including CHN analysis, 1 H & 13 C NMR, mass spectral analysis, molar conductivity measurement, UV-Vis, infrared, magnetic moment in addition to TGA technique. The infrared spectral results ascertained that the ligand acts as monobasic tridentate binding to the metal centers via deprotonated hydroxyl oxygen, azomethine and imidazole nitrogen atoms. The UV-Vis, magnetic susceptibility and molar conductivity data implied octahedral geometry for Co(II) & Ni(II) complexes, tetrahedral for Zn(II) complex and square planar for Cu(II) complex. X-ray structural analysis of Co(II) complex 1 has been reported and discussed. Moreover, the type of interaction between the ligand & its complexes towards salmon sperm DNA (SS-DNA) has been examined by the measurement of absorption spectra and viscosity which confirmed that the ligand and its complexes interact with DNA via intercalation interaction as concluded from the values of binding constants (K b ). Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Hierarchical CoP/Ni 5 P 4 /CoP microsheet arrays as a robust pH-universal electrocatalyst for efficient hydrogen generation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mishra, Ishwar Kumar; Zhou, Haiqing; Sun, Jingying

    Exceptional Pt-like electrocatalytic activity was achieved in a sandwich-like catalyst of CoP/Ni 5 P 4 /CoP microsheet arrays for pH-universal hydrogen evolution through simply wrapping Ni 5 P 4 nanosheet arrays in CoP nanoparticles.

  9. Hierarchical CoP/Ni 5 P 4 /CoP microsheet arrays as a robust pH-universal electrocatalyst for efficient hydrogen generation

    DOE PAGES

    Mishra, Ishwar Kumar; Zhou, Haiqing; Sun, Jingying; ...

    2018-01-01

    Exceptional Pt-like electrocatalytic activity was achieved in a sandwich-like catalyst of CoP/Ni 5 P 4 /CoP microsheet arrays for pH-universal hydrogen evolution through simply wrapping Ni 5 P 4 nanosheet arrays in CoP nanoparticles.

  10. Monometallic Ni(0) and Heterobimetallic Ni(0) /Au(I) Complexes of Tripodal Phosphine Ligands: Characterization in Solution and in the Solid State and Catalysis.

    PubMed

    Cluff, Kyle J; Bhuvanesh, Nattamai; Blümel, Janet

    2015-07-06

    The tridentate chelate nickel complexes [(CO)Ni{(PPh2 CH2 )3 CMe}] (2), [(CO)Ni{(PPh2 CH2 CH2 )3 SiMe}] (6), and [Ph3 PNi{(PPh2 CH2 CH2 )3 SiMe}] (7), as well as the bidentate complex [(CO)2 Ni{(PPh2 CH2 )2 CMeCH2 PPh2 }] (3) and the heterobimetallic complex [(CO)2 Ni{(PPh2 CH2 )2 CMeCH2 Ph2 PAuCl}] (4), have been synthesized and fully characterized in solution. All (1) H and (13) C NMR signal assignments are based on 2D-NMR methods. Single crystal X-ray structures have been obtained for all complexes. Their (31) P CP/MAS (cross polarization with magic angle spinning) NMR spectra have been recorded and the isotropic lines identified. The signals were assigned with the help of their chemical shift anisotropy (CSA) data. All complexes have been tested regarding their catalytic activity for the cyclotrimerization of phenylacetylene. Whereas complexes 2-4 display low catalytic activity, complex 7 leads to quantitative conversion of the substrate within four hours and is highly selective throughout the catalytic reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Structure and magnetic properties of mechanically alloyed Co and Co-Ni

    NASA Astrophysics Data System (ADS)

    Guessasma, S.; Fenineche, N.

    The influence of milling process on magnetic properties of Co and Co-Ni materials is studied. Coercivity, squareness ratio and crystallite size of mechanically alloyed Co-Ni material were related to milling time. For Co material, coercivity, cubic phase ratio and crystallite size were related to milling energy considering the vial and plateau rotation velocities. An artificial neural network (ANN) combining the parameters for both materials is used to predict magnetic and structure results versus milling conditions. Predicted results showed that milling energy is mostly dependent on the ratio vial to plateau rotation velocities and that milling times larger than 40 h do not add significant change to both structure and magnetic responses. Magnetic parameters were correlated to crystallite size and the D 6 law was only valid for small sizes.

  12. Effect of modification methods on the surface properties and n-butane isomerization performance of La/Ni-promoted SO42-/ZrO2-Al2O3

    NASA Astrophysics Data System (ADS)

    Wang, Pengzhao; Zhang, Jiaoyu; Han, Chaoyi; Yang, Chaohe; Li, Chunyi

    2016-08-01

    The La and/or Ni was introduced into alumina-promoted sulfated zirconia by impregnation and co-precipitation to improve the catalytic property of n-butane isomerization. Catalysts characterization shows that the addition of La/Ni has a remarkable influence on the surface and textual properties depending on the modification method. The impregnation of La/Ni facilitates the transformation of a small amount of tetragonal zirconia into monoclinic phase, while the co-precipitation improves the stability of tetragonal ZrO2. H2-TPR indicates that the addition of La/Ni changes the interaction between SO42- and supports, which affects the acidity on the surface. Specifically, the Lewis acidity is significantly enhanced by either modification method. The co-precipitation reserves almost all of the Brønsted acid sites, while the impregnation causes a remarkable decrease of Brønsted acid sites. Reaction results demonstrate that the co-precipitation exhibits a significant advantage over impregnation that the higher conversion of n-butane and selectivity to isobutane are obtained on the catalyst prepared by co-precipitation. The increase of catalytic activity is ascribed to the accelerated activation rate of n-butane molecules by hydride subtraction on the Lewis acid sites at higher reaction temperature. Furthermore, the addition of La/Ni improves the selectivity to isobutane by inhibiting the bimolecular reaction.

  13. Plasma-Sprayed High Entropy Alloys: Microstructure and Properties of AlCoCrFeNi and MnCoCrFeNi

    NASA Astrophysics Data System (ADS)

    Ang, Andrew Siao Ming; Berndt, Christopher C.; Sesso, Mitchell L.; Anupam, Ameey; S, Praveen; Kottada, Ravi Sankar; Murty, B. S.

    2015-02-01

    High entropy alloys (HEAs) represent a new class of materials that present novel phase structures and properties. Apart from bulk material consolidation methods such as casting and sintering, HEAs can also be deposited as a surface coating. In this work, thermal sprayed HEA coatings are investigated that may be used as an alternative bond coat material for a thermal barrier coating system. Nanostructured HEAs that were based on AlCoCrFeNi and MnCoCrFeNi were prepared by ball milling and then plasma sprayed. Splat studies were assessed to optimise the appropriate thermal spray parameters and spray deposits were prepared. After mechanical alloying, aluminum-based and manganese-based HEA powders revealed contrary prominences of BCC and FCC phases in their X-ray diffraction patterns. However, FCC phase was observed as the major phase present in both of the plasma-sprayed AlCoCrFeNi and MnCoCrFeNi coatings. There were also minor oxide peaks detected, which can be attributed to the high temperature processing. The measured porosity levels for AlCoCrFeNi and MnCoCrFeNi coatings were 9.5 ± 2.3 and 7.4 ± 1.3 pct, respectively. Three distinct phase contrasts, dark gray, light gray and white, were observed in the SEM images, with the white regions corresponding to retained multicomponent HEAs. The Vickers hardness (HV0.3kgf) was 4.13 ± 0.43 and 4.42 ± 0.60 GPa for AlCoCrFeNi and MnCoCrFeNi, respectively. Both type of HEAs coatings exhibited anisotropic mechanical behavior due to their lamellar, composite-type microstructure.

  14. Self-templated formation of uniform NiCo2O4 hollow spheres with complex interior structures for lithium-ion batteries and supercapacitors.

    PubMed

    Shen, Laifa; Yu, Le; Yu, Xin-Yao; Zhang, Xiaogang; Lou, Xiong Wen David

    2015-02-02

    Despite the significant advancement in preparing metal oxide hollow structures, most approaches rely on template-based multistep procedures for tailoring the interior structure. In this work, we develop a new generally applicable strategy toward the synthesis of mixed-metal-oxide complex hollow spheres. Starting with metal glycerate solid spheres, we show that subsequent thermal annealing in air leads to the formation of complex hollow spheres of the resulting metal oxide. We demonstrate the concept by synthesizing highly uniform NiCo2O4 hollow spheres with a complex interior structure. With the small primary building nanoparticles, high structural integrity, complex interior architectures, and enlarged surface area, these unique NiCo2O4 hollow spheres exhibit superior electrochemical performances as advanced electrode materials for both lithium-ion batteries and supercapacitors. This approach can be an efficient self-templated strategy for the preparation of mixed-metal-oxide hollow spheres with complex interior structures and functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Free metal ion depletion by "Good's" buffers. III. N-(2-acetamido)iminodiacetic acid, 2:1 complexes with zinc(II), cobalt(II), nickel(II), and copper(II); amide deprotonation by Zn(II), Co(II), and Cu(II).

    PubMed

    Lance, E A; Rhodes, C W; Nakon, R

    1983-09-01

    Potentiometric, visible, infrared, electron spin, and nuclear magnetic resonance studies of the complexation of N-(2-acetamido)iminodiacetic acid (H2ADA) by Ca(II), Mg(II), Mn(II), Zn(II), Co(II), Ni(II), and Cu(II) are reported. Ca(II) and Mg(II) were found not to form 2:1 ADA2- to M(II) complexes, while Mn(II), Cu(II), Ni(II), Zn(II), and Co(II) did form 2:1 metal chelates at or below physiological pH values. Co(II) and Zn(II), but not Cu(II), were found to induce stepwise deprotonation of the amide groups to form [M(H-1ADA)4-(2)]. Formation (affinity) constants for the various metal complexes are reported, and the probable structures of the various metal chelates in solution are discussed on the basis of various spectral data.

  16. Laser photoelectron spectroscopy of MnH - 2, FeH - 2, CoH - 2, and NiH - 2: Determination of the electron affinities for the metal dihydrides

    NASA Astrophysics Data System (ADS)

    Miller, Amy E. S.; Feigerle, C. S.; Lineberger, W. C.

    1986-04-01

    The laser photoelectron spectra of MnH-2, FeH-2, CoH-2, and NiH-2 and the analogous deuterides are reported. Lack of vibrational structure in the spectra suggests that all of the dihydrides and their negative ions have linear geometries, and that the transitions observed in the spectra are due to the loss of nonbonding d electrons. The electron affinities for the metal dihydrides are determined to be 0.444±0.016 eV for MnH2, 1.049±0.014 eV for FeH2, 1.450±0.014 eV for CoH2, and 1.934±0.008 eV for NiH2. Electronic excitation energies are provided for excited states of FeH2, CoH2, and NiH2. Electron affinities and electronic excitation energies for the dideuterides are also reported. A limit on the electron affinity of CrH2 of ≥2.5 eV is determined. The electron affinities of the dihydrides directly correlate with the electron affinities of the high-spin states of the monohydrides, and with the electron affinities of the metal atoms. These results are in agreement with a qualitative model developed for bonding in the monohydrides.

  17. Effect of Co on Discontinuous Precipitation Transformation with TCP Phase in Ni-based Alloy Containing Re

    NASA Astrophysics Data System (ADS)

    Shi, Qianying; An, Ning; Huo, Jiajie; Zheng, Yunrong; Feng, Qiang

    2017-05-01

    The effect of Co on discontinuous precipitation (DP) transformation involving the formation of topologically close-packed (TCP) phase was investigated in three Ni-Cr-Re model alloys containing different levels of Co. One typical TCP phase, σ, was generated within DP cellular colonies along the migrating grain boundaries in experimental alloys during aging treatment. As a result of the increased solubility of Re in the γ matrix and enlarged interlamellar spacing of σ precipitates inside of growing DP colonies, Co addition suppressed the formation of σ phase and associated DP colonies. This study suggests that Co could potentially serve as a microstructural stabilizer in Re-containing Ni-base superalloys, which provides an alternative method for the composition optimization of superalloys.

  18. Microstructure and Properties of a High-Strength Cu-Ni-Si-Co-Zr Alloy

    NASA Astrophysics Data System (ADS)

    Chenna Krishna, S.; Srinath, J.; Jha, Abhay K.; Pant, Bhanu; Sharma, S. C.; George, Koshy M.

    2013-07-01

    A high-strength Cu-Ni-Si alloy was developed with the additions of Co and Zr. The aging curve for the alloy was generated using hardness. Electron microscopy studies were conducted to analyze the phases in the alloy. Two types of phases, one of copper matrix and the other of Ni-Si-Co-Zr intermetallic phase, could be identified using scanning electron microscopy. Transmission electron microscopy studies confirmed the presence of two types of precipitates in solution-treated and aged (STA) condition, i.e., Ni2Si and Co2Si. Mechanical properties and electrical conductivity were evaluated in solution-treated (ST) and STA conditions. Aging of the ST samples at 500 °C for 3 h has shown an increase of 72 and 15% in yield strength (YS) and electrical conductivity, respectively. This increase in YS and conductivity on aging is primarily attributed to the formation of fine Ni2Si and Co2Si precipitates.

  19. Structure investigations of ferromagnetic Co-Ni-Al alloys obtained by powder metallurgy.

    PubMed

    Maziarz, W; Dutkiewicz, J; Lityńska-Dobrzyńska, L; Santamarta, R; Cesari, E

    2010-03-01

    Elemental powders of Co, Ni and Al in the proper amounts to obtain Co(35)Ni(40)Al(25) and Co(40)Ni(35)Al(25) nominal compositions were ball milled in a high-energy mill for 80 h. After 40 h of milling, the formation of a Co (Ni, Al) solid solution with f.c.c. structure was verified by a change of the original lattice parameter and crystallite size. Analytical transmission electron microscopy observations and X-ray diffraction measurements of the final Co (Ni, Al) solid solution showed that the crystallite size scattered from 4 to 8 nm and lattice parameter a = 0.36086 nm. The chemical EDS point analysis of the milled powder particles allowed the calculation of the e/a ratio and revealed a high degree of chemical homogeneity of the powders. Hot pressing in vacuum of the milled powders resulted in obtaining compacts with a density of about 70% of the theoretical one. An additional heat treatment increased the density and induced the martensitic transformation in a parent phase. Selected area diffraction patterns and dark field images obtained from the heat-treated sample revealed small grains around 300 nm in diameter consisting mainly of the ordered gamma phase (gamma'), often appearing as twins, and a small amount of the L1(0) ordered martensite.

  20. Separation of Ni and Co by D2EHPA in the Presence of Citrate Ion

    NASA Astrophysics Data System (ADS)

    Nadimi, Hamed; Haghshenas Fatmehsari, Davoud; Firoozi, Sadegh

    2017-10-01

    Recycling processes for the recovery of metallic content from the electronic wastes are environmentally friendly and economical. This paper reports a method for the recovery and separation of Ni and Co from the sulfate solution by the use of D2EHPA. In this regard, the influence of citrate ion, as a carboxylate ligand, was examined in the separation conditions of Ni and Co via D2EHPA (a poor selective extractant for Ni and Co separation). It was found that the Δ {pH}_{0.5}^{Ni-Co} (the difference between pH values corresponding to 50 pct extraction of metallic ion) increases to 1.5 at the citrate concentration of 0.05 M; this Δ {pH}_{0.5}^{Ni-Co} value is much higher than that obtained in the absence of citrate ion (0.1). Fourier Transform Infrared Spectroscopy (FT-IR) indicated that the citrate ion is co-absorbed during the metallic ions absorption by D2EHPA meaning that the metal-organic complexes contain Co/Ni and citrate ion. Also, the stoichiometric coefficients of the Ni and Co extraction reaction were proposed by applying the slope analysis method.

  1. Insight into the phase evolution of a NiMgAl catalyst from the reduction stage to the post-reaction stage during the dry reforming of methane [Insight into the phase evolution of NiMgAl catalyst from reduction to post-reaction for dry reforming of methane

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bao, Zhenghong; Zhan, Yiqiu; Street, Jason

    Herein, phase evolution of a NiMgAl oxide catalyst at the reduction stage was qualitatively analysed and quantitatively determined by employing the continuous changes in its XRD intensity and TPR information. In conclusion, the stable crystallite size of both the active metal and spinel support was responsible for the long stability of the NiMgAl catalyst without carbon deposition during the DRM reaction.

  2. Insight into the phase evolution of a NiMgAl catalyst from the reduction stage to the post-reaction stage during the dry reforming of methane [Insight into the phase evolution of NiMgAl catalyst from reduction to post-reaction for dry reforming of methane

    DOE PAGES

    Bao, Zhenghong; Zhan, Yiqiu; Street, Jason; ...

    2017-05-04

    Herein, phase evolution of a NiMgAl oxide catalyst at the reduction stage was qualitatively analysed and quantitatively determined by employing the continuous changes in its XRD intensity and TPR information. In conclusion, the stable crystallite size of both the active metal and spinel support was responsible for the long stability of the NiMgAl catalyst without carbon deposition during the DRM reaction.

  3. Phase formation and morphological stability of ultrathin Ni-Co-Pt silicide films formed on Si(100)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Xu, Peng; Wu, Dongping, E-mail: dongpingwu@fudan.edu.cn; Kubart, Tomas

    Ultrathin Ni, Co, and Pt films, each no more than 4 nm in thickness, as well as their various combinations are employed to investigate the competing growth of epitaxial Co{sub 1-y}Ni{sub y}Si{sub 2} films against polycrystalline Pt{sub 1-z}Ni{sub z}Si. The phase formation critically affects the morphological stability of the resulting silicide films, with the epitaxial films being superior to the polycrystalline ones. Any combination of those metals improves the morphological stability with reference to their parent individual metal silicide films. When Ni, Co, and Pt are all included, the precise initial location of Pt does little to affect the final phasemore » formation in the silicide films and the epitaxial growth of Co{sub 1-x}Ni{sub x}Si{sub 2} films is always perturbed, in accordance to thermodynamics that shows a preferential formation of Pt{sub 1-z}Ni{sub z}Si over that of Co{sub 1-y}Ni{sub y}Si{sub 2}.« less

  4. The study of new complex compounds of Ni (II) and Co (II) with N- hydroxy-succinimide and their potential applications as sensors

    NASA Astrophysics Data System (ADS)

    Sibiescu, Doina; Tutulea, Mihaela-Dana; Mîţă, Carmen; Stan, Corneliu; Roţca, Ioan; Vizitiu, Mihaela

    2010-11-01

    In this paper, the study of obtaining new coordination compounds of Ni (II) and Co(II) using as ligand, N-hydroxy-succinimide, was presented. Also, the stability constants of these compounds in aqueous medium were determined. The obtaining conditions and the stability of the new compounds were accomplished in aqueous solutions using characteristic methods for coordination compounds: pH-metry, conductometry and UV-VIS absorption spectroscopy. The combination ratios and the stability constants were determined with methods characteristic for studies in solutions. From experimental data resulted that the combination ratio of central metallic atoms with the ligand N-hydroxy-succinimide was: 1:1 and respectively 1:2. In the experiments were used salts of NiCl2.6H2O and CoCl2.6H2O. The optimal domain of pH stability of the studied compounds is limited between 5.74 - 5.86 for Co- N-hydroxy-succinimide (for molar ratio 1:1 and 1:2) and respectively 5.69 - 5.87 for Ni-N-hydroxysuccinimide( for molar ratio 1:1 and 1:2, too). It is important to mention that these compounds were used with very good results in determination of wastewaters from textile, metallurgical, chemical and food industry. Complexion reactions with this ligand are very sensitive for the cations in this paper mentioned. Therefore it is used most often with success in analytical chemistry and also it is posibil to use as sensors. The new complex compounds has electronics transitions at λ = 517 nm for both complexes Co-N-hydroxy-succinimide at molar ratio 1:1 and 1:2 and also at the same λ = 397nm for Ni-N-hydroxysuccinimide at molar ratio 1:1 and 1:2. These complexes compounds was separated and recrystallized from aqueous solution. From the spectrophotometric data it was determined the type and the nature of the electronics transitions by Dq parameters.

  5. DNA cleavage, antibacterial, antifungal and anthelmintic studies of Co(II), Ni(II) and Cu(II) complexes of coumarin Schiff bases: synthesis and spectral approach.

    PubMed

    Patil, Sangamesh A; Prabhakara, Chetan T; Halasangi, Bhimashankar M; Toragalmath, Shivakumar S; Badami, Prema S

    2015-02-25

    The metal complexes of Co(II), Ni(II) and Cu(II) have been synthesized from 6-formyl-7,8-dihydroxy-4-methylcoumarin with o-toluidine/3-aminobenzotrifluoride. The synthesized Schiff bases and their metal complexes were structurally characterized based on IR, (1)H NMR, (13)C NMR, UV-visible, ESR, magnetic, thermal, fluorescence, mass and ESI-MS studies. The molar conductance values indicate that complexes are non-electrolytic in nature. Elemental analysis reveals ML2·2H2O [M = Co(II), Ni(II) and Cu(II)] stoichiometry, where 'L' stands for a singly deprotonated ligand. The presence of co-ordinated water molecules were confirmed by thermal studies. The spectroscopic studies suggest the octahedral geometry. Redox behavior of the complexes were confirmed by cyclic voltammetry. All the synthesized compounds were screened for their antibacterial (Escherichia coli, Pseudomonas auregenosa, klebsiella, Proteus, Staphylococcus aureus and salmonella) antifungal (Candida, Aspergillus niger and Rhizopus), anthelmintic (Pheretima posthuma) and DNA cleavage (Calf Thymus DNA) activity. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Synthesis, characterization and in vitro anticancer activity of 18-membered octaazamacrocyclic complexes of Co(II), Ni(II), Cd(II) and Sn(II)

    NASA Astrophysics Data System (ADS)

    Kareem, Abdul; Zafar, Hina; Sherwani, Asif; Mohammad, Owais; Khan, Tahir Ali

    2014-10-01

    An effective series of 18 membered octaazamacrocyclic complexes of the type [MLX2], where X = Cl or NO3 have been synthesized by template condensation reaction of oxalyl dihydrazide with dibenzoylmethane and metal salt in 2:2:1 molar ratio. The formation of macrocyclic framework, stereochemistry and their overall geometry have been characterized by various physico-chemical studies viz., elemental analysis, electron spray ionization-mass spectrometry (ESI-MS), I.R, UV-Vis, 1H NMR, 13C NMR spectroscopy, X-ray diffraction (XRD) and TGA/DTA studies. These studies suggest formation of octahedral macrocyclic complexes of Co(II), Ni(II), Cd(II) and Sn(II). The molar conductance values suggest nonelectrolytic nature for all the complexes. Thermogravimatric analysis shows that all the complexes are stable up to 600 °C. All these complexes have been tested against different human cancer cell lines i.e. human hepatocellular carcinoma (Hep3B), human cervical carcinoma (HeLa), human breast adenocarcinoma (MCF7) and normal cells (PBMC). The newly synthesized 18-membered octaazamacrocyclic complexes during in vitro anticancer evaluation, displayed moderate to good cytotoxicity on liver (Hep3B), cervical (HeLa) and breast (MCF7) cancer cell lines, respectively. The most effective anticancer cadmium complex (C34H28N10CdO10) was found to be active with IC50 values, 2.44 ± 1.500, 3.55 ± 1.600 and 4.82 ± 1.400 in micro-molar on liver, cervical and breast cancer cell lines, respectively.

  7. Electrocatalytic activity of LaNiO3 toward H2O2 reduction reaction: Minimization of oxygen evolution

    NASA Astrophysics Data System (ADS)

    Amirfakhri, Seyed Javad; Meunier, Jean-Luc; Berk, Dimitrios

    2014-12-01

    The catalytic activity of LaNiO3 toward H2O2 reduction reaction (HPRR), with a potential application in the cathode side of fuel cells, is studied in alkaline, neutral and acidic solutions by rotating disk electrode. The LaNiO3 particles synthesised by citrate-based sol-gel method have sizes between 30 and 70 nm with an active specific surface area of 1.26 ± 0.05 m2 g-1. LaNiO3 shows high catalytic activity toward HPRR in 0.1 M KOH solution with an exchange current density based on the active surface area (j0A) of (7.4 ± 1) × 10-6 A cm-2 which is noticeably higher than the j0A of N-doped graphene. The analysis of kinetic parameters suggests that the direct reduction of H2O2, H2O2 decomposition, O2 reduction and O2 desorption occur through HPRR on this catalyst. In order to control and minimize oxygen evolution from the electrode surface, the effects of catalyst loading, bulk concentration of H2O2, and using a mixture of LaNiO3 and N-doped graphene are studied. Although the mechanism of HPRR is independent of the aforementioned operating conditions, gas evolution decreases by increasing the catalyst loading, decreasing the bulk concentration of H2O2, and addition of N-doped graphene to LaNiO3.

  8. In situ x-ray diffraction studies of a new LiMg{sub 0.125}Ni{sub 0.75}O{sub 2} cathode material

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yang, X.Q.; Sun, X.; McBreen, J.

    A Synchrotron x-ray source was used for In Situ x-ray diffraction studies during charge on a new LiMg{sub 0.125}Ti{sub 0.125}Ni{sub 0.75} cathode material synthesized by FMC Corp. It had been demonstrated by Gao that this new material has superior thermal stability than LiNiO{sub 2} and LiCo{sub 0.2}Ni{sub 0.8}O{sub 2} at over-charged state. In this current paper, studies on the relationship between the structural changes and thermal stability at over-charged state for these materials are presented. For the first time, the thermal stability of these materials are related to their structural changes during charge, especially to the formation and lattice constantmore » change of a hexagonal phase (H3). The spectral evidence support the hypothesis that the improvement of thermal stability is obtained by suppressing the formation of H3 phase and reducing the shrinkage of its lattice constant c when charged above 4.3 V.« less

  9. Determination of the diffusion coefficient and phase-transfer rate parameter in LaNi{sub 5} and MmNi{sub 3.6}Co{sub 0.8}Mn{sub 0.4}Al{sub 0.3} using microelectrodes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lundqvist, A.; Lindbergh, G.

    1998-11-01

    A potential-step method for determining the diffusion coefficient and phase-transfer parameter in metal hydrides by using microelectrodes was investigated. It was shown that a large potential step is not enough to ensure a completely diffusion-limited mass transfer if a surface-phase transfer reaction takes place at a finite rate. It was shown, using a kinetic expression for the surface phase-transfer reaction, that the slope of the logarithm of the current vs. time curve will be constant both in the case of the mass-transfer limited by diffusion or by diffusion and a surface-phase transfer. The diffusion coefficient and phase-transfer rate parameter weremore » accurately determined for MmNi{sub 3.6}Co{sub 0.8}Mn{sub 0.4}Al{sub 0.3} using a fit to the whole transient. The diffusion coefficient was found to be (1.3 {+-} 0.3) {times} 10{sup {minus}13} m{sup 2}/s. The fit was good and showed that a pure diffusion model was not enough to explain the observed transient. The diffusion coefficient and phase-transfer rate parameter were also estimated for pure LaNi{sub 5}. A fit of the whole curve showed that neither a pure diffusion model nor a model including phase transfer could explain the whole transient.« less

  10. The magnetic Curie temperature and exchange coupling between cations in tetragonal spinel oxide Mn2.5M0.5O4 (M = Co, Ni, Mn, Cr, and Mg) films

    NASA Astrophysics Data System (ADS)

    Kuo, K.; Cheng, C. W.; Chern, G.

    2012-04-01

    Mn3O4 is a Jahn-Taller tetragonal ferrite that has a relatively low Curie temperature (Tc) of ˜43 K due to weak coupling between the canting spins. In this study, we fabricated a series of 100-nm-thick Mn2.5M0.5O4 (M = Co, Ni, Mn, Cr, and Mg) films via oxygen-plasma-assisted molecular beam epitaxy and measured the structural and magnetic properties of these films. These films show single phase quality, and the c-axis lattice parameter of pure Mn3O4 is 0.944 nm, with a c/a ratio ˜1.16, consistent with the bulk values. The replacement of Mn by M (M = Co, Ni, Cr, and Mg) changes the lattice parameters, and the c/a ratio varies between 1.16 and 1.06 depending upon the cation distribution of the films. The magnetic Curie temperatures of these films also vary in the range of 25-66 K in that Ni and Co enhance the Tc whereas Mg reduces the Tc (Cr shows no effect on the Tc). These changes to the Tc are related to both the element electronic state and the cation distributions in these compounds. As a non-collinear spin configuration can induce electrical polarization, the present study provides a systematic way to enhance the magnetic transition temperature in tetragonal spinel ferrites.

  11. Synthesis, characterization and anti-microbial activity of a novel macrocyclic ligand derived from the reaction of 2,6-pyridinedicarboxylic acid with homopiperazine and its Co(II), Ni(II), Cu(II), and Zn(II) complexes

    NASA Astrophysics Data System (ADS)

    Soleimani, Esmaiel

    2011-05-01

    The preparation of a novel macrocyclic ligand ( 1), N,N'-diethylhomopiperazinyl,2,6-pyridinedicarboxylate and its Co(II), Ni(II), Cu(II), and Zn(II) complexes are described. The ligand was prepared in EtOH from the reaction of dipotassium salt of 2,6-pyridinedicarboxylic acid with 1,2-dibromoethane in the presence of homopiperazine. Reaction of macrocyclic ligand ( 1) in EtOH with CoCl 2.6H 2O, NiCl 2.6H 2O, CuCl 2.2H 2O, and ZnCl 2·2H 2O yielded the complexes with the general formula [M(L)Cl 2] {where M = Co(II) ( 2), Ni(II) ( 3), Cu(II) ( 4), Zn ( 5), respectively}. The analysis of IR, 1H and 13C NMR spectral data of macrocyclic ligand ( 1) and its Zn(II) complex ( 5) together with their molar conductivity values, and the magnetic moments of the complexes suggest that the macrocyclic ligand ( 1) is bonded to metal(II) ions through two oxygen atoms of ester moiety and the two nitrogen atoms of homopiperazine ring. The electronic spectral data of these complexes in DMSO are in good agreement with the octahedral coordination of M(II) ions. The ligand field parameters for these complexes, i.e. splitting energy and Racah parameter were calculated to be 14,945 and 673 cm -1 for the Co(II) ( 2), 16,260 and 774 cm -1 for the Ni(II) ( 3) complexes respectively. The spliting energy of 17,262 cm -1 was obtained for the Cu(II) complex ( 4).

  12. Thermodynamics and Kinetics of Three Mg-H-VN Complexes in Mg:GaN from Combined First-Principles Calculation and Experiment

    NASA Astrophysics Data System (ADS)

    Lee, Donghwa; Mitchell, Brandon; Fujiwara, Y.; Dierolf, V.

    2014-05-01

    An understanding of the formation and dissociation process of Mg-H defects in GaN is of paramount importance for high efficient GaN-based solid-state lighting. Through a combination of first-principle calculations and experimental observations, we find the existence of three types of Mg related centers forming different Mg-H-VN complexes in Mg:GaN. Our study shows that the three different arrangements, which differ by the relative position of the H, determine the degree of acceptor passivation by changing their charge state from +3 to +1. The energetic study demonstrates that the relative stability of the defect complexes can vary with the location of the Fermi level, as well as thermal annealing and electron beam irradiation. The inclusion of a VN is shown to produce an additional variance in optical spectra associated with Mg acceptor activation, resulting from changes in the defect configurations and charge states. Our study shows that these three Mg-H-VN complexes are key components for understanding the Mg acceptor activation and passivation processes.

  13. Synthesis mechanism and preparation of LaMgAl11O19 powder for plasma spraying

    NASA Astrophysics Data System (ADS)

    He, Mingtao; Meng, Huimin; Wang, Yuchao; Ren, Pengwei

    2018-06-01

    Lanthanide magnesium hexaaluminate (LaMgAl11O19) powders were successfully synthesized by the solid-state reaction method. The objective of this study was to investigate the synthesis mechanism of LaMgAl11O19 and prepare LaMgAl11O19 powders suitable for plasma spraying. The results show that LaAlO3 reacts with MgAl2O4 and Al2O3 to form LaMgAl11O19 at approximately 1300 °C. Single-phase LaMgAl11O19 powders were prepared successfully by solid-state reaction at a synthesis temperature of 1600 °C for 6 h. Unlike the particles in the synthesized powders, those of the centrifugally spray-dried powders have a spherical shape with uniform granularity and good flowability, density, and particle size distribution, making them suitable for plasma spraying. The synthesized powders and centrifugally spray-dried powders remained as a single phase after heat treatment at 1300 °C for 100 h, indicating that LaMgAl11O19 has excellent high-temperature stability.

  14. Colossal permittivity and the polarization mechanism of (Mg, Mn) co-doped LaGaO3 ceramics

    NASA Astrophysics Data System (ADS)

    Luo, Tingting; Liu, Zhifu; Zhang, Faqiang; Li, Yongxiang

    2018-03-01

    Mg and Mn co-doped LaGa0.7-xMgxMn0.3O3 (x = 0, 0.05, 0.10, 0.15) ceramics were prepared by a solid-state reaction method. The electrical properties of the LaGa0.7-xMgxMn0.3O3 ceramics were studied in detail by dielectric spectra, impedance spectra, and I-V characteristic analysis. Colossal permittivity up to 104 could be obtained across the frequency range up to 104 Hz. The impedance analysis of the co-doped LaGaO3 ceramics indicated that the Mott's variable range hopping (VRH) polarization should be the main origin of colossal permittivity. Mg and Mn co-doping suppressed the formation of Mn3+ and enhanced the VRH polarization, resulting in increased permittivity. Partial localization of electrons by Mg reduced the long-range electron hopping and led to the decrease in dielectric loss.

  15. Mechanisms of radiation-induced segregation in CrFeCoNi-based single-phase concentrated solid solution alloys

    DOE PAGES

    He, Mo-Rigen; Wang, Shuai; Shi, Shi; ...

    2016-12-31

    Single-phase concentrated solid solution alloys have attracted wide interest due to their superior mechanical properties and enhanced radiation tolerance, which make them promising candidates for the structural applications in next-generation nuclear reactors. However, little has been understood about the intrinsic stability of their as-synthesized, high-entropy configurations against radiation damage. In this paper, we report the element segregation in CrFeCoNi, CrFeCoNiMn, and CrFeCoNiPd equiatomic alloys when subjected to 1250 kV electron irradiations at 400 °C up to a damage level of 1 displacement per atom. Cr/Fe/Mn/Pd can deplete and Co/Ni can accumulate at radiation-induced dislocation loops, while the actively segregating elementsmore » are alloy-specific. Moreover, electron-irradiated matrix of CrFeCoNiMn and CrFeCoNiPd shows L1 0 (NiMn)-type ordering decomposition and <001>-oriented spinodal decomposition between Co/Ni and Pd, respectively. Finally, these findings are rationalized based on the atomic size difference and enthalpy of mixing between the alloying elements, and identify a new important requirement to the design of radiation-tolerant alloys through modification of the composition.« less

  16. Phase stability and B-site ordering in La{sub 2}NiMnO{sub 6} thin films

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jin, Xiao-Wei; Lu, Lu; Liu, Ming

    2016-07-18

    Thin films of multiferroic double-perovskite La{sub 2}NiMnO{sub 6} are prepared on (001)-oriented SrTiO{sub 3}, (La{sub 0.289}Sr{sub 0.712})(Al{sub 0.633}Ta{sub 0.356})O{sub 3}, and LaSrAlO{sub 4} substrates by pulsed laser deposition. Microstructure investigation by advanced electron microscopy shows that the La{sub 2}NiMnO{sub 6} films have a monoclinic structure on the SrTiO{sub 3} substrates and a rhombohedral structure on the (La{sub 0.289}Sr{sub 0.712})(Al{sub 0.633}Ta{sub 0.356})O{sub 3} and LaSrAlO{sub 4} substrates. Atomic-scale elemental maps of the monoclinic and rhombohedral phases reveal a short-range and/or partial ordering of the B-sites. In addition, domains and columnar grains are found in the films. Our results demonstrate that themore » phase and microstructure of the La{sub 2}NiMnO{sub 6} films can be tuned by epitaxial strains induced by different substrates.« less

  17. Thiolate-bridged dinuclear iron(tris-carbonyl)–nickel complexes relevant to the active site of [NiFe] hydrogenase

    PubMed Central

    Ohki, Yasuhiro; Yasumura, Kazunari; Kuge, Katsuaki; Tanino, Soichiro; Ando, Masaru; Li, Zilong; Tatsumi, Kazuyuki

    2008-01-01

    The reaction of NiBr2(EtOH)4 with a 1:2–3 mixture of FeBr2(CO)4 and Na(SPh) generated a linear trinuclear Fe–Ni–Fe cluster (CO)3Fe(μ-SPh)3Ni(μ-SPh)3Fe(CO)3, 1, whereas the analogous reaction system FeBr2(CO)4/Na(StBu)/NiBr2(EtOH)4 (1:2–3:1) gave rise to a linear tetranuclear Fe–Ni–Ni–Fe cluster [(CO)3Fe(μ-StBu)3Ni(μ-Br)]2, 2. By using this tetranuclear cluster 2 as the precursor, we have developed a new synthetic route to a series of thiolate-bridged dinuclear Fe(CO)3–Ni complexes, the structures of which mimic [NiFe] hydrogenase active sites. The reactions of 2 with SC(NMe2)2 (tmtu), Na{S(CH2)2SMe} and ortho-NaS(C6H4)SR (R = Me, tBu) led to isolation of (CO)3Fe(μ-StBu)3NiBr(tmtu), 3, (CO)3Fe(StBu)(μ-StBu)2Ni{S(CH2)2SMe}, 4, and (CO)3Fe(StBu)(μ-StBu)2Ni{S(C6H4)SR}, 5a (R = Me) and 5b (R = tBu), respectively. On the other hand, treatment of 2 with 2-methylthio-phenolate (ortho-O(C6H4)SMe) in methanol resulted in (CO)3Fe(μ-StBu)3Ni(MeOH){O(C6H4)SMe}, 6a. The methanol molecule bound to Ni is labile and is readily released under reduced pressure to afford (CO)3Fe(StBu)(μ-StBu)2Ni{O(C6H4)SMe}, 6b, and the coordination geometry of nickel changes from octahedral to square planar. Likewise, the reaction of 2 with NaOAc in methanol followed by crystallization from THF gave (CO)3Fe(μ-StBu)3Ni(THF)(OAc), 7. The dinuclear complexes, 3-7, are thermally unstable, and a key to their successful isolation is to carry out the reactions and manipulations at −40°C. PMID:18511566

  18. AcsF Catalyzes the ATP-dependent Insertion of Nickel into the Ni,Ni-[4Fe4S] Cluster of Acetyl-CoA Synthase*

    PubMed Central

    Gregg, Christina M.; Goetzl, Sebastian; Jeoung, Jae-Hun

    2016-01-01

    Acetyl-CoA synthase (ACS) catalyzes the reversible condensation of CO, CoA, and a methyl-cation to form acetyl-CoA at a unique Ni,Ni-[4Fe4S] cluster (the A-cluster). However, it was unknown which proteins support the assembly of the A-cluster. We analyzed the product of a gene from the cluster containing the ACS gene, cooC2 from Carboxydothermus hydrogenoformans, named AcsFCh, and showed that it acts as a maturation factor of ACS. AcsFCh and inactive ACS form a stable 2:1 complex that binds two nickel ions with higher affinity than the individual components. The nickel-bound ACS-AcsFCh complex remains inactive until MgATP is added, thereby converting inactive to active ACS. AcsFCh is a MinD-type ATPase and belongs to the CooC protein family, which can be divided into homologous subgroups. We propose that proteins of one subgroup are responsible for assembling the Ni,Ni-[4Fe4S] cluster of ACS, whereas proteins of a second subgroup mature the [Ni4Fe4S] cluster of carbon monoxide dehydrogenases. PMID:27382049

  19. Magnetic properties of Mn0.1Mg0.2TM0.7Fe2O4 (TM = Zn, Co, or Ni) prepared by hydrothermal processes: The effects of crystal size and chemical composition

    NASA Astrophysics Data System (ADS)

    Nhlapo, T. A.; Msomi, J. Z.; Moyo, T.

    2018-02-01

    Nano-crystalline Zn-, Co-, and Ni-substituted Mn-Mg ferrites were prepared by hydrothermal process and annealed at 1100 °C. Annealing conditions are critical on the crystalline phase. TEM and XRD data reveal particle sizes between 8 nm and 15 nm for the as-prepared fine powders, which increase to about 73 nm after sintering at 1100 °C. Mӧssbauer spectra show well resolved magnetic splitting in bulk samples. The as-prepared fine powders show weak hyperfine splitting and broad central doublets associated with fine particles. Magnetization data reveal a high coercive field at about 300 K of about 945 Oe in the Co-based nanosized oxide, which reduces to about 360 Oe after thermal annealing at 1100 °C. The magnetization curves of Zn- and Ni-based samples show much lower coercive fields indicative of superparamagnetic nanoparticles. The crystallite size and chemical composition have significant effects on the properties of Mn0.1Mg0.2(Zn,Co,Ni)0.7Fe2O4 investigated.

  20. Influences on the H2-sorption properties of Mg of Co (with various sizes) and CoO addition by reactive grinding and their thermodynamic stabilities

    NASA Astrophysics Data System (ADS)

    Song, Myoung Youp; Lee, DongSub; Kwon, IkHyun

    2004-02-01

    We attempted to improve the H2-sorption properties of Mg by mechanical grinding under H2 (reactive grinding) with Co (with various particle sizes) and with CoO. The thermodynamic stabilities of the added Co and CoO were also investigated. CoO addition has the best influence and addition of smaller particles of Co (0.5-1.5 μm) has a better effect than the addition of larger particles of Co on the H2-sorption properties of Mg. The activated Mg+10 wt.% CoO sample has about 5.54 wt% hydrogen-storage capacity at 598 K and the highest hydriding rate, showing an Ha value of 2.39 wt.% after 60 min at 598 K, 11.2 bar H2. The order of the hydriding rates after activation is the same as that of the specific surface areas of the samples. The reactive grinding of Mg with Co or CoO and hydriding-dehydriding cycling increase the H2-sorption rates by facilitating nucleation of magnesium hydride or α solid solution of Mg and H (by creating defects on the surface of the Mg particles and by the additive), and by making cracks on the surface of Mg particles and reducing the particle size of Mg, thus shortening the diffusion distances of hydrogen atoms. The cobalt oxide is stable even after 14 hydriding cycles at 598 K under 11.2 bar H2. Discharge capacities are measured for the sampple Mg+10 wt.%CoO and Mg+10wt.%Co (0.5-1.5 μm) with good hydrogen-storage properties.

  1. Effects of cation stoichiometry on electronic and structural properties of LaNiO{sub 3}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Smith, Cole R.; Lang, Andrew C.; Taheri, Mitra L.

    2015-07-15

    LaNiO{sub 3} films with varying La:Ni ratios were deposited onto SrTiO{sub 3} (001) substrates via molecular beam epitaxy to elucidate the effects of cation off-stoichiometry. The physical properties of La-deficient films are found to differ substantially from those of Ni-deficient films, with La-deficient films exhibiting lower electrical resistivities and smaller c-axis parameters than Ni-deficient films. No evidence of secondary phases is observed; however, transmission electron microscopy reveals an abundance of defects, the nature of which differs in lanthanum- and nickel-deficient films. This work illustrates the nontrivial role that cation stoichiometry can play on the functional properties of complex oxides.

  2. Preconcentration and solid phase extraction method for the determination of Co, Cu, Ni, Zn and Cd in environmental and biological samples using activated carbon by FAAS.

    PubMed

    Kiran, K; Suresh Kumar, K; Suvardhan, K; Janardhanam, K; Chiranjeevi, P

    2007-08-17

    2-{[1-(2-Hydroxynaphthyl) methylidene] amino} benzoic acid (HNMABA) was synthesized for solid phase extraction (SPE) to the determination of Co, Cu, Ni, Zn and Cd in environmental and biological samples by flame atomic absorption spectrophotometry (FAAS). These metals were sorbed as HNMABA complexes on activated carbon (AC) at the pH range of 5.0+/-0.2 and eluted with 6 ml of 1M HNO3 in acetone. The effects of sample volume, eluent volume and recovery have been investigated to enhance the sensitivity and selectivity of proposed method. The effect of interferences on the sorption of metal ions was studied. The concentration of the metal ions detected after preconcentration was in agreement with the added amount. The detection limits for the metals studied were in the range of 0.75-3.82 microg ml(-1). The proposed system produced satisfactory results for the determination of Co, Cu, Ni, Zn and Cd metals in environmental and biological samples.

  3. [H{sub 2}en]{sub 2}{l_brace}La{sub 2}M(SO{sub 4}){sub 6}(H{sub 2}O){sub 2}{r_brace} (M=Co, Ni): First organically templated 3d-4f mixed metal sulfates

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yuan Yanping; Wang Ruiyao; Kong Deyuan

    2005-06-15

    The first organically templated 3d-4f mixed metal sulfates, [H{sub 2}en]{sub 2}{l_brace}La{sub 2}M(SO{sub 4}){sub 6}(H{sub 2}O){sub 2}{r_brace} (M=Co 1, Ni 2) have been synthesized and structurally determined from non-merohedrally twinned crystals. The two compounds are isostructural and their structures feature a three-dimensional anionic network formed by the lanthanum(III) and nickel(II) ions bridged by sulfate anions. The La(III) ions in both compounds are 10-coordinated by four sulfate anions in bidentate chelating fashion, and two sulfate anions in a unidentate fashion. The transition metal(II) ion is octahedrally coordinated by six oxygens from four sulfate anions and two aqua ligands. The doubly protonated enthylenediaminemore » cations are located at the tunnels formed by 8-membered rings (four La and four sulfate anions)« less

  4. Potential energy surfaces of LaH + and LaH + 2

    NASA Astrophysics Data System (ADS)

    Das, Kalyan K.; Balasubramanian, K.

    1991-03-01

    Using the complete active space multiconfiguration self-consistent field (CAS-MCSCF) followed by full second-order configuration interaction (SOCI) calculations, 16 electronic states of LaH+ and 8 electronic states of LaH+2 are investigated. The potential energy surface of these electronic states of LaH+2 and LaH+ are computed. These calculations show that the 3F(5d2) ground state of La+ ion forms a weak complex with H2. The La+(1D) excited state inserts into H2 with a small barrier (<8 kcal/mol) to form the 1A1 ground state of LaH+2 (re=2.057 Å, θe=106°). At the SOCI level of theory LaH+2 is found to be 11 kcal/mol more stable than La+(3F)+H2. Our calculations explain the experimental observations on La++H2→LaH++H reaction. The adiabatic ionization potential (IP) of LaH2 and LaH are calculated as 5.23 and 5.33 eV, respectively. The ground state of LaH+ was found to be a 2Δ state. We compute De(LaH+) and De(HLa-H+) as 2.54 eV in excellent agreement with the experimental De(LaH+)=2.57 eV measured by Armentrout and co-workers. The spin-orbit effects of LaH+ were also studied using the relativistic configuration interaction (RCI) method.

  5. Aqueous two-phase extraction of nickel dimethylglyoximato complex and its application to spectrophotometric determination of nickel in stainless steel.

    PubMed

    Yoshikuni, Nobutaka; Baba, Takayuki; Tsunoda, Natsuki; Oguma, Koichi

    2005-03-31

    A polyethylene glycol (PEG)-based aqueous two-phase system has been established for the extraction of Ni-dimethylglyoximato complex. Appropriate amounts of PEG solution and solid (NH(4))(2)SO(4) were added to the Ni-dimethylglyoximato complex which had been formed in the presence of sodium tartrate and K(2)S(2)O(8) at pH 12 in a separatory funnel and shaken vigorously for about 1min. The mixture was allowed to stand for 10min and then the absorbance of the extracted complex in the upper PEG-rich phase was measured at 470nm. Beer's law was obeyed over the range of 0.26-2.1ppm Ni. The proposed extraction method has been applied to the determination of Ni in steel. A steel sample was decomposed with an appropriate acid mixture. An aliquot of the sample solution was taken, treated with H(3)PO(4) and most of the iron and copper were removed by hydroxide precipitation using solid BaCO(3) to control the pH of the sample solution in advance of the extraction of Ni. The analytical results obtained for Ni in steel certified reference material JSS 650-10 (The Japan Iron and Steel Federation), BCS 323 (Bureau of Analysed Samples Ltd.) and NIST SRM 361 and 362 (National Institute of Standards and Technology) were in good agreement with certified values.

  6. Crystal structures of NiSO4·9H2O and NiSO4·8H2O: magnetic properties, stability with respect to morenosite (NiSO4·7H2O), the solid-solution series (Mg x Ni1-x )SO4·9H2O

    NASA Astrophysics Data System (ADS)

    Fortes, A. D.; Knight, K. S.; Gibbs, A. S.; Wood, I. G.

    2018-02-01

    Since being discovered initially in mixed-cation systems, a method of forming end-member NiSO4·9H2O and NiSO4·8H2O has been found. We have obtained powder diffraction data from protonated analogues (with X-rays) and deuterated analogues (using neutrons) of these compounds over a range of temperatures, allowing us to determine their crystal structures—including all H-atoms—and to characterise the transitions on warming from 220 to 278 K; glass → 9-hydrate → 8-hydrate + ice → 7-hydrate + ice → partial melt (7-hydrate + liquid). NiSO4·8D2O is triclinic, space-group P\\bar {1} , Z = 2, with unit cell parameters at 150 K, a = 6.12463(8) Å, b = 6.8401(1) Å, c = 12.5339(2) Å, α = 92.846(1)°, β = 97.822(1)°, γ = 96.627(1)° and V = 515.58(1) Å3. The structure consists of two symmetry-inequivalent Ni(D2O)6 octahedra on sites of \\bar {1} symmetry. These are directly joined by a water-water H-bond to form chains of octahedra parallel with the c-axis at x = 0. Two interstitial water molecules serve both to bridge the Ni(D2O)6 octahedral chains in the b-c plane and also to connect with the SO4 2- tetrahedral oxyanion. These tetrahedra are linked by the two interstitial water molecules in a reticular motif to form sheets perpendicular to c. NiSO4·9D2O is monoclinic, space-group P21/c, Z = 4, with unit-cell parameters at 150 K, a = 6.69739(6) Å, b = 11.8628(1) Å, c = 14.5667(1) Å, β = 94.9739(8)° and V = 1152.96(1) Å3. The structure is isotypic with the Mg analogue described elsewhere (Fortes et al., Acta Cryst B 73:47‒64, 2017b). It shares the motif of H-bonded octahedral chains with NiSO4·8D2O, although in the enneahydrate these run parallel with the b-axis at x = 0. Three interstitial water molecules bridge the Ni(D2O)6 octahedra to the SO4 2- tetrahedral oxyanion. The tetrahedra sit at x ≈ 0.5 and are linked by two of the three interstitial water molecules in a pentagonal motif to form ribbons parallel with b. A solid-solution series

  7. LaFe 0.9Ni 0.1O 3 perovskite catalyst with enhanced activity and coke-resistance for dry reforming of ethane

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhao, Baohuai; Yan, Binhang; Yao, Siyu

    In this work, a LaFe 0.9Ni 0.1O 3 perovskite catalyst was evaluated for dry reforming of ethane (DRE), with two conventional oxide supported Ni catalysts (Ni/La 2O 3 and NiFe/La 2O 3) being used as references. LaFe 0.9Ni 0.1O 3 showed the best activity and high coke-/sintering-resistance. TEM, TGA, and Raman characterizations confirmed that the deactivation of Ni/La 2O 3 was owing to the growth of Ni particles and the accumulation of coke, although the formation of La 2O 2CO 3 was able to remove part of the coke during the reaction. The introduction of Fe-related species inhibited the cokemore » formation while decreased the activity due to the loss of active sites. A portion of Ni ions in the perovskite lattice could be reduced to form highly dispersed and stable Ni nanoparticles on the surface during the reaction and oxygen vacancies were left in the perovskite lattice. Pulse reactor studies revealed that the oxygen vacancies in the perovskite could facilitate the activation and dissociation of CO 2 to form CO and reactive oxygen species. Additionally, C 2H 6 was activated with the assistance of oxygen from the surface or subsurface of LaFe 0.9Ni 0.1O 3 to form CO, rather than directly dissociated to surface carbon species as observed over Ni/La 2O 3.« less

  8. LaFe 0.9Ni 0.1O 3 perovskite catalyst with enhanced activity and coke-resistance for dry reforming of ethane

    DOE PAGES

    Zhao, Baohuai; Yan, Binhang; Yao, Siyu; ...

    2017-12-29

    In this work, a LaFe 0.9Ni 0.1O 3 perovskite catalyst was evaluated for dry reforming of ethane (DRE), with two conventional oxide supported Ni catalysts (Ni/La 2O 3 and NiFe/La 2O 3) being used as references. LaFe 0.9Ni 0.1O 3 showed the best activity and high coke-/sintering-resistance. TEM, TGA, and Raman characterizations confirmed that the deactivation of Ni/La 2O 3 was owing to the growth of Ni particles and the accumulation of coke, although the formation of La 2O 2CO 3 was able to remove part of the coke during the reaction. The introduction of Fe-related species inhibited the cokemore » formation while decreased the activity due to the loss of active sites. A portion of Ni ions in the perovskite lattice could be reduced to form highly dispersed and stable Ni nanoparticles on the surface during the reaction and oxygen vacancies were left in the perovskite lattice. Pulse reactor studies revealed that the oxygen vacancies in the perovskite could facilitate the activation and dissociation of CO 2 to form CO and reactive oxygen species. Additionally, C 2H 6 was activated with the assistance of oxygen from the surface or subsurface of LaFe 0.9Ni 0.1O 3 to form CO, rather than directly dissociated to surface carbon species as observed over Ni/La 2O 3.« less

  9. The distribution alloying elements in alnico 8 and 9 magnets: Site preference of ternary Ti, Fe, Co, and Ni additions in DO 3 Fe 3Al, Co 3Al, and Ni 3Al based intermetallic phases

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Samolyuk, G. D.; Újfalussy, B.; Stocks, G. M.

    Recently, interest in alnico magnetic alloys has been rekindled due to their potential to substitute for rare-earth based permanent magnets provided modest improvements in their coercivity can be achieved without loss of saturation magnetization. Recent experimental studies have indicated that atomic and magnetic structure of the two phases (one AlNi-based, the other FeCo-based) that comprise these spinodally decomposed alloy is not as simple as previously thought. A key issue that arises is the distribution of Fe, Co and Ti within the AlNi-based matrix phase. In our paper we report the results of first-principles calculations of the site preference of ternarymore » alloying additions in DO 3 Fe 3Al, Co 3Al and Ni 3Al alloys, as models for the aluminide phase. For compound compositions that are Al rich, which corresponds to experimental situation, Ti and Fe are found to occupy the sites, while Co and Ni prefer the sites of the DO 3 lattice. Finally, an important finding is that the magnetic moments of transition metals in Fe 3Al and Co 3Al are ordered ferromagnetically, whereas the Ni3Al were found to be nonmagnetic unless the Fe or Co are added as a ternary element.« less

  10. The distribution alloying elements in alnico 8 and 9 magnets: Site preference of ternary Ti, Fe, Co, and Ni additions in DO 3 Fe 3Al, Co 3Al, and Ni 3Al based intermetallic phases

    DOE PAGES

    Samolyuk, G. D.; Újfalussy, B.; Stocks, G. M.

    2014-11-07

    Recently, interest in alnico magnetic alloys has been rekindled due to their potential to substitute for rare-earth based permanent magnets provided modest improvements in their coercivity can be achieved without loss of saturation magnetization. Recent experimental studies have indicated that atomic and magnetic structure of the two phases (one AlNi-based, the other FeCo-based) that comprise these spinodally decomposed alloy is not as simple as previously thought. A key issue that arises is the distribution of Fe, Co and Ti within the AlNi-based matrix phase. In our paper we report the results of first-principles calculations of the site preference of ternarymore » alloying additions in DO 3 Fe 3Al, Co 3Al and Ni 3Al alloys, as models for the aluminide phase. For compound compositions that are Al rich, which corresponds to experimental situation, Ti and Fe are found to occupy the sites, while Co and Ni prefer the sites of the DO 3 lattice. Finally, an important finding is that the magnetic moments of transition metals in Fe 3Al and Co 3Al are ordered ferromagnetically, whereas the Ni3Al were found to be nonmagnetic unless the Fe or Co are added as a ternary element.« less

  11. Synthesis, characterization and in vitro antimicrobial studies of Co(II), Ni(II) and Cu(II) complexes derived from macrocyclic compartmental ligand

    NASA Astrophysics Data System (ADS)

    El-Gammal, O. A.; Bekheit, M. M.; El-Brashy, S. A.

    2015-02-01

    New Co(II), Ni(II) and Cu(II) complexes derived from tetradentate macrocyclic nitrogen ligand, (1E,4E,8E,12E)-5,8,13,16-tetramethyl-1,4,9,12-tetrazacyclohexadeca-4,8,12,16-tetraene (EDHDH) have been synthesized. The complexes have been characterized by elemental analysis, spectral (IR, UV-Vis, 1H NMR and ESR (for Cu(II) complex)) mass, and magnetic as well as thermal analysis measurements. The complexes afforded the formulae: [Cu(EDHDH)Cl2]·2EtOH and [M(EDHDH)X2]·nH2O where M = Co(II) and Ni(II), X = Cl- or OH-, n = 1,0, respectively. The data revealed an octahedral arrangement with N4 tetradentate donor sites in addition to two Cl atoms occupying the other two sites. ESR spectrum of Cu2+ complex confirmed the suggested geometry with values of a α2and β2 indicating that the in-plane σ-bonding and in-plane π-bonding are appreciably covalent, and are consistent with very strong σ-in-plane bonding in the complexes. The molecular modeling is drawn and showed the bond length, bond angle, chemical reactivity, energy components (kcal/mol) and binding energy (kcal/mol) for all the title compounds using DFT method. Also, the thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. Moreover, the in vitro antibacterial studies of all compounds screened against pathogenic bacteria (two Gram +ve and two Gram -ve) to assess their inhibiting potential. The assay indicated that the inhibition potential is metal ion dependent. The ligand, EDHDH, Co(II) and Cu(II) complexes exhibited a remarkable antibacterial activity against Streptococcus Pyogenes as Gram +ve and Proteus vulgaris as Gram -ve bacterial strains. On the other hand, Ni(II) complex revealed a moderate antibacterial activity against both Gram +ve organisms and no activity against Gram -ve bacterial strain.

  12. Extraction and separation of Co(II) and Ni(II) from acidic sulfate solutions using Aliquat 336.

    PubMed

    Nayl, A A

    2010-01-15

    Extraction and separation of Co(II) and Ni(II) from acidic sulfate solutions by solvent extraction technique were studied using different forms of Aliquat 336 diluted with kerosene. The extraction percent of each metal ion was found to increase with increasing pH and extractant concentration. Co(II) was preferentially extracted by different forms of Aliquat 336 over Ni(II) under the same extraction conditions. From analysis of the experimental results, the extraction mechanism of R(4)N-forms was proposed with Co(II). It was found that the highest separation factor (S(Co/Ni)) value of 606.7 was obtained with 0.36 M R(4)N-SCN in kerosene from 2.0M H(2)SO(4) solution at pH 4.8 and shaking time of 20 min. Stripping of the two metal ions from the organic phase was also investigated. Based on the experimental results, a separation method was developed and tested to separate high purity Co(II), Ni(II) and Ln(III) from Ni-MH batteries leached by 2.0M H(2)SO(4). Based on the experimental results, a flow sheet was developed and tested and 0.34 g Co, 1.39 g Ln and 5.2g Ni were obtained from the leaching process.

  13. Quaternary M{sub 0.25}Cu{sub 0.25}Mg{sub 0.5}Fe{sub 2}O{sub 4} (M = Ni, Zn, Co, Mn) ferrite oxides: Synthesis, characterization and magnetic properties

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ciocarlan, Radu George; Laboratory of Adsorption and Catalysis, Department of Chemistry, University of Antwerpen; Pui, Aurel, E-mail: aurel@uaic.ro

    2016-09-15

    Highlights: • Superparamagnetic quaternary nanoferrite (M{sub 0.25}Cu{sub 0.25}Mg{sub 0.5}Fe{sub 2}O{sub 4,} where M = Mn, Zn, Co, Ni) were obtained. • C, O, H and metals were observed by XPS analysis. • Phases purity were confirmed by XRD diffraction and crystallite size (3–10 nm) were determind. - Abstract: We report the synthesis of M{sub 0.25}Cu{sub 0.25}Mg{sub 0.5}Fe{sub 2}O{sub 4} (where M = Mn, Zn, Co, Ni) nanoparticles using the coprecipitation method in the presence of carboxymethyl cellulose (CMC) as the in-situ surfactant. The crystalline structure and surface morphology were examined by means of X-ray diffraction (XRD) and scanning electron microscopymore » (SEM) and it was established that the average diameter of the magnetic nanoparticles (MNPs) is in the range of 3–10 nm. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) show that the MNPs are activated by the hydrophilic groups of the surfactant, which coat them and enhance their stability. The vibrating sample magnetometry measurements show the superparamagnetic behavior of the nanoparticles. Due to their small crystallite size, which implies large surface area, and their functionalization with organic groups, the obtained nanoparticles could have medical and catalytic applications.« less

  14. A Biomimetic Nickel Complex with a Reduced CO2 Ligand Generated by Formate Deprotonation and Its Behaviour towards CO2.

    PubMed

    Zimmermann, Philipp; Hoof, Santina; Braun-Cula, Beatrice; Herwig, Christian; Limberg, Christian

    2018-04-10

    Reduced CO 2 species are key intermediates in a variety of natural and synthetic processes. In the majority of systems, however, they elude isolation or characterisation owing to high reactivity or limited accessibility (heterogeneous systems), and their formulations thus often remain uncertain or are based on calculations only. We herein report on a Ni-CO 2 2- complex that is unique in many ways. While its structural and electronic features help understand the CO 2 -bound state in Ni,Fe carbon monoxide dehydrogenases, its reactivity sheds light on how CO 2 can be converted into CO/CO 3 2- by nickel complexes. In addition, the complex was generated by a rare example of formate β-deprotonation, a mechanistic step relevant to the nickel-catalysed conversion of H x CO y z- at electrodes and formate oxidation in formate dehydrogenases. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Methanol steam reforming over Ni-CeO 2 model and powder catalysts: Pathways to high stability and selectivity for H 2/CO 2 production

    DOE PAGES

    Liu, Zongyuan; Yao, Siyu; Johnston-Peck, Aaron; ...

    2017-08-25

    Here, nickel-ceria has been reported as a very good catalysts for the reforming of methane. Here, the methanol steam reforming reaction on both powder (Ni-CeO 2) and model (Ni-CeO 2-x(111)) catalysts was investigated. The active phase evolution and surface species transformation on powder catalysts were studied via in situ X-ray diffraction (XRD) and diffuse reflectance infrared transform spectroscopy (DRIFTS). Phase transitions of NiO → NiC → Ni and CeO 2 → CeO 2-x were observed during the reaction. The simultaneous production of H 2/CO 2 demonstrates that the active phase of the catalysts contains metallic Ni supported over partially reducedmore » ceria. The DRIFTS experiments indicate that a methoxy to formate transition is associated with the reduction of ceria whereas the formation of carbonate species results from the presence of metallic Ni. A study of the reaction of methanol with Ni-CeO 2-x(111) by X-ray photoelectron spectroscopy (XPS) points to the essential role of metal-support interactions in an oxygen transfer from ceria to Ni that contributes to the high selectivity of the catalysts.« less

  16. Methanol steam reforming over Ni-CeO 2 model and powder catalysts: Pathways to high stability and selectivity for H 2/CO 2 production

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liu, Zongyuan; Yao, Siyu; Johnston-Peck, Aaron

    Here, nickel-ceria has been reported as a very good catalysts for the reforming of methane. Here, the methanol steam reforming reaction on both powder (Ni-CeO 2) and model (Ni-CeO 2-x(111)) catalysts was investigated. The active phase evolution and surface species transformation on powder catalysts were studied via in situ X-ray diffraction (XRD) and diffuse reflectance infrared transform spectroscopy (DRIFTS). Phase transitions of NiO → NiC → Ni and CeO 2 → CeO 2-x were observed during the reaction. The simultaneous production of H 2/CO 2 demonstrates that the active phase of the catalysts contains metallic Ni supported over partially reducedmore » ceria. The DRIFTS experiments indicate that a methoxy to formate transition is associated with the reduction of ceria whereas the formation of carbonate species results from the presence of metallic Ni. A study of the reaction of methanol with Ni-CeO 2-x(111) by X-ray photoelectron spectroscopy (XPS) points to the essential role of metal-support interactions in an oxygen transfer from ceria to Ni that contributes to the high selectivity of the catalysts.« less

  17. Microstructures and mechanical properties of compositionally complex Co-free FeNiMnCr 18 FCC solid solution alloy

    DOE PAGES

    Wu, Z.; Bei, H.

    2015-07-01

    Recently, a structurally-simple but compositionally-complex FeNiCoMnCr high entropy alloy was found to have excellent mechanical properties (e.g., high strength and ductility). To understand the potential of using high entropy alloys as structural materials for advanced nuclear reactor and power plants, it is necessary to have a thorough understanding of their structural stability and mechanical properties degradation under neutron irradiation. Furthermore, this requires us to develop a similar model alloy without Co because material with Co will make post-neutron-irradiation testing difficult due to the production of the 60Co radioisotope. In order to achieve this goal, a FCC-structured single-phase alloy with amore » composition of FeNiMnCr 18 was successfully developed. This near-equiatomic FeNiMnCr 18 alloy has good malleability and its microstructure can be controlled by thermomechanical processing. By rolling and annealing, the as-cast elongated-grained-microstructure is replaced by homogeneous equiaxed grains. The mechanical properties (e.g., strength and ductility) of the FeNiMnCr 18 alloy are comparable to those of the equiatomic FeNiCoMnCr high entropy alloy. Both strength and ductility increase with decreasing deformation temperature, with the largest difference occurring between 293 and 77 K. Extensive twin-bands which are bundles of numerous individual twins are observed when it is tensile-fractured at 77 K. No twin bands are detected by EBSD for materials deformed at 293 K and higher. Ultimately the unusual temperature-dependencies of UTS and uniform elongation could be caused by the development of the dense twin substructure, twin-dislocation interactions and the interactions between primary and secondary twinning systems which result in a microstructure refinement and hence cause enhanced strain hardening and postponed necking.« less

  18. Subsolidus and melting phase relations in the system CaCO3-MgCO3-FeCO3 at 35 kbar: from experiments to predictions based on a thermodynamic model

    NASA Astrophysics Data System (ADS)

    Franzolin, E.; Schmidt, M. W.; Poli, S.

    2009-12-01

    At convergent margins volatile components, most notably CO2 and H2O, stored in oceanic sediments and MORB are recycled into the mantle. Mafic protoliths become enriched in CO2 and H2O, stored in carbonates and hydrous phases, by hydrothermal alteration. As carbonates are more refractory than hydrous phases, CO2 is more likely to survive in the oceanic lithosphere beyond sub-arc depths [1,2]. Despite the main role of carbonates on cycling crustal and atmospheric CO2 into the mantle, experimental data within the system CaCO3-MgCO3-FeCO3 are scarce. To bridge this gap, piston-cylinder experiments have been performed at 35 kbar, 900-1100 °C to determine subsolidus relations, and up to 1300 °C to constrain melting relations. Pure synthetic calcite, natural magnesite and synthetic siderite have been mixed in different proportions in double Pt-C capsules, to avoid major siderite oxidation. Subsolidus experiments reveal the presence of two miscibility gaps at 900 °C: the solvus dolomite-calcite, which closes at XMgCO3 ~ 0.7, and the solvus dolomite-magnesite, which ranges to the Fe-side of the ternary. Increasing the temperature, the two miscibility gaps became narrower until complete solid solutions between CaCO3-Ca0.5Mg0.5CO3 at 1100 °C, and between CaCO3-FeCO3 at 1000 °C, are observed. The system is characterized by strong compositional asymmetry, thermodynamically described with a van Laar macroscopic formalism [3], and by R-3<=>R-3c phase transitions due to cation disordering, treated by redefining the compositional space with an independent set of end-members that describe both composition and states of ordering. The result is a solid solution model able to reproduce both the phase relations experimentally observed at 35 kbar and those experimentally determined and naturally observed at lower pressure [4-5]. Our model can be reliable extended to pressures of the breakdown of dolomite, e.g. 5-6 GPa, 600-1000 °C. Melting experiments carried out at 1250 °C along

  19. Computational Design of Iron Diphosphine Complexes with Pendant Amines for Hydrogenation of CO2 to Methanol: A Mimic of [NiFe] Hydrogenase.

    PubMed

    Chen, Xiangyang; Jing, Yuanyuan; Yang, Xinzheng

    2016-06-20

    Inspired by the active-site structure of the [NiFe] hydrogenase, we have computationally designed the iron complex [P(tBu) 2 N(tBu) 2 )Fe(CN)2 CO] by using an experimentally ready-made diphosphine ligand with pendant amines for the hydrogenation of CO2 to methanol. Density functional theory calculations indicate that the rate-determining step in the whole catalytic reaction is the direct hydride transfer from the Fe center to the carbon atom in the formic acid with a total free energy barrier of 28.4 kcal mol(-1) in aqueous solution. Such a barrier indicates that the designed iron complex is a promising low-cost catalyst for the formation of methanol from CO2 and H2 under mild conditions. The key role of the diphosphine ligand with pendent amine groups in the reaction is the assistance of the cleavage of H2 by forming a Fe-H(δ-) ⋅⋅⋅H(δ+) -N dihydrogen bond in a fashion of frustrated Lewis pairs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Correlation between charge input and cycle life of MgNi electrode for Ni-MH batteries

    NASA Astrophysics Data System (ADS)

    Ruggeri, Stéphane; Roué, Lionel

    Amorphous MgNi material has been prepared by mechanically alloying magnesium and nickel powders for 10 h. Its cycle life as a negative electrode for nickel-metal hydride (Ni-MH) batteries has been studied with charge inputs varying from 0 to 600 mAh/g. For charge inputs lower than 400 mAh/g, the first cycle discharge capacity is superior to the charge input capacity. This surplus discharge capacity can be associated with the alloy oxidation to Mg(OH) 2 and Ni(OH) 2. For charge inputs higher than 400 mAh/g, the initial discharge capacity becomes inferior to the charge input capacity due to the progressive decrease of the charge efficiency related to the hydrogen evolution side reaction. From the second charge/discharge cycle, no additional discharge capacity appears and no discharge capacity degradation occurs for charge inputs inferior or equal to 233 mAh/g. In contrast, for higher charge input values, an important decay in the discharge capacity appears, which is accentuated with increasing charge input. The thresholds charge input of 233 mAh/g corresponds to an amount of hydrogen absorbed into the alloy of 0.8 wt.% (MgNiH 0.7). For higher absorbed hydrogen amounts, it is assumed that extended electrode pulverization occurs, which breaks the passive surface layer of Mg(OH) 2 formed during the first charge/discharge cycle. This creates unprotected fresh MgNi surfaces and consequently, leads to electrode capacity degradation. The stability of the MgNi electrode for absorbed hydrogen content lower than 0.8 wt.% may be related to its amorphous character, which favors a gradual volume expansion upon hydrogen absorption in contrast to crystalline compounds characterized by an abrupt α-to-β lattice expansion.

  1. Microstructure and corrosion properties of CrMnFeCoNi high entropy alloy coating

    NASA Astrophysics Data System (ADS)

    Ye, Qingfeng; Feng, Kai; Li, Zhuguo; Lu, Fenggui; Li, Ruifeng; Huang, Jian; Wu, Yixiong

    2017-02-01

    Equimolar CrMnFeCoNi high entropy alloy (HEA) is one of the most notable single phase multi-component alloys up-to-date with promising mechanical properties at cryogenic temperatures. However, the study on the corrosion behavior of CrMnFeCoNi HEA coating has still been lacking. In this paper, HEA coating with a nominal composition of CrMnFeCoNi is fabricated by laser surface alloying and studied in detail. Microstructure and chemical composition are determined by X-ray diffraction (XRD), optical microscope (OM), scanning electron microscope (SEM) and energy dispersive spectrometer (EDS). Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) are used to investigate the corrosion behavior. The coating forms a simple FCC phase with an identical dendritic structure composed of Fe/Co/Ni-rich dendrites and Mn/Ni-rich interdendrites. Both in 3.5 wt.% NaCl solution and 0.5 M sulfuric acid the coating exhibits nobler corrosion resistance than A36 steel substrate and even lower icorr than 304 stainless steel (304SS). EIS plots coupled with fitted parameters reveal that a spontaneous protective film is formed and developed during immersion in 0.5 M sulfuric acid. The fitted Rt value reaches its maximum at 24 h during a 48 h' immersion test, indicating the passive film starts to break down after that. EDS analysis conducted on a corroded surface immersed in 0.5 M H2SO4 reveals that corrosion starts from Cr-depleted interdendrites.

  2. Impact of initial catalyst form on the 3D structure and performance of ball-milled Ni-catalyzed MgH 2 for hydrogen storage

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    House, Stephen D.; Vajo, John J.; Ren, Chai

    Although it has been shown that the hydrogen storage kinetics of metal hydrides can be significantly improved by the addition of transition metal-based catalysts, relatively little attention has been paid to the impact that the form in which these catalysts are introduced during synthesis has on the resulting structure and how this alters performance. Two mixtures of MgH 2 doped with Ni were prepared via high-energy ball-milling under identical conditions, one using a pure Ni nanopowder catalyst and the other using anhydrous NiCl 2. The resulting Ni catalyst particles of the NiCl 2-doped material were 10-100 times smaller, as wellmore » as more uniform in size and shape. Electron tomography revealed that the additive form also altered its incorporation and 3D spatial distribution, with Ni particles limited to the outer surface in the NiCl 2-doped case. The significantly lower desorption performance measured in the NiCl 2-doped material is attributed to regions of MgCl 2 acting as barriers between the MgH 2 and Ni, hindering the ability of the latter to effectively catalyze the reactions. Finally, this work demonstrates the hazards in assuming different catalyst forms produce similar final structures and highlights the potential of catalyst form as a synthesis tool for optimizing the material structure and performance.« less

  3. Impact of initial catalyst form on the 3D structure and performance of ball-milled Ni-catalyzed MgH 2 for hydrogen storage

    DOE PAGES

    House, Stephen D.; Vajo, John J.; Ren, Chai; ...

    2017-02-24

    Although it has been shown that the hydrogen storage kinetics of metal hydrides can be significantly improved by the addition of transition metal-based catalysts, relatively little attention has been paid to the impact that the form in which these catalysts are introduced during synthesis has on the resulting structure and how this alters performance. Two mixtures of MgH 2 doped with Ni were prepared via high-energy ball-milling under identical conditions, one using a pure Ni nanopowder catalyst and the other using anhydrous NiCl 2. The resulting Ni catalyst particles of the NiCl 2-doped material were 10-100 times smaller, as wellmore » as more uniform in size and shape. Electron tomography revealed that the additive form also altered its incorporation and 3D spatial distribution, with Ni particles limited to the outer surface in the NiCl 2-doped case. The significantly lower desorption performance measured in the NiCl 2-doped material is attributed to regions of MgCl 2 acting as barriers between the MgH 2 and Ni, hindering the ability of the latter to effectively catalyze the reactions. Finally, this work demonstrates the hazards in assuming different catalyst forms produce similar final structures and highlights the potential of catalyst form as a synthesis tool for optimizing the material structure and performance.« less

  4. Cation substitution in synthetic meridianiite (MgSO4·11H2O) I: X-ray powder diffraction analysis of quenched polycrystalline aggregates

    NASA Astrophysics Data System (ADS)

    Fortes, A. Dominic; Browning, Frank; Wood, Ian G.

    2012-05-01

    Meridianiite, MgSO4·11H2O, is the most highly hydrated phase in the binary MgSO4-H2O system. Lower hydrates in the MgSO4-H2O system have end-member analogues containing alternative divalent metal cations (Ni2+, Zn2+, Mn2+, Cu2+, Fe2+, and Co2+) and exhibit extensive solid solution with MgSO4 and with one another, but no other undecahydrate is known. We have prepared aqueous MgSO4 solutions doped with these other cations in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. The solid products have been characterised by X-ray powder diffraction, and the onset of partial melting has been quantified using a thermal probe. We have established that of the seven end-member metal sulfates studied, only MgSO4 forms an undecahydrate; ZnSO4 forms an orthorhombic heptahydrate (synthetic goslarite), MnSO4, FeSO4, and CoSO4 form monoclinic heptahydrates (syn. mallardite, melanterite, bieberite, respectively), and CuSO4 crystallises as the well-known triclinic pentahydrate (syn. chalcanthite). NiSO4 forms a new hydrate which has been indexed with a triclinic unit cell of dimensions a = 6.1275(1) Å, b = 6.8628(1) Å, c = 12.6318(2) Å, α = 92.904(2)°, β = 97.678(2)°, and γ = 96.618(2)°. The unit-cell volume of this crystal, V = 521.74(1) Å3, is consistent with it being an octahydrate, NiSO4·8H2O. Further analysis of doped specimens has shown that synthetic meridianiite is able to accommodate significant quantities of foreign cations in its structure; of the order 50 mol. % Co2+ or Mn2+, 20-30 mol. % Ni2+ or Zn2+, but less than 10 mol. % of Cu2+ or Fe2+. In three of the systems we examined, an `intermediate' phase occurred that differed in hydration state both from the Mg-bearing meridianiite end-member and the pure dopant end-member hydrate. In the case of CuSO4, we observed a melanterite-structured heptahydrate at Cu

  5. Insight into destabilization mechanism of Mg-based hydrides interstitially co-doped with nonmetals: a DFT study

    NASA Astrophysics Data System (ADS)

    Wu, Zhen; Zhu, Luying; Yang, Fusheng; Zhang, Zaoxiao; Nyamsi, Serge N.

    2018-04-01

    Mg-based metal hydride is one of the most promising materials for hydrogen energy storage. However, the high thermal stability due to strong bonding effects between the atoms limits its practical application. In order to reduce the thermal stability, a method of doping double nonmetals into Mg-based system was proposed in this study. The density functional theory (DFT) calculation results showed that the thermal stabilities of both the B-N co-doped Mg-based alloy and its hydride are reduced compared with pure Mg-based system. The relative formation enthalpies of the alloy and its hydride are 0.323 and 0.595 eV atom-1, respectively. The values are much higher than those for either singly B- or N-doped Mg-based system. The more significant destabilization by doping double nonmetal elements than single element is mainly attributed to a dual effect in weakening Mg-Ni/NiH4 bonds, caused by criss-cross interactions between B-Ni and N-Mg bonds.

  6. AFLOWLIB.ORG: a Distributed Materials Properties Repository from High-throughput Ab initio Calculations

    DTIC Science & Technology

    2011-11-15

    uncle) fcc (uncle) hcp (uncle) phase-diagram Ag Al Al Au Au Bi Bi Ca Ca Cd Cd Ce Ce Co Co Cr Cr Cu Cu Fe Fe Ga Ga Gd Gd Ge Ge Hf...Hf Hg Hg In In Ir Ir La La Li Li Mg Mg Mn Mn Mo Mo Na Na Nb Nb Ni Ni Os Os Pb Pb Pd Pd Pt Pt Rb Rb Re Re Rh Rh Ru Ru Sb Sb Sc...2 S. Curtarolo, A. N. Kolmogorov, and F. H. Cocks, High-throughput ab initio analysis of the Bi-In, Bi- Mg , Bi-Sb, In- Mg , In-Sb, and Mg -Sb systems

  7. Ni-Al films induced surface modification of La2Mg17 alloy leading to improved dehydrogenation properties

    NASA Astrophysics Data System (ADS)

    Zhang, Huaiwei; Fu, Li; Xuan, Weidong; Qin, Haiying; Ji, Zhenguo

    2018-05-01

    The effects of surface coating with Ni-Al nano-films to the hydrogenation properties of the La2Mg17 alloy are studied in the paper. The reversible hydrogen storage capacities, thermodynamics and kinetics process are all improved for the coating samples, and the comprehensive performances reach the best when the sputtering time is 5min with the film thickness 71.7 nm. The dehydrogenation temperature of the coating sample can be reduced to about 560K from above 720K comparing to the body alloy. The XPS analysis shows that the Ni-Al film coating layer can act as the catalyst in the dehydrogenation process.

  8. Single-phase ceramics with La 1- xSr xGa 1- yMg yO 3- δ composition from precursors obtained by mechanosynthesis

    NASA Astrophysics Data System (ADS)

    Moure, A.; Castro, A.; Tartaj, J.; Moure, C.

    Dense ceramics with La 0.80Sr 0.20Ga 0.85Mg 0.15O 2.825 and La 0.80Sr 0.15Ga 0.85Mg 0.20O 2.825 compositions have been prepared by sintering of mechanosynthesized precursors. The perovskite is synthesized after 85 h of milling in a planetary mill. Single phases have been obtained at conditions that are not possible if traditional solid-state reaction (SSR) method is used. The influence of milling time and composition in the reactivity of the precursors is studied. Highest purity is obtained in Sr = 0.15 and Mg = 0.20 composition, with relative density higher than 97%. The total elimination of typical secondary phases for these compositions, as SrLaGaO 4 and SrLaGa 3O 7, allows the total conductivity of the ceramics to be improved. The influence of the grain size and the nature of the grain boundaries on the electrical characteristic of the ceramics are also discussed.

  9. Mechanical properties, microstructural and thermal evolution of Mg65Ni20Y15-xSix (X = 1, 2, 3) alloys by mechanical alloying

    NASA Astrophysics Data System (ADS)

    Kursun, Celal; Gogebakan, Musa; Eskalen, Hasan

    2018-03-01

    We report on a work of the influence of the mechanical alloying on the microstructure, thermal and mechanical features of Mg65Ni20Y15-xSix (X = 1, 2, 3) alloys. The Mg-based alloys were produced by mechanical alloying technique from mixtures of pure crystalline Mg, Ni, Y and Si powders. These alloys were investigated using a variety of analytical techniques including x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry (EDX) and differential scanning calorimetry (DSC). The mechanical properties of the alloys were investigated by Vickers microhardness (HV) tester. After 75 h of milling time, three different intermetallic phases were obtained. These phases were defined as Mg24Y5, Mg2Ni3Si and Mg2Ni by XRD data. The particle and crystallite sizes of the Mg-based alloys were decreased by increasing milling time and they were calculated 2 μm and ˜9 nm, respectively. From the EDX analysis, it was determined that compositional homogeneity of the Mg-based alloys was fairly high. The microhardness values of the Mg65Ni20Y15-xSix (X = 1, 2, 3) alloys increased by increasing Si into the alloys and were determined 101, 131 and 158 HV, respectively.

  10. Effect of amorphous Mg{sub 50}Ni{sub 50} on hydriding and dehydriding behavior of Mg{sub 2}Ni alloy

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Guzman, D., E-mail: danny.guzman@uda.cl; Ordonez, S.; Fernandez, J.F.

    Composite Mg{sub 2}Ni (25 wt.%) amorphous Mg{sub 50}Ni{sub 50} was prepared by mechanical milling starting with nanocrystalline Mg{sub 2}Ni and amorphous Mg{sub 50}Ni{sub 50} powders, by using a SPEX 8000 D mill. The morphological and microstructural characterization of the powders was performed via scanning electron microscopy and X-ray diffraction. The hydriding characterization of the composite was performed via a solid gas reaction method in a Sievert's-type apparatus at 363 K under an initial hydrogen pressure of 2 MPa. The dehydriding behavior was studied by differential thermogravimetry. On the basis of the results, it is possible to conclude that amorphous Mg{submore » 50}Ni{sub 50} improved the hydriding and dehydriding kinetics of Mg{sub 2}Ni alloy upon cycling. A tentative rationalization of experimental observations is proposed. - Research Highlights: {yields} First study of the hydriding behavior of composite Mg{sub 2}Ni (25 wt.%) amorphous Mg{sub 50}Ni{sub 50}. {yields} Microstructural characterization of composite material using XRD and SEM was obtained. {yields} An improved effect of Mg{sub 50}Ni{sub 50} on the Mg{sub 2}Ni hydriding behavior was verified. {yields} The apparent activation energy for the hydrogen desorption of composite was obtained.« less

  11. Growth and optical properties of Co,Nd:LaMgAl11O19

    NASA Astrophysics Data System (ADS)

    Xu, Peng; Xia, Changtai; Di, Juqing; Xu, Xiaodong; Sai, Qinglin; Wang, Lulu

    2012-12-01

    Nd,Co:LaMgAl11O19 (abbreviated as Co,Nd:LMA) was grown using the Czochralski method. The structure, polarized absorption spectrum, fluorescence spectrum, and fluorescence decay time were analyzed. The as-grown crystal had very wide absorption bands at 794 nm, which can be pumped by GaAs laser diode without temperature stabilization. Two strong emission bands were present at 1056 nm and 1082 nm with full-width at half-maximum (FWHM) of 6 and 8 nm, respectively. The large FWHM is due to the inhomogeneity of the Nd ion sites. The lifetimes of the 4F3/2 manifold of Co,Nd:LMA at room temperature monitored at 905 nm, 1056 nm, and 1344 nm were 292, 288, and 350 μs, respectively, which was caused by the different contribution of the three different sites with D3h and C2v symmetry. The absorption band of Co is from 1.3 μm to 1.6 μm, and Co,Nd:LMA still has a strong emission around the 1.38 μm, indicating that the Co,Nd:LMA can be applied as a potential self-Q-switched material operating at 1.3 μm.

  12. Hydrogenation thermodynamics of melt-spun magnesium rich Mg-Ni nanocrystalline alloys with the addition of multiwalled carbon nanotubes and TiF3

    NASA Astrophysics Data System (ADS)

    Hou, Xiaojiang; Hu, Rui; Zhang, Tiebang; Kou, Hongchao; Li, Jinshan

    2016-02-01

    Based on the complexity of hydrogen absorption/desorption process and from the perspective of overall control, the as-cast Mg-10wt%Ni (Mg10Ni) alloy has been successively optimized by melt-spinning and surface catalyzed to realize the internal refinement as well as surface modification. The isothermal hydrogenation behavior of modified Mg-rich alloys has been investigated in this work. The results indicate that melt-spun Mg10Ni catalyzed by multiwalled carbon nanotubes (MWCNTs) coupling with TiF3 possesses superior activation properties and can absorb 6.23 wt% at 250 °C under 2.5 MPa. It is worth mentioning that the hydrogenation capacities of Mg10Ni-MWCNTs-TiF3 are 5.93 wt% and 5.99 wt% within the initial 1 min and 5 min, respectively. Meanwhile, the catalytic effect of MWCNTs and TiF3 has been discussed. The improved activation performance as well as the thermodynamics properties of Mg10Ni catalyzed by MWCNTs and TiF3 is attributed to the synergistic effect on dissociation of H2 molecules, diffusion of H-atoms and heterogeneous nucleation of hydrides.

  13. The Crystal Structure and Magnetic Behavior of Quinary Osmate and Ruthenate Double Perovskites La ABB'O 6 ( A = Ca, Sr; B = Co, Ni; B' = Ru, Os)

    DOE PAGES

    Morrow, Ryan; McGuire, Michael A.; Yan, Jiaqiang; ...

    2018-02-23

    In this work, six LaABB'O 6 (A = Ca, Sr; B = Co, Ni; B' = Ru, Os) double perovskites were synthesized, several for the first time, and their crystal structures and magnetic behavior were characterized with neutron powder diffraction and direct-current and alternating-current magnetometry. All six compounds crystallize with P2 1/n space group symmetry, resulting from a –a –c + octahedral tilting and complete rock salt ordering of transition-metal ions. Despite the electronic configurations of the transition-metal ions, either d 8–d 3 or d 7–d 3, not one of the six compounds shows ferromagnetism as predicted by the Goodenough–Kanamorimore » rules. LaSrNiOsO 6, LaSrNiRuO 6, and LaCaNiRuO 6 display long-range antiferromagnetic order, while LaCaNiOsO 6, LaCaCoOsO 6, and LaSrCoOsO 6 exhibit spin-glass behavior. These compounds are compared to the previously studied LaCaCoRuO 6 and LaSrCoRuO 6, both of which order antiferromagnetically. Lastly, the observed variations in magnetic properties can be attributed largely to the response of competing superexchange pathways due to changes in B–O–B' bond angles, differences in the radial extent of the 4d (B' = Ru) and 5d (B' = Os) orbitals, and filling of the t 2g orbitals of the 3d ion.« less

  14. The Crystal Structure and Magnetic Behavior of Quinary Osmate and Ruthenate Double Perovskites La ABB'O 6 ( A = Ca, Sr; B = Co, Ni; B' = Ru, Os)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Morrow, Ryan; McGuire, Michael A.; Yan, Jiaqiang

    In this work, six LaABB'O 6 (A = Ca, Sr; B = Co, Ni; B' = Ru, Os) double perovskites were synthesized, several for the first time, and their crystal structures and magnetic behavior were characterized with neutron powder diffraction and direct-current and alternating-current magnetometry. All six compounds crystallize with P2 1/n space group symmetry, resulting from a –a –c + octahedral tilting and complete rock salt ordering of transition-metal ions. Despite the electronic configurations of the transition-metal ions, either d 8–d 3 or d 7–d 3, not one of the six compounds shows ferromagnetism as predicted by the Goodenough–Kanamorimore » rules. LaSrNiOsO 6, LaSrNiRuO 6, and LaCaNiRuO 6 display long-range antiferromagnetic order, while LaCaNiOsO 6, LaCaCoOsO 6, and LaSrCoOsO 6 exhibit spin-glass behavior. These compounds are compared to the previously studied LaCaCoRuO 6 and LaSrCoRuO 6, both of which order antiferromagnetically. Lastly, the observed variations in magnetic properties can be attributed largely to the response of competing superexchange pathways due to changes in B–O–B' bond angles, differences in the radial extent of the 4d (B' = Ru) and 5d (B' = Os) orbitals, and filling of the t 2g orbitals of the 3d ion.« less

  15. Phase Evolution and Mechanical Properties of AlCoCrFeNiSi x High-Entropy Alloys Synthesized by Mechanical Alloying and Spark Plasma Sintering

    NASA Astrophysics Data System (ADS)

    Kumar, Anil; Swarnakar, Akhilesh Kumar; Chopkar, Manoj

    2018-05-01

    In the current investigation, AlCoCrFeNiSi x (x = 0, 0.3, 0.6 and 0.9 in atomic ratio) high-entropy alloy systems are prepared by mechanical alloying and subsequently consolidated by spark plasma sintering. The microstructural and mechanical properties were analyzed to understand the effect of Si addition in AlCoCrFeNi alloy. The x-ray diffraction analysis reveals the supersaturated solid solution of the body-centered cubic structure after 20 h of ball milling. However, the consolidation promotes the transformation of body-centered phases partially into the face-centered cubic structure and sigma phases. A recently proposed geometric model based on the atomic stress theory has been extended for the first time to classify single phase and multi-phases on the high-entropy alloys prepared by mechanical alloying and spark plasma sintering process. Improved microhardness and better wear resistance were achieved as the Si content increased from 0 to 0.9 in the present high-entropy alloy.

  16. An "intermediate spin" nickel hydride complex stemming from delocalized Ni2(μ-H)2 bonding.

    PubMed

    Yao, Shu A; Corcos, Amanda R; Infante, Ivan; Hillard, Elizabeth A; Clérac, Rodolphe; Berry, John F

    2014-10-01

    The nickel hydride complex [Cp'Ni(μ-H)]2 (1, Cp' = 1,2,3,4-tetraisopropylcyclopentadienyl) is found to have a strikingly short Ni-Ni distance of 2.28638(3) Å. Variable temperature and field magnetic measurements indicate an unexpected triplet ground state for 1 with a large zero-field splitting of +90 K (63 cm(-1)). Electronic structure calculations (DFT and CASSCF/CASPT2) explain this ground state as arising from half occupation of two nearly degenerate Ni-Ni π* orbitals.

  17. Study of xCo0.8Ni0.2Fe2O4+(1-x) Pb0.99625 La0.0025Zr0.55Ti0.45O3 magnetoelectric composites

    NASA Astrophysics Data System (ADS)

    Dipti; Singh, Sangeeta; Juneja, J. K.; Raina, K. K.; Kotnala, R. K.; Prakash, Chandra

    2016-06-01

    We are reporting here, the studies of the structural, dielectric, ferroelectric and magnetic properties of magnetoelectric composites of La modified lead zirconate titanate (PLZT) and Ni modified cobalt ferrite (CNFO) with compositional formula xCo0.8Ni0.2Fe2O4+(1-x) Pb0.99625La0.0025Zr0.55Ti0.45O3 (x=0.00, 0.05, 0.10, 0.15 and 1.00 by weight) prepared by the solid state reaction method. Coexistence of both the phases in composites was confirmed by X-Ray diffraction technique. The microstructure and average grain size were determined from Scanning Electron Micrograph (SEM) in backscattered mode. Both the phases could be observed clearly. The variations of dielectric properties with frequency and temperature were also studied. P-E and M-H hysteresis measurements were carried. Magnetoelectric coupling (ME) coefficient for samples with x=0.05 and 0.10 were measured as a function of DC magnetic field. Maximum value of ME coefficient (1.2 mV/cm Oe) and piezoelectric coefficient (96 pC/N) for x=0.05 were observed.

  18. Fluorite transition metal hydride induced destabilization of the MgH2 system in MgH2/TMH2 multilayers ( TM=Sc , Ti, V, Cr, Y, Zr, Nb, La, Hf)

    NASA Astrophysics Data System (ADS)

    Tao, S. X.; Notten, P. H. L.; van Santen, R. A.; Jansen, A. P. J.

    2010-09-01

    The structural changes in MgH2 induced by contact with fluorite transition metal hydrides ( TMH2 , TM=Sc , Ti, V, Cr, Y, Zr, Nb, La, Hf) have been studied using density-functional theory calculations. Models of MgH2(rutile)/TiH2(fluorite) and MgH2(fluorite)/TiH2(fluorite) multilayers with different Mg:TM ratios have been designed. With a fixed thickness of the TMH2 layer, structure transformation of MgH2 from rutile to fluorite occurs with a decrease in thickness of the MgH2 layer. The hydrogen desorption energy from the fluorite MgH2 layer in the multilayers is significantly lower than that of the bulk rutile MgH2 . The structural deformation of the MgH2 layer due to the strain induced by TMH2 is found to be responsible for the destabilization of the Mg-H bond: the more structural deformation, the more destabilization of the Mg-H. Our results provide an important insight for the development of new hydrogen-storage materials with desirable thermodynamic properties.

  19. High pressure synthesis of a hexagonal close-packed phase of the high-entropy alloy CrMnFeCoNi

    DOE PAGES

    Tracy, Cameron L.; Park, Sulgiye; Rittman, Dylan R.; ...

    2017-05-25

    High pressure x-ray diffraction measurements reveal that the face-centered cubic (fcc) high-entropy alloy CrMnFeCoNi transforms martensitically to a hexagonal close-packed (hcp) phase at ~14 GPa. We attribute this to suppression of the local magnetic moments, destabilizing the fcc phase. Similar to fcc-to-hcp transformations in Al and the noble gases, this transformation is sluggish, occurring over a range of >40 GPa. But, the behavior of CrMnFeCoNi is unique in that the hcp phase is retained following decompression to ambient pressure, yielding metastable fcc-hcp mixtures.

  20. Reactivity of a series of isostructural cobalt pincer complexes with CO2, CO, and H(+).

    PubMed

    Shaffer, David W; Johnson, Samantha I; Rheingold, Arnold L; Ziller, Joseph W; Goddard, William A; Nielsen, Robert J; Yang, Jenny Y

    2014-12-15

    The preparation and characterization of a series of isostructural cobalt complexes [Co(t-Bu)2P(E)Py(E)P(t-Bu)2(CH3CN)2][BF4]2 (Py = pyridine, E = CH2, NH, O, and X = BF4 (1a-c)) and the corresponding one-electron reduced analogues [Co(t-Bu)2P(E)Py(E)P(t-Bu)2(CH3CN)2][BF4]2 (2a-c) are reported. The reactivity of the reduced cobalt complexes with CO2, CO, and H(+) to generate intermediates in a CO2 to CO and H2O reduction cycle are described. The reduction of 1a-c and subsequent reactivity with CO2 was investigated by cyclic voltammetry, and for 1a also by infrared spectroelectrochemistry. The corresponding CO complexes of (2a-c) were prepared, and the Co-CO bond strengths were characterized by IR spectroscopy. Quantum mechanical methods (B3LYP-d3 with solvation) were used to characterize the competitive reactivity of the reduced cobalt centers with H(+) versus CO2. By investigating a series of isostructural complexes, correlations in reactivity with ligand electron withdrawing effects are made.

  1. UV Spectra of Tris(2,2'-bipyridine)-M(II) Complex Ions in Vacuo (M = Mn, Fe, Co, Ni, Cu, Zn).

    PubMed

    Xu, Shuang; Smith, James E T; Weber, J Mathias

    2016-11-21

    We present electronic spectra in the π-π* region of a series of tris(bpy)-M(II) complex ions (bpy = 2,2'-bipyridine; M = Mn, Fe, Co, Ni, Cu, Zn) in vacuo for the first time. By applying photodissociation spectroscopy to cryogenically cooled and mass selected [M II (bpy) 3 ] 2+ ions, we obtain the intrinsic spectra of these ions at low temperature without perturbation by solvent interaction or crystal lattice shifts. This allows spectroscopic analysis of these complex ions in greater detail than possible in the condensed phase. We interpret our experimental data by comparison with time-dependent density functional theory.

  2. Investigation on hydrogenation performance of Mg{sub 2}Ni+10 wt.% NbN composite

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhao, Xin; Han, Shumin; State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004

    2015-01-15

    The Mg{sub 2}Ni+10 wt.% NbN composite was prepared by mechanical milling and its hydrogen absorption/desorption properties and microstructure were systematically investigated. XRD results indicated that NbN was stable during ball milling process while partly decomposed into NbN{sub 0.95} and NbH during hydriding/dehydriding cycles irreversibly. The composite exhibited excellent hydrogenation/dehydrogenation kinetics performance with 2.71 wt.% hydrogen absorbed in 60 s at 423 K and 0.81 wt.% hydrogen released in 2 h at 523 K, respectively. The H diffusion constant of the composite reached 14.98×10{sup −5} s{sup −1} which was more than twice increased than that of pure Mg{sub 2}Ni powder. Themore » superior hydrogen storage properties of the composite were ascribed to the refined grain size and abundant N-defect points provided by NbN and NbN{sub 0.95} in the composite. - Graphical abstract: The Mg{sub 2}Ni+10 wt.% NbN composite displays improvements on particle size distribution as well as hydrogen storage properties compared with that of pure Mg{sub 2}Ni. - Highlights: • NbN is introduced into Mg{sub 2}Ni hydride by Ar protected ball-milling. • Surfaces of the additive NbN particle are reduced by Mg{sub 2}NiH{sub 4}. • Hydrogenation kinetic property at 423 K is double improved. • Dehydrogenation capacity at 523 K of composites is beyond double improved.« less

  3. Glucose- and Cellulose-Derived Ni/C-SO3H Catalysts for Liquid Phase Phenol Hydrodeoxygenation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kasakov, Stanislav; Zhao, Chen; Barath, Eszter

    2015-01-19

    Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalyzed the reduction of phenol to cyclohexanolmore » in water. The state of 3 – 5 nm grafted Ni particles was analyzed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt.% C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support.« less

  4. Synthesis, spectral, antitumor, antioxidant and antimicrobial studies on Cu(II), Ni(II) and Co(II) complexes of 4-[(1H-Benzoimidazol-2-ylimino)-methyl]-benzene-1,3-diol.

    PubMed

    El-wakiel, Nadia; El-keiy, Mai; Gaber, Mohamed

    2015-08-05

    A new Schiff base of 2-aminobenzimidazole with 2,4-dihydroybezaldehyde (H₃L), and its Cu(II), Ni(II) and Co(II) complexes have been synthesized and characterized by elemental analyses, molar conductance, thermal analysis (TGA), inductive coupled plasma (ICP), magnetic moment measurements, IR, EI-mass, UV-Vis. and ESR spectral studies. On the basis of spectral studies and analytical data, it is evident that the Schiff base acts as dibasic tridentate ligand coordinating via deprotonated OH, NH and azomethine nitrogen atom. The results showed that Co(II) and Ni(II) complexes have tetrahedral structure while Cu(II) complexes has octahedral geometry. The kinetic and thermodynamic parameters of the thermal decomposition stages have been evaluated. The studied complexes were tested for their in vitro antimicrobial activities against some bacterial strains. The anticancer activity of the ligand and its metal complexes is evaluated against human liver Carcinoma (HEPG2) cell. These compounds exhibited a moderate and weak activity against the tested HEPG2 cell lines with IC₅₀ of 9.08, 18.2 and 19.7 μg/ml for ligand, Cu(II) and Ni(II) complexes, respectively. In vitro antioxidant activity of the newly synthesized compounds has also been evaluated. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Adsorption and co-adsorption of graphene oxide and Ni(II) on iron oxides: A spectroscopic and microscopic investigation.

    PubMed

    Sheng, Guodong; Huang, Chengcai; Chen, Guohe; Sheng, Jiang; Ren, Xuemei; Hu, Baowei; Ma, Jingyuan; Wang, Xiangke; Huang, Yuying; Alsaedi, Ahmed; Hayat, Tasawar

    2018-02-01

    Graphene oxide (GO) may strongly interact with toxic metal ions and mineral particles upon release into the soil environment. We evaluated the mutual effects between GO and Ni (Ni(II)) with regard to their adsorption and co-adsorption on two minerals (goethite and hematite) in aqueous phase. Results indicated that GO and Ni could mutually facilitate the adsorption of each other on both goethite and hematite over a wide pH range. Addition of Ni promoted GO co-adsorption mainly due to the increased positive charge of minerals and cation-π interactions, while the presence of GO enhanced Ni co-adsorption predominantly due to neutralization of positive charge and strong interaction with oxygen-containing functional groups on adsorbed GO. Increasing adsorption of GO and Ni on minerals as they coexist may thus reduce their mobility in soil. Extended X-ray absorption fine structure (EXAFS) spectroscopy data revealed that GO altered the microstructure of Ni on minerals, i.e., Ni formed edge-sharing surface species (at R Ni-Fe ∼3.2 Å) without GO, while a GO-bridging ternary surface complexes (at R Ni-C ∼2.49 Å and R Ni-Fe ∼4.23 Å) was formed with GO. These findings improved the understanding of potential fate and toxicity of GO as well as the partitioning processes of Ni ions in aquatic and soil environments. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. CO2/H2O adsorption equilibrium and rates on metal-organic frameworks: HKUST-1 and Ni/DOBDC.

    PubMed

    Liu, Jian; Wang, Yu; Benin, Annabelle I; Jakubczak, Paulina; Willis, Richard R; LeVan, M Douglas

    2010-09-07

    Metal-organic frameworks (MOFs) have recently attracted intense research interest because of their permanent porous structures, huge surface areas, and potential applications as novel adsorbents and catalysts. In order to provide a basis for consideration of MOFs for removal of carbon dioxide from gases containing water vapor, such as flue gas, we have studied adsorption equilibrium of CO(2), H(2)O vapor, and their mixtures and also rates of CO(2) adsorption in two MOFs: HKUST-1 (CuBTC) and Ni/DOBDC (CPO-27-Ni or Ni/MOF-74). The MOFs were synthesized via solvothermal methods, and the as-synthesized products were solvent exchanged and regenerated before experiments. Pure component adsorption equilibria and CO(2)/H(2)O binary adsorption equilibria were studied using a volumetric system. The effects of H(2)O adsorption on CO(2) adsorption for both MOF samples were determined, and the results for 5A and NaX zeolites were included for comparison. The hydrothermal stabilities for the two MOFs over the course of repetitive measurements of H(2)O and CO(2)/H(2)O mixture equilibria were also studied. CO(2) adsorption rates from helium for the MOF samples were investigated by using a unique concentration-swing frequency response (CSFR) system. Mass transfer into the MOFs is rapid with the controlling resistance found to be macropore diffusion, and rate parameters were established for the mechanism.

  7. Electrocatalytic reduction of CO2 with CCC-NHC pincer nickel complexes.

    PubMed

    Cope, James D; Liyanage, Nalaka P; Kelley, Paul J; Denny, Jason A; Valente, Edward J; Webster, Charles Edwin; Delcamp, Jared H; Hollis, T Keith

    2017-08-22

    A CCC-NHC pincer Ni(ii)Cl complex was prepared according to the metallation/transmetallation methodology. It was fully characterized by electrochemical, NMR spectroscopic, theoretical, and X-ray crystallographic methods. The complex and its cation were evaluated for electrocatalytic reduction of CO 2 under a variety of conditions and found to provide some of the fastest catalytic rates and highest substrate selectivities (CO 2 vs. H + ) reported. Rates improved in the presence of water and, significantly, catalysis occurred at the first reduction potential, presumably at the Ni(i) state. Controlled potential electrolysis (CPE) was found to yield CO at 34% and formate at 47% Faradaic efficiency (FE).

  8. Phase transitions, magnetotransport and magnetocaloric effects in a new family of quaternary Ni-Mn-In-Z Heusler alloys.

    PubMed

    Kazakov, Alexander; Prudnikov, Valerii; Granovsky, Alexander; Perov, Nikolai; Dubenko, Igor; Pathak, Arjun Kumar; Samanta, Tapas; Stadler, Shane; Ali, Naushad; Zhukov, Arcady; Ilyin, Maxim; Gonzalez, Julian

    2012-09-01

    The magnetic, magnetotransport, and magnetocaloric properties near compound phase transitions in Ni50Mn35In14Z (Z = In, Ge, Al), and Ni48Co2Mn35In15 Heusler alloys have been studied using VSM and SQUID magnetometers (at magnetic fields (H) up to 5 T), four-probe method (at H = 0.005-1.5 T), and an adiabatic magnetocalorimeter (for H changes up to deltaH = 1.8 T), respectively. The martensitic transformation (MT) is accompanied by large magnetoresistance (up to 70%), a significant change in resistivity (up to 200%), and a sign reversal of the ordinary Hall effect coefficient, all related to a strong change in the electronic spectrum at the MT. The field dependences of the Hall resistance are complex in the vicinity of the MT, indicating a change in the relative concentrations of the austenite and martensite phases at strong fields. Negative and positive changes in adiabatic temperatures of about -2 K and +2 K have been observed in the vicinity of MT and Curie temperatures, respectively, for deltaH = 1.8 T.

  9. Elucidation of reaction mechanism involved in the formation of LaNiO3 from XRD and TG analysis

    NASA Astrophysics Data System (ADS)

    Dharmadhikari, Dipti V.; Athawale, Anjali A.

    2013-06-01

    The present work is focused on the synthesis and elucidation of reaction mechanism involved in the formation of LaNiO3 with the help of X-ray diffraction (XRD) and thermogravimetric (TG) analysis. LaNiO3 was synthesized by hydrothermal method by heating at 160°C under autogenous pressure for 6h. Pure phase product was obtained after calcining the hydrothermally activated product for 6h at 700°C. The various phases of the product obtained after hydrothermal treatment and calcination followed by the formation of pure phase nanocrystalline lanthanum nickel oxide could be determined from XRD analysis of the samples. The reaction mechanism and phase formation temperature has been interpreted by thermogravimetric analysis of the hydrothermally synthesized product and XRD analysis.

  10. Examination of Multiphase (Zr,Ti)(V,Cr,Mn,Ni)2 Ni-MH Electrode Alloys: Part II. Solid-State Transformation of the Interdendritic B2 Phase

    NASA Astrophysics Data System (ADS)

    Bendersky, L. A.; Wang, K.; Boettinger, W. J.; Newbury, D. E.; Young, K.; Chao, B.

    2010-08-01

    Solidification microstructure of multicomponent (Zr,Ti)-Ni-(V,Cr,Mn,Co) alloys intended for use as negative electrodes in Ni-metal hydride (Ni-MH) batteries was studied in Part I of this series of articles. Part II of the series examines the complex internal structure of the interdendritic grains formed by solid-state transformation and believed to play an important role in the electrochemical charge/discharge characteristics of the overall alloy composition. By studying one alloy, Zr21Ti12.5V10Cr5.5Mn5.1Co5.0Ni40.2Al0.5Sn0.3, it is shown that the interdendritic grains solidify as a B2 (Ti,Zr)44(Ni,TM)56 phase, and then undergo transformation to Zr7Ni10-type, Zr9Ni11-type, and martensitic phases. The transformations obey orientation relationships between the high-temperature B2 phase and the low-temperature Zr-Ni-type intermetallics, and consequently lead to a multivariant structure. The major orientation relationship for the orthorhombic Zr7Ni10 type is [011]Zr7Ni10//[001]B2; (100)Zr7Ni10//(100)B2. The orientation relationship for the tetragonal Zr9Ni11 type is [001]Zr9Ni11//[001]B2; (130)Zr9Ni11//(100)B2. Binary Ni-Zr and ternary Ti-Ni-Zr phase diagrams were used to rationalize the formation of the observed domain structure.

  11. Complexes in the Photocatalytic Reaction of CO2 and H2O: Theoretical Studies

    PubMed Central

    Luo, Dongmei; Zhang, Ning; Hong, Sanguo; Wu, Huanwen; Liu, Zhihua

    2010-01-01

    Complexes (H2O/CO2, e–(H2O/CO2) and h+–(H2O/CO2)) in the reaction system of CO2 photoreduction with H2O were researched by B3LYP and MP2 methods along with natural bond orbital (NBO) analysis. Geometries of these complexes were optimized and frequencies analysis performed. H2O/CO2 captured photo-induced electron and hole produced e–(H2O/CO2) and h+–(H2O/CO2), respectively. The results revealed that CO2 and H2O molecules could be activated by the photo-induced electrons and holes, and each of these complexes possessed two isomers. Due to the effect of photo-induced electrons, the bond length of C=O and H-O were lengthened, while H-O bonds were shortened, influenced by holes. The infrared (IR) adsorption frequencies of these complexes were different from that of CO2 and H2O, which might be attributed to the synergistic effect and which could not be captured experimentally. PMID:21152274

  12. Onset of phase separation in the double perovskite oxide La2MnNiO6

    NASA Astrophysics Data System (ADS)

    Spurgeon, Steven R.; Sushko, Peter V.; Devaraj, Arun; Du, Yingge; Droubay, Timothy; Chambers, Scott A.

    2018-04-01

    Identification of kinetic and thermodynamic factors that control crystal nucleation and growth represents a central challenge in materials synthesis. Here we report that apparently defect-free growth of La2MnNiO6 (LMNO) thin films supported on SrTiO3 (STO) proceeds up to 1-5 nm, after which it is disrupted by precipitation of NiO phases. Local geometric phase analysis and ensemble-averaged x-ray reciprocal space mapping show no change in the film strain away from the interface, indicating that mechanisms other than strain relaxation induce the formation of the NiO phases. Ab initio simulations suggest that the electrostatic potential build-up associated with the polarity mismatch at the film-substrate interface promotes the formation of oxygen vacancies with increasing thickness. In turn, oxygen deficiency promotes the formation of Ni-rich regions, which points to the built-in potential as an additional factor that contributes to the NiO precipitation mechanisms. These results suggest that the precipitate-free region could be extended further by either incorporating dopants that suppress the built-in potential or by increasing the oxygen fugacity in order to suppress the formation of oxygen vacancies.

  13. Spectroscopic and mycological studies of Co(II), Ni(II) and Cu(II) complexes with 4-aminoantipyrine derivative

    NASA Astrophysics Data System (ADS)

    Sharma, Amit Kumar; Chandra, Sulekh

    2011-10-01

    Complexes of the type [M(L)X 2], where M = Co(II), Ni(II) and Cu(II), have been synthesized with novel NO-donor Schiff's base ligand, 1,4-diformylpiperazine bis(4-imino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one) which is obtained by the acid catalyzed condensation of 1,4-diformylpiperazine with 4-aminoantipyrine. The elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, UV, NMR, mass and EPR studies of the compounds led to the conclusion that the ligand acts as tetradentate chelate. The Schiff's base ligand forms hexacoordinated complexes having octahedral geometry for Ni(II) and tetragonal geometry for Co(II) and Cu(II) complexes. The mycological studies of the compounds were examined against the several opportunistic pathogens, i.e., Alternaria brassicae, Aspergillus niger and Fusarium oxysporum. The Cu(II) complexes were found to have most fungicidal behavior.

  14. Viscosities of Fe Ni, Fe Co and Ni Co binary melts

    NASA Astrophysics Data System (ADS)

    Sato, Yuzuru; Sugisawa, Koji; Aoki, Daisuke; Yamamura, Tsutomu

    2005-02-01

    Viscosities of three binary molten alloys consisting of the iron group elements, Fe, Ni and Co, have been measured by using an oscillating cup viscometer over the entire composition range from liquidus temperatures up to 1600 °C with high precision and excellent reproducibility. The viscosities measured showed good Arrhenius linearity for all the compositions. The viscosities of Fe, Ni and Co as a function of temperature are as follows: \\eqalign{ & \\log \\eta={-}0.6074 + 2493/T\\qquad for\\quad Fe\\\\ & \\log \\eta={-}0.5695 + 2157/T\\qquad for\\quad Ni \\\\ & \\log \\eta={-}0.6620 + 2430/T\\qquad for\\quad Co.} The isothermal viscosities of Fe-Ni and Fe-Co binary melts increase monotonically with increasing Fe content. On the other hand, in Ni-Co binary melt, the isothermal viscosity decreases slightly and then increases with increasing Co. The activation energy of Fe-Co binary melt increased slightly on mixing, and those of Fe-Ni and Ni-Co melts decreased monotonically with increasing Ni content. The above behaviour is discussed based on the thermodynamic properties of the alloys.

  15. Polarity-driven oxygen vacancy formation in ultrathin LaNiO 3 films on SrTiO 3

    DOE PAGES

    Tung, I-Cheng; Luo, Guangfu; Lee, June Hyuk; ...

    2017-10-18

    Oxide heterostructures offer a pathway to control emergent phases in complex oxides, but their creation often leads to boundaries that have a polar discontinuity. In order to fabricate atomic-scale arrangements of dissimilar materials, we need a clear understanding of the pathways by which materials resolve polarity issues. By examining the real-time lattice structure in-situ during growth for the case of polar LaNiO 3 synthesized on non-polar SrTiO 3 (001), we demonstrate how films in ultra-thin limit form as LaNiO 2.5 and then evolve into LaNiO 3 as the thickness increases. Theory explains how the polar energetics drives the formation ofmore » oxygen vacancies and the stability of these phases with thickness and structure.« less

  16. Microstructural Characteristics and Oxidation Behavior of Low-Pressure Cold-Sprayed CoNiCrAlY Coatings

    NASA Astrophysics Data System (ADS)

    Zhang, Lin-wei; Lu, Lei; Wang, Lu; Ning, Xian-jin; Wang, Quan-sheng; Wang, Ri-xin

    2017-10-01

    CoNiCrAlY coatings were deposited by low-pressure cold spraying and subsequently heat-treated at 1050 °C for 4 h in a vacuum environment. The microstructural characteristics and oxidation behavior of CoNiCrAlY coatings were investigated. The as-sprayed coating exhibited low porosity and oxygen content. The high plastic deformation of the sprayed particles led to significant refinement of γ-matrix and dissolution of β-(Ni,Co)Al phase in the as-sprayed coating. After heat treatment, the single phase (γ) in the as-sprayed coating was converted into a γ/β microstructure, and a continuous single α-Al2O3 scale was formed on the coating surface. Vacuum heat treatment can postpone the formation of spinel oxides within 100 h. After being oxidized at 1050 °C for 400 h, the heat-treated coating exhibited better oxidation resistance than the as-sprayed coating. The reduced growth rate of the oxide scale and the suppression of the formation of spinel oxides can be attributed to the vacuum heat treatment, as well as the intrinsic microstructure of the cold-sprayed coating. Finally, the effects of the microstructural changes induced during the cold spraying process on the growth of the thermally grown oxide and the oxidation mechanisms of the CoNiCrAlY coatings were discussed.

  17. Csbnd H⋯Ni and Csbnd H⋯π(chelate) interactions in nickel(II) complexes involving functionalized dithiocarbamates and triphenylphosphine

    NASA Astrophysics Data System (ADS)

    Sathiyaraj, E.; Thirumaran, S.; Selvanayagam, S.; Sridhar, B.; Ciattini, Samuele

    2018-05-01

    New bis(N-benzyl-N-substituted benzyldithiocarbamato-S,S‧)nickel(II) (1-3) and (N-benzyl-N-substituted benzyldithiocarbamato-S,S‧)(isothiocyanato-N)- (triphenylphosphane)nickel(II) (4-6) [where substituted benzyl = 2-HOsbnd C6H4sbnd CH2sbnd (1,4), 3-HOsbnd C6H4sbnd CH2sbnd (2,5), 4-Fsbnd C6H4sbnd CH2sbnd (3,6)] were synthesized and characterized using IR, electronic, and NMR (1H and 13C) spectra. X-ray structural analysis of homoleptic complex (1) and heteroleptic complexes (5 and 6) confirmed the presence of four coordinated nickel in a distorted square planar arrangement with NiS4 and NiS2PN chromophores, respectively. The νC-S stretching vibrations are observed around 990 cm-1 without any splitting supporting the bidentate coordination of the dithiocarbamate ligand. Electronic spectral studies of all the complexes (1-6) indicate that the geometry of the nickel atom is probably square planar. NMR spectra of all homoleptic and heteroleptic complexes (1-6) reveal a weak signal associated with the backbone carbon (N13CS2) in the region 204.0-210.0 ppm with a weak intensity characteristic of the quaternary carbon signals. The greater trans influence of triphenylphosphine in complexes 5 and 6 is supported by the long Nisbnd S distance compared to other Nisbnd S distance which is opposite to the NCS- ligand. In the structure of complex 5, C-H⋯π(chelate) interactions results in polymeric chain. Both structures show intramolecular Ni⋯H interactions but that on 6 is the strongest. C-H⋯π interactions are also found in 1, 5 and 6. Hirshfeld surface analysis and the associated 2D fingerprint plots of 1, 5 and 6 have been studied to evaluate intermolecular interactions. The molecular geometries of complexes 1, 5 and 6 have been optimized by abinitio HF method using LANL2DZ program.

  18. Crystal structure stability and electronic properties of the layered nickelate La4Ni3O10

    NASA Astrophysics Data System (ADS)

    Puggioni, Danilo; Rondinelli, James M.

    2018-03-01

    We investigate the crystal structure and the electronic properties of the trilayer nickelate La4Ni3O10 by means of quantum-mechanical calculations in the framework of the density-functional theory. We find that, at low temperature, La4Ni3O10 undergoes a hitherto unreported structural phase transition and transforms to a new monoclinic P 21/a phase. This phase exhibits electronic properties in agreement with recent angle-resolved photoemission spectroscopy data reported in H. Li et al., [Nat. Commun. 8, 704 (2017), 10.1038/s41467-017-00777-0] and should be considered in models focused on explaining the observed ˜140 K metal-to-metal phase transition.

  19. Nanostructured Mg 2Ni materials prepared by cold rolling and used as negative electrode for Ni-MH batteries

    NASA Astrophysics Data System (ADS)

    Pedneault, Sylvain; Huot, Jacques; Roué, Lionel

    In the present work, cold rolling has been investigated as a new means of producing Mg-based metal hydrides for nickel-metal hydride (Ni-MH) batteries. Structure and electrochemical evolution of 2Mg-Ni cold-rolled samples were investigated as a function of the number of rolling passes as well as heat treatment. It was found that nanocrystalline Mg 2Ni alloy can be obtained by an appropriate three step process involving rolling, heat treatment and rolling again. It was shown that the number of primary and secondary rolling passes must be carefully optimized in order to favour the complete formation of Mg 2Ni alloy having a nanocrystalline structure (∼10 nm in crystallite size) without excessive sample oxidation. Actually, the best result was obtained by first rolling 90 times, followed by a heat treatment at 400 °C for 4 h and roll again 20 times. The resulting material displayed an initial discharge capacity of 205 mAh g -1, which is quite similar to that obtained with ball-milled Mg 2Ni alloy.

  20. Properties of mechanically alloyed Mg-Ni-Ti ternary hydrogen storage alloys for Ni-MH batteries

    NASA Astrophysics Data System (ADS)

    Ruggeri, Stéphane; Roué, Lionel; Huot, Jacques; Schulz, Robert; Aymard, Luc; Tarascon, Jean-Marie

    MgNiTi x, Mg 1- xTi xNi and MgNi 1- xTi x (with x varying from 0 to 0.5) alloys have been prepared by high energy ball milling and tested as hydrogen storage electrodes. The initial discharge capacities of the Mg-Ni-Ti ternary alloys are inferior to the MgNi electrode capacity. However, an exception is observed with MgNi 0.95Ti 0.05, which has an initial discharge capacity of 575 mAh/g compared to 522 mAh/g for the MgNi electrode. The Mg-Ni-Ti ternary alloys show improved cycle life compared to Mg-Ni binary alloys with the same Mg/Ni atomic ratio. The best cycle life is observed with Mg 0.5Ti 0.5Ni electrode which retains 75% of initial capacity after 10 cycles in comparison to 39% for MgNi electrodes, in addition to improved high-rate dischargeability (HRD). According to the XPS analysis, the cycle life improvement of the Mg 0.5Ti 0.5Ni electrode can be related to the formation of TiO 2 which limits Mg(OH) 2 formation. The anodic polarization curve of Mg 0.5Ti 0.5Ni electrode shows that the current related to the active/passive transition is much less important and that the passive region is more extended than for the MgNi electrode but the corrosion of the electrode is still significant. This suggests that the cycle life improvement would be also associated with a decrease of the particle pulverization upon cycling.

  1. Structural and Biological Behaviour of Co(II), Cu(II) and Ni(II) Metal Complexes of Some Amino Acid Derived Schiff-Bases

    PubMed Central

    Chohan, Zahid H.; Praveen, M.; Ghaffar, A.

    1997-01-01

    Biologically active tridentate amino acid (Alanine, Glycine & Tyrosine) derived Schiff-bases and their Co(II), Cu(II) & Ni(II) complexes have been synthesised and characterised on the basis of their conductance and magnetic measurements, elemental analysis and 13C-NMR, 1H-NMR, IR and electronic spectral data. These Schiff-bases and their complexes have been evaluated for their antibacterial activity against bacterial species such as Staphylococcus aureus, Escherichia coli, Klebsiella pneumonae, Proteus vulgarus and Pseudomonas aeruginosa and this activity data show the metal complexes to be more antibacterial than the Schiff-bases against one or more bacterial species. PMID:18475798

  2. Structural and magnetic aspects of La4(Co1-xNix)3O10+δ (0 ≤ x ≤ 1)

    NASA Astrophysics Data System (ADS)

    Nagell, Marius Uv; Kumar, Susmit; Sørby, Magnus H.; Fjellvåg, Helmer; Olafsen Sjåstad, Anja

    2015-10-01

    The Ruddlesden-Popper (RP3) type oxides, La4Co3O10+δ and La4Ni3O10+δ, form a complete solid solution. Powder X-ray and neutron diffraction data show that La4(Co1-xNix)3O10+δ is isostructural to the monoclinic La4Co3O10+δ structure (P21/a) described for all compositions without any further structural distortions as suggested in the literature. A slight elongation of the Co/Ni-O bonds facing the rock salt interlayer occurs for Ni-rich compositions. The magnetic properties of the solid solution series are mapped in the temperature range from 4 to 300 K, and the results are presented in a magnetic phase diagram. Three regimes with antiferromagnetic order (AF) exist at low temperatures, TN < 10 - 30 K. For x = 0.00, the AF is ascribed to Co(II), whereas a broader AF regime around x = 0.50 is ascribed mainly to Ni(II). Pauli paramagnetism is observed close to metallic La4Ni3O10+δ, x > 0.80. The possibility to tune the oxidation state of the transition metal atoms is demonstrated for La4Co3O10+δ, and exemplified by weakening of a temperature-induced spin transition at around 480 K.

  3. Orientation and faulted structure of γ'-phases in lanthanum-alloyed Ni-Al-Cr superalloy

    NASA Astrophysics Data System (ADS)

    Nikonenko, Elena; Shergaeva, Lyubov'; Popova, Natalya; Koneva, Nina; Qin, Rongshan; Gromov, Victor; Fedorischeva, Marina

    2017-12-01

    The paper presents the transmission and the scanning electron microscope investigations of thin foils of Ni-Al-Cr-based superalloy, which is obtained by the directional crystallization technique. This superalloy contains γ'- and γ- phases. Additionally, lanthanum is introduced in the superalloy in 0.015, 0.10 and 0.30 wt % concentrations. The superalloy specimens are then subjected to 1273 K annealing during 10 and 25 h. It is shown that γ'-phase is major. In the superalloy, lanthanides La2Ni3 and Al2La are detected along with carbide La2C3 particles located on dislocations of the major phase. The amount of phases in the superalloy depends on its thermal treatment and lanthanum concentration. The investigations include the effect of annealing on scalar density of dislocations in γ'-phase. It is demonstrated that lanthanum alloying modifies the preferred orientation of γ'-phase. Annealing of lanthanum-alloyed superalloy causes the orientation dispersion. In γ'-phase, the correlation is observed between the degree of heterogeneity of solid solution and scalar dislocation density. It is shown that this heterogeneity results in the formation of high-density dislocations in γ'- phase.

  4. Comparative study on microstructure and martensitic transformation of aged Ni-rich NiTi and NiTiCo shape memory alloys

    NASA Astrophysics Data System (ADS)

    El-Bagoury, Nader

    2016-05-01

    In this article the influence of aging heat treatment conditions of 250, 350, 450 and 550 °C for 3 h on the microstructure, martensitic transformation temperatures and mechanical properties of Ni51Ti49Co0 and Ni47 Ti49Co4 shape memory alloys was investigated. This comparative study was carried out using X-ray diffraction analysis, scanning electron microscope, energy dispersive spectrometer, differential scanning calorimeter and Vickers hardness tester. The results show that the microstructure of both aged alloys contains martensite phase and Ti2Ni in addition to some other precipitates. The martensitic transformation temperature was increased steadily by increasing the ageing temperature and lowering the value of valence electron number (ev/a) and concentration. Moreover, the hardness measurements were gradually increased at first by increasing the aging temperature from 250 to 350 °C. Further elevating in aging temperature to 450 and 550 °C decreases the hardness value.

  5. Structures and unimolecular chemistry of M(Pro2-H)(+) (M = Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn) by IRMPD spectroscopy, SORI-CID, and theoretical studies.

    PubMed

    Jami-Alahmadi, Yasaman; Fridgen, Travis D

    2016-01-21

    M(Pro2-H)(+) complexes were electrosprayed and isolated in an FTICR cell where their unimolecular chemistries and structures were explored using SORI-CID and IRMPD spectroscopy. These experiments were augmented by computational methods such as electronic structure, simulated annealing, and atoms in molecules (AIM) calculations. The unimolecular chemistries of the larger metal cation (Ca(2+), Sr(2+) and Ba(2+)) complexes predominantly involve loss of neutral proline whereas the complexes involving the smaller Mg(2+) and transition metal dications tend to lose small neutral molecules such as water and carbon dioxide. Interestingly, all complexes involving transition metal dications except for Cu(Pro2-H)(+) lose H2 upon collisional or IRMPD activation. IRMPD spectroscopy shows that the intact proline in the transition metal complexes and Cu(Pro2-H)(+) is predominantly canonical (charge solvated) while for the Ca(2+), Sr(2+), and Ba(2+) complexes, proline is in its zwitterionic form. The IRMPD spectra for both Mg(Pro2-H)(+) and Mn(Pro2-H)(+) are concluded to have contributions from both charge-solvated and canonical structures.

  6. On the nature of Ni···Ni interaction in a model dimeric Ni complex.

    PubMed

    Kamiński, Radosław; Herbaczyńska, Beata; Srebro, Monika; Pietrzykowski, Antoni; Michalak, Artur; Jerzykiewicz, Lucjan B; Woźniak, Krzysztof

    2011-06-07

    A new dinuclear complex (NiC(5)H(4)SiMe(2)CHCH(2))(2) (2) was prepared by reacting nickelocene derivative [(C(5)H(4)SiMe(2)CH=CH(2))(2)Ni] (1) with methyllithium (MeLi). Good quality crystals were subjected to a high-resolution X-ray measurement. Subsequent multipole refinement yielded accurate description of electron density distribution. Detailed inspection of experimental electron density in Ni···Ni contact revealed that the nickel atoms are bonded and significant deformation of the metal valence shell is related to different populations of the d-orbitals. The existence of the Ni···Ni bond path explains the lack of unpaired electrons in the complex due to a possible exchange channel.

  7. Direct arylation/alkylation/magnesiation of benzyl alcohols in the presence of Grignard reagents via Ni-, Fe-, or Co-catalyzed sp3 C-O bond activation.

    PubMed

    Yu, Da-Gang; Wang, Xin; Zhu, Ru-Yi; Luo, Shuang; Zhang, Xiao-Bo; Wang, Bi-Qin; Wang, Lei; Shi, Zhang-Jie

    2012-09-12

    Direct application of benzyl alcohols (or their magnesium salts) as electrophiles in various reactions with Grignard reagents has been developed via transition metal-catalyzed sp(3) C-O bond activation. Ni complex was found to be an efficient catalyst for the first direct cross coupling of benzyl alcohols with aryl/alkyl Grignard reagents, while Fe, Co, or Ni catalysts could promote the unprecedented conversion of benzyl alcohols to benzyl Grignard reagents in the presence of (n)hexylMgCl. These methods offer straightforward pathways to transform benzyl alcohols into a variety of functionalities.

  8. Spectroscopic evaluation of Co(II), Ni(II) and Cu(II) complexes derived from thiosemicarbazone and semicarbazone

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Kumar, Anil

    2007-12-01

    Co(II), Ni(II) and Cu(II) complexes were synthesized with thiosemicarbazone (L 1) and semicarbazone (L 2) derived from 2-acetyl furan. These complexes were characterized by elemental analysis, molar conductance, magnetic moment, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO corresponds to non-electrolytic nature. All the complexes are of high-spin type. On the basis of different spectral studies six coordinated geometry may be assigned for all the complexes except Co(L) 2(SO 4) and Cu(L) 2(SO 4) [where L = L 1 and L 2] which are of five coordinated square pyramidal geometry.

  9. Influence of Laser Power on the Microstructure and Mechanical Properties of a Laser Welded-Brazed Mg Alloy/Ni-Coated Steel Dissimilar Joint

    NASA Astrophysics Data System (ADS)

    Tan, Caiwang; Xiao, Liyuan; Liu, Fuyun; Chen, Bo; Song, Xiaoguo; Li, Liqun; Feng, Jicai

    2017-05-01

    In this work, we describe a method to improve the bonding of an immiscible Mg/steel system using Ni as an interlayer by coating it on the steel surface. Laser welding-brazing of AZ31B Mg alloy to Ni-coated Q235 steel using Mg-based filler was performed in a lap configuration. The influence of laser power on the weld characteristics, including joint appearance, formation of interfacial reaction layers and mechanical properties was investigated. The results indicated that the presence of the Ni-coating promoted the wetting of the liquid filler metal on the steel surface. A thermal gradient along the interface led to the formation of heterogeneous interfacial reaction layers. When using a low laser power of 1600 W, the reaction products were an FeAl phase in the direct laser irradiation zone, an AlNi phase close to the intermediate zone and mixtures of AlNi phase and an (α-Mg + Mg2Ni) eutectic structure near the interface at the seam head zone. For high powers of more than 2000 W, the FeAl phase grew thicker in the direct laser irradiation zone and a new Fe(Ni) transition layer formed at the interface of the intermediate zone and the seam head zone. However, the AlNi phase and (α-Mg + Mg2Ni) eutectic structure were scattered at the Mg seam. All the joints fractured at the fusion zone, indicating that the improved interface was not the weakest joint region. The maximum tensile-shear strength of the Mg/Ni-coated steel joint reached 190 N/mm, and the joint efficiency was 70% with respect to the Mg alloy base metal.

  10. The distribution alloying elements in alnico 8 and 9 magnets: Site preference of ternary Ti, Fe, Co, and Ni additions in DO{sub 3} Fe{sub 3}Al, Co{sub 3}Al, and Ni{sub 3}Al based intermetallic phases

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Samolyuk, G. D.; Stocks, G. M.; Újfalussy, B.

    Recently, interest in alnico magnetic alloys has been rekindled due to their potential to substitute for rare-earth based permanent magnets provided modest improvements in their coercivity can be achieved without loss of saturation magnetization. Recent experimental studies have indicated that atomic and magnetic structure of the two phases (one AlNi-based, the other FeCo-based) that comprise these spinodally decomposed alloy is not as simple as previously thought. A key issue that arises is the distribution of Fe, Co, and Ti within the AlNi-based matrix phase. In this paper, we report the results of first-principles calculations of the site preference of ternarymore » alloying additions in DO{sub 3} Fe{sub 3}Al, Co{sub 3}Al, and Ni{sub 3}Al alloys, as models for the aluminide phase. For compound compositions that are Al rich, which correspond to experimental situation, Ti and Fe are found to occupy the α sites, while Co and Ni prefer the γ sites of the DO{sub 3} lattice. An important finding is that the magnetic moments of transition metals in Fe{sub 3}Al and Co{sub 3}Al are ordered ferromagnetically, whereas the Ni{sub 3}Al were found to be nonmagnetic unless the Fe or Co is added as a ternary element.« less

  11. Excitons in strongly correlated oxide nanocrystals NicMg1-cO

    NASA Astrophysics Data System (ADS)

    Sokolov, V. I.; Churmanov, V. N.; Pustovarov, V. A.; Gruzdev, N. B.; Uimin, M. A.; Byzov, I. V.; Zatsepin, A. F.; Kuznetsova, J. A.

    2018-05-01

    This paper reports about excitons in strongly correlated oxide nanocrystals NicMg1-cO (c = 0.008 and c = 1). At 8 K two weak peaks were firstly observed in the optical density spectrum of NiO nanocrystals at the energies of 3.510 eV and 3.543 eV. The intensity of the peaks subsides with an increase of temperature and a decrease of nanoparticle sizes from 25 nm to 10 nm. The peaks were attributed to the formation of p-d charge transfer excitons {d9h}. A tunneling annihilation for {d9h} excitons diminishes their lifetime drastically, even at low temperatures. This fact is considered as an inherent feature in the p-d charge transfer excitons {d9h}, which makes them significantly different from the Wannier-Mott excitons for semiconductors with direct allowed transitions. We believe that energy shift between two peaks originates due to the spin-orbit splitting of the top of the valence band, equals 33 meV. In p-d charge transfer photoluminescence excitation spectrum of NicMg1-cO (c = 0.008), we have revealed two [d9h] exciton lines near the charge transfer band edge. Energy shift of these lines (equals 25 meV) is due to the spin-orbit splitting of MgO valence band top.

  12. Onset of phase separation in the double perovskite oxide La 2 MnNiO 6

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Spurgeon, Steven R.; Sushko, Peter V.; Devaraj, Arun

    2018-04-01

    Identification of kinetic and thermodynamic factors that control crystal nucleation and growth represents a central challenge in materials synthesis. Here we report that apparently defect-free growth of La2MnNiO6 (LMNO) thin films supported on SrTiO3 (STO) proceeds up to 1–5 nm, after which it is disrupted by precipitation of NiO phases. Local geometric phase analysis and ensemble-averaged x-ray reciprocal space mapping show no change in the film strain away from the interface, indicating that mechanisms other than strain relaxation induce the formation of the NiO phases. Ab initio simulations suggest that the electrostatic potential build-up associated with the polarity mismatch atmore » the film-substrate interface promotes the formation of oxygen vacancies with increasing thickness. In turn, oxygen deficiency promotes the formation of Ni-rich regions, which points to the built-in potential as an additional factor that contributes to the NiO precipitation mechanisms. These results suggest that the precipitate-free region could be extended further by either incorporating dopants that suppress the built-in potential or by increasing the oxygen fugacity in order to suppress the formation of oxygen vacancies.« less

  13. New Findings on the Phase Transitions in Li(sub 1-x)CoO(sub 2) and Li(sub 1-x)NiO(sub 2) Cathode Materials During Cycling: In Situ Synchrotron X-Ray Diffraction Studies

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yang, X. Q.; Sun, X.; McBreen, J.

    The authors have utilized synchrotron x-ray radiation to perform ''in situ'' x-ray diffraction studies on Li{sub 1-x}CoO{sub 2} and Li{sub 1-x}NiO{sub 2} cathodes. A C/10 charging rate was used for a Li/Li{sub 1-x}CoO{sub 2} cell. For the Li/Li{sub 1-x}NiO{sub 2} cells, C/13 and C/84 rates were applied. The in situ XRD data were collected during the first charge from 3.5 to 5.2 V. For the Li{sub 1-x}CoO{sub 2} cathode, in the composition range of x = 0 to x = 0.5, a new intermediate phase H2a was observed in addition to the two expected hexagonal phases H1 and H2. Inmore » the region very close to x = 0.5, some spectral signatures for the formation of a monoclinic phase M1 were also observed. Further, in the x = 0.8 to x = 1 region, the formation of a CdI{sub 2} type hexagonal phase has been confirmed. However, this new phase is transformed from a CdCl{sub 2} type hexagonal phase, rather than from a monoclinic phase M2 as previously reported in the literature. For the Li{sub 1-x}NiO{sub 2} system, by taking the advantage of the high resolution in 2{theta} angles through the synchrotron based XRD technique, they were able to identify a two-phase coexistence region of hexagonal phase H1 and H2, which has been mistakenly indexed as a single phase region for monoclinic phase M1. Interesting similarities and differences between these two systems are also discussed.« less

  14. Self-assembly of a [Ni8] carbonate cube incorporating four μ4-carbonato linkers through fixation of atmospheric CO2 by ligated [Ni2] complexes.

    PubMed

    Ghosh, Aloke Kumar; Pait, Moumita; Shatruk, Michael; Bertolasi, Valerio; Ray, Debashis

    2014-02-07

    The communication reports the synthesis, characterization, and magnetic behavior of a novel μ4-carbonato supported and imidazole capped ligated nickel cage [Ni8(μ-H2bpmp)4(μ4-CO3)4(ImH)8](NO3)4·2H2O (1) through self-assembly of ligand bound ferromagnetic Ni2 building blocks. Structural analysis indicates newer geometrical features for the coordination cage formation and dominant interdimer antiferromagnetic coupling resulting in a diamagnetic ground state.

  15. Investigation of the mineralogy and the sorption mechanism of Ni, Cu, Co and Mo by turbostratic phyllomanganates of Mn-nodules from the eastern equatorial Pacific Ocean using XAS

    NASA Astrophysics Data System (ADS)

    Wegorzewski, A.; Webb, S.; Grangeon, S.; Kuhn, T.

    2016-12-01

    Mn-nodules are Mn-Fe (oxy)hydroxides bearing high amounts of economically important metals such as Ni, Cu, Co, Mo, as well as high field strength elements. According to that nodules are interesting for science and industry. Especially the sorption sites of metals (Ni, Cu, Mo) by the mineral phases are important to understand their coordination environment and further to tailor a specific metallurgical treatment in order to optimize the metal extraction procedure. Nodules used for this study were sampled from the German license area within the Clarion Clipperton Zone in the Pacific. These nodules grow on the seafloor in 4200 m depth by metal precipitation from oxic (hydrogenetic growth) and/or suboxic waters (suboxic diagenetic growth; Halbach et al., 1988). They show a complex texture characterized by irregular, concentrically banded nm- to µm-thick layered growth structures (LGS). Electronmicroprobe and X-ray diffraction analyses reveal: suboxic diagenetic LGS have high Mn/Fe ratios (9-826; Mn ≈ 40 wt. %; Fe ≈ 0.5 wt %), high Ni (0.3-2.6 wt %) and Cu (0.5-3.0 wt %) contents but low Co content (0.02±0.01 wt %). Mineralogically those LGS are turbostratic phyllomanganates (vernadite), which consist of [MnO6]-octahedral layers, separated from each other by cations (e.g., Na, Mg) and water in the interlayer, forming 7 and 10 Å phyllomanganates (Bode et al., 2007). In contrast hydrogenetic LGS show low Mn/Fe ratios (<5), low Ni+Cu content (<1 wt%) but enrichment in Co (≤0.5 wt%). Those LGS are of δ-MnO2, which is epitaxially intergrown with an amorphous FeOOH phase. In general, phyllomanganates have a high opportunity to incorporate metals due to their negative layer charge deficit cause by abundant isomorphic substitution of Mn4+ by Mn3+ and vacancies within MnO2 sheets. The negative charge deficit can be balanced by hydrated interlayer cations (e.g., Na, Mg) or due to metals adsorption at cation vacancy sites, incorporation into the MnO2 sheet and

  16. Enhanced magneto-caloric effect upon Co substitution in Ni-Mn-Sn thin films

    NASA Astrophysics Data System (ADS)

    Modak, Rajkumar; Raja, M. Manivel; Srinivasan, A.

    2018-02-01

    Mn rich Ni-Mn-Sn and Ni-Mn-Co-Sn alloy films were deposited on Si (1 0 0) substrate by dc magnetron sputtering from Ni50Mn37Sn13 alloy target at 1.8 Pa Ar pressure with 70 W dc power. Co was introduced by placing Co chips on the Ni-Mn-Sn target. As-deposited films were vacuum annealed at 823 K for 1 h. X-ray diffraction patterns of the films revealed modulated 14 M structure of the martensite phase at room temperature. Magnetic entropy change (ΔSm) across the Curie temperature of the ferromagnetic films was estimated from initial isothermal magnetization curves using Maxwell's equation. ΔSm and refrigeration capacity (RC) of Ni-Mn-Sn and Ni-Mn-Co-Sn films increased with increasing film thickness. Upon Co substitution in Mn/Sn site(s), ΔSm and RC increased more remarkably. The change is more prominent in the case of 360 nm films, wherein a 3.8-fold increase in ΔSM and 8.9-fold increase in RC was observed. Introduction of Co increased the magnetic moment and broadened the magnetic transition. These factors increased ΔSm and RC in Co substituted Ni-Mn-Sn alloy. Since TC shifted to higher temperatures with Co substitution, operating temperature of these magnetic refrigerants also shifted to higher temperature. This study indicates the possibility of developing high temperature cooling devices and waste energy harvesters using these films.

  17. Electronic structure and O vacancy formation/migration in La0.825(Mg/Ca/Ba)0.125CoO3

    NASA Astrophysics Data System (ADS)

    Omotayo Akande, Salawu; Gan, Li-Yong; Schwingenschlögl, Udo

    2016-04-01

    The effect of A-site hole doping (Mg2+, Ca2+ or Ba2+) on the electronic and magnetic properties as well as the O vacancy formation and migration in perovskite LaCoO3 is studied using first-principles calculations. All three dopants are found to facilitate O vacancy formation. Substitution of La3+ with Ba2+/Mg2+ yields the lowest O vacancy formation energy for low/intermediate spin Co, implying that not only the structure but also the spin state of Co is a key parameter. Only for low spin Co the ionic radius is correlated with the O migration barrier. Enhanced migration for intermediate spin Co is ascribed to the availability of additional space at the transition state.

  18. Design, spectral characterization, thermal, DFT studies and anticancer cell line activities of Co(II), Ni(II) and Cu(II) complexes of Schiff bases derived from 4-amino-5-(pyridin-4-yl)-4H-1,2,4-triazole-3-thiol.

    PubMed

    Tyagi, Prateek; Chandra, Sulekh; Saraswat, B S; Yadav, Deepak

    2015-06-15

    A series of two biologically active Schiff base ligands L(1), L(2) have been synthesized in equimolar reaction of 4-amino-5-(pyridin-4-yl)-4H-1,2,4-triazole-3-thiol with thiophene-2-carbaldehyde and furan-2-carbaldehyde. The synthesized Schiff bases were used for complexation with different metal ions like Co(II), Ni(II) and Cu(II) by using a molar ratio of ligand: metal as 1:1 and 2:1. The characterization of Schiff bases and metal complexes was done by (1)H NMR, UV-Vis, TGA, IR, mass spectrometry and molar conductivity studies. The in DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On the basis of the spectral studies an octahedral geometry has been assigned for Co(II), Ni(II) and Cu(II) complexes. The effect of these complexes on proliferation of human breast cancer cell line (MCF-7) and human hepatocellular liver carcinoma cell line (Hep-G2) were studied and compared with those of free ligand. The anticancer cell line results reveal that all metal complexes show moderate to significant % cytotoxicity on cell line HepG2 and MCF-7. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. High catalytic activity and stability of Ni/CexZr1-xO2/MSU-H for CH4/CO2 reforming reaction

    NASA Astrophysics Data System (ADS)

    Chang, Xiaoqian; Liu, Bingsi; Xia, Hong; Amin, Roohul

    2018-06-01

    How to reduce emission of CO2 as greenhouse gases, which resulted in global warming, is of very important significance. A series of Ni/CexZr1-xO2/MSU-H catalysts was prepared by means of hexagonally ordered mesoporous MSU-H with thermal and hydrothermal stabilities, which is cheap and can be synthesized in the large scale. The 10%Ni/Ce0.75Zr0.25O2/MSU-H catalyst presents high catalytic activity, stability and the ability of coke-resistance for CH4/CO2 reforming reaction due to high SBET (428 m2/g) and smaller Nio nanoparticle size (3.14 nm). The high dispersed Nio nanoparticles over MSU-H promoted the decomposition of CH4 and the carbon species accumulated on active Nio sites reacting with crystal lattice oxygen in Ce0.75Zr0.25O2 to form CO molecules. In the meantime, the remained oxygen vacancies on the interface between Nio and Ce0.75Zr0.25O2 could be supplemented via CO2. HRTEM images and XRD results of Ni/Ce0.75Zr0.25O2/MSU-H verified that high dispersion of Ni nanoparticles over Ni/Ce0.75Zr0.25O2/MSU-H correlated closely with the synergistic action between Ce0.75Zr0.25O2 and MSU-H as well as hexagonally ordered structure of MSU-H, which can provide effectively the oxygen storage capacity and inhibit the formation of coke.

  20. Physical Properties of NiFeCrCo-based High-Entropy Alloys

    NASA Astrophysics Data System (ADS)

    Zaddach, Alexander Joseph

    Conventional alloy design has been based on improving the properties of a single base, or solvent, element through relatively small additions of other elements. More recently, research has been conducted on alloys that contain multiple principal elements, particularly multi-component equiatomic alloys. When such alloys form solid solution phases, they are termed "high-entropy alloys" (HEAs) due to their high configurational entropy. These alloys often have favorable properties compared to conventional dilute solution alloys, but their compositional complexity and relative novelty means that they remain difficult to design and their basic properties are often unknown. The motivation for this work is a detailed experimental exploration of some of the basic physical properties of NiFeCrCo-based alloys. NiFeCrCoMn was one of the first equiatomic HEAs developed. As the compositional space within this single system is extremely large, this work focuses primarily on equiatomic alloys and a limited subset of non-equiatomic alloys chosen for their specific properties. Several alloys are prepared using both conventional methods (arc melting) and nonequilibrium methods (mechanical alloying). Properties studied include stacking fault energy, bulk mechanical properties, single crystal elastic constants, and magnetic properties. The equiatomic NiFeCrCo and NiFeCrCoMn alloys were found to have a moderate to low stacking fault energy, 18 -- 30 mJ m-2. As they are single-phase, fcc alloys, they have high tensile ductility. Additionally, they also exhibit high work-hardening rates, resulting in high toughness. NiFeCrCo outperforms the 5-component equiatomic alloy in ductility and toughness. A 5-component alloy with higher Co content to reduce the stacking fault energy also performs well. The single crystal elastic constants were measured using nanoindentation modulus measurements of grains of known orientation. The measured elastic constants were consistent with those calculated

  1. Hierarchical NiCo2 O4 nanosheets grown on Ni nanofoam as high-performance electrodes for supercapacitors.

    PubMed

    Gao, Guoxin; Wu, Hao Bin; Ding, Shujiang; Liu, Li-Min; Lou, Xiong Wen David

    2015-02-18

    A high-performance electrode for supercapacitors is designed and synthesized by growing electroactive NiCo2 O4 nanosheets on conductive Ni nanofoam. Because of the structural advantages, the as-prepared Ni@NiCo2 O4 hybrid nanostructure exhibits significantly improved electrochemical performance with high capacitance, excellent rate capability, and good cycling stability. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. High-pressure and high-temperature phase diagram for Fe0.9Ni0.1-H alloy

    NASA Astrophysics Data System (ADS)

    Shibazaki, Yuki; Terasaki, Hidenori; Ohtani, Eiji; Tateyama, Ryuji; Nishida, Keisuke; Funakoshi, Ken-ichi; Higo, Yuji

    2014-03-01

    Planetary cores are considered to consist of an iron-nickel (Fe-Ni) alloy and light elements and hydrogen is one of plausible light elements in the core. Here we have performed in situ X-ray diffraction experiments on an Fe0.9Ni0.1-H system up to 15.1 GPa and 1673 K, and investigated the effect of Ni on phase relations of FeHx under high pressure and high temperature. The experimental system in the present work was oversaturated with hydrogen. We found a face-center-cubic (fcc) phase (with hydrogen concentration up to x∼1) and a body-center-cubic (bcc) phase (x < 0.1) as stable phases. The partial melting was observed below 6 GPa. We could not observe a double-hexagonal-close-packed (dhcp) phase because of limitations in pressure and temperature conditions. The stability field of each phase of Fe0.9Ni0.1Hx was almost same as that of FeHx. The solidus of Fe0.9Ni0.1Hx was 500-700 K lower than the melting curve of Fe and its liquidus was 400-600 K lower than that of Fe in the pressure range of this study. Both the solidus and liquidus of Fe0.9Ni0.1Hx were depressed at around 3.5 GPa, as was the solidus of FeHx. The hydrogen contents in fcc-Fe0.9Ni0.1Hx just below solidus were slightly lower than those of fcc-FeHx, which suggests that nickel is likely to prevent dissolution of hydrogen into iron. Due to the lower hydrogen solubilities in Fe0.9Ni0.1 compared to Fe, the solidus of Fe0.9Ni0.1Hx is about 100-150 K higher than that of FeHx.

  3. Photoelectron velocity-map imaging and theoretical studies of heteronuclear metal carbonyls MNi(CO){sub 3}{sup −} (M = Mg, Ca, Al)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Xie, Hua, E-mail: ljiang@dicp.ac.cn, E-mail: xiehua@dicp.ac.cn, E-mail: zctang@dicp.ac.cn; Zou, Jinghan; Yuan, Qinqin

    2016-03-28

    The heteronuclear metal carbonyl anions MNi(CO){sub 3}{sup −} (M = Mg, Ca, Al) have been investigated using photoelectron velocity-map imaging spectroscopy. Electron affinities of neutral MNi(CO){sub 3} (M = Mg, Ca, Al) are measured from the photoelectron spectra to be 1.064 ± 0.063, 1.050 ± 0.064, and 1.541 ± 0.040 eV, respectively. The C–O stretching mode in these three clusters is observed and the vibrational frequency is determined to be 2049, 2000, and 2041 cm{sup −1} for MgNi(CO){sub 3}, CaNi(CO){sub 3}, and AlNi(CO){sub 3}, respectively. Density functional theory calculations are carried out to elucidate the geometric and electronic structures and to aid the experimental assignments. Itmore » has been found that three terminal carbonyls are preferentially bonded to the nickel atom in these heterobinuclear nickel carbonyls MNi(CO){sub 3}{sup −1/0}, resulting in the formation of the Ni(CO){sub 3} motif. Ni remains the 18-electron configuration for MgNi(CO){sub 3} and CaNi(CO){sub 3} neutrals, but not for AlNi(CO){sub 3}. This is different from the homobinuclear nickel carbonyl Ni–Ni(CO){sub 3} with the involvement of three bridging ligands. Present findings would be helpful for understanding CO adsorption on alloy surfaces.« less

  4. Nanostructural origin of semiconductivity and large magnetoresistance in epitaxial NiCo2O4/Al2O3 thin films

    NASA Astrophysics Data System (ADS)

    Zhen, Congmian; Zhang, XiaoZhe; Wei, Wengang; Guo, Wenzhe; Pant, Ankit; Xu, Xiaoshan; Shen, Jian; Ma, Li; Hou, Denglu

    2018-04-01

    Despite low resistivity (~1 mΩ cm), metallic electrical transport has not been commonly observed in inverse spinel NiCo2O4, except in certain epitaxial thin films. Previous studies have stressed the effect of valence mixing and the degree of spinel inversion on the electrical conduction of NiCo2O4 films. In this work, we studied the effect of nanostructural disorder by comparing the NiCo2O4 epitaxial films grown on MgAl2O4 (1 1 1) and on Al2O3 (0 0 1) substrates. Although the optimal growth conditions are similar for the NiCo2O4 (1 1 1)/MgAl2O4 (1 1 1) and the NiCo2O4 (1 1 1)/Al2O3 (0 0 1) films, they show metallic and semiconducting electrical transport, respectively. Post-growth annealing decreases the resistivity of NiCo2O4 (1 1 1)/Al2O3 (0 0 1) films, but the annealed films are still semiconducting. While the semiconductivity and the large magnetoresistance in NiCo2O4 (1 1 1)/Al2O3 (0 0 1) films cannot be accounted for in terms of non-optimal valence mixing and spinel inversion, the presence of anti-phase boundaries between nano-sized crystallites, generated by the structural mismatch between NiCo2O4 and Al2O3, may explain all the experimental observations in this work. These results reveal nanostructural disorder as being another key factor for controlling the electrical transport of NiCo2O4, with potentially large magnetoresistance for spintronics applications.

  5. Conversion of CH4/CO2 to syngas over Ni-Co/Al2O3-ZrO2 nanocatalyst synthesized via plasma assisted co-impregnation method: Surface properties and catalytic performance

    NASA Astrophysics Data System (ADS)

    Rahemi, Nader; Haghighi, Mohammad; Akbar Babaluo, Ali; Fallah Jafari, Mahdi; Khorram, Sirous

    2013-09-01

    Ni/Al2O3 catalyst promoted by Co and ZrO2 was prepared by co-impregnation method and treated with glow discharge plasma. The catalytic activity of the synthesized nanocatalysts has been tested toward conversion of CH4/CO2 to syngas. The physicochemical characterizations like XRD, EDX, FESEM, TEM, BET, FTIR, and XPS show that plasma treatment results in smaller particle size, more surface concentration, and uniform morphology. The dispersion of nickel in plasma-treated nanocatalyst was also significantly improved, which was helpful for controlling the ensemble size of active phase atoms on the support surface. Improved physicochemical properties caused 20%-30% enhancement in activity of plasma-treated nanocatalyst that means to achieve the same H2 or CO yield, the plasma-treated nanocatalyst needed about 100 °C lower reaction temperature. The H2/CO ratio got closer to 1 at higher temperatures and finally at 850 °C H2/CO = 1 is attained for plasma-treated nanocatalyst. Plasma-treated nanocatalyst due to smaller Ni particles and strong interaction between active phase and support has lower tendency to keep carbon species on its structure and hence excellent stability can be observed for this catalyst.

  6. Family of defect-dicubane Ni4Ln2 (Ln = Gd, Tb, Dy, Ho) and Ni4Y2 complexes: rare Tb(III) and Ho(III) examples showing SMM behavior.

    PubMed

    Zhao, Lang; Wu, Jianfeng; Ke, Hongshan; Tang, Jinkui

    2014-04-07

    Reactions of Ln(III) perchlorate (Ln = Gd, Tb, Dy, and Ho), NiCl2·6H2O, and a polydentate Schiff base resulted in the assembly of novel isostructural hexanuclear Ni4Ln2 complexes [Ln = Gd (1), Tb (2), Dy (3), Ho (4)] with an unprecedented 3d-4f metal topology consisting of two defect-dicubane units. The corresponding Ni4Y2 (5) complex containing diamagnetic Y(III) atoms was also isolated to assist the magnetic studies. Interestingly, complexes 2 and 3 exhibit SMM characteristics and 4 shows slow relaxation of the magnetization. The absence of frequency-dependent in-phase and out-of-phase signals for the Ni-Y species suggests that the Ln ions' contribution to the slow relaxation must be effectual as previously observed in other Ni-Dy samples. However, the observation of χ″ signals with zero dc field for the Ni-Tb and Ni-Ho derivatives is notable. Indeed, this is the first time that such a behavior is observed in the Ni-Tb and Ni-Ho complexes.

  7. Synthesis, characterization, thermal and biological evaluation of Cu (II), Co (II) and Ni (II) complexes of azo dye ligand containing sulfamethaxazole moiety

    NASA Astrophysics Data System (ADS)

    Mallikarjuna, N. M.; Keshavayya, J.; Maliyappa, M. R.; Shoukat Ali, R. A.; Venkatesh, Talavara

    2018-08-01

    A novel bioactive Cu (II), Co (II) and Ni (II) complexes of the azo dye ligand (L) derived from sulfamethoxazole were synthesized. The structures of the newly synthesized compounds were characterized by elemental analysis, molar conductance, magnetic susceptibility, FTIR, UV-visible, 1H NMR, mass, thermal and powder XRD spectral techniques. Molar conductivity measurements in DMSO solution confirmed the non-electrolytic nature of the complexes. All the synthesized metal complexes were found to be monomeric and showed square planar geometry except the Co (II) complex which has six coordinate, octahedral environment. The metal complexes have exhibited potential growth inhibitory effect against tested bacterial strains as compared to the free ligand. The ligand and complexes have also shown significant antioxidant and Calf Thymus DNA cleavage activities. Further, the in silico molecular docking studies were performed to predict the possible binding sites of the ligand (L) and its metal complexes with target receptor Glu-6P.

  8. Electrochemical studies of DNA interaction and antimicrobial activities of MnII, FeIII, CoII and NiII Schiff base tetraazamacrocyclic complexes

    NASA Astrophysics Data System (ADS)

    Kumar, Anuj; Vashistha, Vinod Kumar; Tevatia, Prashant; Singh, Randhir

    2017-04-01

    Tetraazamacrocyclic complexes of MnII, FeIII, CoII and NiII have been synthesized by template method. These tetraazamacrocycles have been analyzed with various techniques like molar conductance, IR, UV-vis, mass spectral and cyclic voltammetric studies. On the basis of all these studies, octahedral geometry has been assigned to these tetraazamacrocyclic complexes. The DNA binding properties of these macrocyclic complexes have been investigated by electronic absorption spectra, fluorescence spectra, cyclic voltammetric and differential pulse voltammetric studies. The cyclic voltammetric data showed that ipc and ipa were effectively decreased in the presence of calf thymus DNA, which is a strong evidence for the interaction of these macrocyclic complexes with the calf thymus DNA (ct-DNA). The heterogeneous electron transfer rate constant found in the order: KCoII > KNiII > KMnII which indicates that CoII macrocyclic complex has formed a strong intercalated intermediate. The Stern-Volmer quenching constant (KSV) and voltammetric binding constant were found in the order KSV(CoII) > KSV(NiII) > KSV(MnII) and K+(CoII) > K+(NiII) > K+(MnII) which shows that CoII macrocyclic complex exhibits the high interaction affinity towards ct-DNA by the intercalation binding. Biological studies of the macrocyclic complexes compared with the standard drug like Gentamycin, have shown antibacterial activities against E. coli, P. aeruginosa, B. cereus, S. aureus and antifungal activity against C. albicans.

  9. Effects of F-treatment on degradation of Mg 2Ni electrode fabricated by mechanical alloying

    NASA Astrophysics Data System (ADS)

    Kim, Jun Sung; Lee, Chang Rae; Choi, Jae Woong; Kang, Sung Goon

    The effects of surface fluorination on the electrochemical charge-discharge properties of a Mg 2Ni electrode, prepared by mechanical alloying in Ni-MH batteries are investigated. After 20 h milling, Mg and Ni powder form nanocrystalline Mg 2Ni. The discharge capacity of this alloy increases greatly on the initial cycle but, due to the formation of a Mg(OH) 2 passive layer, displays rapid degradation in alkaline solution within 10 cycles. In a 6 M KOH+ x M KF electrolyte ( x=0.5, 1, and 2), a continuous and stable fluorinated layer is formed and the durability of the Mg 2Ni electrode increases marketly and a high rate discharge capability is obtained (90-100 mAh/g). Addition of 2 M KF leads to the highest durability of all the electrodes tested. The improvement is due to a thin MgF 2—flourinated layer, which reduces the charge-transfer resistance and protects the Mg 2Ni electrode from forming a Mg(OH) 2 layer.

  10. Use of Hydrogen Chemisorption and Ethylene Hydrogenation as Predictors for Aqueous Phase Reforming of Lactose over Ni@Pt and Co@Pt Bimetallic Overlayer Catalysts

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lai, Qinghua; Skoglund, Michael D.; Zhang, Chen

    Overlayer Pt on Ni (Ni@Pt) or Co (Co@Pt) were synthesized and tested for H2 generation from APR of lactose. H2 chemisorption descriptor showed that Ni@Pt and Co@Pt overlayer catalysts had reduced H2 adsorption strength compared to a Pt only catalyst, which agree with computational predictions. The overlayer catalysts also demonstrated lower activity for ethylene hydrogenation than the Pt only catalyst, which likely resulted from decreased H2 binding strength decreasing the surface coverage of H2. XAS results showed that overlayer catalysts exhibited higher white line intensity than the Pt catalyst, which indicates a negative d-band shift for the Pt overlayer, furthermore » providing evidence for overlayer formation. Lactose APR studies showed that lactose can be used as feedstock to produce H2 and CO under desirable reaction conditions. The Pt active sites of Ni@Pt and Co@Pt overlayer catalysts showed significantly enhanced H2 production selectivity and activity when compared with that of a Pt only catalyst. The single deposition overlayer with the largest d-band shift showed the highest H2 activity. The results suggest that overlayer formation using directed deposition technique could modify the behavior of the surface metal and ultimately modify the APR activity.« less

  11. Synthesis, Characterization, Electrochemical Studies, and In Vitro Antibacterial Activity of Novel Thiosemicarbazone and Its Cu(II), Ni(II), and Co(II) Complexes

    PubMed Central

    Khan, Salman A.; Asiri, Abdullah M.; Al-Amry, Khalid; Malik, Maqsood Ahmad

    2014-01-01

    Metal complexes were prepared by the reaction of thiosemicarbazone with CuCl2, NiCl2, CoCl2, Cu(OAc)2, Ni(OAc)2, and Co(OAc)2. The thiosemicarbazone coordinates to metal through the thionic sulfur and the azomethine nitrogen. The thiosemicarbazone was obtained by the thiosemicarbazide with 3-acetyl-2,5-dimethylthiophene. The identities of these compounds were elucidated by IR, 1H, 13C-NMR, and GC-MS spectroscopic methods and elemental analyses. The antibacterial activity of these compounds was first tested in vitro by the disc diffusion assay against two Gram-positive and two Gram-negative bacteria, and then the minimum inhibitory concentration (MIC) was determined by using chloramphenicol as reference drug. The results showed that compound 1.1 is better inhibitor of both types of tested bacteria as compared to chloramphenicol. PMID:24523641

  12. Enhanced hydrogen sorption kinetics of Mg 50Ni-LiBH 4 composite by CeCl 3 addition

    NASA Astrophysics Data System (ADS)

    Gennari, F. C.; Puszkiel, J. A.

    Mg 50Ni-LiBH 4 and Mg 50Ni-LiBH 4-CeCl 3 composites have been prepared by short times of ball milling under argon atmosphere. Combination of HP-DSC and volumetric techniques show that Mg 50Ni-LiBH 4-CeCl 3 composite not only uptakes hydrogen faster than Mg 50Ni-LiBH 4, but also releases hydrogen at a lower temperature (225 °C). The presence of CeCl 3 has a catalytic role, but it does not modify the thermodynamic properties of the composite which corresponds to MgH 2. Experimental studies on the hydriding/dehydriding mechanisms demonstrate that LiBH 4 and Ni lead to the formation of MgNi 3B 2 in both composites. In addition, XRD/DSC analysis and thermodynamic calculations demonstrate that the addition of CeCl 3 accounts for the enhancement of the hydrogen absorption/desorption kinetics through the interaction with LiBH 4. The in situ formation and subsequent decomposition of Ce(BH 4) 3 provides a uniform distribution of nanosize CeB 4 compound, which plays an important role in improving the kinetic properties of MgH 2.

  13. Neutron powder diffraction study on the structures of LaNi 5- xAl xD y compounds

    NASA Astrophysics Data System (ADS)

    Du, Honglin; Zhang, Wenyong; Wang, Changsheng; Han, Jingzhi; Yang, Yingchang; Chen, Bo; Xie, Chaomei; Sun, Kai; Zhang, Baisheng

    2003-10-01

    The structures of LaNi 5- xAl xD y ( x=0.75, 0.25, y=1.01, 1.10, 1.91 and 3.1) were systematically investigated by neutron and X-ray diffraction. D atoms are found to enter the 6m site of the α-phase but not the reported 12n site, while the 6m and 12n sites of the β-phase. In the case of LaNi 4.75Al 0.25D y with lower Al content and symmetry, D atoms do not enter the α-phase but occupy the 4h site besides the 6m and 12n sites of the β-phase. The relationship between structures and properties is also discussed.

  14. Effect of annealing on the temperature dependence of inelastic tunneling contributions vis-à-vis tunneling magnetoresistance and barrier parameters in CoFe/MgO/NiFe magnetic tunnel junctions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bhusan Singh, Braj; Chaudhary, Sujeet, E-mail: sujeetc@physics.iitd.ac.in

    The effect of annealing on the changes in the inelastic tunneling contributions in tunneling conductance of ion beam sputtered CoFe/MgO/NiFe magnetic tunnel junctions (MTJs) is investigated. The inelastic contributions are evaluated using hopping conduction model of Glazman and Matveev in the temperature range of 25–300 K. The hopping through number of series of localized states present in the barrier due to structural defects increases from 9 (in as deposited MTJ) to 18 after annealing (at 200 °C/1 h); although no changes in the interface roughness of CoFe-MgO and MgO-NiFe interfaces are observed as revealed by the x-ray reflectance studies on planar MTJs. Themore » bias dependence of tunneling magnetoresistance (TMR) at 25 K is found to get improved after annealing as revealed by the value V{sub 1/2} (the bias value at which the TMR reaches to half of its value at nearly zero bias); which is 78 mV (in MTJ annealed at 200 °C/1 h) 2.5 times the value of 33 mV (in as deposited MTJ). At 25 K the inelastic tunneling spectra revealed the presence of zero bias anomaly and magnon excitations in the range of 10–15 mV. While the barrier height exhibited a strong temperature dependence with nearly 100% increase from the value at 300 K to 25 K, the temperature dependence of TMR becomes steep after annealing.« less

  15. Hydrometallurgical recovery of metals: Ce, La, Co, Fe, Mn, Ni and Zn from the stream of used Ni-MH cells.

    PubMed

    Sobianowska-Turek, Agnieszka

    2018-04-11

    The utilization of the stream of waste secondary nickel-metal hydride (Ni-MH) and lithium-ion (Li-ion) cells, representing annually about 33% of all consumer batteries and accumulators placed on the Polish market, will soon become a big challenge for both legislators and plants dealing with the recycling of this type of hazardous waste. It is due to the fact that no company in Poland operating on the market has a complete technology for the processing of a full stream of waste chemical energy sources produced in this country. Until now, the most commonly used techniques of processing this type of waste were pyrometallurgical process. In this paper, the quantitative and qualitative characteristics of the stream of waste batteries and accumulators collected at separate collection points are presented. The results of metal recovery: caesium, lanthanum, cobalt, iron, manganese, nickel and zinc from the stream of waste Ni-MH cells, type R6 (AA), using hydrometallurgical methods are also offered. The paper demonstrates that one-stage leaching at an initial temperature of 25.0 °C, with 3 M H 2 SO 4 and at the solid to liquid ratio of s/l = 1/10, within 75 min, at a mixing speed of 500 rpm and in a strongly acidic environment should be adopted as optimal parameters for acid leaching of the paramagnetic fraction created after mechanical machining of Ni-MH battery, for which the leaching rates of individual metals were as follows: Ce - 97.7%, La - 88.7%, Co - 79.4%, Fe - 68.5%, Mn - 91.9%, Ni - 66.2% and Zn - 100%. Copyright © 2018 Elsevier Ltd. All rights reserved.

  16. Electrical resistivity of Co-Ni-Pd and Co-Pd alloys

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jen, S.U.; Chen, T.P.; Chang, S.A.

    1991-11-15

    Three series of ferromagnetic alloys have been made: Co{sub 100{minus}{ital x}}Pd{sub {ital x}}, Co{sub 25}Ni{sub 75{minus}{ital y}}Pd{sub {ital y}} and Co{sub 5{minus}{ital z}}Ni{sub {ital z}}Pd{sub 95}. The electrical resistivity {rho} of these alloys was measured from 4 to 300 K. Their high field ({ital H}{gt}2 T) susceptibility {chi}{sub HF} was obtained with superconducting quantum interference device measurements at 5 K. Comparing the residual resistivity {rho}{sub 0} of Co-Ni and Co-Pd, it is found that the spin-up resistivity {rho}{sub {up arrow}} of Co-Ni follows the Nordheim's rule, while that of Co-Pd peaks at {ital x}=85. This indicates the spin-up {ital d}more » band of Co-Pd is not full for all the {ital x} values. Also, {chi}{sub HF} data reveal the same tendency of the spin-up band. Based on the deviation from Matthiessen's rule of the two-current model, we estimate {alpha}={rho}{sub 0{down arrow}} /{rho}{sub 0{up arrow}}{congruent}2 for the dilute {ital PdCo} alloy, where {rho}{sub 0}={rho}{sub 0{down arrow}} {rho}{sub 0{up arrow}}/({rho}{sub 0{up arrow}}+{rho}{sub 0{down arrow}} ), from the residual resistivity of the ternary Co{sub 5{minus}{ital z}}Ni{sub {ital z}}Pd{sub 95} alloy and from the temperature dependence of {rho}({ital T}) of the binary Co{sub 5}Pd{sub 95} alloy« less

  17. Effects of Ni content on nanocrystalline Fe-Co-Ni ternary alloys synthesized by a chemical reduction method

    NASA Astrophysics Data System (ADS)

    Chokprasombat, Komkrich; Pinitsoontorn, Supree; Maensiri, Santi

    2016-05-01

    Magnetic properties of Fe-Co-Ni ternary alloys could be altered by changing of the particle size, elemental compositions, and crystalline structures. In this work, Fe50Co50-xNix nanoparticles (x=10, 20, 40, and 50) were prepared by the novel chemical reduction process. Hydrazine monohydrate was used as a reducing agent under the concentrated basic condition with the presence of poly(vinylpyrrolidone). We found that the nanoparticles were composed of Fe, Co and Ni with compositions according to the molar ratio of the metal sources. Interestingly, the particles were well-crystalline at the as-prepared state without post-annealing at high temperature. Increasing Ni content resulted in phase transformation from body centered cubic (bcc) to face centered cubic (fcc). For the fcc phase, the average particle size decreased when increased the Ni content; the Fe50Ni50 nanoparticles had the smallest average size with the narrowest size distribution. In additions, the particles exhibited ferromagnetic properties at room temperature with the coercivities higher than 300 Oe, and the saturation magnetiation decreased with increasing Ni content. These results suggest that the structural and magnetic properties of Fe-Co-Ni alloys could be adjusted by varying the Ni content.

  18. The effect of milling time on the synthesis of Cu{sub 54}Mg{sub 22}Ti{sub 18}Ni{sub 6} alloy

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kursun, C., E-mail: celalkursun@ksu.edu.tr; Gogebakan, M., E-mail: gogebakan@ksu.edu.tr

    In the present work, nanocrystalline Cu{sub 54}Mg{sub 22}Ti{sub 18}Ni{sub 6} alloy was produced by mechanical alloying from mixtures of pure crystalline Cu, Mg, Ti and Ni powders using a Fritsch planetary ball mill with a ball to powder ratio of 10:1. Morphological changes, microstructural evolution and thermal behaviour of the Cu-Mg-Ti-Ni powders at different stages of milling were characterised by X-ray diffraction (XRD), scanning electron microscopy with energy-dispersive X-ray detection (SEM/EDX) and differential thermal analysis (DTA). This alloy resulted in formation of single phase solid solution with FCC structure α-Cu (Mg, Ti, Ni) after 80 h of milling. In the initialmore » stage of milling different sized and shaped elemental powders became uniform during mechanical alloying. The homogeneity of the Cu{sub 54}Mg{sub 22}Ti{sub 18}Ni{sub 6} alloy increased with increasing milling time. The EDX result also confirmed the compositional homogeneity of the powder alloy. The crystallite size of alloy was calculated below 10 nm from XRD data.« less

  19. Structural, spectroscopic and thermal characterization of 2-tert-butylaminomethylpyridine-6-carboxylic acid methylester and its Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and UO(2)(II) complexes.

    PubMed

    Mohamed, Gehad G; El-Gamel, Nadia E A

    2005-04-01

    Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and UO(2)(II) complexes with the ligand 2-tert-butylaminomethylpyridine-6-carboxylic acid methylester (HL(2)) have been prepared and characterized by elemental analyses, molar conductance, magnetic moment, thermal analysis and spectral data. 1:1 M:HL(2) complexes, with the general formula [M(HL(2))X(2)].nH(2)O (where M = Co(II) (X = Cl, n = 0), Ni(II) (X = Cl, n = 3), Cu(II) (grey colour, X = AcO, n = 1), Cu(II) (yellow colour, X = Cl, n = 0) and Zn(II) (X = Br, n = 0). In addition, the Fe(III) and UO(2)(II) complexes of the type 1:2 M:HL(2) and with the formulae [Fe(L(2))(2)]Cl and [UO(2)(HL(2))(2)](NO(3))(2) are prepared. From the IR data, it is seen that HL(2) ligand behaves as a terdentate ligand coordinated to the metal ions via the pyridyl N, carboxylate O and protonated NH group; except the Fe(III) complex, it coordinates via the deprotonated NH group. This is supported by the molar conductance data, which show that all the complexes are non-electrolytes, while the Fe(III) and UO(2)(II) complexes are 1:1 electrolytes. IR and H1-NMR spectral studies suggest a similar behaviour of the Zn(II) complex in solid and solution states. From the solid reflectance spectral data and magnetic moment measurements, the complexes have a trigonal bipyramidal (Co(II), Ni(II), Cu(II) and Zn(II) complexes) and octahedral (Fe(III), UO(2)(II) complexes) geometrical structures. The thermal behaviour of the complexes is studied and the different dynamic parameters are calculated applying Coats-Redfern equation.

  20. Raman spectroscopy of DNA-metal complexes. II. The thermal denaturation of DNA in the presence of Sr2+, Ba2+, Mg2+, Ca2+, Mn2+, Co2+, Ni2+, and Cd2+.

    PubMed

    Duguid, J G; Bloomfield, V A; Benevides, J M; Thomas, G J

    1995-12-01

    Differential scanning calorimetry, laser Raman spectroscopy, optical densitometry, and pH potentiometry have been used to investigate DNA melting profiles in the presence of the chloride salts of Ba2+, Sr2+, Mg2+, Ca2+, Mn2+, Co2+, Ni2+, and Cd2+. Metal-DNA interactions have been observed for the molar ratio [M2+]/[PO2-] = 0.6 in aqueous solutions containing 5% by weight of 160 bp mononucleosomal calf thymus DNA. All of the alkaline earth metals, plus Mn2+, elevate the melting temperature of DNA (Tm > 75.5 degrees C), whereas the transition metals Co2+, Ni2+, and Cd2+ lower Tm. Calorimetric (delta Hcal) and van't Hoff (delta HVH) enthalpies of melting range from 6.2-8.7 kcal/mol bp and 75.6-188.6 kcal/mol cooperative unit, respectively, and entropies from 17.5 to 24.7 cal/K mol bp. The average number of base pairs in a cooperative melting unit () varied from 11.3 to 28.1. No dichotomy was observed between alkaline earth and transition DNA-metal complexes for any of the thermodynamic parameters other than their effects on Tm. These results complement Raman difference spectra, which reveal decreases in backbone order, base unstacking, distortion of glycosyl torsion angles, and rupture of hydrogen bonds, which occur after thermal denaturation. Raman difference spectroscopy shows that transition metals interact with the N7 atom of guanine in duplex DNA. A broader range of interaction sites with single-stranded DNA includes ionic phosphates, the N1 and N7 atoms of purines, and the N3 atom of pyrimidines. For alkaline earth metals, very little interaction was observed with duplex DNA, whereas spectra of single-stranded complexes are very similar to those of melted DNA without metal. However, difference spectra reveal some metal-specific perturbations at 1092 cm-1 (nPO2-), 1258 cm-1 (dC, dA), and 1668 cm-1 (nC==O, dNH2 dT, dG, dC). Increased spectral intensity could also be observed near 1335 cm-1 (dA, dG) for CaDNA. Optical densitometry, employed to detect DNA

  1. Crystal structure, DNA binding, cleavage, antioxidant and antibacterial studies of Cu(II), Ni(II) and Co(III) complexes with 2-((furan-2-yl)methylimino)methyl)-6-ethoxyphenol Schiff base

    NASA Astrophysics Data System (ADS)

    Venkateswarlu, Kadtala; Kumar, Marri Pradeep; Rambabu, Aveli; Vamsikrishna, Narendrula; Daravath, Sreenu; Rangan, Krishnan; Shivaraj

    2018-05-01

    Three novel binary metal complexes; 1 [Cu(L)2], 2 [Ni(L)2] and 3 [Co(L)3] where, L (2-(((furan-2-yl) methylimino)methyl)-6-ethoxyphenol, C14H15NO3), were synthesized and characterized by various spectral techniques. Based on spectral studies square planar geometry is assigned for Cu(II) and Ni(II) complexes, whereas Co(III) owned octahedral geometry. Ligand, [Cu(L)2] and [Ni(L)2] are crystallized and found to be monoclinic crystal systems. CT-DNA absorption binding studies revealed that the complexes show good binding propensity (Kb = 5.02 × 103 M-1, 2.77 × 103 M-1, 1.63 × 104 M-1 for 1, 2 and 3 respectively). The role of these complexes in the oxidative and photolytic cleavage of supercoiled pBR322 DNA was studied and found that the complexes cleave the pBR322 DNA effectively. The catalytic ability of 1, 2 and 3 follows the order: 3 > 1 >2. Antioxidant studies of the new complexes revealed that they exhibit significant antioxidant activity against DPPH radical. The Schiff base and its metal complexes have been screened for antibacterial studies by Minimum Inhibitory Concentration method. It is observed that all metal complexes showed more activity than free ligand.

  2. Hydrogen Storage Characteristics of Nanocrystalline and Amorphous Nd-Mg-Ni-Based NdMg12-Type Alloys Synthesized via Mechanical Milling

    NASA Astrophysics Data System (ADS)

    Zhang, Yanghuan; Shang, Hongwei; Hou, Zhonghui; Yuan, Zeming; Yang, Tai; Qi, Yan

    2016-12-01

    In this study, Mg was partially substituted by Ni with the intent of improving the hydrogen storage kinetics performance of NdMg12-type alloy. Mechanical milling technology was adopted to fabricate the nanocrystalline and amorphous NdMg11Ni + x wt pct Ni ( x = 100, 200) alloys. The effects of Ni content and milling duration on the microstructures and hydrogen storage kinetics of as-milled alloys have been systematically investigated. The structures were characterized by XRD and HRTEM. The electrochemical hydrogen storage properties were tested by an automatic galvanostatic system. Moreover, the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter connected with a H2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. The results reveal that the increase of Ni content dramatically ameliorates the gaseous and electrochemical hydrogen storage kinetics performance of the as-milled alloys. Furthermore, high rate discharge ability (HRD) reach the maximum value with the variation of milling time. The maximum HRDs of the NdMg11Ni + x wt pct Ni ( x = 100, 200) alloys are 80.24 and 85.17 pct. The improved gaseous hydrogen storage kinetics of alloys via increasing Ni content and milling time can be attributed to a decrease in the hydrogen desorption activation energy.

  3. Phase transformations in the reaction cell of TiNi-based sintered systems

    NASA Astrophysics Data System (ADS)

    Artyukhova, Nadezhda; Anikeev, Sergey; Yasenchuk, Yuriy; Chekalkin, Timofey; Gunther, Victor; Kaftaranova, Maria; Kang, Ji-Hoon; Kim, Ji-Soon

    2018-05-01

    The present work addresses the structural-phase state changes of porous TiNi-based compounds fabricated by reaction sintering (RS) of Ti and Ni powders with Co, Mo, and no additives introduced. The study also emphasizes the features of a reaction cell (RC) during the transition from the solid- to liquid-phase sintering. Mechanisms of phase transformations occurring in the solid phase, involving the low-melting Ti2Ni phase within the RC, have been highlighted. Also, the intermediate Ti2Ni phase had a crucial role to provide both the required RS behavior and modified phase composition of RS samples, and besides, it is found to be responsible for the near-equiatomic TiNi saturation of the melt. Both cobalt and molybdenum additives are shown to cause additional structuring of the transition zone (TZ) at the Ti2Ni‑TiNi interface and broadening of this zone. The impact of Co and Mo on the Ti2Ni phase is evident through fissuring of this phase layer, which is referred to solidified stresses increased in the layer due to post-alloying defects in the structure.

  4. Hierarchical NiCo2O4 Hollow Sphere as a Peroxidase Mimetic for Colorimetric Detection of H2O2 and Glucose

    PubMed Central

    Huang, Wei; Lin, Tianye; Cao, Yang; Lai, Xiaoyong; Peng, Juan; Tu, Jinchun

    2017-01-01

    In this work, the hierarchical NiCo2O4 hollow sphere synthesized via a “coordinating etching and precipitating” process was demonstrated to exhibit intrinsic peroxidase-like activity. The peroxidase-like activity of NiCo2O4, NiO, and Co3O4 hollow spheres were comparatively studied by the catalytic oxidation reaction of 3,3,5,5-tetramethylbenzidine (TMB) in presence of H2O2, and a superior peroxidase-like activity of NiCo2O4 was confirmed by stronger absorbance at 652 nm. Furthermore, the proposed sensing platform showed commendable response to H2O2 with a linear range from 10 μM to 400 μM, and a detection limit of 0.21 μM. Cooperated with GOx, the developed novel colorimetric and visual glucose-sensing platform exhibited high selectivity, favorable reproducibility, satisfactory applicability, wide linear range (from 0.1 mM to 4.5 mM), and a low detection limit of 5.31 μM. In addition, the concentration-dependent color change would offer a better and handier way for detection of H2O2 and glucose by naked eye. PMID:28124997

  5. Ni-Co laterite deposits

    USGS Publications Warehouse

    Marsh, Erin E.; Anderson, Eric D.

    2011-01-01

    Nickel-cobalt (Ni-Co) laterite deposits are an important source of nickel (Ni). Currently, there is a decline in magmatic Ni-bearing sulfide lode deposit resources. New efforts to develop an alternative source of Ni, particularly with improved metallurgy processes, make the Ni-Co laterites an important exploration target in anticipation of the future demand for Ni. This deposit model provides a general description of the geology and mineralogy of Ni-Co laterite deposits, and contains discussion of the influences of climate, geomorphology (relief), drainage, tectonism, structure, and protolith on the development of favorable weathering profiles. This model of Ni-Co laterite deposits represents part of the U.S. Geological Survey Mineral Resources Program's effort to update the existing models to be used for an upcoming national mineral resource assessment.

  6. In Situ Natural Abundance 17 O and 25 Mg NMR Investigation of Aqueous Mg(OH) 2 Dissolution in the Presence of Supercritical CO 2

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hu, Mary Y.; Deng, Xuchu; Thanthiriwatte, K. Sahan

    We report the development of an in situ high pressure NMR capability that permits natural abundance 17O and 25Mg NMR characterization of dissolved species in aqueous solution and in the presence of supercritical CO 2 fluid (scCO 2). The dissolution of Mg(OH) 2 (brucite) in a multiphase water/scCO 2 fluid at 90 atm pressure and 50 C was studied in situ, with relevance to geological carbon sequestration. 17O NMR spectra allowed identification and distinction of various fluid species including dissolved CO 2 in the H 2O-rich phase, scCO 2, aqueous H 2O, and HCO 3 -. The widely separated spectralmore » peaks for various species can all be observed both dynamically and quantitatively at concentrations of as low as 20 mM. Measurement of the concentrations of these individual species also allows an in situ estimate of the hydrogen ion concentration, or pCH + values, of the reacting solutions. The concentration of Mg 2+ can be observed by natural abundance 25Mg NMR at a concentration as low as 10 mM. Quantum chemistry calculations of the NMR chemical shifts on cluster models aided in the interpretation of the experimental results. Evidence for the formation of polymeric Mg 2+ clusters at high concentrations in the H 2O-rich phase, a possible critical step needed for magnesium carbonate formation, was found. The approach and findings enable insight into metal carbonation reactions associated with geological carbon sequestration that cannot be probed by ex situ methods.« less

  7. Local lattice distortion in NiCoCr, FeCoNiCr and FeCoNiCrMn concentrated alloys investigated by synchrotron X-ray diffraction

    DOE PAGES

    Tong, Yang; Jin, Ke; Bei, Hongbin; ...

    2018-05-26

    Severe lattice distortion is presumptively considered as a core effect of high-entropy alloys, but quantitative measurements are still missing. Here, we demonstrate that the lattice distortion in high-entropy alloys can be quantitatively analyzed based on pair distribution function obtained from synchrotron X-ray diffraction. By applying this method to equiatomic NiCoCr, FeCoNiCr and FeCoNiCrMn concentrated alloys, we found that the local lattice distortion in the NiCoCr (0.23%) and FeCoNiCrMn (0.24%) alloys are comparable while negligible in the FeCoNiCr alloy (0.04%). Furthermore, the origin of local lattice distortion in the NiCoCr and FeCoNiCrMn concentrated alloys was discussed.

  8. Local lattice distortion in NiCoCr, FeCoNiCr and FeCoNiCrMn concentrated alloys investigated by synchrotron X-ray diffraction

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tong, Yang; Jin, Ke; Bei, Hongbin

    Severe lattice distortion is presumptively considered as a core effect of high-entropy alloys, but quantitative measurements are still missing. Here, we demonstrate that the lattice distortion in high-entropy alloys can be quantitatively analyzed based on pair distribution function obtained from synchrotron X-ray diffraction. By applying this method to equiatomic NiCoCr, FeCoNiCr and FeCoNiCrMn concentrated alloys, we found that the local lattice distortion in the NiCoCr (0.23%) and FeCoNiCrMn (0.24%) alloys are comparable while negligible in the FeCoNiCr alloy (0.04%). Furthermore, the origin of local lattice distortion in the NiCoCr and FeCoNiCrMn concentrated alloys was discussed.

  9. Tri-reforming of surrogate blogs over Ni/Mg/ceria-zirconia/alumina pellet catalysts

    DOE PAGES

    Zhao, Xianhui; Ngo, Huong T.; Walker, Devin M.; ...

    2018-01-23

    The performance of catalytic tri-reforming under industrially relevant situations (e.g., pellet catalysts, pressurized reactor) was investigated using surrogate biogas as the feedstock. Tri-reforming using Ni/Mg/Ce 0.6Zr 0.4O 2/Al 2O 3 pellet catalysts was studied in a bench scale fixed-bed reactor. The feed molar ratio for CH 4: CO 2: air was fixed as 1.0: 0.70: 0.95. The effects of temperature (800 – 860 °C), pressure (1 – 6 bar), and H 2O/CH 4 molar feed ratio (0.23 – 0.65) were examined. Pressure has substantial impact on the reaction and transport rates and equilibrium conversions, making it a key variable. Atmore » 860 °C, CO 2 conversion increased from 4 to 61% and H 2/CO molar ratio decreased from 2.0 to 1.1 as the pressure changed from 1 to 6 bar. CO 2 conversion and H 2/CO molar ratio were also influenced by the temperature and H 2O/CH 4 molar ratio. At 3 bar, CO 2 conversion varied between 4 and 43% and the H 2/CO molar ratio varied between 1.2 and 1.9 as the temperature changed from 800 to 860 °C. At 3 bar and 860 °C, CO 2 conversion decreased from 35 to 8% and H 2/CO molar ratio increased from 1.7 to 2.4 when the H 2O/CH 4 molar ratio was increased from 0.23 to 0.65. This work demonstrates that the tri-reforming technology is feasible for converting biogas under scaled-up conditions in a fixed-bed reactor.« less

  10. Fabrication of Mg-X-O (X = Fe, Co, Ni, Cr, Mn, Ti, V, and Zn) barriers for magnetic tunnel junctions

    NASA Astrophysics Data System (ADS)

    Yakushiji, K.; Kitagawa, E.; Ochiai, T.; Kubota, H.; Shimomura, N.; Ito, J.; Yoda, H.; Yuasa, S.

    2018-05-01

    We fabricated magnetic tunnel junctions with a 3d-transition material(X)-doped MgO (Mg-X-O) barrier, and evaluated the effect of the doping on magnetoresistance (MR) and microstructure. Among the variations of X (X = Fe, Co, Ni, Cr, Mn, Ti, V, and Zn), X = Fe and Mn showed a high MR ratio of more than 100%, even at a low resistance-area product of 3 Ωμm2. The microstructure analysis revealed that (001) textured orientation formed for X = Fe and Mn despite substantial doping (about 10 at%). The elemental mappings indicated that Fe atoms in the Mg-Fe-O barrier were segregated at the interfaces, while Mn atoms were evenly involved in the Mg-Mn-O barrier. This suggests that MgO has high adaptability for Fe and Mn dopants in terms of high MR ratio.

  11. Robust hydrogen-bonded self-assemblies from biimidazole complexes. Synthesis and structural characterization of [M(biimidazole)2(OH2)2]2+ (M = Co2+, Ni2+) complexes and carboxylate modules.

    PubMed

    Atencio, Reinaldo; Chacón, Mirbel; González, Teresa; Briceño, Alexander; Agrifoglio, Giuseppe; Sierraalta, Anibal

    2004-02-21

    A robust heteromeric hydrogen-bonded synthon [R2(2) (9)-Id] is exploited to drive the modular self-assembly of four coordination complexes [M(H2biim)2(OH2)2]2+ (M = Co2+, Ni2+) and carboxylate counterions. This strategy allowed us to build molecular architectures of 0-, 1-, and 2-dimensions. A hydrogen-bonded 2D-network with cavities has been designed, which maintains its striking integrity after reversible water desorption-resorption processes.

  12. Applications of the First-principles LDA+Usc Method to Spin-crossover Minerals: the NAL Phase and (Mg,Fe)CO3 ferromagnesite

    NASA Astrophysics Data System (ADS)

    Hsu, H.

    2016-12-01

    Spin crossover (SCO) in iron-bearing minerals has attracted tremendous attention in recent years, as SCO usually leads to anomalous changes of the elastic, conducting, and thermodynamic properties of these minerals. Possible geophysical effects of SCO have been anticipated as well. With the development of the local density approximation + self-consistent Hubbard U (LDA+Usc) method, first-principles calculations have elucidated SCO in many lower-mantle minerals. The success of LDA+Usc lies in its capability to correctly identify the ground state in a wide pressure range and to accurately determine the mechanism of SCO, including the transition pressure PT. In this talk, two recent LDA+Usc studies of SCO minerals are presented: the "new aluminous (NAL) phase" [1] and (Mg,Fe)CO3 ferromagnesite [2]. The former is considered as a main host of aluminum in the subducted basalt and may be related to the seismic heterogeneities, and the latter is believed to be the major carbon carrier in the Earth's lower mantle and play a key role in the deep carbon cycle. For both minerals, the abrupt change of iron quadrupole splitting and the volume/elastic anomalies accompanying the SCO obtained in our calculations are in great agreement with experiments. Our calculations also suggest that the spin transition pressure PT in the NAL phase is not very sensitive to temperature, due to its nearly degenerate low-spin (LS) states, in contrast with (Mg,Fe)O ferropericlase and (Mg,Fe)CO3 systems, in which PT significantly increases with temperature. By examining the overall performance of the LDA+Usc method in the NAL phase and ferromagnesite, along with our previous calculations for ferropericlase and Fe-bearing MgSiO3 bridgmanite [3-5], we have established LDA+Usc a highly reliable method to study iron-bearing minerals and related materials under high pressure. [1] H. Hsu, in preparation. [2] S.-C. Huang and H. Hsu, Phys. Rev. B (Rapid Comm.), in press. [3] H. Hsu and R. M. Wentzcovitch

  13. Composite Ni-Co-fly ash coatings on 5083 aluminium alloy

    NASA Astrophysics Data System (ADS)

    Panagopoulos, C. N.; Georgiou, E. P.; Tsopani, A.; Piperi, L.

    2011-03-01

    Ni-Co-fly ash coatings were deposited on zincate treated 5083 wrought aluminium alloy substrates with the aid of the electrodeposition technique. Structural and chemical characterization of the produced composite coatings was performed with the aid of X-ray diffraction (XRD), scanning electron microscopy (SEM) and electron dispersive X-ray analysis (EDS) techniques. The Ni-Co-fly ash coatings were found to consist of a crystalline Ni-Co solid solution with dispersed fly ash particles. In addition, chemical analysis of the Ni-Co matrix showed that it consisted of 80 wt.% Ni and 20 wt.% Co. The co-deposition of fly ash particles leads to a significant increase of the microhardness of the coating. The corrosion behaviour of the Ni-Co-fly ash/zincate coated aluminium alloy, in a 0.3 M NaCl solution (pH = 3.5), was studied by means of potentiodynamic corrosion experiments.

  14. Defect formation in LaGa(Mg,Ni)O3-δ : A statistical thermodynamic analysis validated by mixed conductivity and magnetic susceptibility measurements

    NASA Astrophysics Data System (ADS)

    Naumovich, E. N.; Kharton, V. V.; Yaremchenko, A. A.; Patrakeev, M. V.; Kellerman, D. G.; Logvinovich, D. I.; Kozhevnikov, V. L.

    2006-08-01

    A statistical thermodynamic approach to analyze defect thermodynamics in strongly nonideal solid solutions was proposed and validated by a case study focused on the oxygen intercalation processes in mixed-conducting LaGa0.65Mg0.15Ni0.20O3-δ perovskite. The oxygen nonstoichiometry of Ni-doped lanthanum gallate, measured by coulometric titration and thermogravimetric analysis at 923-1223K in the oxygen partial pressure range 5×10-5to0.9atm , indicates the coexistence of Ni2+ , Ni3+ , and Ni4+ oxidation states. The formation of tetravalent nickel was also confirmed by the magnetic susceptibility data at 77-600K , and by the analysis of p -type electronic conductivity and Seebeck coefficient as function of the oxygen pressure at 1023-1223K . The oxygen thermodynamics and the partial ionic and hole conductivities are strongly affected by the point-defect interactions, primarily the Coulombic repulsion between oxygen vacancies and/or electron holes and the vacancy association with Mg2+ cations. These factors can be analyzed by introducing the defect interaction energy in the concentration-dependent part of defect chemical potentials expressed by the discrete Fermi-Dirac distribution, and taking into account the probabilities of local configurations calculated via binomial distributions.

  15. Metallic glassy Zr70Ni20Pd10 powders for improving the hydrogenation/dehydrogenation behavior of MgH2

    PubMed Central

    El-Eskandarany, M. Sherif

    2016-01-01

    Because of its low density, storage of hydrogen in the gaseous and liquids states possess technical and economic challenges. One practical solution for utilizing hydrogen in vehicles with proton-exchange fuel cells membranes is storing hydrogen in metal hydrides. Magnesium hydride (MgH2) remains the best hydrogen storage material due to its high hydrogen capacity and low cost of production. Due to its high activation energy and poor hydrogen sorption/desorption kinetics at moderate temperatures, the pure form of MgH2 is usually mechanically treated by high-energy ball mills and catalyzed with different types of catalysts. These steps are necessary for destabilizing MgH2 to enhance its kinetics behaviors. In the present work, we used a small mole fractions (5 wt.%) of metallic glassy of Zr70Ni20Pd10 powders as a new enhancement agent to improve its hydrogenation/dehydrogenation behaviors of MgH2. This short-range ordered material led to lower the decomposition temperature of MgH2 and its activation energy by about 121 °C and 51 kJ/mol, respectively. Complete hydrogenation/dehydrogenation processes were successfully achieved to charge/discharge about 6 wt.%H2 at 100 °C/200 °C within 1.18 min/3.8 min, respectively. In addition, this new nanocomposite system shows high performance of achieving continuous 100 hydrogen charging/discharging cycles without degradation. PMID:27220994

  16. A study of the properties and microstructure of Ni 81Fe 19 ultrathin films with MgO

    NASA Astrophysics Data System (ADS)

    Li, Minghua; Han, Gan; Ding, Lei; Wang, Xiaocui; Liu, Yang; Feng, Chun; Wang, Haicheng; Yu, Guanghua

    2012-01-01

    The anisotropic magnetoresistance (AMR) of a Ta (5 nm)/MgO (3 nm)/Ni81Fe19 (10 nm)/MgO (2 nm)/Ta (3 nm) film with MgO-Nano Oxide Layer (NOL) increases dramatically from 1.05% to 3.24% compared with a Ta (5 nm)/Ni81Fe19 (10 nm)/Ta (3 nm) film without the MgO-NOL layer after annealing at 380 °C for 2 h. Although the MgO destroys the NiFe (1 1 1) texture, it enhances the specular electron scattering of the conduction electrons at the NOL interface and suppresses the interface reactions and diffusion at the Ta/NiFe and NiFe/Ta interfaces. The NiFe (1 1 1) texture was formed after the annealing, resulting in a higher AMR ratio. X-ray photoelectron spectroscope results show that Mg and Mg2+ were present in the MgOx films.

  17. Oxygen Evolution Activity of Co-Ni Nanochain Alloys: Promotion by Electron Injection.

    PubMed

    Yuan, Xiaotao; Riaz, Muhammad Sohail; Wang, Xin; Dong, Chenlong; Zhang, Zhe; Huang, Fuqiang

    2018-03-12

    Metal alloy nanoparticles have shown promising applications in electrocatalysis. However, the nanoparticles usually suffer from limited charge-transfer efficiency, which can be solved by preparing one-dimensional materials. Herein, Co-Ni alloy nanochains are prepared by a direct-current arc-discharge method. The nanochains, comprised of mutually coupled uniform nanospheres, can range up to several micrometers in size. When the alloy is exposed to air or under the electro-oxidation process, a metal-metal-oxide heterostructure is obtained. The alloy can inject electrons into the oxide, which makes it more suitable for electrocatalysis. The composition of the samples can be changed by varying the ratio of Ni/Co (i.e., Co, Co 7 Ni 3 , Co 5 Ni 5 , Co 3 Ni 7 , Ni) in the synthesis process. The nanochains show good oxygen evolution performance that correlates with the Ni/Co ratio. Co 7 Ni 3 demonstrates optimal activity with an onset point of 1.50 V vs. reversible hydrogen electrode (RHE) and overpotential of 350 mV at 10 mA cm -2 . The alloy nanochains also show excellent durability with 95.0 % current retention after a long-term test for 12 h. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Noteworthy performance of La(1-x)Ca(x)MnO3 perovskites in generating H2 and CO by the thermochemical splitting of H2O and CO2.

    PubMed

    Dey, Sunita; Naidu, B S; Govindaraj, A; Rao, C N R

    2015-01-07

    Perovskite oxides of the composition La1-xCaxMnO3 (LCM) have been investigated for the thermochemical splitting of H2O and CO2 to produce H2 and CO, respectively. The study was carried out in comparison with La1-xSrxMnO3, CeO2 and other oxides. The LCM system exhibits superior characteristics in high-temperature evolution of oxygen, and in reducing CO2 to CO and H2O to H2. The best results were obtained with La0.5Ca0.5MnO3 whose performance is noteworthy compared to that of other oxides including ceria. The orthorhombic structure of LCM seems to be a crucial factor.

  19. Synthetic Active Site Model of the [NiFeSe] Hydrogenase.

    PubMed

    Wombwell, Claire; Reisner, Erwin

    2015-05-26

    A dinuclear synthetic model of the [NiFeSe] hydrogenase active site and a structural, spectroscopic and electrochemical analysis of this complex is reported. [NiFe('S2Se2')(CO)3] (H2'S2Se2' = 1,2-bis(2-thiabutyl-3,3-dimethyl-4-selenol)benzene) has been synthesized by reacting the nickel selenolate complex [Ni('S2Se2')] with [Fe(CO)3bda] (bda = benzylideneacetone). X-ray crystal structure analysis confirms that [NiFe('S2Se2')(CO)3] mimics the key structural features of the enzyme active site, including a doubly bridged heterobimetallic nickel and iron center with a selenolate terminally coordinated to the nickel center. Comparison of [NiFe('S2Se2')(CO)3] with the previously reported thiolate analogue [NiFe('S4')(CO)3] (H2'S4' = H2xbsms = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene) showed that the selenolate groups in [NiFe('S2Se2')(CO)3] give lower carbonyl stretching frequencies in the IR spectrum. Electrochemical studies of [NiFe('S2Se2')(CO)3] and [NiFe('S4')(CO)3] demonstrated that both complexes do not operate as homogenous H2 evolution catalysts, but are precursors to a solid deposit on an electrode surface for H2 evolution catalysis in organic and aqueous solution. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  20. Enhanced damage resistance and novel defect structure of CrFeCoNi under in situ electron irradiation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    He, Mo -Rigen; Wang, Shuai; Jin, Ke

    Defect production and growth in CrFeCoNi, a single-phase concentrated solid solution alloy, is characterized using in situ electron irradiation inside a transmission electron microscope operated at 400–1250 kV and 400 °C. All observed defects are interstitial-type, either elliptical Frank loops or polygonal (mostly rhombus) perfect loops. Both forms of loops in CrFeCoNi exhibit a sublinear power law of growth that is > 40 times slower than the linear defect growth in pure Ni. Lastly, this result shows how compositional complexity impacts the production of Frenkel pairs and the agglomeration of interstitials into loops, and, thus, enhances the radiation tolerance.

  1. Enhanced damage resistance and novel defect structure of CrFeCoNi under in situ electron irradiation

    DOE PAGES

    He, Mo -Rigen; Wang, Shuai; Jin, Ke; ...

    2016-07-25

    Defect production and growth in CrFeCoNi, a single-phase concentrated solid solution alloy, is characterized using in situ electron irradiation inside a transmission electron microscope operated at 400–1250 kV and 400 °C. All observed defects are interstitial-type, either elliptical Frank loops or polygonal (mostly rhombus) perfect loops. Both forms of loops in CrFeCoNi exhibit a sublinear power law of growth that is > 40 times slower than the linear defect growth in pure Ni. Lastly, this result shows how compositional complexity impacts the production of Frenkel pairs and the agglomeration of interstitials into loops, and, thus, enhances the radiation tolerance.

  2. Synthesis and studies on Cu(II), Co(II), Ni(II) complexes of Knoevenagel β-diketone ligands.

    PubMed

    Sumathi, S; Tharmaraj, P; Sheela, C D; Anitha, C

    2012-11-01

    Transition metal complexes of various acetylacetone based ligands of the type ML [where M=Cu(II), Ni(II), Co(II); L=3-(aryl)-pentane-2,4-dione] have been synthesized. The structural features have been derived from their elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, (1)H NMR, Mass and ESR spectral studies. Conductivity measurements reveal that all the complexes are non-electrolytic in nature. Spectroscopic and other analytical data of the complexes suggest octahedral geometry for other metal(II) complexes. The redox behavior of the copper(II) complexes have been studied by cyclic voltammetry. The free ligands and their metal complexes have been screened for their in vitro biological activities against the bacteria Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus as well as the fungus Candida albicans by well diffusion method. The zone of inhibition value indicates that the most of the metal(II) complexes are found to possess increased activities compared to those of the free ligands. All synthesized compounds may serve as potential photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation (SHG) efficiency of the ligands (L1-L3) was found to be considerable effect than that of urea and KDP (potassium dihydrogen phosphate). Copyright © 2012 Elsevier B.V. All rights reserved.

  3. Synthesis and studies on Cu(II), Co(II), Ni(II) complexes of Knoevenagel β-diketone ligands

    NASA Astrophysics Data System (ADS)

    Sumathi, S.; Tharmaraj, P.; Sheela, C. D.; Anitha, C.

    2012-11-01

    Transition metal complexes of various acetylacetone based ligands of the type ML [where M = Cu(II), Ni(II), Co(II); L = 3-(aryl)-pentane-2,4-dione] have been synthesized. The structural features have been derived from their elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, 1H NMR, Mass and ESR spectral studies. Conductivity measurements reveal that all the complexes are non-electrolytic in nature. Spectroscopic and other analytical data of the complexes suggest octahedral geometry for other metal(II) complexes. The redox behavior of the copper(II) complexes have been studied by cyclic voltammetry. The free ligands and their metal complexes have been screened for their in vitro biological activities against the bacteria Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus as well as the fungus Candida albicans by well diffusion method. The zone of inhibition value indicates that the most of the metal(II) complexes are found to possess increased activities compared to those of the free ligands. All synthesized compounds may serve as potential photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation (SHG) efficiency of the ligands (L1-L3) was found to be considerable effect than that of urea and KDP (potassium dihydrogen phosphate).

  4. Crystal growth of incommensurate members of 2H-hexagonal perovskite related oxides: Ba{sub 4}M{sub z}Pt{sub 3−z}O{sub 9} (M=Co, Ni, Cu, Zn, Mg, Pt)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ferreira, Timothy; Morrison, Gregory; Yeon, Jeongho

    2016-04-15

    Millimeter sized crystals of six oxides of approximate composition Ba{sub 4}M{sub z}Pt{sub 3-z}O{sub 9} (M=Co, Ni, Cu, Zn, Mg, Pt) were grown from molten K{sub 2}CO{sub 3} fluxes and found to crystallize in a 2H hexagonal perovskite-related structure type. The compositions of these incommensurate structures, which belong to the A{sub 3n+3m}A′{sub n}B{sub 3m+n}O{sub 9m+6n} family of 2H hexagonal perovskite related oxides, were characterized by X-ray diffraction, energy dispersive spectroscopy, and magnetic susceptibility measurements. The specific synthetic considerations, crystal growth conditions, and magnetic susceptibility measurements are discussed. - Graphical abstract: SEM image and average commensurate unit cell of Ba{sub 4}Pt{sub 3}O{submore » 9.} - Highlights: • Single crystals of the series Ba{sub 4}A′{sub z}Pt{sub 3-z}O{sub 9} were grown via a molten carbonate flux. • Ba{sub 4}Pt{sub 3}O{sub 9} and all substitutional variants are incommensurate, composite structures. • All compounds have an approximate stoichiometry of Ba{sub 4}A′Pt{sub 2}O{sub 9.}.« less

  5. Synthetic Active Site Model of the [NiFeSe] Hydrogenase

    PubMed Central

    Wombwell, Claire; Reisner, Erwin

    2015-01-01

    A dinuclear synthetic model of the [NiFeSe] hydrogenase active site and a structural, spectroscopic and electrochemical analysis of this complex is reported. [NiFe(‘S2Se2’)(CO)3] (H2‘S2Se2’=1,2-bis(2-thiabutyl-3,3-dimethyl-4-selenol)benzene) has been synthesized by reacting the nickel selenolate complex [Ni(‘S2Se2’)] with [Fe(CO)3bda] (bda=benzylideneacetone). X-ray crystal structure analysis confirms that [NiFe(‘S2Se2’)(CO)3] mimics the key structural features of the enzyme active site, including a doubly bridged heterobimetallic nickel and iron center with a selenolate terminally coordinated to the nickel center. Comparison of [NiFe(‘S2Se2’)(CO)3] with the previously reported thiolate analogue [NiFe(‘S4’)(CO)3] (H2‘S4’=H2xbsms=1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene) showed that the selenolate groups in [NiFe(‘S2Se2’)(CO)3] give lower carbonyl stretching frequencies in the IR spectrum. Electrochemical studies of [NiFe(‘S2Se2’)(CO)3] and [NiFe(‘S4’)(CO)3] demonstrated that both complexes do not operate as homogenous H2 evolution catalysts, but are precursors to a solid deposit on an electrode surface for H2 evolution catalysis in organic and aqueous solution. PMID:25847470

  6. Electrochemical properties of LaNi{sub 5{minus}x}Ge{sub x} alloys in Ni-MH batteries

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Witham, C.; Hightower, A.; Fultz, B.

    1997-11-01

    Electrochemical studies were performed on LaNi{sub 5{minus}x}Ge{sub x} metal hydride alloys with 0 {le} x {le} 0.5. The authors carried out single-electrode studies to understand the effects of the Ge substituent on the hydrogen absorption characteristics, the electrochemical capacity, and the electrochemical kinetics of hydrogen absorption and desorption. The electrochemical characteristics of the Ge-substituted alloys are compared to those of the Sn-substituted alloys reported earlier. LaNi{sub 5{minus}x}Ge{sub x} alloys show compositional trends similar to LaNi{sub 5{minus}x}Sn{sub x} alloys, but unlike the Sn-substituted alloys, Ge-substituted alloys continue to exhibit facile kinetics for hydrogen absorption/desorption at high solute concentrations. Cycle lives ofmore » LaNi{sub 5{minus}x}Ge{sub x} electrodes were measured in 300 mAh laboratory test cells and were found to be superior to the Sn-substituted LaNi{sub 5} and comparable to a Mm(Ni, Co, Mn, Al){sub 5} alloy. The optimum Ge content for LaNi{sub 5{minus}x}Ge{sub x} metal hydride alloys in alkaline rechargeable cells is in the range 0.4 {le} x {le} 0.5.« less

  7. Preparation and electrochemical properties of NiO-Co3O4 composite as electrode materials for supercapacitors

    NASA Astrophysics Data System (ADS)

    Wang, X. W.; Zheng, D. L.; Yang, P. Z.; Wang, X. E.; Zhu, Q. Q.; Ma, P. F.; Sun, L. Y.

    2017-01-01

    The precursor of NiO-Co3O4 composites was synthesized via a simple hydrothermal process. After that, the precursor was calcined at 300 °C for 3 h to obtain the composite powders. The powders calcined at 300 °C showed amorphous, and the powders calcined at 400 °C and 500 °C for comparison showed the composite phase of NiO and Co3O4. The composite products showed a microstructure of micro-spheres. For the samples calcined at 300 °C for 3 h, the specific capacitance reached 801 F g-1 at a current density of 1 A g-1.

  8. Atomic Layer Deposition of the Metal Pyrites FeS2 , CoS2 , and NiS2.

    PubMed

    Guo, Zheng; Wang, Xinwei

    2018-05-14

    Atomic layer deposition (ALD) of the pyrite-type metal disulfides FeS 2 , CoS 2 , and NiS 2 is reported for the first time. The deposition processes use iron, cobalt, and nickel amidinate compounds as the corresponding metal precursors and the H 2 S plasma as the sulfur source. All the processes are demonstrated to follow ideal self-limiting ALD growth behavior to produce fairly pure, smooth, well-crystallized, stoichiometric pyrite FeS 2 , CoS 2 , and NiS 2 films. By these processes, the FeS 2 , CoS 2 , and NiS 2 films can also be uniformly and conformally deposited into deep narrow trenches with aspect ratios as high as 10:1, which thereby highlights the broad and promising applicability of these ALD processes for conformal film coatings on complex high-aspect-ratio 3D architectures in general. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Sorption, desorption, and speciation of Cd, Ni, and Fe by four calcareous soils as affected by pH.

    PubMed

    Tahervand, Samaneh; Jalali, Mohsen

    2016-06-01

    The sorption, desorption, and speciation of cadmium (Cd), nickel (Ni), and iron (Fe) in four calcareous soils were investigated at the pH range of 2-9. The results indicated that sorption of Fe by four soils was higher than 80 % at pH 2, while in the case of Cd and Ni was less than 30 %. The most common sequence of metal sorption at pH 2-9 for four soils was in the order of Fe ≫ Ni > Cd. Cadmium and Ni sorption as a function of pH showed the predictable trend of increasing metal sorption with increase in equilibrium pH, while the Fe sorption trend was different and characterized by three phases. With regard to the order of Cd, Ni, and Fe sorption on soils, Cd and Ni showed high affinity for organic matter (OM), whereas Fe had high tendency for calcium carbonate (CaCO3). Results of metal desorption using 0.01 M NaCl demonstrated that metal sorption on soils containing high amounts of CaCO3 was less reversible in comparison to soils containing high OM. In general, Cd and Ni desorption curves were characterized by three phases; (1) the greatest desorption at pH 2, (2) the low desorption at pH 3-7, and (3) the least desorption at pH > 7. The MINTEQ speciation solubility program showed that the percentage of free metals declined markedly with increase of pH, while the percentage of carbonate and hydroxyl species increased. Furthermore, MINTEQ predicted that saturation index (SI) of metals increased with increasing pH.

  10. Impact of El Niño and La Niña on SeaWiFS, MODIS-A and VIIRS Chlorophyll-a Measurements Along the Equator During 1997 to 2016

    NASA Astrophysics Data System (ADS)

    Halpern, D.; Franz, B. A.; Kuring, N. A.

    2016-12-01

    The Ocean Biology Processing Group at NASA's GSFC recently reprocessed satellite ocean color measurements (SeaWiFS, MODIS-A and VIIRS) to improve accuracy and enhance time-series interoperability and consistency between multi-mission datasets. We chose the 1°S-1°N region along the equator to examine the behavior of Chl-a in El Niño and La Niña events because this latitudinal width represented the scale of Ekman upwelling, which is hypothesized to be a primary mechanism of Chl-a variations along the equator. An El Niño (La Niña) event has five consecutive 3-month-average sea surface temperature anomalies (SSTAs) greater (less) than 0.5°C in the 5°S-5°N, 170°W-120°W region and a super El Niño event occurs when SSTA is greater than 2.0°C. The September 1997 (onset of SeaWiFS data) to July 2016 period contained two super El Niño events, four typical El Niño events and four La Niña events. In the equatorial Pacific Ocean from 135°E (longitude of the westernmost data) to 150°E, the average typical El Niño and La Niña values were approximately the same (0.13 mg m-3). From 150°E to 165°W, the approximate bowl-shaped longitudinal pattern of Chl-a data in the average typical El Niño reached minimum (0.08 mg m-3) at 170°E and then increased to a relatively uniform value of 0.20 mg m-3 from 160°W to the Galapagos, where Chl-a reached 0.45 mg m-3. Eastward from 150°E, Chl-a values in the average typical La Niña increased approximately linearly to 0.21 mg m-3 at 170°E, where Chl-a was 175% larger than that in the average typical El Niño. Chl-a values in the average typical La Niña were approximately 0.22 mg m-3 until the Galapagos, where values reached 0.55 mg m-3. Average Chl-a values in the super El Niño event in 2015-2016 were similar to those associated with the average typical El Niño, but the bottom of the bowl-shaped pattern was shallower and wider. However, the longitudinal pattern of Chl-a in the super El Niño of 1997-1998 differed

  11. Site occupancy trend of Co in Ni{sub 2}MnIn: Ab initio approach

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pal, Soumyadipta, E-mail: soumyadipta.pal@gmail.com; Mahadevan, Priya; Biswas, C.

    2015-06-24

    The trend of site occupation of Co at Ni sites of Ni{sub 2}MnIn system is studied in austenitic phase having L2{sub 1} structure by ab initio density functional theory (DFT) calculation. The Co atoms prefer to be at Ni sites rather than Mn site and are ferromagetically coupled with Ni and Mn. The ground state has tetragonal structure for Ni{sub 1.5}Co{sub 0.5}MnIn and Ni{sub 1.25}Co{sub 0.75}MnIn. The Co tends to form cluster.

  12. Influence of Annealing on Microstructure and Mechanical Properties of a Nanocrystalline CrCoNi Medium-Entropy Alloy

    PubMed Central

    Schuh, Benjamin; Völker, Bernhard; Todt, Juraj; Kormout, Karoline S.; Schell, Norbert; Hohenwarter, Anton

    2018-01-01

    An equiatomic CrCoNi medium-entropy alloy was subjected to high-pressure torsion. This process led to a refinement of the microstructure to a grain size of about 50 nm, combined with a strong increase in the materials hardness. Subsequently, the thermodynamic stability of the medium entropy alloy was evaluated by isothermal and isochronal heat treatments. Annealed samples were investigated by scanning and transmission electron microscopy as well as X-ray diffraction, and were subjected to tensile tests to establish microstructure-property relationships. Furthermore, a comparison of mechanical properties with a grade 316L stainless steel was performed in order to evaluate if the CrCoNi alloy is competitive with commercially available structural materials in the nanocrystalline state. A minority phase embedded in the face-centered cubic matrix of the CrCoNi alloy could be observed in multiple annealed states, as well as the as-received and high-pressure torsion processed material. For 200 h of annealing at 500 °C, it was determined that the minority phase has a hexagonal-closed-packed crystal structure. A possible explanation for the formation of the phase is a preferential segregation of Co to stacking faults. PMID:29695142

  13. Synthesis, spectroscopic characterization, DNA interaction and biological activities of Mn(II), Co(II), Ni(II) and Cu(II) complexes with [(1H-1,2,4-triazole-3-ylimino)methyl]naphthalene-2-ol

    NASA Astrophysics Data System (ADS)

    Gaber, Mohamed; El-Wakiel, Nadia A.; El-Ghamry, Hoda; Fathalla, Shaimaa K.

    2014-11-01

    Manganese(II), cobalt(II), nickel(II) and copper(II) complexes of [(1H-1,2,4-triazole-3-ylimino)methyl]naphthalene-2-ol have been synthesized. The structure of complexes have been characterized by elemental analysis, molar conductance, magnetic moment measurements and spectral (IR, 1H NMR, EI-mass, UV-Vis and ESR), and thermal studies. The results showed that the chloro and nitrato Cu(II) complexes have octahedral geometry while Ni(II), Co(II) and Mn(II) complexes in addition to acetato Cu(II) complex have tetrahedral geometry. The possible structures of the metal complexes have been computed using the molecular mechanic calculations using the hyper chem. 8.03 molecular modeling program to confirm the proposed structures. The kinetic and thermodynamic parameters of the thermal decomposition steps were calculated from the TG curves. The binding modes of the complexes with DNA have been investigated by UV-Vis absorption titration. The results showed that the mode of binding of the complexes to DNA is intercalative or non-intercalative binding modes. Schiff base and its metal complexes have been screened for their in vitro antimicrobial activities against Gram positive bacteria (Staphylococcus aureus), Gram negative bacteria (Escherichia coli and Pesudomonas aeruginosa), fungi (Asperigllus flavus and Mucer) and yeast (Candida albicans and Malassezia furfur).

  14. Mesoscale Modeling of Kinetic Phase Behaviors in Mg-B-H (Subcontract Report)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yu, H.; Thornton, K.; Wood, B. C.

    Storage of hydrogen on board vehicles is one of the critical enabling technologies for creating hydrogenfueled transportation systems that can reduce oil dependency and mitigate the long-term effects of fossil fuels on climate change. Stakeholders in developing hydrogen infrastructure are currently focused on highpressure storage at 350 bar and 700 bar, in part because no viable solid-phase storage material has emerged. Nevertheless, solid-state materials, including high-density hydrides, remain of interest because of their unique potential to meet all DOE targets and deliver hydrogen at lower pressures and higher on-board densities. A successful solution would significantly reduce costs and ensure themore » economic viability of a U.S. hydrogen infrastructure. The Mg(BH 4) 2-MgB 2 system represents a highly promising solution because of its reasonable reaction enthalpy, high intrinsic capacity, and demonstrated reversibility, yet suffers from poor reaction kinetics. This subcontract aims to deliver a phase-field model for the kinetics of the evolution of the relevant phases within the Mg-B-H system during hydrogenation and dehydrogenation. This model will be used within a broader theory, synthesis, and characterization framework to study the properties of geometry-selected nanoparticles of pristine and doped MgB 2/Mg(BH 4) 2 with two aims: (1) understand the intrinsic limitations in (de)hydrogenation; (2) devise strategies for improving thermodynamics and kinetics through nanostructuring.« less

  15. Magnetic properties of Co/Ni grain boundaries after annealing

    NASA Astrophysics Data System (ADS)

    Coutts, Chris; Arora, Monika; Hübner, René; Heinrich, Bret; Girt, Erol

    2018-05-01

    Magnetic and microstructural properties of <111> textured Cu/N×[Co/Ni] films are studied as a function of the number of bilayer repeats N and annealing temperature. M(H) loop measurements show that coercivity, Hc, increases with annealing temperature and that the slope of the saturation curve at Hc has a larger reduction for smaller N. An increase of the magnetic anisotropy (Ku) to saturation magnetization (Ms) ratio after annealing N×[Co/Ni] with N < 15 only partially describes the increase to Hc. Energy-dispersive X-ray spectroscopy analyses performed in scanning transmission electron microscopy mode across cross-sections of as-deposited and annealed Cu/16×[Co/Ni] films show that Cu diffuses from the seed layer into grain boundaries of Co/Ni. Diffusion of Cu reduces exchange coupling (Hex) between the magnetic grains and explains the increase in Hc. Additionally, the difference in the slope of the M(H) curves at Hc between the thick (N = 16) and thin (N = 4) magnetic multilayers is due to Cu diffusion more effectively decoupling magnetic grains in the thinner multilayer.

  16. Solvothermal synthesis, characterization and optical properties of ZnO, ZnO-MgO and ZnO-NiO, mixed oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Aslani, Alireza; Arefi, Mohammad Reza; Babapoor, Aziz; Amiri, Asghar; Beyki-Shuraki, Khalil

    2011-03-01

    ZnO-MgO and ZnO-NiO mixed oxides nanoparticles were produced from a solution containing Zinc acetate, Mg and Ni nitrate by Solvothermal method. The calcination process of the ZnO-MgO and ZnO-NiO composites nanoparticles brought forth polycrystalline two-phase ZnO-MgO and ZnO-NiO nanoparticles of 40-80 nm in diameters. ZnO, MgO and NiO were crystallized into würtzite and rock salt structures, respectively. The optical properties of ZnO-MgO and ZnO-NiO nanoparticles were obtained by solid state UV and solid state florescent. The XRD, SEM and Raman spectroscopies of these nanoparticles were analyzed.

  17. An experimental study of ^{{{{Fe}}^{2 + } {-}{{Mg}}}} K_{{D}} between orthopyroxene and rhyolite: a strong dependence on H2O in the melt

    NASA Astrophysics Data System (ADS)

    Waters, Laura E.; Lange, Rebecca A.

    2017-06-01

    The effect of temperature, pressure, and dissolved H2O in the melt on the Fe2+-Mg exchange coefficient between orthopyroxene and rhyolite melt was investigated with a series of H2O fluid-saturated phase-equilibrium experiments. Experiments were conducted in a rapid-quench cold-seal pressure vessel over a temperature and pressure range of 785-850 °C and 80-185 MPa, respectively. Oxygen fugacity was buffered with the solid Ni-NiO assemblage in a double-capsule assembly. These experiments, when combined with H2O-undersaturated experiments in the literature, show that ^{{{{Fe}}^{2 + } {-}{{Mg}}}} K_{{D}} between orthopyroxene and rhyolite liquid increases strongly (from 0.23 to 0.54) as a function of dissolved water in the melt (from 2.7 to 5.6 wt%). There is no detectable effect of temperature or pressure over an interval of 65 °C and 100 MPa, respectively, on the Fe2+-Mg exchange coefficient values. The data show that Fe-rich orthopyroxene is favored at high water contents, whereas Mg-rich orthopyroxene crystallizes at low water contents. It is proposed that the effect of dissolved water in the melt on the composition of orthopyroxene is analogous to its effect on the composition of plagioclase. In the latter case, dissolved hydroxyl groups preferentially complex with Na+ relative to Ca2+, which reduces the activity of the albite component, leading to a more anorthite-rich (calcic) plagioclase. Similarly, it is proposed that dissolved hydroxyl groups preferentially complex with Mg2+ relative to Fe2+, thus lowering the activity of the enstatite component, leading to a more Fe-rich orthopyroxene at high water contents in the melt. The experimental results presented in this study show that reversely zoned pyroxene (i.e., Mg-rich rims) in silicic magmas may be a result of H2O degassing and not necessarily the result of mixing with a more mafic magma.

  18. A new family of Ni4 and Ni6 aggregates from the self-assembly of [Ni2] building units: role of carboxylate and carbonate bridges.

    PubMed

    Pait, Moumita; Bauzá, Antonio; Frontera, Antonio; Colacio, Enrique; Ray, Debashis

    2015-05-18

    Carboxylato (R = (t)Bu and Et) and carbonato bridges have been utilized for nickel(II)-based aggregates [Ni4(μ-H2L)2(μ3-OH)2(μ1,3-O2CBu(t))2](NO3)2·H2O·2DMF (1·H2O·2DMF), Ni4(μ-(hy)HL)2(μ3-OMe)2(μ1,1-N3)2(μ1,3-O2CEt)2]·4H2O (2·4H2O), and Ni6(μ4-L)(μ3-L)2(μ6-CO3)(H2O)8](ClO4)·9H2O (3·9H2O). Building blocks [Ni2(μ-H2L)](3+), [Ni2(μ-(hy)HL)](3+), and [Ni2(μ-L)](+) originating from [Ni2(μ-H2L)](3+) have been trapped in these complexes. The complexes have been characterized by X-ray crystallography, magnetic measurements, and density functional theory (DFT) analysis. In 1, the magnetic interactions are transmitted through the μ3-phenoxido/μ3-hydroxido/syn-syn-(t)BuCO2(-), μ3-phenoxido/μ3- hydroxido, and double μ3-phenoxido/double μ3-hydroxido bridges with J = +11.4 cm(-1), J1 = -2.1 cm(-1), and J2 = -2.8 cm(-1), respectively. In 2, the interactions are ferromagnetic, with J1 = +27.5 cm(-1), J2 = +20.62 cm(-1), and J3 = +1.52 cm(-1) describing the magnetic couplings through the μ-phenoxidoo/μ3-methoxido, μ-azido/μ3-methoxido, and μ3-methoxido/μ3-methoxido exchange pathways, respectively. Complex 3 gives J1 = -3.30 cm(-1), J2 = +1.7 cm(-1), and J3 = -12.8 cm(-1) for exchange pathways mediated by μ-phenoxido/μ-carbonato, μ-alkoxido/μ-alkooxido/μ-syn-syn-carbonato, and the μ-phenoxido/μ-carbonato, respectively. Interestingly, 1 and 3 below 20 K and 35 K, respectively, show an abrupt increase of the χMT product to reach a magnetic-field-dependent maximum, which is associated with a slightly frequency-dependent out-of-phase alternating-current peak. DFT calculations have also been performed on 1-3 to explain the exchange interaction mechanisms and to support the magnitude and sign of the magnetic coupling constants between the Ni(II) ions.

  19. Phase Transformation and Aging Behavior of Al0.5CoCrFeNiSi0.2 High-Entropy Alloy

    NASA Astrophysics Data System (ADS)

    Zhang, C.; Wu, G. F.; Dai, P. Q.

    2015-05-01

    An Al0.5CoCrFeNiSi0.2 high-entropy alloy was prepared by vacuum arc melting. The alloy was aged from 700 to 1100 °C. The effects of aging on the phase transformation and mechanical performances were explored. The as-cast alloy showed a dendritic (DR) microstructure. The DR region was an Fe,Cr-rich FCC phase, while the interdendritic (ID) region was a spinodal structure composed of Fe,Cr-rich BCC (A2) and Ni,Al-rich BCC (B2) phases. At aging temperatures between 700 and 900 °C, the Fe,Cr-rich BCC (A2) phase in the ID region transformed into σ and Fe,Cr-rich FCC phases. Meanwhile, some Ni,Al-rich FCC phase particles precipitated from the DR region. During aging at 1100 °C, the DR microstructure disappeared, and a microstructure composed of Fe,Cr-rich FCC and Ni,Al-rich BCC (B2) phases both possessing a lamellar shape was developed. The alloy exhibited evident hardening and lower tensile strain when the aging temperature was lower than 1000 °C, which was mainly attributed to the generation of the σ phase in the ID region. However, a contrasting behavior was observed when the aging temperature was higher than 1000 °C, which was attributed to the redissolution of the σ phase and the microstructure coarsening.

  20. Analysis of the El Niño/La Niña-Southern Oscillation variability and malaria in the Estado Sucre, Venezuela.

    PubMed

    Delgado-Petrocelli, Laura; Córdova, Karenia; Camardiel, Alberto; Aguilar, Víctor H; Hernández, Denise; Ramos, Santiago

    2012-09-01

    The last decade has seen an unprecedented, worldwide acceleration of environmental and climate changes. These processes impact the dynamics of natural systems, which include components associated with human communities such as vector-borne diseases. The dynamics of environmental and climate variables, altered by global change as reported by the Intergovernmental Panel on Climate Change, affect the distribution of many tropical diseases. Complex systems, e.g. the El Niño/La Niña-Southern Oscillation (ENSO), in which environmental variables operate synergistically, can provoke the reemergence and emergence of vector-borne diseases at new sites. This research investigated the influence of ENSO events on malaria incidence by determining the relationship between climate variations, expressed as warm, cold and neutral phases, and their relation to the number of malaria cases in some north-eastern municipalities of Venezuela (Estado Sucre) during the period 1990-2000. Significant differences in malaria incidence were found, particularly in the La Niña ENSO phases (cold) of moderate intensity. These findings should be taken into account for surveillance and control in the future as they shed light on important indicators that can lead to reduced vulnerability to malaria.

  1. H2CO3(s): a new candidate for CO2 capture and sequestration.

    PubMed

    Tossell, J A

    2009-04-01

    To reduce the magnitude of anthropogenic global warming it is necessary to remove CO2(g) from the effluent streams of coal-fired power plants and to sequester the CO2 either as a liquid or by reaction with other compounds. A major difficulty in achieving this goal arises from the very weak acidity of CO2(g), causing it to react only incompletely with weak bases, although this weak interaction does provide a means for "stripping" the CO2 from the acid-base complex at high temperatures. Reaction with strong bases like Na0H yields more stable complexes, but massive amounts of chemical reactants would need to be purchased and chemical products like NaHCO3 then stored. However, when gas-phase CO2 reacts with the weak base water (or when bicarbonate reacts with strong acid) the unstable product monomeric "H2CO3" can be formed. The free energy required is about 16 kcal/mol in the gas phase and about 10 kcal/mol in aqueous solution. This energy can be supplied by particle or photon excitation and is only a small fraction ofthe energy released when a mole of CH4 is converted to a mole of CO2. Although this monomeric compound is highly unstable, its oligomers are considerably more stable, due to internal H-bonding, with free energies for the larger oligomers in the gas phase which are about 4 kcal/(mol of H2CO3) lower, only about 6 kcal/mol H2CO3 higher than the gas-phase combination of CO2 and H2O at room temperature. Also, at lower temperature the entropic penalty for the oligomer is less and oligomeric H2CO3 becomes stable around the sublimation temperature of dry ice. This indicates that it may be possible to capture gas-phase CO2 directly, using only cheap and abundant H2O as a reactant, and to store the resulting (H2CO3)n as a oligomeric solid at only moderately cold temperatures. These conclusions are based on quantum computations that accurately reproduce the structures, spectra, and stabilities of H2CO3 oligomers. Methods for producing and characterizing the H2CO3

  2. Thermoelectric properties of a doped LaNiO3 perovskite system prepared using a spark-plasma sintering process

    NASA Astrophysics Data System (ADS)

    Tak, Jang-Yeul; Choi, Soon-Mok; Seo, Won-Seon; Cho, Hyung Koun

    2013-07-01

    Both perovskites LaNiO3 and LaCuO3 have a limitation associated with phase transitions for high-temperature thermoelectric applications. The optimized conditions were investigated to obtain the LaNi1- x Cu x O3- δ perovskite single phase showing a Cu-doping effect into Ni sites against unintended deoxidized phases. Three advantages of synergetic effects due to the simultaneous presence of nickel and copper were investigated: a low melting temperature of CuO as compared to that of NiO, the absence of intermediated deoxidized phases in the LaCuO3 system, and the Cu doping effect, which suppresses the formation of intermediate secondary phases. A solid solution was also fabricated using a spark-plasma sintering (SPS) process for the purpose of sintering LaNi1- x Cu x O3- δ compositions at a low sintering temperature.

  3. Heteromorphic NiCo2S4/Ni3S2/Ni Foam as a Self-Standing Electrode for Hydrogen Evolution Reaction in Alkaline Solution.

    PubMed

    Liu, Hui; Ma, Xiao; Rao, Yuan; Liu, Yang; Liu, Jialiang; Wang, Luyang; Wu, Mingbo

    2018-04-04

    Considerable works have been devoted on developing high-efficiency nonplatinum electrocatalysts for hydrogen evolution reaction (HER). Herein, 3D heteromorphic NiCo 2 S 4 /Ni 3 S 2 nanosheets network has been constructed on Ni foam (denoted as NiCo 2 S 4 /Ni 3 S 2 /NF) serving as a self-standing electrocatalyst through directly thermal sulfurization of a single-source NiCo-layered double hydroxide precursor. The resultant NiCo 2 S 4 /Ni 3 S 2 /NF electrode exhibits outstanding electrocatalytic HER performance with an extremely low onset overpotential of 15 mV and long-term durability in alkaline solution. Such enhanced HER performance can be credited to (1) the massive exposed active sites provided by mixed transition metal chalcogenides (NiCo 2 S 4 and Ni 3 S 2 ), (2) the strong interfacial interaction at NiCo 2 S 4 /Ni 3 S 2 heterojunction interfaces with the strengthened H binding, and (3) the porous highly conductive Ni foam substrate with accelerated electron transfer. This work opens up a new direction to fabricate effective and non-noble-metal electrodes for water splitting and hydrogen generation.

  4. Realization of magnetostructural coupling by modifying structural transitions in MnNiSi-CoNiGe system with a wide Curie-temperature window.

    PubMed

    Liu, Jun; Gong, Yuanyuan; Xu, Guizhou; Peng, Guo; Shah, Ishfaq Ahmad; Ul Hassan, Najam; Xu, Feng

    2016-03-16

    The magnetostructural coupling between structural and magnetic transitions leads to magneto-multifunctionalities of phase-transition alloys. Due to the increasing demands of multifunctional applications, to search for the new materials with tunable magnetostructural transformations in a large operating temperature range is important. In this work, we demonstrate that by chemically alloying MnNiSi with CoNiGe, the structural transformation temperature of MnNiSi (1200 K) is remarkably decreased by almost 1000 K. A tunable magnetostructural transformation between the paramagnetic hexagonal and ferromagnetic orthorhombic phase over a wide temperature window from 425 to 125 K is realized in (MnNiSi)1-x(CoNiGe)x system. The magnetic-field-induced magnetostructural transformation is accompanied by the high-performance magnetocaloric effect, proving that MnNiSi-CoNiGe system is a promising candidate for magnetic cooling refrigerant.

  5. An S-Oxygenated [NiFe] Complex Modelling Sulfenate Intermediates of an O2 -Tolerant Hydrogenase.

    PubMed

    Lindenmaier, Nils J; Wahlefeld, Stefan; Bill, Eckhard; Szilvási, Tibor; Eberle, Christopher; Yao, Shenglai; Hildebrandt, Peter; Horch, Marius; Zebger, Ingo; Driess, Matthias

    2017-02-13

    To understand the molecular details of O 2 -tolerant hydrogen cycling by a soluble NAD + -reducing [NiFe] hydrogenase, we herein present the first bioinspired heterobimetallic S-oxygenated [NiFe] complex as a structural and vibrational spectroscopic model for the oxygen-inhibited [NiFe] active site. This compound and its non-S-oxygenated congener were fully characterized, and their electronic structures were elucidated in a combined experimental and theoretical study with emphasis on the bridging sulfenato moiety. Based on the vibrational spectroscopic properties of these complexes, we also propose novel strategies for exploring S-oxygenated intermediates in hydrogenases and similar enzymes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. A Ni(iii) complex stabilized by silica nanoparticles as an efficient nanoheterogeneous catalyst for oxidative C-H fluoroalkylation.

    PubMed

    Khrizanforov, Mikhail N; Fedorenko, Svetlana V; Strekalova, Sofia O; Kholin, Kirill V; Mustafina, Asiya R; Zhilkin, Mikhail Ye; Khrizanforova, Vera V; Osin, Yuri N; Salnikov, Vadim V; Gryaznova, Tatyana V; Budnikova, Yulia H

    2016-07-26

    We have developed Ni(III)-doped silica nanoparticles ([(bpy)xNi(III)]@SiO2) as a recyclable, low-leaching, and efficient oxidative functionalization nanocatalyst for aromatic C-H bonds. The catalyst is obtained by doping the complex [(bpy)3Ni(II)] on silica nanoparticles along with its subsequent electrooxidation to [(bpy)xNi(III)] without an additional oxidant. The coupling reaction of arenes with perfluoroheptanoic acid occurs with 100% conversion of reactants in a single step at room temperature under nanoheterogeneous conditions. The catalyst content is only 1% with respect to the substrates under electrochemical regeneration conditions. The catalyst can be easily separated from the reaction mixture and reused a minimum of five times. The results emphasize immobilization on the silica support and the electrochemical regeneration of Ni(III) complexes as a facile route for developing an efficient nanocatalyst for oxidative functionalization.

  7. Phase Separation Kinetics in Isopycnic Mixtures of H2O/CO2/Ethoxylated Alcohol Surfactants

    NASA Technical Reports Server (NTRS)

    Lesemann, Markus; Paulaitis, Michael E.; Kaler, Eric W.

    1999-01-01

    Ternary mixtures of H2O and CO2 with ethoxylated alcohol (C(sub i)E(sub j)) surfactants form three coexisting liquid phases at conditions where two of the phases have equal densities (isopycnic phases). Isopycnic phase behavior has been observed for mixtures containing C8E5, C10E6, and C12E6 surfactants, but not for those mixtures containing either C4E1 or C8E3 surfactants. Pressure-temperature (PT) projections for this three-phase equilibrium were determined for H2O/CO2/C8E5 and H2O/CO2/C10E6 mixtures at temperatures from approximately 25 to 33 C and pressures between 90 and 350 bar. Measurements of the microstructure in H2O/CO2/C12E6 mixtures as a function of temperature (25-31 C), pressure (63.1-90.7 bar), and CO2 composition (0-3.9 wt%) have also been carried out to show that while micellar structure remains essentially un-changed, critical concentration fluctuations increase as the phase boundary and plait point are approached. In this report, we present our first measurements of the kinetics of isopycnic phase separation for ternary mixtures of H2O/CO2/C8E5.

  8. Upper critical and irreversibility fields in Ni- and Co-doped pnictide bulk superconductors

    NASA Astrophysics Data System (ADS)

    Nikolo, Martin; Singleton, John; Solenov, Dmitry; Jiang, Jianyi; Weiss, Jeremy; Hellstrom, Eric

    2018-05-01

    A comprehensive study of upper critical and irreversibility magnetic fields in Ba(Fe0.95Ni0.05)2As2 (large grain and small grain samples), Ba(Fe0.94Ni0.06)2As2, Ba(Fe0.92Co0.08)2As2, and Ba(Fe0.92Co0.09)2As2 polycrystalline bulk pnictide superconductors was made in pulsed fields of up to 65 T. The full magnetic field-temperature (H-T) phase diagrams, starting at 1.5 K, were measured. The higher temperature, upper critical field Hc2 data are well described by the one-band Werthamer, Helfand, and Hohenberg (WHH) model. At low temperatures, the experimental data depart from the fitted WHH curves, suggesting an emergence of a new phase that could be attributed to the Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) state. The large values of the Maki fitting parameter α indicate that the Zeeman pair breaking dominates over the orbital pair breaking and spin-paramagnetic pair-breaking effect is significant in these materials. Possible multi-band structure of these materials is lumped into effective parameters of the single-band model. Table of measured physical parameters allows us to compare these pnictide superconductors for different Co- and Ni- doping levels and granularity.

  9. Performance of intermediate temperature (600-800 °C) solid oxide fuel cell based on Sr and Mg doped lanthanum-gallate electrolyte

    NASA Astrophysics Data System (ADS)

    Gong, Wenquan; Gopalan, Srikanth; Pal, Uday B.

    The solid electrolyte chosen for this investigation was La 0.9Sr 0.1Ga 0.8Mg 0.2O 3 (LSGM). To select appropriate electrode materials from a group of possible candidate materials, AC complex impedance spectroscopy studies were conducted between 600 and 800 °C on symmetrical cells that employed the LSGM electrolyte. Based on the results of the investigation, LSGM electrolyte supported solid oxide fuel cells (SOFCs) were fabricated with La 0.6Sr 0.4Co 0.8Fe 0.2O 3-La 0.9Sr 0.1Ga 0.8Mg 0.2O 3 (LSCF-LSGM) composite cathode and nickel-Ce 0.6La 0.4O 2 (Ni-LDC) composite anode having a barrier layer of Ce 0.6La 0.4O 2 (LDC) between the LSGM electrolyte and the Ni-LDC anode. Electrical performances of these cells were determined and the electrode polarization behavior as a function of cell current was modeled between 600 and 800 °C.

  10. Spin polarization of graphene and h -BN on Co(0001) and Ni(111) observed by spin-polarized surface positronium spectroscopy

    NASA Astrophysics Data System (ADS)

    Miyashita, A.; Maekawa, M.; Wada, K.; Kawasuso, A.; Watanabe, T.; Entani, S.; Sakai, S.

    2018-05-01

    In spin-polarized surface positronium annihilation measurements, the spin polarizations of graphene and h -BN on Co(0001) were higher than those on Ni(111), while no significant differences were seen between graphene and h -BN on the same metal. The obtained spin polarizations agreed with those expected from first-principles calculations considering the positron wave function and the electron density of states from the first surface layer to the vacuum region. The higher spin polarizations of graphene and h -BN on Co(0001) as compared to Ni(111) simply reflect the spin polarizations of these metals. The comparable spin polarizations of graphene and h -BN on the same metal are attributed to the creation of similar electronic states due to the strong influence of the metals: the Dirac cone of graphene and the band gap of h -BN disappear as a consequence of d -π hybridization.

  11. Porous LaCo1-xNixO3-δ Nanostructures as an Efficient Electrocatalyst for Water Oxidation and for a Zinc-Air Battery.

    PubMed

    Vignesh, Ahilan; Prabu, Moni; Shanmugam, Sangaraju

    2016-03-09

    Perovskites have emerged as promising earth-abundant alternatives to precious metals for catalyzing the oxygen evolution reaction (OER). Herein, we report the synthesis of a series of porous perovskite nanostructures, LaCo0.97O3-δ, with systematic Ni substitution in Co octahedral sites. Their electrocatalytic activity during the water oxidation reaction was studied in alkaline electrolytes. The electrocatalytic OER activity and stability of the perovskite nanostructure was evaluated using the rotating disk electrode technique. We show that the progressive replacement of Co by Ni in the LaCo0.97O3-δ perovskite structure greatly altered the electrocatalytic activity and that the La(Co0.71Ni0.25)0.96O3-δ composition exhibited the lowest OER overpotential of 324 and 265 mV at 10 mA cm(-2) in 0.1 M KOH and 1 M KOH, respectively. This value was much lower than that of the noble metal catalysts, IrO2, Ru/C, and Pt/C. Furthermore, the La(Co0.71Ni0.25)0.96O3-δ nanostructure showed outstanding electrode stability, with no observable decrease in performance up to 114th cycle in the auxiliary linear sweep voltammetry that lasted for 10 h in chronoamperometry studies. The excellent oxygen evolution activity of the La(Co0.71Ni0.25)0.96O3-δ perovskite nanostructure can be attributed to its intrinsic structure, interconnected particle arrangement, and unique redox characteristics. The enhanced intrinsic electrocatalytic activity of the La(Co0.71Ni0.25)0.96O3-δ catalyst was correlated with several parameters, such as the electrochemical surface area, the roughness factor, and the turnover frequency, with respect to variation in the transition metals of the perovskite structure. Subsequently, La(Co0.71Ni0.25)0.96O3-δ was utilized as the air cathode in a zinc-air battery application.

  12. Novel topotactically transformed carbon-CoO-NiO-NiCo₂O₄ nanosheet hybrid hetero-structured arrays as ultrahigh performance supercapacitors.

    PubMed

    Wang, Hai; Guo, Junling; Qing, Chen; Sun, Daming; Wang, Bixiao; Tang, Yiwen

    2014-08-14

    A novel carbon-CoO-NiO-NiCo2O4 integrated electrode has been designed by reducing the hetero-structured NiCo2O4 nanosheet array with C2H2 on the nickel foam at a low temperature of 350 °C. The topotactical transformation from NiCo2O4 to the integrated electrode has been first conceived and investigated. Such unique nanoarchitectures exhibit excellent electrochemical performance with ultrahigh capacitance and desirable cycle life at high rates.

  13. Extraction of Mg(OH)2 from Mg silicate minerals with NaOH assisted with H2O: implications for CO2 capture from exhaust flue gas.

    PubMed

    Madeddu, Silvia; Priestnall, Michael; Godoy, Erik; Kumar, R Vasant; Raymahasay, Sugat; Evans, Michael; Wang, Ruofan; Manenye, Seabelo; Kinoshita, Hajime

    2015-01-01

    The utilisation of Mg(OH)2 to capture exhaust CO2 has been hindered by the limited availability of brucite, the Mg(OH)2 mineral in natural deposits. Our previous study demonstrated that Mg(OH)2 can be obtained from dunite, an ultramafic rock composed of Mg silicate minerals, in highly concentrated NaOH aqueous systems. However, the large quantity of NaOH consumed was considered an obstacle for the implementation of the technology. In the present study, Mg(OH)2 was extracted from dunite reacted in solid systems with NaOH assisted with H2O. The consumption of NaOH was reduced by 97% with respect to the NaOH aqueous systems, maintaining a comparable yield of Mg(OH)2 extraction, i.e. 64.8-66%. The capture of CO2 from a CO2-N2 gas mixture was tested at ambient conditions using a Mg(OH)2 aqueous slurry. Mg(OH)2 almost fully dissolved and reacted with dissolved CO2 by forming Mg(HCO3)2 which remained in equilibrium storing the CO2 in the aqueous solution. The CO2 balance of the process was assessed from the emissions derived from the power consumption for NaOH production and Mg(OH)2 extraction together with the CO2 captured by Mg(OH)2 derived from dunite. The process resulted as carbon neutral when dunite is reacted at 250 °C for durations of 1 and 3 hours and CO2 is captured as Mg(HCO3)2.

  14. Forming a structure of the CoNiFe alloys by X-ray irradiation

    NASA Astrophysics Data System (ADS)

    Valko, Natalia; Kasperovich, Andrey; Koltunowicz, Tomasz N.

    The experimental data of electrodeposition kinetics researches and structure formation of ternary CoNiFe alloys deposited onto low-carbon steel 08kp in the presence of X-rays are presented. Relations of deposit rate, current efficiencies, element and phase compositions of CoNiFe coatings formed from sulfate baths with respect to cathode current densities (0.5-3A/dm2), electrolyte composition and irradiation were obtained. It is shown that, the CoNiFe coatings deposited by the electrochemical method involving exposure of the X-rays are characterized by more perfect morphology surfaces with less developed surface geometry than reference coatings. The effect of the X-ray irradiation on the electrodeposition of CoNiFe coatings promotes formatting of alloys with increased electropositive component and modified phase composition.

  15. Bonding and vibrations of CO molecules adsorbed at transition metal impurity sites on the MgO (001) surface. A density functional model cluster study

    NASA Astrophysics Data System (ADS)

    Neyman, K. M.; Rösch, N.

    1993-11-01

    First principles density functional cluster investigations of adsorption at the (001) surface of pure and doped magnesium oxide are carried out to characterize and compare the interaction of CO molecules with main group (Mg 2+) and d metal (Co 2+, Ni 2+, Cu 2+) surface cationic centers of the ionic substrate. The geometry of the adsorption complexes, the binding mechanism and spectroscopic manifestations of the surface species are analyzed. Special attention is payed to vibrational frequencies and intensities. The calculations qualitatively reproduce observed trends in the adsorption-induced frequency shifts for the series of the surface aggregates Mg 5cCO→Ni 5cCO→CO 5cCO and the corresponding change of the infrared intensities of the CO vibrational mode. For the transition metal impurity sites these results are rationalized in terms of a small, but notable Md πCOπ interaction.

  16. Ternary semiconductors NiZrSn and CoZrBi with half-Heusler structure: A first-principles study

    NASA Astrophysics Data System (ADS)

    Fiedler, Gregor; Kratzer, Peter

    2016-08-01

    The ternary semiconductors NiZrSn and CoZrBi with C 1b crystal structure are introduced by calculating their basic structural, electronic, and phononic properties using density functional theory. Both the gradient-corrected PBE functional and the hybrid functional HSE06 are employed. While NiZrSn is found to be a small-band-gap semiconductor (Eg=0.46 eV in PBE and 0.60 eV in HSE06), CoZrBi has a band gap of 1.01 eV in PBE (1.34 eV in HSE06). Moreover, effective masses and deformation potentials are reported. In both materials A B C , the intrinsic point defects introduced by species A (Ni or Co) are calculated. The Co-induced defects in CoZrBi are found to have a higher formation energy compared to Ni-induced defects in NiZrSn. The interstitial Ni atom (Nii) as well as the VNiNii complex introduce defect states in the band gap, whereas the Ni vacancy (VNi) only reduces the size of the band gap. While Nii is electrically active and may act as a donor, the other two types of defects may compensate extrinsic doping. In CoZrBi, only the VCoCoi complex introduces a defect state in the band gap. Motivated by the reported use of NiZrSn for thermoelectric applications, the Seebeck coefficient of both materials, both in the p -type and the n -type regimes, is calculated. We find that CoZrBi displays a rather large thermopower of up to 500 μ V /K when p doped, whereas NiZrSn possesses its maximum thermopower in the n -type regime. The reported difficulties in achieving p -type doping in NiZrSn could be rationalized by the unintended formation of Nii2 + in conjunction with extrinsic acceptors, resulting in their compensation. Moreover, it is found that all types of defects considered, when present in concentrations as large as 3%, tend to reduce the thermopower compared to ideal bulk crystals at T =600 K. For NiZrSn, the calculated thermodynamic data suggest that additional Ni impurities could be removed by annealing, leading to precipitation of a metallic Ni2ZrSn phase.

  17. NiCo2S4 nanosheet-decorated 3D, porous Ni film@Ni wire electrode materials for all solid-state asymmetric supercapacitor applications.

    PubMed

    Saravanakumar, Balasubramaniam; Jayaseelan, Santhana Sivabalan; Seo, Min-Kang; Kim, Hak-Yong; Kim, Byoung-Suhk

    2017-12-07

    Wire type supercapacitors with high energy and power densities have generated considerable interest in wearable applications. Herein, we report a novel NiCo 2 S 4 -decorated 3D, porous Ni film@Ni wire electrode for high performance supercapacitor application. In this work, a facile method is introduced to fabricate a 3D, porous Ni film deposited on a Ni wire as a flexible electrode, followed by decoration with NiCo 2 S 4 as an electroactive material. The fabricated NiCo 2 S 4 -decorated 3D, porous Ni film@Ni wire electrode displays a superior performance with an areal and volumetric capacitance of 1.228 F cm -2 and 199.74 F cm -3 , respectively, at a current density of 0.2 mA cm -1 with a maximum volumetric energy and power density (E V : 6.935 mW h cm -3 ; P V : 1.019 W cm -3 ). Finally, the solid state asymmetric wire type supercapacitor is fabricated using the fabricated NiCo 2 S 4 -decorated 3D, porous Ni film@Ni wire as a positive electrode and N-doped reduced graphene oxide (N-rGO) as a negative electrode and this exhibits good areal and volumetric capacitances of C A : 0.12 F cm -2 and C V : 19.57 F cm -2 with a higher rate capability (92%). This asymmetric wire type supercapacitor demonstrates a low leakage current and self-discharge with a maximum volumetric energy (E V : 5.33 mW h cm -3 ) and power (P V : 855.69 mW cm -3 ) density.

  18. Shape-Controlled Synthesis of NiCo2 O4 Microstructures and Their Application in Supercapacitors.

    PubMed

    Xiang, Nannan; Ni, Yonghong; Ma, Xiang

    2015-09-01

    The shape-controlled synthesis of NiCo2 O4 microstructures through a facile hydrothermal method and subsequent calcinations was explored. By employing CoSO4 , NiSO4 , and urea as the starting reactants, flower-like NiCo2 O4 microstructures were obtained at 100 °C after 5 h without the assistance of any additive and subsequent calcination at 300 °C for 2 h; dumbbell-like NiCo2 O4 microstructures were prepared at 150 °C after 5 h in the presence of trisodium citrate and subsequent calcination at 300 °C for 2 h. The as-prepared NiCo2 O4 microstructures were characterized by X-ray powder diffraction, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and (high-resolution) transmission electron microscopy. Both the flower-like and dumbbell-like NiCo2 O4 microstructures could be used as electrode materials for supercapacitors, and they exhibited excellent electrochemical performance, including high specific capacitance, good rate capability, and excellent long-term cycle stability. Simultaneously, the shape-dependent electrochemical properties of the product were investigated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Tuning exchange bias by Co doping in Mn₅₀Ni{sub 41–x}Sn₉Co{sub x} melt-spun ribbons

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhao, D. W.; Li, G. K.; Wang, S. Q.

    2014-09-14

    In Mn₅₀Ni{sub 41–x}Sn₉Co{sub x} ribbons, the exchange bias field is very sensitive to the Co content. Based on both theoretical and experimental studies, it has been found that with increasing Co content, the pinned phase (ferromagnetic phase) remains almost unchanged while the pinning phase is changed from a canonical spin glass to a cluster spin glass and finally to a ferromagnetic phase. Changing the Co content in Mn₅₀Ni{sub 41–x}Sn₉Co{sub x} alloys has been proven to be an effective way of tuning the magnetic anisotropy and the phase structure of the pinning phase. With different Co contents, a continuous tuning ofmore » the exchange bias field from 345 Oe to 3154 Oe is realized.« less

  20. La Niña diversity and Northwest Indian Ocean Rim teleconnections

    USGS Publications Warehouse

    Hoell, Andrew; Funk, Christopher C.; Barlow, Mathew

    2014-01-01

    The differences in tropical Pacific sea surface temperature (SST) expressions of El Niño-Southern Oscillation (ENSO) events of the same phase have been linked with different global atmospheric circulation patterns. This study examines the dynamical forcing of precipitation during October–December (OND) and March–May (MAM) over East Africa and during December–March (DJFM) over Central-Southwest Asia for 1950–2010 associated with four tropical Pacific SST patterns characteristic of La Niña events, the cold phase of ENSO. The self-organizing map method along with a statistical distinguishability test was used to isolate La Niña events, and seasonal precipitation forcing was investigated in terms of the tropical overturning circulation and thermodynamic and moisture budgets. Recent La Niña events with strong opposing SST anomalies between the central and western Pacific Ocean (phases 3 and 4), force the strongest global circulation modifications and drought over the Northwest Indian Ocean Rim. Over East Africa during MAM and OND, subsidence is forced by an enhanced tropical overturning circulation and precipitation reductions are exacerbated by increases in moisture flux divergence. Over Central-Southwest Asia during DJFM, the thermodynamic forcing of subsidence is primarily responsible for precipitation reductions, with moisture flux divergence acting as a secondary mechanism to reduce precipitation. Eastern Pacific La Niña events in the absence of west Pacific SST anomalies (phases 1 and 2), are associated with weaker global teleconnections, particularly over the Indian Ocean Rim. The weak regional teleconnections result in statistically insignificant precipitation modifications over East Africa and Central-Southwest Asia.

  1. Nonlinearities in the Evolutional Distinctions Between El Niño and La Niña Types

    NASA Astrophysics Data System (ADS)

    Ashok, K.; Shamal, M.; Sahai, A. K.; Swapna, P.

    2017-12-01

    Using the HadISST, SODA reanalysis, and various other observed and reanalyzed data sets for the period 1950-2010, we explore nonlinearities in the subsurface evolutional distinctions between El Niño types and La Niña types from a few seasons before the onset. Cluster analysis carried out over both summer and winter suggests that while the warm-phased events of both types are distinguishable, several cold phased events are clustered together. Further, we apply a joint Self-Organizing Map (SOM) analysis using the monthly sea surface temperature anomaly (SSTA) and thermocline-depth anomalies in tropical Pacific (TP). Results reveal that the evolutionary paths of El Niño Modoki (EM) and El Niño (EL) are, broadly, different. Subsurface temperature composites of EL and EM show different onset characteristics. During an EL, warm anomaly in the west spreads eastward along the thermocline and reaches the surface in the east in March-May of year(0). During an EM, warm anomaly already exists in the central tropical Pacific and then reaches the surface in the east in September-November of year(0). Composited SSTAs during La Niña (LN) and La Niña Modoki (LM) are distinguishable only at 80% confidence level, but the composited subsurface temperature anomalies show differences in the location of the coldest anomaly as well as evolution at 90% confidence level. Thus, the El Niño flavor distinction is potentially predictable at longer leads.

  2. Preparation of a Ni-MgO-Al2O3 catalyst with high activity and resistance to potassium poisoning during direct internal reforming of methane in molten carbonate fuel cells

    NASA Astrophysics Data System (ADS)

    Jang, Won-Jun; Jung, You-Shick; Shim, Jae-Oh; Roh, Hyun-Seog; Yoon, Wang Lai

    2018-02-01

    Steam reforming of methane (SRM) is conducted using a series of Ni-MgO-Al2O3 catalysts for direct internal reforming (DIR) in molten carbonate fuel cells (MCFCs). Ni-MgO-Al2O3 catalysts are prepared by the homogeneous precipitation method with a variety of MgO loading amounts ranging from 3 to 15 wt%. In addition, each precursor concentrations are systemically changed (Ni: 1.2-4.8 mol L-1; Mg: 0.3-1.2 mol L-1; Al: 0.4-1.6 mol L-1) at the optimized composition (10 wt% MgO). The effects of MgO loading and precursor concentration on the catalytic performance and resistance against poisoning of the catalyst by potassium (K) are investigated. The Ni-MgO-Al2O3 catalyst with 10 wt% MgO and the original precursor concentration (Ni: 1.2 mol L-1; Mg: 0.3 mol L-1; Al: 0.4 mol L-1) exhibits the highest CH4 conversion and resistance against K poisoning even at the extremely high gas space velocity (GHSV) of 1,512,000 h-1. Excellent SRM performance of the Ni-MgO-Al2O3 catalyst is attributed to strong metal (Ni) to alumina support interaction (SMSI) when magnesium oxide (MgO) is co-precipitated with the Ni-Al2O3. The enhanced interaction of the Ni with MgO-Al2O3 support is found to protect the active Ni species against K poisoning.

  3. Isopycnic Phases and Structures in H2O/CO2/Ethoxylated Alcohol Surfactant Mixtures

    NASA Technical Reports Server (NTRS)

    Paulaitis, Michael E.; Zielinski, Richard G.; Kaler, Eric W.

    1996-01-01

    Ternary mixtures of H2O and CO2 with ethoxylated alcohol (C(i)E(j)) surfactants can form three coexisting liquid phases at conditions where two of the phases have the same density (isopycnic phases). Isopycnic phase behavior has been observed for mixtures containing the surfactants C8E5, C10E6, and C12E6, but not for those mixtures containing either C4E1 or CgE3. Pressure-temperature (PT) projections for this isopycnic three-phase equilibrium were determined for H2O/CO2/C8E5 and H2O/CO2/C10E6 mixtures at temperatures from approximately 25 to 33 C and pressures between 90 and 350 bar. As a preliminary to measuring the microstructure in isopycnic three component mixtures, phase behavior and small angle neutron scattering (SANS) experiments were performed on mixtures of D2O/CO2/ n-hexaethyleneglycol monododecyl ether (C12E6) as a function of temperature (25-31 C), pressure (63.1-90.7 bar), and CO2 composition (0-3.9 wt%). Parameters extracted from model fits of the SANS spectra indicate that, while micellar structure remains essentially unchanged, critical concentration fluctuations increase as the phase boundary and plait point are approached.

  4. Synthesis, characterization, experimental and theoretical structure of novel Dichloro(bis{2-[1-(4-methoxyphenyl)-1H-1,2,3-triazol-4-yl-κN3]pyridine-κN})metal(II) compounds, metal = Mn, Co and Ni

    NASA Astrophysics Data System (ADS)

    Conradie, J.; Conradie, M. M.; Tawfiq, K. M.; Al-Jeboori, M. J.; Coles, S. J.; Wilson, C.; Potgieter, J. H.

    2018-06-01

    The syntheses, characterizations and structures of three novel dichloro(bis{2-[1-(4-methoxyphenyl)-1H-1,2,3-triazol-4-yl-κN3]pyridine-κN})metal(II), [M(L)2Cl2], complexes (metal = Mn, Co and Ni) are presented. In the solid state the molecules are arranged in infinite hydrogen-bonded 3D supramolecular structures, further stabilized by weak intermolecular π…π interactions. The DFT results for all the different spin states and isomers of dichloro(bis{2-[1-phenyl-1H-1,2,3-triazol-4-yl-κN3]pyridine-κN})metal(II) complexes, [M(L1)2Cl2], support experimental measurements, namely that (i) d5 [Mn(L1)2Cl2] is high spin with S = 5/2; (ii) d7 [Co(L1)2Cl2] has a spin state of S = 3/2, (iii) d8 [Ni(L1)2Cl2] has a spin state of S = 1; and (iv) for all [M(L1)2Cl2] and [M(L)2Cl2] complexes, with M = Mn, Co and Ni, the cis-cis-trans and the trans-trans-trans isomers, with the pyridyl groups trans to each other, have the lowest energy.

  5. Chemical complexity induced local structural distortion in NiCoFeMnCr high-entropy alloy

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhang, Fuxiang; Tong, Yang; Jin, Ke

    In order to study chemical complexity-induced lattice distortion in high-entropy alloys, the static Debye–Waller (D-W) factor of NiCoFeMnCr solid solution alloy is measured with low temperature neutron diffraction, ambient X-ray diffraction, and total scattering methods. Here, the static atomic displacement parameter of the multi-element component alloy at 0 K is 0.035–0.041 Å, which is obvious larger than that of element Ni (~0 Å). The atomic pair distance between individual atoms in the alloy investigated with extended X-ray absorption fine structure (EXAFS) measurements indicates that Mn has a slightly larger bond distance (~0.4%) with neighbor atoms than that of others.

  6. Chemical complexity induced local structural distortion in NiCoFeMnCr high-entropy alloy

    DOE PAGES

    Zhang, Fuxiang; Tong, Yang; Jin, Ke; ...

    2018-06-16

    In order to study chemical complexity-induced lattice distortion in high-entropy alloys, the static Debye–Waller (D-W) factor of NiCoFeMnCr solid solution alloy is measured with low temperature neutron diffraction, ambient X-ray diffraction, and total scattering methods. Here, the static atomic displacement parameter of the multi-element component alloy at 0 K is 0.035–0.041 Å, which is obvious larger than that of element Ni (~0 Å). The atomic pair distance between individual atoms in the alloy investigated with extended X-ray absorption fine structure (EXAFS) measurements indicates that Mn has a slightly larger bond distance (~0.4%) with neighbor atoms than that of others.

  7. Incorporation of Mg, Sr, Ba, U, and B in High-Mg Calcite Benthic Foraminifers Cultured Under Controlled pCO2

    NASA Astrophysics Data System (ADS)

    Not, C.; Thibodeau, B.; Yokoyama, Y.

    2018-01-01

    Measurement of elemental ratios (E/Ca) has been performed in two symbiont-bearing species of high-Mg calcite benthic foraminifers (hyaline, Baculogypsina sphaerulata and porcelaneous, Amphisorus hemprichii), cultured under five pCO2 levels, representing preindustrial, modern, and three predicted future values. E/Ca ratios were analyzed by Laser Ablation coupled with Inductively Coupled Plasma Mass Spectrometer (LA-ICP-MS). We measured several E/Ca, such as Mg/Ca, Sr/Ca, Ba/Ca, U/Ca, and B/Ca simultaneously. We observed that high-Mg calcite benthic foraminifers possess higher E/Ca than low-Mg calcite foraminifers, irrespective of their calcification mode (hyaline or porcelaneous). In both modes of calcification, Mg, Sr, Ba, U, and B incorporation could be controlled by Rayleigh fractionation. However, more data are needed to validate and quantify the relative importance of this process and closely investigate the presence/absence of other mechanism. Therefore, it highlights the need for a multielemental approach when looking at trace element incorporation. Finally, no significant relationship was observed between the different ratios and the pCO2 of the water, suggesting that none of the Mg/Ca, Sr/Ca, Ba/Ca, U/Ca, and B/Ca is sensitive to bottom water pCO2 or pH for these species.

  8. Capture of Hydrogen Using ZrNi

    NASA Technical Reports Server (NTRS)

    Patton, Lisa; Wales, Joshua; Lynch, David; Parrish, Clyde

    2005-01-01

    Water, as ice, is thought to reside in craters at the lunar poles along with CH4 and H2 . A proposed robotic mission for 2012 will utilize metal/metal hydrides for H2 recovery. Specifications are 99% capture of H2 initially at 5 bar and 100C (or greater), and degassing completely at 300C. Of 47-systems examined using the van't Hoff equation, 4 systems, Mg/MgH2, Mg2Ni/Mg2NiH4, ZrNi/ZrNiH2.8, and Pd/PdH0.77, were considered likely candidates for further examination. It is essential, when selecting a system, to also examine questions regarding activation, kinetics, cyclic stability, and gas impurity effects. After considering those issues, ZrN1 was selected as the most promising candidate, as it is easily activated and rapidly forms ZrNiH 2.8 . In addition, it resists oxide poisoning by CO2, and H2O, while some oxidation by O2 is recommended for improved activation . The presence of hydrogen in the as received Zr-Ni alloy from Alfa Aesar posed additional technical problems. X-ray diffraction of the Zr-Ni powder (-325 mesh), with a Zr:Ni wt% ratio of 70:30, was found to consist of ZrH2, ZrNiH2.8, and ZrNi. ZrH2 in the alloy presented the risk that after degassing that both Zr and ZrNi would be present, and thus lead to erroneous results regarding the reactivity of ZrNi with H2 . Fortunately, ZrH2 is a highly stable hydride that does not degas H2 to any significant extent at temperatures below 300C. Based on equilibrium calculations for the decomposition of ZrH2, only 1 millionth of the hydride decomposed at 300C under a N2 atmosphere flowing at 25 ccm for 64 hours, the longest time for pretreatment employed in the investigation. It was possible, from the X-ray results and knowledge of the Zr:Ni ratio, to compute the composition of a pretreated specimen as being 76 wt% ZrNi and the balance ZrH2.

  9. 1H,1H,5H-Perfluoropentyl-1,1,2,2-tetrafluoroethylether as a co-solvent for high voltage LiNi1/3Co1/3Mn1/3O2/graphite cells

    NASA Astrophysics Data System (ADS)

    Wang, Chengyun; Zuo, Xiaoxi; Zhao, Minkai; Xiao, Xin; Yu, Le; Nan, Junmin

    2016-03-01

    1H,1H,5H-Perfluoropentyl-1,1,2,2-tetrafluoroethylether (F-EAE) mixed with ethylene carbonate (EC), diethyl carbonate (DEC), and lithium hexafluorophosphate (LiPF6) is evaluated as a co-solvent high-potential electrolyte of LiNi1/3Co1/3Mn1/3O2/graphite batteries. Linear sweep voltammetry (LSV) and cyclic voltammetry (CV) indicate that the EC/DEC-based electrolyte with F-EAE possesses a high oxidation potential (>5.2 V vs. Li/Li+) and excellent film-forming characteristics. With 40 wt% F-EAE in the electrolyte, the capacity retention of the LiNi1/3Co1/3Mn1/3O2/graphite pouch cells that are cycled between 3.0 and 4.5 V is significantly improved from 28.8% to 86.8% after 100 cycles. In addition, electrochemical impedance spectroscopy (EIS) of three-electrode pouch cells, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) are used to characterize the effects of F-EAE on the enhanced capacity retention. It is demonstrated that F-EAE facilitates the formation of a stable surface electrolyte interface (SEI) layer with low impedance on the anode and effectively suppresses an increase in the charge-transfer resistance on the cathode. These results suggest that F-EAE can serve as an alternative electrolyte solvent for 4.5 V high voltage rechargeable lithium-ion batteries.

  10. Photo- and electrocatalytic H2 production by new first-row transition-metal complexes based on an aminopyridine pentadentate ligand.

    PubMed

    Call, Arnau; Codolà, Zoel; Acuña-Parés, Ferran; Lloret-Fillol, Julio

    2014-05-12

    The synthesis and characterisation of the pentadentate ligand 1,4-di(picolyl)-7-(p-toluenesulfonyl)-1,4,7-triazacyclononane (Py2(Ts)tacn) and their metal complexes of general formula [M(CF3SO3)(Py2(Ts)tacn)][CF3SO3], (M = Fe (1Fe), Co (1Co) and Ni (1Ni)) are reported. Complex 1Co presents excellent H2 photoproduction catalytic activity when using [Ir(ppy)2(bpy)]PF6 (PSIr) as photosensitiser (PS) and Et3N as electron donor, but 1Ni and 1Fe result in a low activity and a complete lack of it, respectively. On the other hand, all three complexes have excellent electrocatalytic proton reduction activity in acetonitrile, when using trifluoroacetic acid (TFA) as a proton source with moderate overpotentials for 1Co (0.59 V vs. SCE) and 1Ni (0.56 V vs. SCE) and higher for 1Fe (0.87 V vs. SCE). Under conditions of CH3CN/H2O/Et3N (3:7:0.2), 1Co (5 μM), with PSIr (100 μM) and irradiating at 447 nm gives a turnover number (TON) of 690 (n H2/n1Co) and initial turnover frequency (TOF) (TON×t(-1)) of 703 h(-1) for H2 production. It should be noted that 1Co retains 25 % of the catalytic activity for photoproduction of H2 in the presence of O2. The inexistence of a lag time for H2 evolution and the absence of nanoparticles during the first 30 min of the reaction suggest that the main catalytic activity observed is derived from a molecular system. Kinetic studies show that the reaction is -0.7 order in catalyst, and time-dependent diffraction light scattering (DLS) experiments indicate formation of metal aggregates and then nanoparticles, leading to catalyst deactivation. By a combination of experimental and computational studies we found that the lack of activity in photochemical water reduction by 1Fe can be attributed to the 1Fe (II/I) redox couple, which is significantly lower than the PSIr (III/II) , while for 1Ni the pKa value (-0.4) is too small in comparison with the pH (11.9) imposed by the use of Et3N as electron donor. © 2014 WILEY-VCH Verlag GmbH

  11. Alloying Behavior and Properties of FeSiBAlNiCo x High Entropy Alloys Fabricated by Mechanical Alloying and Spark Plasma Sintering

    NASA Astrophysics Data System (ADS)

    Wang, Wen; Li, Boyu; Zhai, Sicheng; Xu, Juan; Niu, Zuozhe; Xu, Jing; Wang, Yan

    2018-02-01

    In this paper, FeSiBAlNiCo x (x = 0.2, 0.8) high-entropy alloy (HEA) powders were fabricated by mechanical alloying process, and the powders milled for 140 h were sintered by spark plasma sintering (SPS) technique. The microstructures and properties of as-milled powders and as-sintered samples were investigated. The results reveal that the final milling products (140 h) of both sample powders present the fully amorphous structure. The increased Co contents obviously enhance the glass forming ability and thermal stability of amorphous HEA powders, which are reflected by the shorter formation time of fully amorphous phase and the higher onset crystallization temperature, respectively. According to coercivity, the as-milled FeSiBAlNiCo x (x = 0.2, 0.8) powders (140 h) are the semi-hard magnetic materials. FeSiBAlNiCo0.8 HEA powders possess the highest saturation magnetization and largest remanence ratio. The SPS-ed products of both bulk HEAs are composed of body-centered cubic solid solution, and FeSi and FeB intermetallic phases. They possess the high relative density above 97% and excellent microhardness exceeding 1150 HV. The as-sintered bulks undergo the remarkable increase in saturation magnetization compared with the as-milled state. The SPS-ed FeSiBAlNiCo0.8 HEA exhibits the soft magnetic properties. The electrochemical corrosion test is carried out in 3.5% NaCl solution. The SPS-ed FeSiBAlNiCo0.2 HEA reveals the better passivity with low passive current density, and the higher pitting resistance with wide passive region.

  12. Gas-phase noncovalent functionalization of carbon nanotubes with a Ni(II) tetraaza[14]annulene complex

    NASA Astrophysics Data System (ADS)

    Basiuk, Vladimir A.; Henao-Holguín, Laura Verónica; Álvarez-Zauco, Edgar; Bassiouk, María; Basiuk, Elena V.

    2013-04-01

    The noncovalent functionalization of carbon nanotubes (CNTs) with aromatic polyazamacrocyclic compounds, based on π-π-interactions, keeps the intrinsic electronic structure of CNTs totally intact and allows for combining unique properties of the two interacting components. In addition to porphyrins and phthalocyanines, there are other, simpler compounds exhibiting similar properties, potentially useful for photovoltaic, catalytic and electrochemical applications: for example, tetraaza[14]annulenes. Many of them are highly thermally stable, which makes it possible to employ physical vapor deposition for the preparation of macrocycle-nanotube hybrids. One of such compounds is Ni(II) complex of 5,7,12,14-tetramethyldibenzo-1,4,8,11-tetraazacyclotetradeca-3,5,7,10,12,14-hexaene (also called Ni(II)-tetramethyldibenzotetraaza[14]annulene, or NiTMTAA for simplicity). In the present work, we attempted the noncovalent functionalization of both single-walled and multi-walled CNTs with NiTMTAA in the gas phase at two selected temperatures of 220 and 270 °C, which does not require the use of organic solvents and therefore can be considered as ecologically friendly. The nanohybrids obtained were characterized by means of scanning and transmission electron microscopy, energy dispersive X-ray, Fourier-transform infrared and Raman spectroscopy, as well as thermogravimetric analysis. An additional insight into the structure of adsorption complexes of NiTMTAA on CNTs was provided from density functional theory and molecular mechanics calculations.

  13. Crystal structure, equation of state, and elasticity of phase H (MgSiO4H2) at Earth's lower mantle pressures.

    PubMed

    Tsuchiya, Jun; Mookherjee, Mainak

    2015-10-23

    Dense hydrous magnesium silicate (DHMS) phases play a crucial role in transporting water in to the Earth's interior. A newly discovered DHMS, phase H (MgSiO4H2), is stable at Earth's lower mantle, i.e., at pressures greater than 30 GPa. Here we report the crystal structure and elasticity of phase H and its evolution upon compression. Using first principles simulations, we have explored the relative energetics of the candidate crystal structures with ordered and disordered configurations of magnesium and silicon atoms in the octahedral sites. At conditions relevant to Earth's lower mantle, it is likely that phase H is able to incorporate a significant amount of aluminum, which may enhance the thermodynamic stability of phase H. The sound wave velocities of phase H are ~2-4% smaller than those of isostructural δ-AlOOH. The shear wave impedance contrast due to the transformation of phase D to a mixture of phase H and stishovite at pressures relevant to the upper part of the lower mantle could partly explain the geophysical observations. The calculated elastic wave velocities and anisotropies indicate that phase H can be a source of significant seismic anisotropy in the lower mantle.

  14. A first-principles study of the preventive effects of Al and Mg doping on the degradation in LiNi0.8Co0.1Mn0.1O2 cathode materials.

    PubMed

    Min, Kyoungmin; Seo, Seung-Woo; Song, You Young; Lee, Hyo Sug; Cho, Eunseog

    2017-01-18

    First-principles calculations have been used to investigate the effects of Al and Mg doping on the prevention of degradation phenomena in Li(Ni 0.8 Co 0.1 Mn 0.1 )O 2 cathode materials. Specifically, we have examined the effects of dopants on the suppression of oxygen evolution and cation disordering, as well as their correlation. It is found that Al doping can suppress the formation of oxygen vacancies effectively, while Mg doping prevents the cation disordering behaviors, i.e., excess Ni and Li/Ni exchange, and Ni migration. This study also demonstrates that formation of oxygen vacancies can facilitate the construction of the cation disordering, and vice versa. Delithiation can increase the probabilities of formation of all defect types, especially oxygen vacancies. When oxygen vacancies are present, Ni can migrate to the Li site during delithiation. However, Al and Mg doping can inhibit Ni migration, even in structures with preformed oxygen defects. The analysis of atomic charge variations during delithiation demonstrates that the degree of oxidation behavior in oxygen atoms is alleviated in the case of Al doping, indicating the enhanced oxygen stability in this structure. In addition, changes in the lattice parameters during delithiation are suppressed in the Mg-doped structure, which suggests that Mg doping may improve the lattice stability.

  15. Electronic structure and magnetism of epitaxial Ni-Mn-Ga(-Co) thin films with partial disorder: a view across the phase transition

    NASA Astrophysics Data System (ADS)

    Schleicher, B.; Klar, D.; Ollefs, K.; Diestel, A.; Walecki, D.; Weschke, E.; Schultz, L.; Nielsch, K.; Fähler, S.; Wende, H.; Gruner, M. E.

    2017-11-01

    The influence of Co-doping in off-stoichiometric Ni-Mn-Ga and Ni-Mn-Ga-Co thin films on the magnetic coupling of the atoms is investigated with x-ray magnetic circular dichroism in both the martensitic as well as austenitic phase, respectively. Additionally, first principles calculations were performed to compare the experimentally obtained absorption spectra with theoretical predictions. Calculated exchange constants and density of states for the different atomic sites underline the large influence of chemical and magnetic order on the magnetocaloric properties of the material.

  16. Self-sacrifice Template Formation of Hollow Hetero-Ni7S6/Co3S4 Nanoboxes with Intriguing Pseudo-capacitance for High-performance Electrochemical Capacitors

    PubMed Central

    Hua, Hui; Liu, Sijia; Chen, Zhiyi; Bao, Ruiqi; Shi, Yaoyao; Hou, Linrui; Pang, Gang; Hui, Kwun Nam; Zhang, Xiaogang; Yuan, Changzhou

    2016-01-01

    Herein, we report a simple yet efficient self-sacrifice template protocol to smartly fabricate hollow hetero-Ni7S6/Co3S4 nanoboxes (Ni-Co-S NBs). Uniform nickel cobalt carbonate nanocubes are first synthesized as the precursor via solvothermal strategy, and subsequently chemically sulfidized into hollow heter-Ni-Co-S NBs through anion-exchange process. When evaluated as electrode for electrochemical capacitors (ECs), the resultant hetero-Ni-Co-S NBs visually exhibit attractive pesudo-capacitance in KOH just after continuously cyclic voltammetry (CV) scanning for 100 cycles. New insights into the underlying energy-storage mechanism of the hollow hetero-Ni-Co-S electrode, based on physicochemical characterizations and electrochemical evaluation, are first put forward that the electrochemically induced phase transformation gradually occurrs during CV sweep from the hetero-Ni-Co-S to bi-component-active NiOOH and CoOOH, which are the intrinsic charge-storage phases for the appealing Faradaic capacitance (~677 F g−1 at 4 A g−1) of hollow Ni-Co-S NBs at high rates after cycling. When further coupled with negative activated carbon (AC), the AC//hetero-Ni-Co-S asymmetric device with extended electrochemical window of 1.5 V demonstrates high specific energy density of ~31 Wh kg−1. Of significance, we strongly envision that hollow design concept and new findings here hold great promise for enriching synthetic methodologies, and electrochemistry of complex metal sulfides for next-generation ECs. PMID:26865246

  17. Self-sacrifice Template Formation of Hollow Hetero-Ni7S6/Co3S4 Nanoboxes with Intriguing Pseudo-capacitance for High-performance Electrochemical Capacitors

    NASA Astrophysics Data System (ADS)

    Hua, Hui; Liu, Sijia; Chen, Zhiyi; Bao, Ruiqi; Shi, Yaoyao; Hou, Linrui; Pang, Gang; Hui, Kwun Nam; Zhang, Xiaogang; Yuan, Changzhou

    2016-02-01

    Herein, we report a simple yet efficient self-sacrifice template protocol to smartly fabricate hollow hetero-Ni7S6/Co3S4 nanoboxes (Ni-Co-S NBs). Uniform nickel cobalt carbonate nanocubes are first synthesized as the precursor via solvothermal strategy, and subsequently chemically sulfidized into hollow heter-Ni-Co-S NBs through anion-exchange process. When evaluated as electrode for electrochemical capacitors (ECs), the resultant hetero-Ni-Co-S NBs visually exhibit attractive pesudo-capacitance in KOH just after continuously cyclic voltammetry (CV) scanning for 100 cycles. New insights into the underlying energy-storage mechanism of the hollow hetero-Ni-Co-S electrode, based on physicochemical characterizations and electrochemical evaluation, are first put forward that the electrochemically induced phase transformation gradually occurrs during CV sweep from the hetero-Ni-Co-S to bi-component-active NiOOH and CoOOH, which are the intrinsic charge-storage phases for the appealing Faradaic capacitance (~677 F g-1 at 4 A g-1) of hollow Ni-Co-S NBs at high rates after cycling. When further coupled with negative activated carbon (AC), the AC//hetero-Ni-Co-S asymmetric device with extended electrochemical window of 1.5 V demonstrates high specific energy density of ~31 Wh kg-1. Of significance, we strongly envision that hollow design concept and new findings here hold great promise for enriching synthetic methodologies, and electrochemistry of complex metal sulfides for next-generation ECs.

  18. Self-sacrifice Template Formation of Hollow Hetero-Ni7S6/Co3S4 Nanoboxes with Intriguing Pseudo-capacitance for High-performance Electrochemical Capacitors.

    PubMed

    Hua, Hui; Liu, Sijia; Chen, Zhiyi; Bao, Ruiqi; Shi, Yaoyao; Hou, Linrui; Pang, Gang; Hui, Kwun Nam; Zhang, Xiaogang; Yuan, Changzhou

    2016-02-11

    Herein, we report a simple yet efficient self-sacrifice template protocol to smartly fabricate hollow hetero-Ni7S6/Co3S4 nanoboxes (Ni-Co-S NBs). Uniform nickel cobalt carbonate nanocubes are first synthesized as the precursor via solvothermal strategy, and subsequently chemically sulfidized into hollow heter-Ni-Co-S NBs through anion-exchange process. When evaluated as electrode for electrochemical capacitors (ECs), the resultant hetero-Ni-Co-S NBs visually exhibit attractive pesudo-capacitance in KOH just after continuously cyclic voltammetry (CV) scanning for 100 cycles. New insights into the underlying energy-storage mechanism of the hollow hetero-Ni-Co-S electrode, based on physicochemical characterizations and electrochemical evaluation, are first put forward that the electrochemically induced phase transformation gradually occurrs during CV sweep from the hetero-Ni-Co-S to bi-component-active NiOOH and CoOOH, which are the intrinsic charge-storage phases for the appealing Faradaic capacitance (~677 F g(-1) at 4 A g(-1)) of hollow Ni-Co-S NBs at high rates after cycling. When further coupled with negative activated carbon (AC), the AC//hetero-Ni-Co-S asymmetric device with extended electrochemical window of 1.5 V demonstrates high specific energy density of ~31 Wh kg(-1). Of significance, we strongly envision that hollow design concept and new findings here hold great promise for enriching synthetic methodologies, and electrochemistry of complex metal sulfides for next-generation ECs.

  19. Pressure-induced fcc to hcp phase transition in Ni-based high entropy solid solution alloys

    DOE PAGES

    Zhang, Fuxiang; Zhao, Shijun; Jin, Ke; ...

    2017-01-04

    In this research, pressure-induced phase transition from the fcc to a hexagonal close-packed (hcp) structure wasfound in NiCoCrFe solid solution alloy starting at 13.5 GPa. The phase transition is very sluggish and the transition did not complete at ~ 40 GPa. The hcp structure is quenchable to ambient pressure. Only a very small amount (<5%) of hcp phase was found in the isostructural NiCoCr ternary alloy up to the pressure of 45 GPa and no obvious hcp phase was found in NiCoCrFePd system till to 74 GPa. Ab initio Gibbs free energy calculations indicated the energy differences between the fccmore » and the hcp phases for the three alloys are very small, but they are sensitive to temperature. Finally, the critical transition pressure in NiCoCrFe varies from 1 GPa at room temperature to 6 GPa at 500 K.« less

  20. Pressure-induced fcc to hcp phase transition in Ni-based high entropy solid solution alloys

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhang, F. X.; Zhao, Shijun; Jin, Ke

    2017-01-04

    A pressure-induced phase transition from the fcc to a hexagonal close-packed (hcp) structure was found in NiCoCrFe solid solution alloy starting at 13.5 GPa. The phase transition is very sluggish and the transition did not complete at ~40 GPa. The hcp structure is quenchable to ambient pressure. Only a very small amount (<5%) of hcp phase was found in the isostructural NiCoCr ternary alloy up to the pressure of 45 GPa and no obvious hcp phase was found in NiCoCrFePd system till to 74 GPa. Ab initio Gibbs free energy calculations indicated the energy differences between the fcc and themore » hcp phases for the three alloys are very small, but they are sensitive to temperature. The critical transition pressure in NiCoCrFe varies from ~1 GPa at room temperature to ~6 GPa at 500 K.« less

  1. Electronic structure and vacancy formation in La(1 - x) B(x) CoO3 (B=Mg,Ca,Ba and x=0.125)

    NASA Astrophysics Data System (ADS)

    Salawu, Omotayo; Gan, Liyong; Schwingenschlogl, Udo

    2015-03-01

    The LaCoO3 class of materials is of interest for cathodes of solid oxide fuel cells. Spin-polarized density functional theory is applied to cubic La0.75(Mg/Ca/Ba)0.125CoO3. The effect of this cation doping on the electronic and magnetic properties as well as oxygen vacancy formation energy is studied. Oxygen vacancies with proximity to the dopant are energetically favourable in most cases. We discuss the effect of distortions of the CoO6 octahedron on the electronic structure and the formation energy of oxygen vacancies. The order of formation oxygen is found to be Mg > Ca > Ba. Cation doping incorporates holes to the Co-O network which enhances the oxygen vacancy formation.

  2. Ni(II)-tetrahedral complexes: Characterization, antimicrobial properties, theoretical studies and a new family of charge-transfer transitions

    NASA Astrophysics Data System (ADS)

    Sarı, Nurşen; Şahin, Songül Çiğdem; Öğütcü, Hatice; Dede, Yavuz; Yalcin, Soydan; Altundaş, Aliye; Doğanay, Kadir

    2013-04-01

    A new amine containing selenium and their five imine, (SeSchX)(X: -H, F, Cl, Br, CH3), and Ni (II) complexes, [Ni(SeSchX)(H2O)2]Cl/[Ni(SeSchCl)(H2O)Cl], were synthesized. The compounds were characterized by means of elemental analyses, 13C and 1H NMR (for imine), FT-IR, UV-Visible spectroscopy, TGA/DTA and elemental analyses. [Ni(SeSchCl)(H2O)Cl] complex from Ni(II) complexes changes color from yellow to orange in the range pH 5-7. [Ni(SeSchCl)(H2O)Cl] complex has ligand-to-metal charge-transfer (LMCT) transitions in the basic medium. Excitation characteristics and energetic of [Ni(SeSchCl)(H2O)Cl] complex, examined via TD-DFT calculations, reveals transitions of LMCT and π → π* character that matches the experimental values. [Ni(SeSchCl)(H2O)Cl] complex showed the highest antibacterial activity when compared to other complexes reported in this work.

  3. Magnetic, Electric and Optical Properties of Mg-Substituted Ni-Cu-Zn Ferrites

    NASA Astrophysics Data System (ADS)

    Kabbur, S. M.; Ghodake, U. R.; Kambale, Rahul C.; Sartale, S. D.; Chikhale, L. P.; Suryavanshi, S. S.

    2017-10-01

    The Ni0.25- x Mg x Cu0.30Zn0.45Fe2O4 ( x = 0.00 mol, 0.05 mol, 0.10 mol, 0.15 mol, 0.20 mol and 0.25 mol) magnetic oxide system was prepared by a sol-gel auto-combustion method using glycine as a fuel. X-ray diffraction study reveals the formation of pure spinel lattice symmetry along with the presence of a small fraction of unreacted Fe2O3 phase as a secondary phase due to incomplete combustion reaction between fuel and oxidizer. The lattice constant ( a) was found to decrease with the increase of Mg2+ content; the average crystallite size ( D) is observed in the range of 26.78-33.14 nm. At room temperature, all the samples show typical magnetic hysteresis loops with the decrease of magnetic moment ( n B) of Ni-Cu-Zn ferrites with the increase of Mg2+ content. The intrinsic vibrational absorption bands for the tetrahedral and octahedral sites of the spinel structure were confirmed by infrared (IR) spectroscopy. The optical parameters such as refractive index ( η), velocity of IR waves ( v) and jump rates ( J 1, J 2, J) were studied and found to be dependent on the variation of the lattice constant. The Curie temperature ( T c) of Ni-Cu-Zn mixed ferrite was found to decrease with Mg2+ addition. The composition x = 0.15 mol.% with a low dielectric loss tangent of 2% seems to have potential for multilayer chip inductor applications at a wide range of frequencies.

  4. Charge transfer transitions in optical spectra of NicMg1-cO oxides

    NASA Astrophysics Data System (ADS)

    Churmanov, V. N.; Sokolov, V. I.; Pustovarov, V. A.; Gruzdev, N. B.; Uimin, M. A.; Byzov, I. V.; Druzhinin, A. V.; Korolyov, A. V.; Kim, G. A.; Zatsepin, A. F.; Kuznetsova, J. A.

    2017-04-01

    Radiative recombination with charge transfer was observed in NicMg1-cO (c = 0.008) oxides over the 8-300 K temperature range. This recombination occurs as a result of strong hybridization of the Ni2+ ion 3d-states and the band states. The charge transfer radiation excitation spectrum shows vibrational LO repeats of two exciton lines having charge transfer energy intervals of about 35 meV. The NiO nanocrystal absorption spectrum shows two weak peaks with energies of 3.510 and 3.543 eV, which are highly dependent on temperature. They are interpreted as charge transfer excitons at the edge of NiO fundamental absorption. The distance between the charge transfer exciton lines in the NicMg1-cO oxide spectra are caused by spin-orbit splitting of the valence band peak that was formed by the p-states of the oxygen ion.

  5. Noble-metal-free g-C3N4/Ni(dmgH)2 composite for efficient photocatalytic hydrogen evolution under visible light irradiation

    NASA Astrophysics Data System (ADS)

    Cao, Shao-Wen; Yuan, Yu-Peng; Barber, James; Loo, Say Chye Joachim; Xue, Can

    2014-11-01

    We report an economic photocatalytic H2 generation system consisting of earth-abundant elements only by coupling graphitic carbon nitride (g-C3N4) with Ni(dmgH)2 sub-microwires that serve as effective co-catalysts for H2 evolution. This composite photocatalyst exhibits efficient hydrogen evolution under visible-light irradiation in the presence of triethanolamine as electron donor. The optimal coupling of 3.5 wt% Ni(dmgH)2 to g-C3N4 (5 mg composite) allows for a steady H2 generation rate of 1.18 μmol/h with excellent stability. This study demonstrates that the combination of polymeric g-C3N4 semiconductor and small proportion of transition-metal-based co-catalyst could serve as a stable, earth-abundant and low-cost system for solar-to-hydrogen conversion.

  6. pH controlled pathway and systematic hydrothermal phase diagram for elaboration of synthetic lead nickel selenites.

    PubMed

    Kovrugin, Vadim M; Colmont, Marie; Terryn, Christine; Colis, Silviu; Siidra, Oleg I; Krivovichev, Sergey V; Mentré, Olivier

    2015-03-02

    The PbO-NiO-SeO2 ternary system was fully studied using constant hydrothermal conditions at 473 K. It yields the establishment of the corresponding phase diagram using a systematic assignment of reaction products by both powder and single-crystal X-ray diffraction. It leads to the preparation of three novel lead nickel selenites, α-PbNi(SeO3)2 (I), β-PbNi(SeO3)2 (II), and PbNi2(SeO2OH)2(SeO3)2 (III), and one novel lead cobalt selenite, α-PbCo(SeO3)2 (IV), which have been structurally characterized. The crystal structures of the α-forms I, IV, and III are based on a 3D complex nickel selenite frameworks, whereas the β-PbNi(SeO3)2 modification (II) consists of nickel selenite sheets stacked in a noncentrosymmetric structure, second-harmonic generation active. The pH value of the starting solution was shown to play an essential role in the reactive processes. Magnetic measurements of I, III, and IV are discussed.

  7. Fluorine-substitution induced switching of dissociation patterns of C6H4*+ produced by photoelimination of MgF2 from the complexes of mg*+ (multifluorobenzene).

    PubMed

    Liu, Hai-Chuan; Zhang, Xin-Hao; Wu, Yun-Dong; Yang, Shihe

    2005-03-07

    Complexes of fluorinated benzenes (o-C6H4-nF2+n) and Mg*+ are subjected to ultraviolet photodissociation (260-340 nm), producing efficiently benzyne radical cations (C6H4-nFn*+) besides Mg*+ and MgF+. We show that the consecutive dissociation of C6H4-nFn*+ follows the [C4(+) + C2] pattern exclusively for n < or = 2 after the parent complexes absorb one or two photons. However, the dissociation pattern is switched to [C5(+) + C1] and [C1 + C5] for n > or = 3. In particular, upon two-photon absorption at 340 nm by the complexes of Mg*+ (C6HF5) (1) and Mg*+ (C6F6) (2), photoproducts of CF+, C5H+, and C5HF*+ from C6HF3*+ and CF+, C5F+, C5F2*+, and C5F3+ from C6F4*+ are detected, respectively. Theoretical calculations are used to explain the switching of the dissociation patterns induced by the fluorine substitutions. It was found that the formation of C5+ + C1 is energetically more favorable than that of C4(+) + C2 from C6HF3*+ and C6F4*+ and of C1(+) + C5. Except for C5H2F(+) + CF, all the channels of [C5(+) + C1] and [C1(+) + C5] are energetically less favorable than those of [C4(+) + C2] from C6H3F*+ and C6H2F2*+. In most cases, the calculated results agree well with the experimental observations.

  8. Crystal structure and electrochemical characteristics of non-AB 5 type La-Ni system alloys

    NASA Astrophysics Data System (ADS)

    Shi, Siqi; Ouyang, Chuying; Lei, Minsheng

    The La-Ni system compounds have been prepared by arc-melting method under Ar atmosphere. X-ray diffraction analysis reveals that the as-prepared alloys consist of different phases. The electrochemical properties, including activation, maximum discharge capacity, high rate chargeability (HRC), and high rate dischargeability (HRD) of these alloy electrodes have been studied through the charge-discharge recycle testing at different temperatures and charge (or discharge) currents. Among the La-Ni alloy electrodes studied, LaNi 2.28 alloy has the most excellent high rate charging performance, and La 2Ni 7 alloy exhibit the highest high rate dischargeability, while La 7Ni 3 alloy is capable of discharging at low temperature.

  9. Preceding winter La Niña reduces Indian summer monsoon rainfall

    NASA Astrophysics Data System (ADS)

    Chakraborty, Arindam

    2018-05-01

    Leaving out the strong El Niño Southern Oscillation (ENSO) years, our understanding in the interannual variation of the Indian summer monsoon rainfall (ISMR) stands poor for the rest. This study quantifies the role of ENSO in the preceding winter on ISMR with a particular emphasis on ENSO-neutral summer and La Niña winter. Results show that, unlike the simultaneous ENSO-ISMR relationship, La Niña of previous winter reduces mean rainfall over the country by about 4% even during ENSO neutral summer. Moreover, when ENSO changes phase from La Niña in winter to El Niño in summer, ISMR is anomalously lower than during persisting El Niño years (‑14.5% and ‑5.3%, respectively), increasing the probability of severe drought. This suppression effect of La Niña of the preceding winter on summer monsoon precipitation over India is mostly experienced in its western and southern parts. Principal component analysis of the zonal propagation of surface pressure anomalies from winter to summer along Northern Hemisphere subtropics decomposes interannual variations of seasonally persisting anomalies from zonal propagations. The dominant modes are associated with the seasonal transition of the ENSO phase, and are well correlated with date of onset and seasonal mean rainfall of monsoon over India. These results improve our understanding of the interannual variations of ISMR and could be used for diagnostics of general circulation models.

  10. Oxidation of CO on a carbon-based material composed of nickel hydroxide and hydroxyl graphene oxide, (Ni4(OH)3-hGO)--a first-principles calculation.

    PubMed

    Yeh, Chen-Hao; Ho, Jia-Jen

    2015-03-21

    Nickel or nickel hydroxide clusters and graphene oxide (GO) composites are novel nanomaterials in the application of electrochemical catalysts. In this work, we calculated the energy of Ni4 adsorbed onto saturated hydroxyl graphene oxide (hGO), which forms a Ni4(OH)3 cluster on the hydroxyl graphene oxide (Ni4(OH)3-hGO) and releases 4.47 eV (5.22 eV with DFT-D3 correction). We subsequently studied the oxidation of CO on the Ni4(OH)3-hGO system via three mechanisms - LH, ER and carbonated mechanisms. Our results show that the activation energy for oxidation of the first CO molecule according to the ER mechanism is 0.14 eV (0.12 eV with DFT-D3 correction), much smaller than that with LH (Ea = 0.65 eV, 0.61 eV with DFT-D3 correction) and with carbonated (Ea = 1.28 eV, 1.20 eV with DFT-D3 correction) mechanisms. The barrier to oxidation of the second CO molecule to CO2 with the ER mechanism increases to 0.43 eV (0.37 eV with DFT-D3 correction), but still less than that via LH (Ea = 1.09 eV, 1.07 eV with DFT-D3 correction), indicating that CO could be effectively oxidized through the ER mechanism on the Ni4(OH)3/hGO catalyst.

  11. DNA Binding, Cleavage and Antibacterial Activity of Mononuclear Cu(II), Ni(II) and Co(II) Complexes Derived from Novel Benzothiazole Schiff Bases.

    PubMed

    Vamsikrishna, Narendrula; Kumar, Marri Pradeep; Tejaswi, Somapangu; Rambabu, Aveli; Shivaraj

    2016-07-01

    A series of novel bivalent metal complexes M(L1)2 and M(L2)2 where M = Cu(II), Ni(II), Co(II) and L1 = 2-((benzo [d] thiazol-6-ylimino)methyl)-4-bromophenol [BTEMBP], L2 = 1-((benzo [d] thiazol-6-ylimino)methyl) naphthalen-2-ol [BTEMNAPP] were synthesized. All the compounds have been characterized by elemental analysis, SEM, Mass, (1)H NMR, (13)C NMR, UV-Vis, IR, ESR, spectral data and magnetic susceptibility measurements. Based on the analytical and spectral data four-coordinated square planar geometry is assigned to all the complexes. DNA binding properties of these complexes have been investigated by electronic absorption spectroscopy, fluorescence and viscosity measurements. It is observed that these binary complexes strongly bind to calf thymus DNA by an intercalation mode. DNA cleavage efficacy of these complexes was tested in presence of H2O2 and UV light by gel electrophoresis and found that all the complexes showed better nuclease activity. Finally the compounds were screened for antibacterial activity against few pathogens and found that the complexes have potent biocidal activity than their free ligands.

  12. Preparation and characterization of Ni-P/Ni3.1B composite alloy coatings

    NASA Astrophysics Data System (ADS)

    Wang, Yurong; He, Jiawei; Wang, Wenchang; Shi, Jianhua; Mitsuzaki, Naotoshi; Chen, Zhidong

    2014-02-01

    The preparation of Ni-P/Ni3.1B composite alloy coating on the surface of copper was achieved by co-deposition of Ni3.1B nanoparticles with Ni-P coating during electroless plating. Ni-P-B alloy coating was obtained by heat-treating the as-plated Ni-P/Ni3.1B composite coating. The effect of the concentration of sodium alginate, borax, thiourea, Ni3.1B, temperature, and pH value on the deposition rate and B content were investigated and determined to be: 30 g L-1, 10 g L-1, 2 mg L-1, 20 mg L-1, 70 °C and 9.0 , respectively. Sodium alginate and thiourea were played as surfactant for coating Ni3.1B nanoparticles and stabilizer for the plating bath, respectively. Ni-P/Ni3.1B composite coating had good performance such as corrosion resistance and solderability.

  13. Hydrogenated CoOx nanowire@Ni(OH)2 nanosheet core-shell nanostructures for high-performance asymmetric supercapacitors

    NASA Astrophysics Data System (ADS)

    Zhu, Jianxiao; Huang, Lei; Xiao, Yuxiu; Shen, Leo; Chen, Qi; Shi, Wangzhou

    2014-05-01

    We report a facile strategy to prepare 3D core-shell nanowire heterostructures with microporous hydrogenated CoOx (H-CoOx) nanowires as the conducting scaffold to support Ni(OH)2 nanosheets. Benefiting from the H-CoOx nanowire core to provide the effective pathway for charge transport and the core-shell heterostructures with synergistic effects, the H-CoOx@Ni(OH)2 core-shell nanowire electrode achieved the specific capacitance of 2196 F g-1 (areal capacitance of 5.73 F cm-2), which is approximately a 1.4-fold enhancement compared with the Co3O4@Ni(OH)2 core-shell nanowires. An aqueous asymmetric supercapacitor (ASC) device was fabricated by using H-CoOx@Ni(OH)2 nanowires as the positive electrode and reduced graphene oxide @Fe3O4 nanocomposites as the negative electrode. The ASCs achieved high energy density (~45.3 W h kg-1 at 1010 W kg-1), high power density (~7080 W kg-1 at 23.4 W h kg-1) and high cycling stability. Furthermore, after charging for ~1 min, one such 22 cm2 ASC device demonstrated to be able to drive a small windmill (0.8 V, 0.1 W) for 20 min. Two such ASCs connected in series can power up a seven-color LED (3.2 V) efficiently.We report a facile strategy to prepare 3D core-shell nanowire heterostructures with microporous hydrogenated CoOx (H-CoOx) nanowires as the conducting scaffold to support Ni(OH)2 nanosheets. Benefiting from the H-CoOx nanowire core to provide the effective pathway for charge transport and the core-shell heterostructures with synergistic effects, the H-CoOx@Ni(OH)2 core-shell nanowire electrode achieved the specific capacitance of 2196 F g-1 (areal capacitance of 5.73 F cm-2), which is approximately a 1.4-fold enhancement compared with the Co3O4@Ni(OH)2 core-shell nanowires. An aqueous asymmetric supercapacitor (ASC) device was fabricated by using H-CoOx@Ni(OH)2 nanowires as the positive electrode and reduced graphene oxide @Fe3O4 nanocomposites as the negative electrode. The ASCs achieved high energy density (~45.3 W h kg-1 at

  14. Hysteresis and magnetocaloric effect at the magnetostructural phase transition of Ni-Mn-Ga and Ni-Mn-Co-Sn Heusler alloys

    NASA Astrophysics Data System (ADS)

    Basso, Vittorio; Sasso, Carlo P.; Skokov, Konstantin P.; Gutfleisch, Oliver; Khovaylo, Vladimir V.

    2012-01-01

    Hysteresis features of the direct and inverse magnetocaloric effect associated with first-order magnetostructural phase transitions in Ni-Mn-X (X = Ga, Sn) Heusler alloys have been disclosed by differential calorimetry measurements performed either under a constant magnetic field, H, or by varying H in isothermal conditions. We have shown that the magnetocaloric effect in these alloys crucially depends on the employed measuring protocol. Experimentally observed peculiarities of the magnetocaloric effect have been explained in the framework of a model that accounts for different contributions to the Gibbs energy of austenitic gA and martensitic gM phases. Obtained experimental results have been summarized by plotting a phase fraction of the austenite xA versus the driving force gM-gA. The developed approach allows one to predict reversible and irreversible features of the direct as well as inverse magnetocaloric effect in a variety of materials with first-order magnetic phase transitions.

  15. Underlying mechanisms leading to El Niño-to-La Niña transition are unchanged under global warming

    NASA Astrophysics Data System (ADS)

    Yun, Kyung-Sook; Yeh, Sang-Wook; Ha, Kyung-Ja

    2018-05-01

    El Niño's transitions play critical roles in modulating severe weather and climate events. Therefore, understanding the dynamic factors leading to El Niño's transitions and its future projection is a great challenge in predicting the diverse socioeconomic influences of El Niño over the globe. This study focuses on two dynamic factors controlling the El Niño-to-La Niña transition from the present climate and to future climate, using the observation, the historical and the RCP8.5 simulations of Coupled Model Intercomparison phase 5 climate models. The first is the inter-basin coupling between the Indian Ocean and the western North Pacific through the subtropical high variability. The second is the enhanced sensitivity between sea surface temperature and a deep tropical convection in the central tropical Pacific during the El Niño's developing phase. We show that the dynamic factors leading to El Niño-to-La Niña transition in the present climate are unchanged in spite of the increase of greenhouse gas concentrations. We argue that the two dynamic factors are strongly constrained by the climatological precipitation distribution over the central tropical Pacific and western North Pacific as little changed from the present climate to future climate. This implies that two dynamical processes leading to El Niño-to-La Niña transitions in the present climate will also play a robust role in global warming.

  16. High pressure synthesis of a hexagonal close-packed phase of the high-entropy alloy CrMnFeCoNi

    NASA Astrophysics Data System (ADS)

    Tracy, Cameron L.; Park, Sulgiye; Rittman, Dylan R.; Zinkle, Steven J.; Bei, Hongbin; Lang, Maik; Ewing, Rodney C.; Mao, Wendy L.

    2017-05-01

    High-entropy alloys, near-equiatomic solid solutions of five or more elements, represent a new strategy for the design of materials with properties superior to those of conventional alloys. However, their phase space remains constrained, with transition metal high-entropy alloys exhibiting only face- or body-centered cubic structures. Here, we report the high-pressure synthesis of a hexagonal close-packed phase of the prototypical high-entropy alloy CrMnFeCoNi. This martensitic transformation begins at 14 GPa and is attributed to suppression of the local magnetic moments, destabilizing the initial fcc structure. Similar to fcc-to-hcp transformations in Al and the noble gases, the transformation is sluggish, occurring over a range of >40 GPa. However, the behaviour of CrMnFeCoNi is unique in that the hcp phase is retained following decompression to ambient pressure, yielding metastable fcc-hcp mixtures. This demonstrates a means of tuning the structures and properties of high-entropy alloys in a manner not achievable by conventional processing techniques.

  17. Synthesis, spectral characterization, structural investigation and antimicrobial studies of mononuclear Cu(II), Ni(II), Co(II), Zn(II) and Cd(II) complexes of a new potentially hexadentate N2O4 Schiff base ligand derived from salicylaldehyde

    NASA Astrophysics Data System (ADS)

    Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Chalabian, Firoozeh; Elerman, Yalcin; Buyukgungor, Orhan

    2013-01-01

    A new potentially hexadentate N2O4 Schiff base ligand, H2L derived from condensation reaction of an aromatic diamine and salicylaldehyde, and its metal complexes were characterized by elemental analyses, IR, UV-Vis, EI-MS, 1H and 13C NMR spectra, as well as conductance measurements. It has been originated that the Schiff base ligand with Cu(II), Ni(II), Co(II), Cd(II) and Zn(II) ions form mononuclear complexes on 1:1 (metal:ligand) stoichiometry. The conductivity data confirm the non-electrolytic nature of the complexes. Also the crystal structures of the complexes [ZnL] and [CoL] have also been determined by using X-ray crystallographic technique. The Zn(II) and Co(II) complexes show a tetrahedral configuration. Electronic absorption spectra of the Cu(II) and Ni(II) complexes suggest a square-planar geometry around the central metal ion. The synthesized compounds have antibacterial activity against the three Gram-positive bacteria: Bacillus cereus, Enterococcus faecalis and Listeria monocytogenes and also against the three Gram-negative bacteria: Salmonella paraB, Citrobacter freundii and Enterobacter aerogenes. The results showed that in some cases the antibacterial activity of complexes were more than nalidixic acid and amoxicillin as standards.

  18. High-performance cobalt carbonate hydroxide nano-dot/NiCo(CO3)(OH)2 electrode for asymmetric supercapacitors

    NASA Astrophysics Data System (ADS)

    Lee, Damin; Xia, Qi Xun; Yun, Je Moon; Kim, Kwang Ho

    2018-03-01

    Binder-free mesoporous NiCo(CO3)(OH)2 nanowire arrays were grown using a facile hydrothermal technique. The Co2(CO3)(OH)2 in NiCo(CO3)(OH)2 nanowire arrays was well-decorated as nano-dot scale (a few nanometer). In addition, increasing cobalt content in nickel compound matrix, NiCo(CO3)(OH)2 nanowire arrays were separately uniformly grown without agglomeration on Ni foam, providing a high specific surface area to help electrolyte access and ion transfer. The enticing composition and morphology of the NiCo(CO3)(OH)2 nanowire exhibit a superior specific capacity of 1288.2 mAh g-1 at a current density of 3 A g-1 and excellent cycling stability with the capacity retention of 80.7% after 10,000 cycles. Furthermore, an asymmetric supercapacitor composed of the NiCo(CO3)(OH)2 composite as a positive electrode and the graphene as a negative electrode presented a high energy density of 35.5 W h kg-1 at a power density of 2555.6 W kg-1 and satisfactory cycling stability with 71.3% capacity retention after 10,000 cycles. The great combination of the active nano-dot Co2(CO3)(OH)2 and the individually grown NiCo(CO3)(OH)2 nanowires made it a promising electrode material for asymmetric supercapacitors. A well-developed nanoarchitecture of the nano-dot Co2(CO3)(OH)2 decorated NiCo(CO3)(OH)2 composite could pave the way for an excellent electrode design for high-performance supercapacitors.

  19. Peculiarities of thermoelectric half-Heusler phase formation in Gd-Ni-Sb and Lu-Ni-Sb ternary systems

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Romaka, V.V., E-mail: romakav@lp.edu.ua; Romaka, L.; Horyn, A.

    The phase equilibria in the Gd–Ni–Sb and Lu-Ni-Sb ternary systems were studied at 873 K by X-ray and metallographic analyses in the whole concentration range. The interaction of the elements in the Gd–Ni–Sb system results the formation of five ternary compounds at investigated temperature: Gd{sub 5}Ni{sub 2}Sb (Mo{sub 5}SiB{sub 2}-type), Gd{sub 5}NiSb{sub 2} (Yb{sub 5}Sb{sub 3}-type), GdNiSb (MgAgAs-type), Gd{sub 3}Ni{sub 6}Sb{sub 5} (Y{sub 3}Ni{sub 6}Sb{sub 5}-type), and GdNi{sub 0.72}Sb{sub 2} (HfCuSi{sub 2}-type). At investigated temperature the Lu-Ni-Sb system is characterized by formation of the LuNiSb (MgAgAs-type), Lu{sub 5}Ni{sub 2}Sb (Mo{sub 5}SiB{sub 2}-type), and Lu{sub 5}Ni{sub 0.56}Sb{sub 2.44} (Yb{sub 5}Sb{sub 3}-type)more » compounds. The disordering in the crystal structure of half-Heusler GdNiSb and LuNiSb was revealed by EPMA and studied by means of Rietveld refinement and DFT modeling. The performed electronic structure calculations are in good agreement with electrical transport property studies. - Graphical abstract: Crystal structure model and electron localization function of Lu{sub 5}Ni{sub 2}Sb. Display Omitted - Highlights: • Gd-Ni-Sb and Lu-Ni-Sb phase diagrams were constructed at 873 K. • GdNiSb and LuNiSb are characterized by disordered crystal structure. • Crystal structure optimization with DFT calculations confirmed crystal structure disorder in GdNiSb and LuNiSb.« less

  20. The influence of an MgO nanolayer on the planar Hall effect in NiFe films

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, Minghua, E-mail: mhli@ustb.edu.cn; Department of Electrical Engineering, University of California, Los Angeles, California 90095; Zhao, Zhiduo

    2015-03-28

    The Planar Hall Effect (PHE) in NiFe films was studied using MgO as the buffer and capping layer to reduce the shunt effect. The thermal annealing was found to be effective in increasing the sensitivity. The sensitivity of the magnetic field reached as high as 865 V/AT in a MgO (3 nm)/NiFe (5 nm)/MgO(3 nm)/Ta(3 nm) structure after annealing at 500 °C for 2 h, which is close to the sensitivity of semiconductor Hall Effect (HE) sensors. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) were used to study the sample. The results show that the top crystallization of MgO and NiFemore » (111) texture were improved by proper annealing. The smooth and clear bottom MgO/NiFe and top NiFe/MgO interface is evident from our data. In addition, the shunt current of Ta was decreased. These combined factors facilitate the improvement of the sensitivity of the magnetic field.« less

  1. Dynamic Oxygen on Surface: Catalytic Intermediate and Coking Barrier in the Modeled CO 2 Reforming of CH 4 on Ni (111)

    DOE PAGES

    Yuan, Kaidi; Zhong, Jian-Qiang; Zhou, Xiong; ...

    2016-06-08

    We identify Ni-O phases as important intermediates in a model dry (CO 2) reforming of methane catalyzed by Ni (111), based on results from in operando near ambient X-ray photoelectron spectroscopy (NAP-XPS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). We find that under a CO 2 or CO 2-CH 4 atmosphere, the Ni-O phases exist as p(2×2) structured chemisorbed oxygen (Chem-O), epitaxial NiO (111), or oxygen-rich Ni xO y (x2O 3), depending on the chemical potential. The growth rates of the Ni-O phases have a negative correlation with temperature from 600 K to 900 K, proving thatmore » their dynamic concentrations in the reaction are not limited by CO 2 activation, but by their thermal stability. Between 300 K and 800 K (1:1 CH 4 and CO 2 mixture), oxidation by CO 2is dominant, resulting in a fully Ni-O covered surface. Between 800 K and 900 K, a partially oxidized Ni (111) exists which could greatly facilitate the effective conversion of CH 4. As CH 4 is activation-limited and dissociates mainly on metallic nickel, the released carbon species can quickly react with the adjacent oxygen (Ni-O phases) to form CO. After combining with carbon and releasing CO molecules, the Ni-O phases can be further regenerated through oxidation by CO 2. In this way, the Ni-O phases participate in the catalytic process, acting as an intermediate in addition to the previously reported Ni-C phases. We also reveal the carbon phobic property of the Ni-O phases, which links to the intrinsic coking resistance of the catalysts. The low dynamic coverage of surface oxygen at higher temperatures (>900 K) is inferred to be an underlying factor causing carbon aggregation. Therefore solutions based on Ni-O stabilization are proposed in developing coking resisting catalysts.« less

  2. Antiferromagnetic defect structure in LaNi O3 -δ single crystals

    NASA Astrophysics Data System (ADS)

    Wang, Bi-Xia; Rosenkranz, S.; Rui, X.; Zhang, Junjie; Ye, F.; Zheng, H.; Klie, R. F.; Mitchell, J. F.; Phelan, D.

    2018-06-01

    The origins of the metal-insulator and magnetic transitions exhibited by perovskite rare-earth nickelates, RNiO3 (where R is a rare-earth element), remain open issues, with charge disproportionation, magnetic interactions, and lattice response across multiple length scales being among the many possible origins. Recently, growth of single crystals of LaNiO3, which is the only member of these compounds that remains metallic in its ground state, has been reported, opening a new chapter in the investigation of the perovskite nickelates. Here, using a combination of magnetometry, heat capacity, and neutron scattering on as-grown and purposely reduced LaNi O3 -δ crystals, we show that both antiferromagnetic and ferromagnetic phases with a Néel temperature of ˜152 K and a Curie temperature of ˜225 K can be induced by reduction of the oxygen content. Transmission electron microscopy shows that these phases are characterized by ordered oxygen vacancy defect structures that exist as dilute secondary phases in as-grown crystals despite growth in partial oxygen pressures up to at least 130 bar. The demonstration of antiferromagnetism resulting from oxygen vacancy ordered structures implies that stoichiometry must be explicitly considered when interpreting the bulk properties of LaNi O3 -δ single crystals; accordingly, the implications of our results for putative oxygen-stoichiometric LaNiO3 are discussed.

  3. Synthesis, characterization and physicochemical studies of new chelating resin 1, 8-(3, 6-dithiaoctyl)-4-polyvinylbenzenesulphonate (dpvbs) and its metallopolymer Cu(II), Ni(II), Co(II) and Fe(III) complexes

    NASA Astrophysics Data System (ADS)

    Khalil, Tarek E.; Elbadawy, Hemmat A.; El-Dissouky, Ali

    2018-02-01

    A new chelating resin, 1,8-(3,6-dithiaoctyl)-4-polyvinylbenzenesulphonate (dpvbs) has been synthesized by coupling Amberlite XAD-16 with (2,2‧-ethylenedithio) diethanol using pyridine/CH2Cl2 mixture as a solvent. The chelating resin and its metallopolymer Cu(II), Ni(II), Co(II) and Fe(III) complexes have been synthesized and characterized by EDS, SEM, XPS, elemental analysis, spectral (IR, UV/Vis, EPR). The thermal analysis of the resin and its metallopolymer complexes indicated an endothermic spontaneous sorption mechanism with the liberation of water of hydration of the metal ions and that adsorbed by the free resin. At the solid liquid interface, the degrees of freedom increased during the sorption of the metal ions onto the resin. The surface area of polymer support and its metallopolymer complexes are estimated by (BJH) method. The batch equilibrium method was used for studying the metal sorption and selectivity at different pH values and different contact times at room temperature. ICP-AES was used to estimate the metal capacity of the resin for sorption of Cu(II), Ni(II), Co(II) and Fe(III) from aqueous solutions utilizing the batch equilibrium method. The sorption tendency of the metal ions by the resin was found to be: Cu(II) > Fe(III) > Co(II) > Ni(II). Adsorption kinetics was found to be fit the pseudo-second order model.

  4. Metastable phase equilibria in co-deposited Ni(1-x)Zr(x) thin films

    NASA Astrophysics Data System (ADS)

    Rubin, J. B.; Schwarz, R. B.

    We determine the glass forming range (GFR) of co-deposited Ni(1-x)Zr(x) (0 less than x less than 1) thin films by measuring their electrical resistance during in situ constant-heating-rate anneals. The measured GFR is continuous for 0.10 less than x less than 0.87. We calculate the GFR of Ni-Zr melts as a function of composition and cooling rate using homogeneous nucleation theory and a published CALPHAD-type thermodynamic modeling of the equilibrium phase diagram. Assuming that the main competition to the retention of the amorphous structure during the cooling of the liquid comes from the partitionless crystallization of the terminal solid solutions, we calculate that for dT/dt = 10(exp 12) K/s, the GFR extends to x = 0.05 and x = 0.96. Better agreement with the measured values is obtained assuming a lower effective cooling rate during the condensation of the films.

  5. Spatiotemporal change of intraseasonal oscillation intensity over the tropical Indo-Pacific Ocean associated with El Niño and La Niña events

    NASA Astrophysics Data System (ADS)

    Wu, Renguang; Song, Lei

    2018-02-01

    The present study analyzes the intraseasonal oscillation (ISO) intensity change over the tropical Indo-Pacific associated with the El Niño-Southern Oscillation (ENSO) and compares the intensity change between El Niño and La Niña years and between the 10-20-day and 30-60-day ISOs. The ISO intensity change tends to be opposite between El Niño and La Niña years in the developing and mature phases. The intensity change features a contrast between the tropical southeastern Indian Ocean and the tropical western North Pacific (WNP) in the developing phases and between the Maritime Continent and the tropical central Pacific in the mature phase. In the decaying phases, the intensity change shows notable differences between El Niño and La Niña events and between fast and slow decaying El Niño events. Large intensity change is observed over the tropical WNP in the developing summer, over the tropical southeastern Indian Ocean in the developing fall, and over the tropical WNP in the fast decaying El Niño summer due to a combined effect of vertical shear, vertical motion, and lower-level moisture. In the ENSO developing summer and in the El Niño decaying summer, the 10-20-day ISO intensity change displays a northwest-southeast tilted distribution over the tropical WNP, whereas the large 30-60-day ISO intensity change is confined to the off-equatorial WNP. In the La Niña decaying summer, the 30-60-day ISO intensity change features a large zonal contrast across the Philippines, whereas the 10-20-day ISO intensity anomaly is characterized by a north-south contrast over the tropical WNP.

  6. Magnetic characteristics of M2FeV3O11 (M = Mg, Zn, Pb, Co, Ni) compounds

    NASA Astrophysics Data System (ADS)

    Groń, T.; Blonska-Tabero, A.; Filipek, E.; Stokłosa, Z.; Duda, H.; Sawicki, B.

    2018-02-01

    The unusual physical characteristics of the multicomponent oxide systems renewed the interest as the potential cathode materials in high-energy cells. Since the earlier magnetic characteristics were not entirely conclusive, we report the results of dc magnetic measurements including higher harmonics of ac magnetic susceptibility of the M2FeV3O11 (M = Mg, Zn, Pb, Co, Ni) compounds. Ferrimagnetic long-range and antiferromagnetic short-range interactions for all compounds under study at low temperatures as well as superparamagnetic-like behavior with the blocking temperature of 29 K and the freezing parameter of 0.013 were observed. These effects are discussed within the framework of superexchange and double exchange magnetic interactions as well as the mixed valence band of iron ions.

  7. A Trinuclear Ni(II) Enediolate Complex: Synthesis, Characterization, and O2 Reactivity

    PubMed Central

    Arif, Atta M.; Berreau, Lisa M.

    2009-01-01

    Using a new N4-donor chelate ligand having a mixture of hydrophobic phenyl and hydrogen bond donor appendages, a trinuclear Ni(II) complex of the doubly deprotonated form of 2-hydroxy-1,3-diphenylpropane-1,3-dione was isolated, characterized (X-ray crystallography, elemental analysis, UV-vis, 1H NMR, FTIR, magnetic moment measurement), and evaluated for O2 reactivity. This complex, [(6-NA-6-Ph2TPANi)2(μ-PhC(O)C(O)C(O)Ph)2Ni](ClO4)2 (4), has two terminal pseudo octahedral Ni(II) centers supported by the tetradentate chelate ligand, and a central square planar Ni(II) ion ligated by oxygen atoms of two bridging enediolate ligands. In CH3CN, 4 exhibits a deep orange/brown color and λmax = 463 nm (ε = 16,000 M-1cm-1). The room temperature magnetic moment of 4, determined by Evans method, is μeff = 5.3(2) μB. This is consistent with the presence of two non-interacting high-spin Ni(II) centers, a diamagnetic central Ni(II) ion, and an overall quintet ground state. Exposure of a CH3CN solution of 4 to O2 results in the rapid loss of the orange/brown color to give a green solution. The products identified from this reaction are [(κ3-6-NA-6-Ph2TPA)Ni(O2Ph)(H2O)]ClO4 (5), benzil (PhC(O)C(O)Ph), and CO. Identification of 5 was achieved via its independent synthesis and comparison of its 1H NMR and mass spectral features with those of the 6-NA-6-Ph2TPA-containing product generated upon reaction of 4 with O2. The independently prepared sample of 5 was characterized by X-ray crystallography, elemental analysis, UV-vis, mass spectrometry, and FTIR. The O2 reactivity of 4 has relevance to the active site chemistry of Ni(II)-containing acireductone dioxygenase (Ni(II)-ARD). PMID:18959363

  8. Three-dimensional hierarchical NiCo2O4 nanowire@Ni3S2 nanosheet core/shell arrays for flexible asymmetric supercapacitors

    NASA Astrophysics Data System (ADS)

    Liu, Bo; Kong, Dezhi; Huang, Zhi Xiang; Mo, Runwei; Wang, Ye; Han, Zhaojun; Cheng, Chuanwei; Yang, Hui Ying

    2016-05-01

    Three-dimensional (3D) hierarchical NiCo2O4@Ni3S2 core/shell arrays on Ni foam were synthesized by a facile, stepwise synthesis approach. The 3D heterogeneous NiCo2O4 nanostructure forms an interconnected web-like scaffold and serves as the core for the Ni3S2 shell. The as-prepared NiCo2O4@Ni3S2 nanowire array (NWA) electrodes exhibited excellent electrochemical performance, such as high specific areal capacitance and excellent cycling stability. The specific areal capacitance of 3.0 F cm-2 at a current density of 5 mA cm-2 is among the highest values and the only 6.7% capacitance decay after 10 000 cycles demonstrates the excellent cycling stability. A flexible asymmetric supercapacitor (ASC) was fabricated with activated carbon (AC) as the anode and the obtained NiCo2O4@Ni3S2 NWAs as the cathode. The ASC device exhibited a high energy density of 1.89 mW h cm-3 at 5.81 W cm-3 and a high power density of 56.33 W cm-3 at 0.94 mW h cm-3. As a result, the hybrid nanoarchitecture opens a new way to design high performance electrodes for electrochemical energy storage applications.Three-dimensional (3D) hierarchical NiCo2O4@Ni3S2 core/shell arrays on Ni foam were synthesized by a facile, stepwise synthesis approach. The 3D heterogeneous NiCo2O4 nanostructure forms an interconnected web-like scaffold and serves as the core for the Ni3S2 shell. The as-prepared NiCo2O4@Ni3S2 nanowire array (NWA) electrodes exhibited excellent electrochemical performance, such as high specific areal capacitance and excellent cycling stability. The specific areal capacitance of 3.0 F cm-2 at a current density of 5 mA cm-2 is among the highest values and the only 6.7% capacitance decay after 10 000 cycles demonstrates the excellent cycling stability. A flexible asymmetric supercapacitor (ASC) was fabricated with activated carbon (AC) as the anode and the obtained NiCo2O4@Ni3S2 NWAs as the cathode. The ASC device exhibited a high energy density of 1.89 mW h cm-3 at 5.81 W cm-3 and a high power

  9. C-O and O-H Bond Activation of Methanole by Lanthanum

    NASA Astrophysics Data System (ADS)

    Silva, Ruchira; Hewage, Dilrukshi; Yang, Dong-Sheng

    2012-06-01

    The interaction between methanol (CH_3OH) molecules and laser-vaporized La atoms resulted in the cleavage of C-O and O-H bonds and the formation of three major products, LaH_2O_2, LaCH_4O_2 and LaC_2H_6O_2, in a supersonic molecular beam. These products were identified by time-of-flight mass spectrometry, and their electronic spectra were obtained using mass-analyzed threshold ionization (MATI) spectroscopy. From the MATI spectra, adiabatic ionization energies of the three complexes were measured to be 40136 (5), 39366 (5) and 38685 (5) cm-1 for LaH_2O_2, LaCH_4O_2 and LaC_2H_6O_2, respectively. The ionization energies of these complexes decrease as the size of the coordinated organic fragments increases. The most active vibrational transitions of all three complexes were observed to be the M-O stretches in the ionic state. A metal-ligand bending mode with a frequency of 127 cm-1 was also observed for [LaH_2O_2]^+. However, the spectra of the other two complexes were less resolved, due to the existence of a large number of low frequency modes, which could be thermally excited even in the supersonic molecular beams, and of multiple rotational isomers formed by the free rotation of the methyl group in these systems. The electronic transitions responsible for the observed spectra were identified as ^1A_1 (C2v) ← ^2A_1 (C2v) for LaH_2O_2 and ^1A (C_1) ← ^2A (C_1) for LaCH_4O_2 and LaC_2H_6O_2.

  10. Catalytic thermal decomposition of methane to COx-free hydrogen and carbon nanotubes over MgO supported bimetallic group VIII catalysts

    NASA Astrophysics Data System (ADS)

    Awadallah, A. E.; Aboul-Enein, A. A.; El-Desouki, D. S.; Aboul-Gheit, A. K.

    2014-03-01

    Bimetallic Ni-Fe, Ni-Co and Fe-Co supported on MgO catalysts with a total metals content of 50 wt.% were evaluated for decomposition of methane to CO/CO2 free hydrogen and carbon nanomaterials. The catalytic runs were carried out at 700 °C under atmospheric pressure using fixed bed horizontal flow reactor. The materials were characterized by XRD, TEM, Raman spectroscopy, surface analysis and TGA-DTG. The data showed that the bimetallic 25% Fe-25%Co/MgO catalyst exhibited remarkable higher activity and stability up to ˜10 h time-on-stream with respect to H2 production. However, the catalytic activity and durability was greatly declined after incorporating 25%Ni to either 25%Fe or 25%Co/MgO catalysts at all time on stream. The main reason for the catalytic inhibition of Ni containing catalysts is consuming NiO during the formation of rock-salt MgxNi(1-x)O solid solution. However, the almost complete segregation of Fe2O3 and Co3O4 oxides played an important role for the high activity of the Fe-Co based catalyst. TEM images illustrate that the accumulated carbon over all catalysts are multi-walled carbon nanotubes in nature. The TG data showed that a higher yield of MWCNTs was achieved over bimetallic Fe-Co catalyst compared to the Ni-Fe or Ni-Co containing catalysts.

  11. Influence of laser power on microstructure and mechanical properties of laser welded-brazed Mg to Ni coated Ti alloys

    NASA Astrophysics Data System (ADS)

    Tan, Caiwang; Lu, Qingshuang; Chen, Bo; Song, Xiaoguo; Li, Liqun; Feng, Jicai; Wang, Yang

    2017-03-01

    AZ31B Magnesium (Mg) and Ti-6Al-4V titanium (Ti) alloys with Ni coating were joined by laser welding-brazing process using AZ92 Mg based filler. The influence of laser power on microstructure and mechanical properties were investigated. Ni coating was found to significantly promote good wetting-spreading ability of molten filler on the Ti sheet. Acceptable joints without obvious defects were obtained within a relatively wide processing window. In the process metallurgical bonding was achieved by the formation of Ti3Al phase at direct irradiation zone and Al-Ni phase followed by a layer of Mg-Al-Ni ternary compound adjacent to the fusion zone at the intermediate zone. The thickness of reaction layers increased slowly with the increasing laser power. The tensile-shear test indicated that joints produced at the laser power of 1300 W reached 2387 N fracture load, representing 88.5% joint efficiency with respect to the Mg base metal. The corresponding failure occurred in the fusion zone of the Mg base metal, while joints fractured at the interface at lower/higher laser power due to the crack or excessive intermetallic compound (IMC) formation along the interface.

  12. Fish larvae abundance and distribution in the central Gulf of California during strong environmental changes (1997 1998 El Niño and 1998 1999 La Niña)

    NASA Astrophysics Data System (ADS)

    Sánchez-Velasco, Laura; Avalos-García, Carlos; Rentería-Cano, Margarita; Shirasago, Bernardo

    2004-03-01

    The pelagic ecosystem of the Gulf of California was affected by the 1997-1998 El Niño warming event and the 1998-1999 La Niña cooling. Larval fish abundance and distribution were analyzed in the central Gulf during El Niño (November 1997 and March 1998) and La Niña (November 1998 and March 1999). Mean sea-surface temperature (SST) differed significantly between El Niño and La Niña (P < 0.05), with variations up to 4∘ C. The lowest zooplankton biomass and larval abundance were recorded during El Niño, when species with tropical-subtropical affinity dominated. The Bray-Curtis Dissimilarity Index defined two persisting station groups. The oceanic group, located south of Islas Angel de la Guarda and Tiburón, was strongly co-dominated by Benthosema panamense, Engraulis mordax, and Vinciguerria lucetia larvae in November 1997, whereas larvae of these species together with Triphoturus mexicanus, Sardinops caeruleus, and Scomber japonicus larvae co-dominated in November 1998. Abundances of these last two species were drastically reduced during El Niño. Larval Diogenichthys laternatus, B. panamense, V. lucetia, and T. mexicanus co-dominated the oceanic station group in March 1998, but were less prominent in March 1999, except for V. lucetia, which co-dominated with E. mordax larvae. This situation was associated with the peak of maximum intensity of the La Niña. The second station group, located in the vicinity of Big Islands, was dominated by B. panamense larvae in both Novembers and by E. mordax larvae in both Marches; in both cases this probably was more reflective of high larval abundance in the adjacent oceanic area than a preferential habitat in the Big Islands vicinity. Results suggest that the fish larvae abundance and distribution were altered in different ways by the environmental changes caused by the 1997-1998 El Niño and 1998-1999 La Niña.

  13. The structural characterization and H(2) sorption properties of carbon-supported Mg(1-x)Nix nanocrystallites.

    PubMed

    Bogerd, René; Adelhelm, Philipp; Meeldijk, Johannes H; de Jong, Krijn P; de Jongh, Petra E

    2009-05-20

    Magnesium (hydride) is a promising system for the reversible on-board storage of hydrogen, but suffers from slow sorption kinetics and a high thermodynamic stability of the hydride. We explored a combined approach to tackle these problems: nanosizing and carbon-supporting the magnesium, and doping it with nickel. Samples were prepared by melt infiltration with magnesium of nanoporous carbon onto which 1-12 wt% nickel nanoparticles had been predeposited. For loadings up to 15 wt% MgH2, 10-30 nm crystallites with different compositions were formed inside the porous carbon, each giving a specific H2 desorption signature. Surprisingly, higher Mg loadings resulted in more homogeneously mixed samples, which was due to the facilitated wetting of the carbon with the magnesium due to the presence of nickel. Hydrogen release temperatures close to that of Mg2NiH4 were observed for high MgH2 loadings (50 wt%) and small amounts of Ni (Mg(0.95)Ni(0.05)). The favourable H2 desorption properties could mainly be attributed to excellent kinetics due to the efficient mixing of magnesium, nickel and carbon on the nanoscale.

  14. The structural characterization and H2 sorption properties of carbon-supported Mg1-xNix nanocrystallites

    NASA Astrophysics Data System (ADS)

    Bogerd, René; Adelhelm, Philipp; Meeldijk, Johannes H.; de Jong, Krijn P.; de Jongh, Petra E.

    2009-05-01

    Magnesium (hydride) is a promising system for the reversible on-board storage of hydrogen, but suffers from slow sorption kinetics and a high thermodynamic stability of the hydride. We explored a combined approach to tackle these problems: nanosizing and carbon-supporting the magnesium, and doping it with nickel. Samples were prepared by melt infiltration with magnesium of nanoporous carbon onto which 1-12 wt% nickel nanoparticles had been predeposited. For loadings up to 15 wt% MgH2, 10-30 nm crystallites with different compositions were formed inside the porous carbon, each giving a specific H2 desorption signature. Surprisingly, higher Mg loadings resulted in more homogeneously mixed samples, which was due to the facilitated wetting of the carbon with the magnesium due to the presence of nickel. Hydrogen release temperatures close to that of Mg2NiH4 were observed for high MgH2 loadings (50 wt%) and small amounts of Ni (Mg0.95Ni0.05). The favourable H2 desorption properties could mainly be attributed to excellent kinetics due to the efficient mixing of magnesium, nickel and carbon on the nanoscale.

  15. Impact of La Niña and La Niña Modoki on Indonesia rainfall variability

    NASA Astrophysics Data System (ADS)

    Hidayat, R.; Juniarti, MD; Ma’rufah, U.

    2018-05-01

    La Niña events are indicated by cooling SST in central and eastern equatorial Pacific. While La Niña Modoki occurrences are indicated by cooling SST in central Pacific and warming SST in western and eastern equatorial Pacific. These two events are influencing rainfall variability in several regions including Indonesia. The objective of this study is to analyse the impact of La Niña and La Niña Modoki on Indonesian rainfall variability. We found the Nino 3.4 index is highly correlated (r = -0.95) with Indonesian rainfall. Positive rainfall anomalies up to 200 mm/month occurred mostly in Indonesian region during La Niña events, but in DJF several areas of Sumatera, Kalimantan and eastern Indonesia tend to have negative rainfall. During La Niña Modoki events, positive rainfall anomaly (up to 50 mm/month) occurred in Sumatera Island, Kalimantan, Java and eastern Indonesia in DJF and up to 175 mm/month occurred only in Java Island in MAM season. La Niña events have strong cooling SST in central and eastern equatorial Pacific (-1.5°C) in DJF. While La Niña Modoki events warming SST occurred in western and eastern equatorial Pacific (0.75°C) and cooling SST in central Pacific (- 0.75°C) in DJF and MAM. Walker circulation in La Niña Modoki events (on DJF and MAM) showed strong convergence in eastern Pacific, and weak convergence in western Pacific (Indonesia).

  16. Synthesis and characterization of homoleptic group 10 dithiocarbamate complexes and heteroleptic Ni(II) complexes, and the use of the homoleptic Ni(II) for the preparation of nickel sulphide nanoparticles

    NASA Astrophysics Data System (ADS)

    Bobinihi, Felicia F.; Onwudiwe, Damian C.; Hosten, Eric C.

    2018-07-01

    A series of new dithiocarbamate complexes of Ni(II), Pd(II) and Pt(II) of the form [NiL2], [PdL2] and [PtL2] (where L = N-ethyl-N-ethanoldithiocarbamate) have been synthesized and characterized by elemental analysis, FTIR, and 1H and 13C NMR spectroscopy. The nickel complex was utilized to prepare heteroleptic complexes bearing triphenylphosphino (PPh3) and isothiocyanate (sbnd NCS) or isocyanide (sbnd NC) molecules. Furthermore, the structures of the palladium complex and the heteroleptic nickel with PPh3 and NC molecules have been confirmed by X-ray diffraction. The Pd(II) complex indicated a trans arrangement with a distorted square planar geometry around the Pd atom, while the Ni(II) complex revealed a highly distorted geometry with another molecule of triphenylphosphine moiety, held by hydrogen bonding, within the crystal structure. The thermal stability studies of all the complexes conducted by using thermogravimetric analyser (TGA) showed they all have good stability above 200 °C. The nanoparticles synthesized using the homoleptic nickel complex yielded platelets of pure Heazlewoodite phase of Ni3S2 with average size of 7.60 nm. The optical properties of the nanoparticles studied by using UV-vis spectroscopy showed band gap energy of 4.0 eV (355 nm), which was a blue shift of 1.90 eV compared to the bulk and a consequence of quantum confinement effect.

  17. SK-Edge XAS And DFT Calculations on Square-Planar NiII-Thiolate Complexes: Effects of Active And Passive H-Bonding

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dey, A.; Green, K.N.; Jenkins, R.M.

    S K-edge XAS for a low-spin Ni{sup II}-thiolate complex shows a 0.2 eV shift to higher pre-edge energy but no change in Ni-S bond covalency upon H-bonding. This is different from the H-bonding effect we observed in high-spin Fe{sup III}-thiolate complexes where there is a significant decrease in Fe-S bond covalency but no change in energy due to H-bonding (Dey, A.; Okamura, T.-A.; Ueyama, N.; Hedman, B.; Hodgson, K. O.; Solomon, E. I. J. Am. Chem. Soc. 2005, 127, 12046-12053). These differences were analyzed using DFT calculations, and the results indicate that two different types of H-bonding interactions are possiblemore » in metal-thiolate systems. In the high-spin Fe{sup III}-thiolate case, the H-bonding involves a thiolate donor orbital which is also involved in bonding with the metal (active), while in the low-spin Ni{sup II}-thiolate, the orbital involved in H-bonding is nonbonding with respect to the M-S bonding (passive). The contributions of active and passive H-bonds to the reduction potential and Lewis acid properties of a metal center are evaluated.« less

  18. Controllable Fabrication of Amorphous Co-Ni Pyrophosphates for Tuning Electrochemical Performance in Supercapacitors.

    PubMed

    Chen, Chen; Zhang, Ning; He, Yulu; Liang, Bo; Ma, Renzhi; Liu, Xiaohe

    2016-09-07

    Incorporation of two transition metals offers an effective method to enhance the electrochemical performance in supercapacitors for transition metal compound based electrodes. However, such a configuration is seldom concerned in pyrophosphates. Here, amorphous phase Co-Ni pyrophosphates are fabricated as electrodes in supercapacitors. Through controllably adjusting the ratios of Co and Ni as well as the calcination temperature, the electrochemical performance can be tuned. An optimized amorphous Ni-Co pyrophosphate exhibits much higher specific capacitance than monometallic Ni and Co pyrophosphates and shows excellent cycling ability. When employing Ni-Co pyrophosphates as positive electrode and activated carbon as a negative electrode, the fabricated asymmetric supercapacitor cell exhibits favorable capacitance and cycling ability. This study provides facile methods to improve the transition metal pyrophosphate electrodes for efficient electrodes in electrochemical energy storage devices.

  19. Walker Circulation, El Niño and La Niña

    NASA Astrophysics Data System (ADS)

    Halpern, D.

    2014-12-01

    Ocean surface wind vector is likely the critical variable to predict onset, maintenance and dissipation of El Niño and La Niña. Analyses of SeaWinds and ASCAT 10-m height (called "surface") vector winds in the Atlantic, Indian and Pacific Oceans from 1°S-1°N during March 2000 - June 2011 revealed the longitudinal distribution of the surface zonal wind component associated with the Walker Circulation. In the Pacific Ocean east of 140°E and west of 85°W, the mean wind direction was westward towards the maritime continent with maximum mean zonal wind speed (- 6.5 m s-1) at 150°W; east of 85°W the mean direction was toward the convection zone over South America. Four El Niños and five La Niñas occurred from March 2000 - June 2011. In the Pacific from 150°E to 160°W, the average El Niño (La Niña) westward wind speed was 2 m s-1 (1 m s-1) smaller (larger) than normal. In the west Pacific, the variation in westward wind speeds in El Niño and La Niña conditions relative to normal conditions would be expected to substantially uplift the thermocline during El Niño compared to La Niña, which is consistent with conventional wisdom. In the east Pacific from 130°W - 100°W, average El Niño westward wind speeds were less than normal and La Niña conditions by 0.5 m s-1 and 1 m s-1, respectively. The "central" Pacific nature of the El Niños may have influenced the smaller difference between El Niño and La Niña westward wind speeds in the east Pacific compared to the west Pacific. Analyses of longitudinal distributions of thermocline depths will be discussed. Surface zonal wind speeds in the Atlantic and Indian Oceans showed no evidence of El Niño and La Niña; surface meridional winds showed an apparent response in the Indian and Pacific Oceans but not in the Atlantic Ocean. At 700-m height, the MISR zonal wind component in the Atlantic, Indian and Pacific Oceans had similar features as those at the surface, except in the east Pacific where the westward

  20. Effect of pressure on β relaxation in La60Ni15Al25 metallic glass

    NASA Astrophysics Data System (ADS)

    Xu, H. Y.; Sheng, H. W.; Li, M. Z.

    2018-03-01

    The effect of pressure on β relaxation in La60Ni15Al25 metallic glass (MG) was investigated by activation-relaxation technique in combination with molecular dynamics simulation. It is found that the β relaxation behavior and the potential energy landscape are significantly modulated by pressure. With increasing pressure, the atomic motion in β relaxation in La60Ni15Al25 MG changes from hopping-dominated to the string-like-dominated motion with increased activation energy. Moreover, while the hopping motion is gradually suppressed as pressure is increased, the cooperative rearrangements with more atoms involved but very low activation energies are significantly enhanced by pressure. It is further found that the "subbasins" in the potential energy landscape in La60Ni15Al25 MG become deeper and steeper with increasing pressure, leading to the increase of activation energy. Meanwhile, some neighboring "subbasins" merge under pressure accompanied by the disappearance of energy barriers in-between, leading to events with very low activation energies in the β relaxation. The atomic structure analysis reveals that the transformation of atomic motions in β relaxation in La60Ni15Al25 MG under pressure is strongly correlated with the decrease of pentagon-rich atomic clusters and the increase of clusters with fewer pentagons. These findings provide a new understanding of the β relaxation mechanism and some clues for tuning β relaxation in MGs.

  1. Abundances of O, Mg, S, Cr, Mn, Ti, NI and Zn from absorption lines of neutral gas in the Large Magellanic Cloud in front of R136

    NASA Astrophysics Data System (ADS)

    de Boer, K. S.; Fitzpatrick, E. L.; Savage, B. D.

    1985-11-01

    The authors have searched six high-dispersion IUE spectra of R136 for weak absorption lines of C I, O I, Mg I, Mg II, Si I, Si II, P I, Cl I, Cr II, Mn II, Fe I, Ni II, Zn II, CO and C2. The absorption detected is from neutral gas in front of the 30 Doradus H II region. For the first time abundances of Mg, Cr, Mn, Ti, Ni, and Zn are determined for an extragalactic system. The LMC abundances from the absorption lines are a factor of 2 to 3 below those of the Milky Way, in agreement with general results from emission line studies. The density and temperature of the neutral gas are estimates from the observed excitation and ionization at approximately n(H) = 300 cm-3 and T = 100K, implying a gas pressure of about 3×104cm-3K.

  2. On the amorphization behavior and hydrogenation performance of high-energy ball-milled Mg{sub 2}Ni alloys

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kou, Hongchao; Hou, Xiaojiang; Zhang, Tiebang, E-mail: tiebangzhang@nwpu.edu.cn

    2013-06-15

    Amorphous Mg{sub 2}Ni alloy was prepared by high energy ball-milling starting with polycrystalline Mg{sub 2}Ni which was prepared with the help of a metallurgy method by using a SPEX 8000D mill. The microstructural and phase structure characterization of the prepared materials was performed via scanning electron microscopy, transition electron microscope and X-ray diffraction. The thermal stabilities were investigated by differential scanning calorimetry. The apparent activation energies were determined by means of the Kissinger method. The first and second crystallization reactions take place at ∼ 255 °C and ∼ 410 °C, and the corresponding activation energy of crystallization is E{sub a1}more » = 276.9 and E{sub a2} = 382.4 kJ/mol, respectively. At 3 MPa hydrogen pressure and 250 °C, the hydrogen absorption capacities of crystalline, partially and fully amorphous Mg{sub 2}Ni alloy are 2.0 wt.%, 3.2 wt.% and 3.5 wt.% within 30 min, respectively. - Graphical Abstract: We mainly focus on the amorphization behavior of crystalline Mg{sub 2}Ni alloy in the high energy ball-milling process and the crystallization behavior of the amorphous Mg{sub 2}Ni alloy in a follow-up heating process. The relationship of milling, microstructure and hydrogenation properties is established and explained by models. - Highlights: • Amorphous Mg{sub 2}Ni has been obtained by high energy ball milling the as-cast alloy. • The amorphization behavior of polycrystalline Mg{sub 2}Ni is presented. • The crystallization behavior of the amorphous Mg{sub 2}Ni alloy is illustrated. • Establish the relationship of milling, microstructure and hydrogenation properties.« less

  3. Epitaxial Ni-Mn-Ga-Co thin films on PMN-PT substrates for multicaloric applications

    NASA Astrophysics Data System (ADS)

    Schleicher, B.; Niemann, R.; Diestel, A.; Hühne, R.; Schultz, L.; Fähler, S.

    2015-08-01

    Multicaloric stacks consisting of a magnetocaloric film on a piezoelectric substrate promise improved caloric properties as the transition temperature can be controlled by both magnetic and electric fields. We present epitaxially grown magnetocaloric Ni-Mn-Ga-Co thin films on ferroelectric Pb(Mg1/3Nb2/3)0.72Ti0.28O3 substrates. Structure and microstructure of two samples, being in the austenitic and martensitic state at room temperature, are investigated by X-ray diffraction in two- and four-circle geometry and by atomic force microscopy. In addition, high temperature magnetometry was performed on the latter sample. The combination of these methods allows separating the influence of epitaxial growth and martensitic transformation. A preferential alignment of twin boundaries is observed already in the as-deposited state, which indicates the presence of prestress, without applying an electric field to the substrate. A temperature-magnetic field phase diagram is presented, which demonstrates the inverse magnetocaloric effect of the epitaxial Ni-Mn-Ga-Co film.

  4. S K-edge XAS and DFT Calculations on Square Planar NiII-thiolate Complexes: Effects of Active and Passive H-bonding

    PubMed Central

    Dey, Abhishek; Green, Kayla N.; Jenkins, Roxanne M.; Jeffrey, Stephen P.; Darensbourg, Marcetta; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.

    2008-01-01

    S K-edge XAS for a low-spin NiII-thiolate complex shows a 0.2 eV shift to higher pre-edge energy but no change in Ni-S bond covalency upon H-bonding. This is different from the H-bonding effect we observed in high spin FeIII-thiolate complexes where there is a significant decrease in Fe-S bond covalency but no change in energy due to H-bonding (Dey, A.; Okamura, T.-A.; Ueyama, N.; Hedman, B.; Hodgson, K. O.; Solomon, E. I. J. Am. Chem. Soc.; 2005; 127, 12046-12053.). These differences were analyzed using DFT calculations and the results indicate that two different types of H-bonding interactions are possible in metal-thiolate systems. In the high-spin FeIII-thiolate case, the H-bonding involves a thiolate donor orbital which is also involved in bonding with the metal (active), while in the low-spin NiII-thiolate the orbital involved in H-bonding is non-bonding with respect to the M-S bonding (passive). The contributions of active and passive H-bonds to the reduction potential and Lewis acid properties of a metal center are evaluated. PMID:17949080

  5. Role of CeO2 promoter in NiO/α-Al2O3 catalyst for dry reforming of methane

    NASA Astrophysics Data System (ADS)

    Loc, Luu Cam; Phuong, Phan Hong; Tri, Nguyen

    2017-09-01

    A series of Ni/α-Al2O3 (NiAl) catalysts promoted by CeO2 was prepared by co-impregnation methods with content of (NiO+CeO2) being in the range of 10-30 wt%. The NiO:CeO2 weight ratio was fluctuated at 1:1, 1:2 and 1:3. Several techniques, including X-ray powder diffraction (XRD), Hydrogen temperature-programmed reduction (H2-TPR), and transmission electron microscopy (TEM) were used to investigate catalysts' physico-chemical properties. The activity of these catalysts in dry reforming of CH4 was investigated at temperature range of 550-800 °C. The results revealed that the most suitable CeO2 promoted Ni catalyst contained 20 wt% of (NiO+CeO2) and NiO:CeO2 weight ratio of 1:2. The best catalytic performance of catalyst [20(1Ni2Ce)Al] due to a better reducibility resulted in a higher amount of free small particle NiO. At 700 °C and CH4:CO2 molar ratio of 1:1, the conversion of CH4 and CO2 on the most suitable CeO2 promoted Ni catalyst reached 86% and 67%, respectively; H2 and CO selectivity of 90% and H2:CO molar ratio of 1.15 were obtained. Being similar to MgO [1], promoter CeO2 could improve catalytic activity of Ni/α-Al2O3 catalyst at a lower range of temperature. Besides, both MgO and CeO2 had a great impact on improving coke resistance of Ni catalysts. At higher temperature, the role of CeO2 as well as MgO in preventing coke formation on catalyst was clarified by temperature-programmed oxidation (TPO) technique. Coke amount formed after 30-h TOS on 20(1Ni2Ce) catalyst was found to be 22.18 mgC/gcat, being less than on non-promoted catalyst (36.75 mgC/gcat), but more than on 20(1Ni2Mg)Al one (5.25 mgC/gcat).

  6. Synthesis, characterization, antibacterial activities and carbonic anhydrase enzyme inhibitor effects of new arylsulfonylhydrazone and their Ni(II), Co(II) complexes

    NASA Astrophysics Data System (ADS)

    Özdemir, Ümmühan Özmen; Arslan, Fatma; Hamurcu, Fatma

    2010-01-01

    Ethane sulfonic acide hydrazide ( esh: CH 3CH 2SO 2NHNH 2) derivatives as 5-methylsalicyl-aldehydeethanesulfonylhydrazone ( 5msalesh), 5-methyl-2-hydroxyacetophenoneethane sulfonylhydrazone ( 5mafesh) and their Ni(II), Co(II) complexes have been synthesized for the first time. The structure of these compounds has been investigated by elemental analysis, FT-IR, 1H NMR, 13C NMR, LC/MS, UV-vis spectrophotometric method, magnetic susceptibility, thermal studies and conductivity measurements. The antibacterial activities of synthesized compounds were studied against Gram positive bacteria; Staphylococcus aureus, Bacillus subtilis, Bacillus magaterium and Gram negative bacteria; Salmonella enteritidis, Escherichia coli by using the microdilution broth method. The biological activity screening showed that ligands have more activity than complexes against the tested bacteria. The inhibition activities of these compounds on carbonic anhydrase II (CA II) have been investigated by comparing IC 50 and Ki values and it has been found that 5msalesh and its complexes have more enzyme inhibition efficiency than other compounds.

  7. H-atom addition and abstraction reactions in mixed CO, H2CO and CH3OH ices - an extended view on complex organic molecule formation

    NASA Astrophysics Data System (ADS)

    Chuang, K.-J.; Fedoseev, G.; Ioppolo, S.; van Dishoeck, E. F.; Linnartz, H.

    2016-01-01

    Complex organic molecules (COMs) have been observed not only in the hot cores surrounding low- and high-mass protostars, but also in cold dark clouds. Therefore, it is interesting to understand how such species can be formed without the presence of embedded energy sources. We present new laboratory experiments on the low-temperature solid state formation of three complex molecules - methyl formate (HC(O)OCH3), glycolaldehyde (HC(O)CH2OH) and ethylene glycol (H2C(OH)CH2OH) - through recombination of free radicals formed via H-atom addition and abstraction reactions at different stages in the CO→H2CO→CH3OH hydrogenation network at 15 K. The experiments extend previous CO hydrogenation studies and aim at resembling the physical-chemical conditions typical of the CO freeze-out stage in dark molecular clouds, when H2CO and CH3OH form by recombination of accreting CO molecules and H-atoms on ice grains. We confirm that H2CO, once formed through CO hydrogenation, not only yields CH3OH through ongoing H-atom addition reactions, but is also subject to H-atom-induced abstraction reactions, yielding CO again. In a similar way, H2CO is also formed in abstraction reactions involving CH3OH. The dominant methanol H-atom abstraction product is expected to be CH2OH, while H-atom additions to H2CO should at least partially proceed through CH3O intermediate radicals. The occurrence of H-atom abstraction reactions in ice mantles leads to more reactive intermediates (HCO, CH3O and CH2OH) than previously thought, when assuming sequential H-atom addition reactions only. This enhances the probability to form COMs through radical-radical recombination without the need of UV photolysis or cosmic rays as external triggers.

  8. Ohmic contacts to p-GaN Using Au/Ni-Mg-O Metallization

    NASA Astrophysics Data System (ADS)

    Liday, Jozef; Vogrinčič, Peter; Hotový, Ivan; Bonanni, Alberta; Sitter, Helmut; Lalinský, Tibor; Vanko, Gabriel; Řeháček, Vlastimil; Breza, Juraj; Ecke, Gernot

    2010-11-01

    Electrical characteristics and elemental depth profiles of ohmic contacts to p-GaN using Au/Ni-Mg-Ox metallization have been investigated. The objective was to examine the possibilities of increasing the charge carrier concentration in the surface region of GaN by adding Mg, thus of a p-type dopant into the Au/NiOx metallization structure. For this purpose, a Ni-Mg-Ox layer with a low concentration of Mg was deposited on p-GaN by dc reactive magnetron sputtering. The top Au layer was deposited in a similar way. The fabricated contact structures were annealed in N2. When the Ni-Mg layer in the Au/Ni-Mg-Ox/p-GaN structure was deposited in an atmosphere with a low concentration of oxygen (0.2 at%), the structure exhibited a low resistance ohmic nature. The contact resistance was lower than in the case of a Au/Ni-Ox/p-GaN structure without the Mg dopant in the metallic layer. An increase in the concentration of oxygen in the working atmosphere resulted in higher values of the contact resistance of the Au/Ni-Mg-Ox/p-GaN structure. In our opinion the ohmic nature of the contact structure is related to the existence of a metal/p-NiO/p-GaN scheme. The measured values of the contact resistance in the Au/Ni-Mg-Ox/p-GaN structure in comparison with the Au/Ni-Ox/p-GaN structure are caused by an increased charge carrier concentration in the surface region of p-GaN, which is a consequence of Mg diffusion from the Ni-Mg-Ox layer.

  9. Description and crystal structure of albrechtschraufite, MgCa4F2[UO2(CO3)3]2ṡ17-18H2O

    NASA Astrophysics Data System (ADS)

    Mereiter, Kurt

    2013-04-01

    Albrechtschraufite, MgCa4F2[UO2(CO3)3]2ṡ17-18H2O, triclinic, space group Pī, a = 13.569(2), b = 13.419(2), c = 11.622(2) Å, α = 115.82(1), β = 107.61(1), γ = 92.84(1)° (structural unit cell, not reduced), V = 1774.6(5) Å3, Z = 2, D c = 2.69 g/cm3 (for 17.5 H2O), is a mineral that was found in small amounts with schröckingerite, NaCa3F[UO2(CO3)3](SO4)ṡ10H2O, on a museum specimen of uranium ore from Joachimsthal (Jáchymov), Czech Republic. The mineral forms small grain-like subhedral crystals (≤ 0.2 mm) that resemble in appearance liebigite, Ca2[UO2(CO3)3]ṡ ~ 11H2O. 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), 2 V = 65(1)° ( λ = 589 nm), r < v weak. After qualitative tests had shown the presence of Ca, U, Mg, CO2 and H2O, 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 [UO2(CO3)3]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 MgF2(Ocarbonate)3(H2O) 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 CaFO6, CaF2O2(H2O)4, CaFO3(H2O)4 and CaO2(H2O)6 coordination polyhedra. The crystal structure is built up from MgCa3F2[UO2(CO3)3]ṡ8H2O layers parallel to (001) which are linked by Ca[UO2(CO3)3]ṡ5H2O moieties into a framework of the composition MgCa4F2[UO2(CO3)3]ṡ13H2O. Five additional water molecules are located in voids of the framework and show large displacement parameters. One of the water positions is partly vacant, leading to a

  10. Spectromicroscopy study of interfacial Co/NiO(001)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    van der Laan, Gerrit; Telling, Neil; Potenza, Alberto

    2010-09-26

    Photoemission electron microscopy (PEEM) with linearly polarized x-rays is used to determine the orientation of antiferromagnetic domains by monitoring the relative peak intensities at the 3d transition metal L{sub 2} absorption edge. In such an analysis the orientations of the x-ray polarization E and magnetization H with respect to the crystalline axes has to be taken into account. We address this problem by presenting a general expression of the angular dependence for both x-ray absorption spectroscopy and x-ray magnetic linear dichroism (XMLD) for arbitrary direction of E and H in the (001) cubic plane. In cubic symmetry the angular dependentmore » XMLD is a linear combination of two spectra with different photon energy dependence, which reduces to one spectrum when E or H is along a high-symmetry axis. The angular dependent XMLD can be separated into an isotropic term, which is symmetric along H, and an anisotropic term, which depends on the orientation of the crystal axes. The anisotropic term has maximal intensity when E and H have equal but opposite angles with respect to the [100] direction. The Ni{sup 2+} L{sub 2} edge has the peculiarity that the isotropic term vanishes, which means that the maximum in the XMLD intensity is observed not only for E {parallel} H {parallel} [100] but also for (E {parallel} [110], H {parallel} [110]). We apply the angular dependent theory to determine the spin orientation near the Co/NiO(100) interface. The PEEM images show that the ferromagnetic Co moments and antiferromagnetic NiO moments are aligned perpendicular to each other. By rotating the sample with respect to the linear x-ray polarization we furthermore find that the perpendicular coupling with the ferromagnetic Co layer at the interface causes a canting of the antiferromagnetic Ni moments. This shows that taking into account the angular dependence of the XMLD in the detailed analysis of PEEM images leads to an accurate retrieval of the spin axes of the

  11. Synthesis, structural studies and antimicrobial activity of N'-((2Z, 3E)-3-(hydroxyimino)butan-2-ylidene)-2-phenylacetohydrazide and its Co(II), Ni(II) complexes

    NASA Astrophysics Data System (ADS)

    Karadeniz, Şeyma; Ataol, Cigdem Yuksektepe; Şahin, Onur; İdil, Önder; Bati, Hümeyra

    2018-06-01

    A new aroylhydrazoneoxime, N'-((2Z, 3E)-3-(hydroxyimino)butan-2-ylidene)-2-phenylacetohydrazide ligand (LH2) and its Ni(II) and Co(II) complexes, have been synthesized and characterized by elemental and thermal analyses, IR and UV-vis spectroscopy, magnetic moment and X-ray diffraction. The antimicrobial activities of these compounds were tested by using minimal inhibitory concentration method (MIC). The ligand-containing aroylhydrazone and oxime groups and its Ni complex crystallize in the triclinic system and P 1 - space group, while its Co complex crystallizes in the monoclinic system and the C 2/c space group. X-ray results show that the ligand in the keto form is transformed into enolic form when it forms coordination. From elemental analysis data, the stoichiometry of Co(II) complex was found to be 1:2 (metal/ligand), but 1:1 for Ni(II). IR spectra indicate that the ligand acts as monoanionic NNO- tridentate and coordination takes place form through the oxime nitrogen, imine nitrogen, and enolate oxygen atoms.

  12. Design of Novel Precipitate-Strengthened Al-Co-Cr-Fe-Nb-Ni High-Entropy Superalloys

    NASA Astrophysics Data System (ADS)

    Antonov, Stoichko; Detrois, Martin; Tin, Sammy

    2018-01-01

    A series of non-equiatomic Al-Co-Cr-Fe-Nb-Ni high-entropy alloys, with varying levels of Co, Nb and Fe, were investigated in an effort to obtain microstructures similar to conventional Ni-based superalloys. Elevated levels of Co were observed to significantly decrease the solvus temperature of the γ' precipitates. Both Nb and Co in excessive concentrations promoted the formation of Laves and NiAl phases that formed either during solidification and remained undissolved during homogenization or upon high-temperature aging. Lowering the content of Nb, Co, or Fe prevented the formation of the eutectic type Laves. In addition, lowering the Co content resulted in a higher number density and volume fraction of the γ' precipitates, while increasing the Fe content led to the destabilization of the γ' precipitates. Various aging treatments were performed which led to different size distributions of the strengthening phase. Results from the microstructural characterization and hardness property assessments of these high-entropy alloys were compared to a commercial, high-strength Ni-based superalloy RR1000. Potentially, precipitation-strengthened high-entropy alloys could find applications replacing Ni-based superalloys as structural materials in power generation applications.

  13. High-temperature Friction and Wear Resistance of Ni-Co-SiC Composite Coatings

    NASA Astrophysics Data System (ADS)

    Guo, Fang; Sun, Wan-chang; Jia, Zong-wei; Liu, Xiao-jia; Dong, Ya-ru

    2018-05-01

    Ni-Co alloy and SiC micro-particles were co-deposited on 45 steel by electrodeposition for high temperature performance. The high temperature tribological characteristics were studied by use of a ball-on-disk method. The micrographs and phase structure of the Ni-Co-SiC composite coatings after high-temperature friction were observed by using a field emission scanning electron microscope(FESEM). The results reveal that the Ni-Co-SiC composite coating presents better wear resistance and lower friction coefficient at high temperature in comparison with that of Ni-Co coating and 45 steel substrate. The embedded SiC particles could strengthen the alloy coating by dispersion strengthening effect and changing the friction mechanism from adhesive wear to abrasive wear.

  14. Radiation damage buildup and dislocation evolution in Ni and equiatomic multicomponent Ni-based alloys

    NASA Astrophysics Data System (ADS)

    Levo, E.; Granberg, F.; Fridlund, C.; Nordlund, K.; Djurabekova, F.

    2017-07-01

    Single-phase multicomponent alloys of equal atomic concentrations ("equiatomic") have proven to exhibit promising mechanical and corrosion resistance properties, that are sought after in materials intended for use in hazardous environments like next-generation nuclear reactors. In this article, we investigate the damage production and dislocation mobility by simulating irradiation of elemental Ni and the alloys NiCo, NiCoCr, NiCoFe and NiFe, to assess the effect of elemental composition. We compare the defect production and the evolution of dislocation networks in the simulation cells of two different sizes, for all five studied materials. We find that the trends in defect evolution are in good agreement between the different cell sizes. The damage is generally reduced with increased alloy complexity, and the dislocation evolution is specific to each material, depending on its complexity. We show that increasing complexity of the alloys does not always lead to decreased susceptibility to damage accumulation under irradiation. We show that, for instance, the NiCo alloy behaves very similarly to Ni, while presence of Fe or Cr in the alloy even as a third component reduces the saturated level of damage substantially. Moreover, we linked the defect evolution with the dislocation transformations in the alloys. Sudden drops in defect number and large defect fluctuations from the continuous irradiation can be explained from the dislocation activity.

  15. Arrested 1,2-hydrogen migration from silicon to nickel upon oxidation of a three-coordinate Ni(I) silyl complex.

    PubMed

    Iluc, Vlad M; Hillhouse, Gregory L

    2010-09-01

    Reaction of the dimeric Ni(I) chloride complex [(dtbpe)NiCl](2) (1) with dimesitylsilyl potassium affords the three-coordinate Ni(I) silyl complex (dtbpe)Ni(SiHMes(2)) (2). Alternatively, 2 can be prepared by an oxidative-addition reaction of Mes(2)Si(H)OTf (Tf = CF(3)SO(3)) with the nickel(0) complex [(dtbpe)Ni](2)(mu-C(6)H(6)) (3), with (dtbpe)Ni(OTf) (4) formed as an easily separable byproduct. The one-electron oxidation of 2 by ferrocenium affords diamagnetic [(dtbpe)Ni(mu-H)SiMes(2)][BAr(F)(4)] (5), a Ni(II) complex formed by partial 1,2-H migration from silicon to nickel and featuring an unusual 3-center, 2-electron bonding motif between Ni, Si, and the bridging H. Complex 5 was also obtained from Mes(2)SiH(2) activation by the neopentyl complex salt [(dtbpe)Ni(CH(2)CMe(3))][BAr(F)(4)] (6) with elimination of neopentane.

  16. Hydrogen absorption properties of Mg-Ni alloys prepared by bulk mechanical alloying

    NASA Astrophysics Data System (ADS)

    Kuji, Toshiro

    2001-04-01

    The thermodynamic properties of the hydrides of Mg2-xNi (x=0-0.5) alloys produced by bulk mechanical alloying (BMA) were determined from pressure-composition (PC) isotherms for absorption over temperatures from 623 to 423 K. The vant Hoff plot for the plateau pressures of isotherms clearly indicated the existence of high and low temperature hydrides with different entropy and enthalpy for hydride formation. It was found that both the entropy and enthalpy values for the high temperature hydride were more negative than for the low temperature hydride. The phase transition temperature was 525 K for Mg2.0Ni and decreased while increasing the value of x. This allotropic transformation was well confirmed by in-situ XRD observations from RT to 673 K under hydrogen atmosphere or in vacuum.

  17. Investigation of phase stability of novel equiatomic FeCoNiCuZn based-high entropy alloy prepared by mechanical alloying

    NASA Astrophysics Data System (ADS)

    Soni, Vinay Kumar; Sanyal, S.; Sinha, S. K.

    2018-05-01

    The present work reports the structural and phase stability analysis of equiatomic FeCoNiCuZn High entropy alloy (HEA) systems prepared by mechanical alloying (MA) method. In this research effort some 1287 alloy combinations were extensively studied to arrive at most favourable combination. FeCoNiCuZn based alloy system was selected on the basis of physiochemical parameters such as enthalpy of mixing (ΔHmix), entropy of mixing (ΔSmix), atomic size difference (ΔX) and valence electron concentration (VEC) such that it fulfils the formation criteria of stable multi component high entropy alloy system. In this context, we have investigated the effect of novel alloying addition in view of microstructure and phase formation aspect. XRD plots of the MA samples shows the formation of stable solid solution with FCC (Face Cantered Cubic) after 20 hr of milling time and no indication of any amorphous or intermetallic phase formation. Our results are in good agreement with calculation and analysis done on the basis of physiochemical parameters during selection of constituent elements of HEA.

  18. Crystal Phase and Architecture Engineering of Lotus-Thalamus-Shaped Pt-Ni Anisotropic Superstructures for Highly Efficient Electrochemical Hydrogen Evolution.

    PubMed

    Zhang, Zhicheng; Liu, Guigao; Cui, Xiaoya; Chen, Bo; Zhu, Yihan; Gong, Yue; Saleem, Faisal; Xi, Shibo; Du, Yonghua; Borgna, Armando; Lai, Zhuangchai; Zhang, Qinghua; Li, Bing; Zong, Yun; Han, Yu; Gu, Lin; Zhang, Hua

    2018-06-07

    The rational design and synthesis of anisotropic 3D nanostructures with specific composition, morphology, surface structure, and crystal phase is of significant importance for their diverse applications. Here, the synthesis of well-crystalline lotus-thalamus-shaped Pt-Ni anisotropic superstructures (ASs) via a facile one-pot solvothermal method is reported. The Pt-Ni ASs with Pt-rich surface are composed of one Ni-rich "core" with face-centered cubic (fcc) phase, Ni-rich "arms" with hexagonal close-packed phase protruding from the core, and facet-selectively grown Pt-rich "lotus seeds" with fcc phase on the end surfaces of the "arms." Impressively, these unique Pt-Ni ASs exhibit superior electrocatalytic activity and stability toward the hydrogen evolution reaction under alkaline conditions compared to commercial Pt/C and previously reported electrocatalysts. The obtained overpotential is as low as 27.7 mV at current density of 10 mA cm -2 , and the turnover frequency reaches 18.63 H 2 s -1 at the overpotential of 50 mV. This work provides a new strategy for the synthesis of highly anisotropic superstructures with a spatial heterogeneity to boost their promising application in catalytic reactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Vapochromic Behaviour of M[Au(CN)2]2-Based Coordination Polymers (M = Co, Ni)

    PubMed Central

    Lefebvre, Julie; Korčok, Jasmine L.; Katz, Michael J.; Leznoff, Daniel B.

    2012-01-01

    A series of M[Au(CN)2]2(analyte)x coordination polymers (M = Co, Ni; analyte = dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), pyridine; x = 2 or 4) was prepared and characterized. Addition of analyte vapours to solid M(μ-OH2)[Au(CN)2]2 yielded visible vapochromic responses for M = Co but not M = Ni; the IR νCN spectral region changed in every case. A single crystal structure of Zn[Au(CN)2]2(DMSO)2 revealed a corrugated 2-D layer structure with cis-DMSO units. Reacting a Ni(II) salt and K[Au(CN)2] in DMSO yielded the isostructural Ni[Au(CN)2]2(DMSO)2 product. Co[Au(CN)2]2(DMSO)2 and M[Au(CN)2]2(DMF)2 (M = Co, Ni) complexes have flat 2-D square-grid layer structures with trans-bound DMSO or DMF units; they are formed via vapour absorption by solid M(μ-OH2)[Au(CN)2]2 and from DMSO or DMF solution synthesis. Co[Au(CN)2]2(pyridine)4 is generated via vapour absorption by Co(μ-OH2)[Au(CN)2]2; the analogous Ni complex is synthesized by immersion of Ni(μ-OH2)[Au(CN)2]2 in 4% aqueous pyridine. Similar immersion of Co(μ-OH2)[Au(CN)2]2 yielded Co[Au(CN)2]2(pyridine)2, which has a flat 2-D square-grid structure with trans-pyridine units. Absorption of pyridine vapour by solid Ni(μ-OH2)[Au(CN)2]2 was incomplete, generating a mixture of pyridine-bound complexes. Analyte-free Co[Au(CN)2]2 was prepared by dehydration of Co(μ-OH2)[Au(CN)2]2 at 145 °C; it has a 3-D diamondoid-type structure and absorbs DMSO, DMF and pyridine to give the same materials as by vapour absorption from the hydrate. PMID:22737031

  20. Phase equilibria in the La–Mg–Ge system at 500 °C and crystal structure of the new ternary compounds La{sub 11}Mg{sub 2}Ge{sub 7} and LaMg{sub 3−x}Ge{sub 2}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    De Negri, S., E-mail: serena.denegri@unige.it; Solokha, P.; Skrobańska, M.

    2014-10-15

    The whole 500 °C isothermal section of the La–Mg–Ge ternary system was constructed. The existence and crystal structure of three ternary compounds were confirmed: La{sub 2+x}Mg{sub 1−x}Ge{sub 2} (τ{sub 2}, P4/mbm, tP10–Mo{sub 2}FeB{sub 2}, 0≤x≤0.25), La{sub 4}Mg{sub 5}Ge{sub 6} (τ{sub 3}, Cmc2{sub 1}, oS60–Gd{sub 4}Zn{sub 5}Ge{sub 6}) and La{sub 4}Mg{sub 7}Ge{sub 6} (τ{sub 4}, C2/m, mS34, own structure type). Five novel compounds were identified and structurally characterized: La{sub 11}Mg{sub 2}Ge{sub 7} (τ{sub 1}, P4{sub 2}/ncm, tP88-8, own structure type, a=1.21338(5), c=1.57802(6) nm), LaMg{sub 3−x}Ge{sub 2} (τ{sub 5}, P3{sup ¯}1c, hP34-0.44, own structure type, x=0.407(5), a=0.78408(4), c=1.45257(7) nm), La{sub 6}Mg{sub 23}Gemore » (τ{sub 6}, Fm3{sup ¯}m, cF120–Zr{sub 6}Zn{sub 23}Si, a=1.46694(6) nm), La{sub 4}MgGe{sub 10−x} (τ{sub 7}, x=0.37(1), C2/m, mS60-1.46, own structure type, a=0.88403(8), b=0.86756(8), c=1.7709(2) nm, β=97.16°(1) and La{sub 2}MgGe{sub 6} (τ{sub 8}, Cmce, oS72–Ce{sub 2}(Ga{sub 0.1}Ge{sub 0.9}){sub 7}, a=0.8989(2), b=0.8517(2), c=2.1064(3) nm). Disordering phenomena were revealed in several La–Mg–Ge phases in terms of partially occupied sites. The crystal structures of La{sub 11}Mg{sub 2}Ge{sub 7} and LaMg{sub 3−x}Ge{sub 2} are discussed in details. The latter is a √3a×√3a×2c superstructure of the LaLi{sub 3}Sb{sub 2} structure type; the symmetry reduction scheme is shown in the Bärnighausen formalism terms. - Graphical abstract: La–Mg–Ge isothermal section at 500 °C and group–subgroup relation between the LaLi{sub 3}Sb{sub 2} (parent type) and LaMg{sub 3−x}Ge{sub 2} (derivative) structures. - Highlights: • Novel La−Mg−Ge compounds structure determination from X-ray single crystal data. • Disordering phenomena as common features of the studied germanides. • Bärnighausen formalism as a useful tool for accurate structure determination. • Full isothermal section of the

  1. Studies on solid solutions based on layered honeycomb-ordered phases P2-Na{sub 2}M{sub 2}TeO{sub 6} (M=Co, Ni, Zn)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Berthelot, Romain; Schmidt, Whitney; Sleight, A.W.

    2012-12-15

    Three complete solid solutions between the layered phases P2-Na{sub 2}M{sub 2}TeO{sub 6} (M=Co, Ni, Zn) have been prepared by conventional solid state method and investigated through X-ray diffraction, magnetism and optical measurements. All compositions are characterized by a M{sup 2+}/X{sup 6+} honeycomb ordering within the slabs and crystallize in a hexagonal unit cell. However, a structural transition based on a different stacking is observed as nickel (space group P6{sub 3}/mcm) is substituted by zinc or cobalt (space group P6{sub 3}22). All compositions exhibit a paramagnetic Curie-Weiss behavior at high temperatures; and the magnetic moment values confirm the presence of Ni{supmore » 2+} and/or Co{sup 2+} cations. The low-temperature antiferromagnetic order of Na{sub 2}Ni{sub 2}TeO{sub 6} and Na{sub 2}Co{sub 2}TeO{sub 6} is suppressed by zinc substitution. The color of the obtained compositions varies from pink, to light green and white when M=Co, Ni, Zn, respectively. - Graphical abstract: The comparison between the structure of Na{sub 2}Ni{sub 2}TeO{sub 6} (left) and Na{sub 2}M{sub 2}TeO{sub 6} (M=Co, Zn) (right) evidences the stacking difference with distinct atom sequences along the hexagonal c-axis. Highlights: Black-Right-Pointing-Pointer Solid solutions between lamellar phases Na{sub 2}M{sub 2}TeO{sub 6} (M=Co, Ni, Zn) are investigated. Black-Right-Pointing-Pointer A M{sup 2+}/X{sup 6+} honeycomb ordering characterized all the compositions. Black-Right-Pointing-Pointer A structural transition is shown when Ni is replaced by Co or Zn. Black-Right-Pointing-Pointer The low-temperature AFM ordering of Na{sub 2}Ni{sub 2}TeO{sub 6} and Na{sub 2}Co{sub 2}TeO{sub 6} is suppressed by zinc substitution. Black-Right-Pointing-Pointer Color changes from pink to light green and white when M=Co, Ni, Zn, respectively.« less

  2. Tape Casting of High-Performance Low-Temperature Solid Oxide Cells with Thin La0.8Sr0.2Ga0.8Mg0.2O3-δ Electrolytes and Impregnated Nano Anodes.

    PubMed

    Gao, Zhan; Wang, Hongqian; Miller, Elizabeth; Liu, Qinyuan; Senn, Daniel; Barnett, Scott

    2017-03-01

    Low-temperature solid oxide cells (LT-SOCs), operating at 400 to 650 °C, have great potential for commercialization since they can provide lower cost and improved long-term durability. Low operating temperature can also enable high round-trip efficiency of SOCs as reversible energy storage devices. This paper describes Sr 0.8 La 0.2 TiO 3-α (SLT) anode supported LT-SOC with thin La 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 3-δ (LSGM) electrolyte made by tape casting, with screen printed La 0.6 Sr 0.4 Fe 0.8 Co 0.2 O 3-δ (LSCF) cathode and impregnated Ni anode. Optimization of the anode functional layers is described; the best anodes had 68 vol % LSGM and 12.3 vol % Ni and yielded maximum power density of 1.6 Wcm -2 with a cell area specific resistance (ASR) of 0.21 Ωcm 2 at 650 °C. Most of the cell ASR was associated with the cathode. Reversible electrolysis and fuel cell operation yielded similar characteristics with both 50% H 2 -50% H 2 O and syngas fuel. Life testing over 500 h showed that the cathode impedance stabilized after an initial break-in period; the ohmic and anode resistances, though relatively small, increased slightly with time.

  3. Antimicrobial, spectral, magnetic and thermal studies of Cu(II), Ni(II), Co(II), UO(2)(VI) and Fe(III) complexes of the Schiff base derived from oxalylhydrazide.

    PubMed

    Melha, Khlood Abou

    2008-04-01

    The Schiff base ligand, oxalyl [( 2 - hydroxybenzylidene) hydrazone] [corrected].H(2)L, and its Cu(II), Ni(II), Co(II), UO(2)(VI) and Fe(III) complexes were prepared and tested as antibacterial agents. The Schiff base acts as a dibasic tetra- or hexadentate ligand with metal cations in molar ratio 1:1 or 2:1 (M:L) to yield either mono- or binuclear complexes, respectively. The ligand and its metal complexes were characterized by elemental analyses, IR, (1)H NMR, Mass, and UV-Visible spectra and the magnetic moments and electrical conductance of the complexes were also determined. For binuclear complexes, the magnetic moments are quite low compared to the calculated value for two metal ions complexes and this shows antiferromagnetic interactions between the two adjacent metal ions. The ligand and its metal complexes were tested against a Gram + ve bacteria (Staphylococcus aureus), a Gram -ve bacteria (Escherichia coli), and a fungi (Candida albicans). The tested compounds exhibited high antibacterial activities.

  4. Antiferromagnetic defect structure in LaNi O 3 – δ single crystals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wang, Bi -Xia; Rosenkranz, Stephan; Rui, X.

    Here, the origins of the metal-insulator and magnetic transitions exhibited by perovskite rare-earth nickelates, RNiO 3 (where R is a rare-earth element), remain open issues, with charge disproportionation, magnetic interactions, and lattice response across multiple length scales being among the many possible origins. Recently, growth of single crystals of LaNiO 3, which is the only member of these compounds that remains metallic in its ground state, has been reported, opening a new chapter in the investigation of the perovskite nickelates. Here, using a combination of magnetometry, heat capacity, and neutron scattering on as-grown and purposely reduced LaNiO 3–δ crystals, wemore » show that both antiferromagnetic and ferromagnetic phases with a Néel temperature of ~152 K and a Curie temperature of ~225 K can be induced by reduction of the oxygen content. Transmission electron microscopy shows that these phases are characterized by ordered oxygen vacancy defect structures that exist as dilute secondary phases in as-grown crystals despite growth in partial oxygen pressures up to at least 130 bar. The demonstration of antiferromagnetism resulting from oxygen vacancy ordered structures implies that stoichiometry must be explicitly considered when interpreting the bulk properties of LaNiO 3–δ single crystals; accordingly, the implications of our results for putative oxygen-stoichiometric LaNiO 3 are discussed.« less

  5. Antiferromagnetic defect structure in LaNi O 3 – δ single crystals

    DOE PAGES

    Wang, Bi -Xia; Rosenkranz, Stephan; Rui, X.; ...

    2018-06-12

    Here, the origins of the metal-insulator and magnetic transitions exhibited by perovskite rare-earth nickelates, RNiO 3 (where R is a rare-earth element), remain open issues, with charge disproportionation, magnetic interactions, and lattice response across multiple length scales being among the many possible origins. Recently, growth of single crystals of LaNiO 3, which is the only member of these compounds that remains metallic in its ground state, has been reported, opening a new chapter in the investigation of the perovskite nickelates. Here, using a combination of magnetometry, heat capacity, and neutron scattering on as-grown and purposely reduced LaNiO 3–δ crystals, wemore » show that both antiferromagnetic and ferromagnetic phases with a Néel temperature of ~152 K and a Curie temperature of ~225 K can be induced by reduction of the oxygen content. Transmission electron microscopy shows that these phases are characterized by ordered oxygen vacancy defect structures that exist as dilute secondary phases in as-grown crystals despite growth in partial oxygen pressures up to at least 130 bar. The demonstration of antiferromagnetism resulting from oxygen vacancy ordered structures implies that stoichiometry must be explicitly considered when interpreting the bulk properties of LaNiO 3–δ single crystals; accordingly, the implications of our results for putative oxygen-stoichiometric LaNiO 3 are discussed.« less

  6. Assessment of heavy metal contamination in sediment at Sukinda ultramafic complex using HAADF-STEM analysis.

    PubMed

    Equeenuddin, Sk Md; Pattnaik, Binaya Kumar

    2017-10-01

    The Sukinda ultramafic complex in Odisha has the largest chromite reserve in India. Sediment derived from ultramafic rocks has been enriched with various metals. Further, mining activities enhance the influx of metals into sediment by dumping mine overburden and tailings in the open area. Metal concentration in sediment is found in order of Cr Total (Cr) > Mn > Ni > Co > Zn > Cu with average concentration 26,778 mg/kg, 3098 mg/kg, 1813 mg/kg, 184 mg/kg, 116 mg/kg and 44 mg/kg respectively. Concentration of Cr(VI) varies from 5.25 to 26.47 mg/L with an average of 12.27 mg/L. Based on various pollution indices, it is confirmed that the area is severely contaminated. Nano-scale goethite, kaolinite, clinochlore and chromite have been identified and have high concentration of Cr, Co and Ni. Goethite has shown maximum metal retention potential as deciphered by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The HAADF-STEM mapping and principal component analysis indicate that Cr and Co mostly derived from chromite whereas Ni and Zn are derived from serpentine. Later, these metals co-precipitate and/or adsorbed onto the goethite and clay minerals. Fractionation study of metals confirms that Cu is the most mobile element followed by Zn. However, at low pH condition Ni is mobilized and likely to be bioavailable. Though Cr mostly occurs in residual fraction but as its concentration is very high, a small proportion of exchangeable fraction contributes significantly in terms of its bioavailability. Thus bioavailable Cr can pose severe threat to the environment in the Sukinda ultramafic complex. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Investigation on microstructure characterization and property of rapidly solidified Mg-Zn-Ca-Ce-La alloys

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhou Tao, E-mail: tzhou1118@163.com; Chen Zhenhua, E-mail: chenzhenhua45@hotmail.com; Yang Mingbo, E-mail: yangmingbo@cqit.edu.cn

    2012-01-15

    Rapidly solidified (RS) Mg-Zn-Ca-Ce-La (wt.%) alloys have been produced via atomizing the alloy melt and subsequent splat-quenching on the water-cooled copper twin-rollers in the form of flakes. Microstructure characterization, phase compositions and thermal stability of the alloys have been systematically investigated. The results showed that with addition of RE (Ce and La) to the Mg-6Zn-5Ca alloy, the stable intermetallic compounds i.e. the Mg{sub x}Zn{sub y}RE{sub z} phase with a few Ca (about 3 at.%), shortened as the T Prime phase, were formed at the expense of the binary Mg-Zn and Ca{sub 2}Mg{sub 6}Zn{sub 3} phases, which was possibly beneficial tomore » the enhanced thermal stability of the alloy. In the Mg-6Zn-5Ca-3Ce-0.5La alloy, the composition of the T Prime phase in the grain interior was different from that at the grain boundaries, in which the segregation of the La elements was found, and the atomic percentage ratio of Zn to Ce in the T Prime phase within the grains was close to 2. Moreover, the stable Mg{sub 2}Ca phases were detected around the T Prime phases at the grain boundaries in the alloy. - Research Highlights: Black-Right-Pointing-Pointer The phase constitution of RS Mg-6Zn-5Ca alloy can be improved by RE additions. Black-Right-Pointing-Pointer In the Mg-Zn-Ca-Ce-La alloys, the Mg{sub x}Zn{sub y}RE{sub z} phase with a few Ca (T Prime phase) is formed. Black-Right-Pointing-Pointer The formation of the T Prime phase leads to the loss of the Mg-Zn and Ca{sub 2}Mg{sub 6}Zn{sub 3} phases. Black-Right-Pointing-Pointer The composition of the T Prime phase differs from the grain interior to the grain boundary.« less

  8. Synthesis and catalytic activity of electrospun NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation

    NASA Astrophysics Data System (ADS)

    Kim, Il Hee; Lee, Hyerim; Yu, Areum; Jeong, Jae Hwan; Lee, Youngmi; Kim, Myung Hwa; Lee, Chongmok; Dok Kim, Young

    2018-04-01

    NiO/NiCo2O4 nanotubes with a diameter of approximately 100 nm are synthesized using Ni and Co precursors via electro-spinning and subsequent calcination processes. The tubular structure is confirmed via transmission electron microscopy imaging, whereas the structures and elemental compositions of the nanotubes are determined using x-ray diffraction, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy. N2 adsorption isotherm data reveal that the surface of the nanotubes consists of micropores, thereby resulting in a significantly higher surface area (˜20 m2 g-1) than expected for a flat-surface structure (<15 m2 g-1). Herein, we present a study of the catalytic activity of our novel NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation. The catalytic activity of NiO/NiCo2O4 is superior to Pt below 100 °C for CO oxidation. For acetaldehyde oxidation, the total oxidation activity of NiO/NiCo2O4 for acetaldehyde is comparable with that of Pt. Coexistence of many under-coordinated Co and Ni active sites in our structure is suggested be related to the high catalytic activity. It is suggested that our novel NiO/NiCo2O4 tubular structures with surface microporosity can be of interest for a variety of applications, including the catalytic oxidation of harmful gases.

  9. Synthesis and catalytic activity of electrospun NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation.

    PubMed

    Kim, Il Hee; Lee, Hyerim; Yu, Areum; Jeong, Jae Hwan; Lee, Youngmi; Kim, Myung Hwa; Lee, Chongmok; Kim, Young Dok

    2018-04-27

    NiO/NiCo 2 O 4 nanotubes with a diameter of approximately 100 nm are synthesized using Ni and Co precursors via electro-spinning and subsequent calcination processes. The tubular structure is confirmed via transmission electron microscopy imaging, whereas the structures and elemental compositions of the nanotubes are determined using x-ray diffraction, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy. N 2 adsorption isotherm data reveal that the surface of the nanotubes consists of micropores, thereby resulting in a significantly higher surface area (∼20 m 2 g -1 ) than expected for a flat-surface structure (<15 m 2 g -1 ). Herein, we present a study of the catalytic activity of our novel NiO/NiCo 2 O 4 nanotubes for CO and acetaldehyde oxidation. The catalytic activity of NiO/NiCo 2 O 4 is superior to Pt below 100 °C for CO oxidation. For acetaldehyde oxidation, the total oxidation activity of NiO/NiCo 2 O 4 for acetaldehyde is comparable with that of Pt. Coexistence of many under-coordinated Co and Ni active sites in our structure is suggested be related to the high catalytic activity. It is suggested that our novel NiO/NiCo 2 O 4 tubular structures with surface microporosity can be of interest for a variety of applications, including the catalytic oxidation of harmful gases.

  10. Isolation and Characterization of FORMATE/NI(CYCLAM)^{2+} Complexes with Cryogenic Ion Vibrational Predissociation

    NASA Astrophysics Data System (ADS)

    Wolk, Arron B.; Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Mark A.

    2013-06-01

    Transition metal-based organometallic catalysts are a promising means of converting CO_{2} to transportable fuels. Ni(cyclam)^{2+}(cyclam = 1,4,8,11-tetraazacyclotetradecane), a Ni^{II} complex ligated by four nitrogen centers, has shown promise as a catalyst selective for CO_{2} reduction in aqueous solutions. The cyclam ligand has four NH hydrogen bond donors that can adopt five conformations, each offering distinct binding motifs for coordination of CO_{2} close to the metal center. To probe the ligand conformation and the role of hydrogen bonding in adduct binding, we extract Ni(cyclam)^{2+} complexes with the formate anion and some of its analogs from solution using electrospray ionization, and characterize their structures using cryogenic ion vibrational predissociation spectroscopy. Using the signature vibrational features of the embedded carboxylate anion and the NH groups as reporters, we compare the binding motifs of oxalate, benzoate, and formate anions to the Ni(cyclam)^{2+} framework. Finally, we comment on possible routes to generate the singly charged Ni(cyclam)^{+} complex, a key intermediate that has been invoked in the catalytic CO_{2} reduction cycle, but has never been isolated through ion processing techniques.

  11. Association studies to transporting proteins of fac-ReI(CO)3(pterin)(H2O) complex.

    PubMed

    Ragone, Fabricio; Saavedra, Héctor H Martínez; García, Pablo F; Wolcan, Ezequiel; Argüello, Gerardo A; Ruiz, Gustavo T

    2017-01-01

    A new synthetic route to acquire the water soluble complex fac-Re I (CO) 3 (pterin)(H 2 O) was carried out in aqueous solution. The complex has been obtained with success via the fac-[Re I (CO) 3 (H 2 O) 3 ]Cl precursor complex. Re I (CO) 3 (pterin)(H 2 O) has been found to bind strongly with bovine and human serum albumins (BSA and HSA) with intrinsic-binding constants, K b , of 6.5 × 10 5 M -1 and 5.6 × 10 5 M -1 at 310 K, respectively. The interactions of serum albumins with Re I (CO) 3 (pterin)(H 2 O) were evaluated employing UV-vis fluorescence and absorption spectroscopy and circular dichroism. The results suggest that the serum albumins-Re I (CO) 3 (pterin)(H 2 O) interactions occurred in the domain IIA-binding pocket without loss of helical stability of the proteins. The comparison of the fluorescence quenching of BSA and HSA due to the binding to the Re(I) complex suggested that local interaction around the Trp 214 residue had taken place. The analysis of the thermodynamic parameters ΔG 0 , ΔH 0 , and ΔS 0 indicated that the hydrophobic interactions played a major role in both HSA-Re(I) and BSA-Re(I) association processes. All these experimental results suggest that these proteins can be considered as good carriers for transportation of Re I (CO) 3 (pterin)(H 2 O) complex. This is of significant importance in relation to the use of this Re(I) complex in several biomedical fields, such as photodynamic therapy and radiopharmacy.

  12. Thermophysical properties of Ni-containing single-phase concentrated solid solution alloys

    DOE PAGES

    Jin, Ke; Mu, Sai; An, Ke; ...

    2016-12-27

    For this research temperature dependent thermophysical properties, including specific heat capacity, lattice thermal expansion, thermal diffusivity and conductivity, have been systematically studied in Ni and eight Ni-containing single-phase face-centered-cubic concentrated solid solution alloys, at elevated temperatures up to 1273 K. The alloys have similar specific heat values of 0.4–0.5 J·g -1·K -1 at room temperature, but their temperature dependence varies greatly due to Curie and K-state transitions. The lattice, electronic, and magnetic contributions to the specific heat have been separated based on first-principles methods in NiCo, NiFe, Ni-20Cr and NiCoFeCr. The alloys have similar thermal expansion behavior, with the exceptionmore » that NiFe and NiCoFe have much lower thermal expansion coefficient in their ferromagnetic state due to magnetostriction effects. Calculations based on the quasi-harmonic approximation accurately predict the temperature dependent lattice parameter of NiCo and NiFe with < 0.2% error, but underestimated that of Ni-20Cr by 1%, compared to the values determined from neutron diffraction. In addition, all the alloys containing Cr have very similar thermal conductivity, which is much lower than that of Ni and the alloys without Cr, due to the large magnetic disorder.« less

  13. Metal-insulator transition, giant negative magnetoresistance, and ferromagnetism in LaCo1-yNiyO3

    NASA Astrophysics Data System (ADS)

    Hammer, D.; Wu, J.; Leighton, C.

    2004-04-01

    We have investigated the transport and magnetic properties of the perovskite LaCo1-yNiyO3, an alloy of LaCoO3 (a semiconductor that exhibits spin-state transitions) and LaNiO3 (a paramagnetic metal). The metal-insulator transition (MIT) was found to occur at y=0.40. On the insulating side of the transition the conductivity obeys Mott variable range hopping with a characteristic temperature (T0) that varies with y in a manner consistent with the predictions of the scaling theory of electron localization. On the metallic side the low temperature conductivity (down to 0.35 K) varies as T1/2 due to the effects of electron-electron interaction in the presence of disorder. The composition dependence of the low-temperature conductivity in the critical region fits the scaling theory of electron localization with a conductivity critical exponent close to unity, consistent with the scaling of T0 in the insulating phase. A large negative magnetoresistance is observed (up to 70% in 17 T) which increases monotonically with decreasing temperature and is smoothly decreased through the MIT. The magnetic properties show that doping LaCoO3 with Ni leads to a rapid destruction of the low spin-state for Co3+ ions, followed by the onset of distinct ferromagnetic interactions at higher Ni content. Similar to La1-xSrxCoO3, the system shows a smooth evolution from spin-glass to ferromagnetic ground states, which is interpreted in terms of the formation of ferromagnetic clusters. In contrast to La1-xSrxCoO3 further doping does not lead to a bulk ferromagnetlike state with a large TC, despite the clear existence of ferromagnetic interactions. We suggest that this is due to a limitation of the strength of the ferromagnetic interactions, which could be related to the fact that Ni rich clusters are not thermodynamically stable. The ferromagnetic clusters in LaCo1-yNiyO3 do not percolate with increasing y explaining the lack of a high-TC ferromagnetic state and the fact that the MIT is a simple

  14. Ionic liquid ultrasound-assisted dispersive liquid-liquid microextraction based on solidification of the aqueous phase for preconcentration of heavy metals ions prior to determination by LC-UV.

    PubMed

    Werner, Justyna

    2018-05-15

    Ionic liquid ultrasound-assisted dispersive liquid-liquid microextraction based on solidification of the aqueous phase was used for preconcentration of Ni 2+ , Co 2+ , Cd 2+ , Cu 2+ , Pb 2+ in natural water samples prior to liquid chromatography with UV detection. In the proposed method, the ammonium pyrrolidinedithiocarbamate was used as a complexing agent and the phosphonium ionic liquid trihexyl(tetradecyl)phosphonium bis[(2,4,4-trimethyl)pentyl]phosphinate (Cyphos IL 104) was used as an extractant. Ultrasound energy was used to disperse the extractant in the aqueous phase. After microextraction, the ionic liquid and aqueous phases were separated by centrifugation. Then the aqueous phase was frozen and the lighter than water ionic liquid phase containing metal ions complexes with pyrrolidinedithiocarbamate was separated and dissolved in a small volume of methanol prior to injection into the liquid chromatograph. Several parameters including the volume of extractant, the pH of the sample, the concentration of complexing agent, the time of ultrasound energy treatment, the time and speed of centrifugation and the effect of ionic strength were optimized. Under the optimized conditions (10 µL of Cyphos IL 104, pH = 5, 0.3% w/v ammonium pyrrolidinedithiocarbamate, 60 s of ultrasound use, 5 min/5000 rpm (2516×g) of centrifugation, 2.0 mg of NaCl), preconcentration factors were 211, 210, 209, 207 and 211 for Ni 2+ , Co 2+ , Cd 2+ , Cu 2+ and Pb 2+ respectively. Linearity was observed in the ranges 0.2-75.0 µg L -1 for Pb 2+ , Cd 2+ , Co 2+ and 0.5-100.0 µg L -1 for Cu 2+ , Ni 2+ . The limits of detection were 0.03 µg L -1 for Ni 2+ , 0.03 µg L -1 for Co 2+ , 0.03 µg L -1 for Cd 2+ , 0.02 µg L -1 for Cu 2+ , 0.02 µg L -1 for Pb 2+ , respectively. The accuracy of this method was evaluated by preconcentration and determination of Ni 2+ , Co 2+ , Cd 2+ , Cu 2+ , Pb 2+ in certified reference materials (TMRAIN-04 and NIST 1643e

  15. Linear energy relationships for the octahedral preference of Mg, Ca and transition metal ions.

    PubMed

    Pontikis, George; Borden, James; Martínek, Václav; Florián, Jan

    2009-04-16

    The geometry, atomic charges, force constants, and relative energies of the symmetric and distorted M(2+)(H(2)O)(4)(F(-))(2), M(3+)(H(2)O)(4)(F(-))(2), M(2+)(H(2)O)(3)(F(-))(2), and M(3+)(H(2)O)(3)(F(-))(2) metal complexes, M = Mg, Ca, Co, Cu, Fe, Mn, Ni, Zn, Cr, V, were calculated by using the B3LYP/TZVP density functional method in both gas phase and aqueous solution, modeled using the polarized continuum model. The deformation energy associated with moving one water ligand 12 degrees from the initial "octahedral" arrangement, in which all O-M-O, O-M-F, and F-M-F angles are either 90 degrees or 180 degrees, was calculated to examine the angular ligand flexibility. For all M(2+)(H(2)O)(4)(F(-))(2) complexes, this distortion increased the energy of the complex in proportion to the electrostatic potential-derived (ESP) charge of the metal, and in proportion to D(-10), where D is the distance from the distorted ligand to its closest neighbor. The octahedral stability was further examined by calculating the energies for the removal of a water ligand from the octahedral complex to form a square-pyramidal or trigonal-bipyramidal complex. The octahedral preference, defined as the negative of the corresponding binding energy of the ligand, was found to linearly correlate with the ESP charge of the metal in both the gas phase and aqueous solution. The obtained results indicate that quantum-mechanical covalent effects are of secondary importance for both the flexibility and the octahedral preference of M(2+)(H(2)O)(4)(F(-))(2) and M(3+)(H(2)O)(4)(F(-))(2) complexes. This conclusion and supporting data are important for the development of consistent molecular mechanical force fields of the studied metal ions.

  16. In Situ Neutron Diffraction Analyzing Stress-Induced Phase Transformation and Martensite Elasticity in [001]-Oriented Co49Ni21Ga30 Shape Memory Alloy Single Crystals

    NASA Astrophysics Data System (ADS)

    Reul, A.; Lauhoff, C.; Krooß, P.; Gutmann, M. J.; Kadletz, P. M.; Chumlyakov, Y. I.; Niendorf, T.; Schmahl, W. W.

    2018-02-01

    Recent studies demonstrated excellent pseudoelastic behavior and cyclic stability under compressive loads in [001]-oriented Co-Ni-Ga high-temperature shape memory alloys (HT-SMAs). A narrow stress hysteresis was related to suppression of detwinning at RT and low defect formation during phase transformation due to the absence of a favorable slip system. Eventually, this behavior makes Co-Ni-Ga HT-SMAs promising candidates for several industrial applications. However, deformation behavior of Co-Ni-Ga has only been studied in the range of theoretical transformation strain in depth so far. Thus, the current study focuses not only on the activity of elementary deformation mechanisms in the pseudoelastic regime up to maximum theoretical transformation strains but far beyond. It is shown that the martensite phase is able to withstand about 5% elastic strain, which significantly increases the overall deformation capability of this alloy system. In situ neutron diffraction experiments were carried out using a newly installed testing setup on Co-Ni-Ga single crystals in order to reveal the nature of the stress-strain response seen in the deformation curves up to 10% macroscopic strain.

  17. New Cu (II), Co(II) and Ni(II) complexes of chalcone derivatives: Synthesis, X-ray crystal structure, electrochemical properties and DFT computational studies

    NASA Astrophysics Data System (ADS)

    Tabti, Salima; Djedouani, Amel; Aggoun, Djouhra; Warad, Ismail; Rahmouni, Samra; Romdhane, Samir; Fouzi, Hosni

    2018-03-01

    The reaction of nickel(II), copper(II) and cobalt(II) with 4-hydroxy-3-[(2E)-3-(1H-indol-3-yl)prop-2-enoyl]-6-methyl-2H-pyran-2-one (HL) leads to a series of new complexes: Ni(L)2(NH3), Cu(L)2(DMF)2 and Co(L)2(H2O). The crystal structure of the Cu(L)2(DMF)2 complex have been determined by X-ray diffraction methods. The Cu(II) lying on an inversion centre is coordinated to six oxygen atoms forming an octahedral elongated. Additionally, the electrochemical behavior of the metal complexes were investigated by cyclic voltammetry at a glassy carbon electrode (GC) in CH3CN solutions, showing the quasi-reversible redox process ascribed to the reduction of the MII/MI couples. The X-ray single crystal structure data of the complex was matched excellently with the optimized monomer structure of the desired compound; Hirschfeld surface analysis supported the packed crystal lattice 3D network intermolecular forces. HOMO/LUMO energy level and the global reactivity descriptors quantum parameters are also calculated. The electrophilic and nucleophilic potions in the complex surface are theoretically evaluated by molecular electrostatic potential and Mulliken atomic charges analysis.

  18. Phosphine-functionalized NHC Ni(ii) and Ni(0) complexes: synthesis, characterization and catalytic properties.

    PubMed

    Rull, S G; Rama, R J; Álvarez, E; Fructos, M R; Belderrain, T R; Nicasio, M C

    2017-06-13

    Two families of nickel complexes bearing chelating diphenylphosphine-functionalized NHC ligands [Ni II (ArNHCPPh 2 )(allyl)]Cl 1a (Ar = Mes); 1b, (Ar = 2,6-iPr 2 -C 6 H 3 ) and [Ni 0 (ArNHCPPh 2 )(alkene)] 2a (Ar = 2,6-iPr 2 -C 6 H 3 , alkene = styrene); 2b (Ar = 2,6-iPr 2 -C 6 H 3 , alkene = diethyl fumarate) have been prepared and fully characterized. VT-NMR experiments in solution reveal that the allyl derivatives 1a-b are stereochemically nonrigid. The solid-state structure of the Ni 0 derivative 2b is also reported. These complexes display interesting catalytic properties in various cross-coupling reactions. The precatalyst [Ni 0 (ArNHCPPh 2 )(styrene)] 2a was found to be the most active system. The bulkiness of the N-substituent on the imidazole ring and the low oxidation state of the metal center in 2a accounted for its enhanced catalytic performance. This system catalyzed effectively the coupling of (hetero)aryl chlorides with a range of nucleophiles including Grignard reagents, boronic acids, secondary amines and indoles.

  19. Fabrication and performance of a double layered Mn-Co-Ni-O/Mn-Co-Ni-Cu-O thin film detector

    NASA Astrophysics Data System (ADS)

    Zhou, Wei; Yin, Yiming; Yao, Niangjuan; Jiang, Lin; Qu, Yue; Wu, Jing; Gao, Y. Q.; Huang, Jingguo; Huang, Zhiming

    2018-01-01

    A thermal sensitive infrared and THz detector was fabricated by a double layered Mn-Co-Ni-O/Mn-Co-Ni-Cu-O films. The Mn-Co-Ni-O material, as one type of transition metal oxides, has long been used as a candidate for thermal sensors or infrared detectors. The resistivity of a most important Mn-Co-Ni-O thin film, Mn1. 96Co0.96Ni0.48O4(MCN) , is about 200 Ω·cm at room temperature, which ranges about 2 orders larger than that of VOx detectors. Therefore, the thickness of a typical squared Mn-Co-Ni-O IR detector should be about 10 μm, which is too large for focal plane arrays applications. To reduce the resistivity of Mn-Co-Ni-O thin film, 1/6 of Co element was replaced by Cu. Meanwhile, a cover layer of MCN film was deposited onto the Mn-Co-Ni-Cu-O film to improve the long term stability. The detector fabricated by the double layered Mn-Co-Ni-O/Mn-Co-Ni-Cu-O films showed large response to blackbody and 170 GHz radiation. The NEP of the detector was estimated to be the order of 10-8 W/Hz0. 5. By applying thermal isolation structure and additional absorption materials, the detection performance can be largely improved by 1-2 orders according to numerical estimation. The double layered Mn-Co-Ni-O film detector shows great potentials in applications in large scale IR detection arrays, and broad-band imaging.

  20. Electronic and magnetic properties of Fe-, Co-, and Ni-decorated BC3: A first-principles study

    NASA Astrophysics Data System (ADS)

    Zhu, Jingzhong; Zhao, Yinchang; Zulfiqar, Muhammad; Zeng, Shuming; Ni, Jun

    2018-05-01

    The electronic and magnetic properties of Fe-, Co-, and Ni-decorated two dimensional (2D) BC3 are systematically investigated by first-principles calculations. We find that the Fe, Co, and Ni atoms can be strongly adsorbed on the hollow sites of 2D BC3. Fe and Co adatoms are more stable when adsorbed on the hollow sites of the carbon rings in the 2D BC3, while the hollow sites of boron-carbon rings in the 2D BC3 are the most stable sites for the adsorption of Ni adatoms. These proposed metal-BC3 complexes exhibit interesting electronic and magnetic behaviors. In particular, the Fe-BC3 and Co-BC3 complexes are metals with magnetic ground states , while the Ni-BC3 complex behaves as a nonmagnetic semiconductor with a direct bandgap. Furthermore, our magnetic analysis reveals that induced magnetism in the Fe-BC3 and Co-BC3 complexes arises from their local magnetic moments. Functionalization of 2D BC3 through these metal-adatom adsorption appears to be a promising way to extend its applications.

  1. The dual-function chaperone HycH improves assembly of the formate hydrogenlyase complex.

    PubMed

    Lindenstrauß, Ute; Skorupa, Philipp; McDowall, Jennifer S; Sargent, Frank; Pinske, Constanze

    2017-08-11

    The assembly of multi-protein complexes requires the concerted synthesis and maturation of its components and subsequently their co-ordinated interaction. The membrane-bound formate hydrogenlyase (FHL) complex is the primary hydrogen-producing enzyme in Escherichia coli and is composed of seven subunits mostly encoded within the hycA-I operon for [NiFe]-hydrogenase-3 (Hyd-3). The HycH protein is predicted to have an accessory function and is not part of the final structural FHL complex. In this work, a mutant strain devoid of HycH was characterised and found to have significantly reduced FHL activity due to the instability of the electron transfer subunits. HycH was shown to interact specifically with the unprocessed species of HycE, the catalytic hydrogenase subunit of the FHL complex, at different stages during the maturation and assembly of the complex. Variants of HycH were generated with the aim of identifying interacting residues and those that influence activity. The R70/71/K72, the Y79, the E81 and the Y128 variant exchanges interrupt the interaction with HycE without influencing the FHL activity. In contrast, FHL activity, but not the interaction with HycE, was negatively influenced by H37 exchanges with polar residues. Finally, a HycH Y30 variant was unstable. Surprisingly, an overlapping function between HycH with its homologous counterpart HyfJ from the operon encoding [NiFe]-hydrogenase-4 (Hyd-4) was identified and this is the first example of sharing maturation machinery components between Hyd-3 and Hyd-4 complexes. The data presented here show that HycH has a novel dual role as an assembly chaperone for a cytoplasmic [NiFe]-hydrogenase. © 2017 The Author(s). Published by Portland Press Limited on behalf of the Biochemical Society.

  2. Wear behavioral study of as cast and 7 hr homogenized Al25Mg2Si2Cu4Ni alloy at constant load

    NASA Astrophysics Data System (ADS)

    Harlapur, M. D.; Sondur, D. G.; Akkimardi, V. G.; Mallapur, D. G.

    2018-04-01

    In the current study, the wear behavior of as cast and 7 hr homogenized Al25Mg2Si2Cu4Ni alloy has been investigated. Microstructure, SEM and EDS results confirm the presence of different intermetallic and their effects on wear properties of Al25Mg2Si2Cu4Ni alloy in as cast as well as aged condition. Alloying main elements like Si, Cu, Mg and Ni partly dissolve in the primary α-Al matrix and to some amount present in the form of intermetallic phases. SEM structure of as cast alloy shows blocks of Mg2Si which is at random distributed in the aluminium matrix. Precipitates of Al2Cu in the form of Chinese script are also observed. Also `Q' phase (Al-Si-Cu-Mg) be distributed uniformly into the aluminium matrix. Few coarsened platelets of Ni are seen. In case of 7 hr homogenized samples blocks of Mg2Si get rounded at the corners, Platelets of Ni get fragmented and distributed uniformly in the aluminium matrix. Results show improved volumetric wear resistance and reduced coefficient of friction after homogenizing heat treatment.

  3. Fe (III), Co(II), Ni(II), Cu(II) and Zn(II) complexes of schiff bases based-on glycine and phenylalanine: Synthesis, magnetic/thermal properties and antimicrobial activity

    NASA Astrophysics Data System (ADS)

    Sevgi, Fatih; Bagkesici, Ugur; Kursunlu, Ahmed Nuri; Guler, Ersin

    2018-02-01

    Zinc (II), copper (II), nickel (II), cobalt (II) and iron (III) complexes of Schiff bases (LG, LP) derived from 2-hydroxynaphthaldehyde with glycine and phenylalanine were reported and characterized by 1H NMR, 13C NMR, elemental analyses, melting point, FT-IR, magnetic susceptibility and thermal analyses (TGA). TGA data show that iron and cobalt include to the coordinated water and metal:ligand ratio is 1:2 while the complex stoichiometry for Ni (II), Cu (II) and Zn (II) complexes is 1:1. As expected, Ni (II) and Zn (II) complexes are diamagnetic; Cu (II), Co (II) and Fe (III) complexes are paramagnetic character due to a strong ligand of LG and LP. The LG, LP and their metal complexes were screened for their antimicrobial activities against five Gram-positive (Staphylococcus aureus, Methicillin resistant Staphylococcus aureus (MRSA), Bacillus cereus, Streptococcus mutans and Enterococcus faecalis) and three Gram-negative (Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa) and one fungi (Candida albicans) by using broth microdilution techniques. The activity data show that ligands and their metal complexes exhibited moderate to good activity against Gram-positive bacteria and fungi.

  4. Study on immobilization of yeast alcohol dehydrogenase on nanocrystalline Ni-Co ferrites as magnetic support.

    PubMed

    Shakir, Mohammad; Nasir, Zeba; Khan, Mohd Shoeb; Lutfullah; Alam, Md Fazle; Younus, Hina; Al-Resayes, Saud Ibrahim

    2015-01-01

    The covalent binding of yeast alcohol dehydrogenase (YADH) enzyme complex in a series of magnetic crystalline Ni-Co nanoferrites, synthesized via sol-gel auto combustion technique was investigated. The structural analysis, morphology and magnetic properties of Ni-Co nanoferrites were determined by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), vibrating-sample magnetometer (VSM), high resolution transmission electron microscopy (HRTEM) and Fourier transform infrared spectroscopy (FTIR). The comparative analysis of the HRTEM micrographs of bare magnetic nanoferrite particles and particles immobilized with enzyme revealed an uniform distribution of the particles in both the cases without undergoing change in the size which was found to be in the range 20-30 nm. The binding of YADH to Ni-Co nanoferrites and the possible binding mechanism have been suggested by comparing the FTIR results. The binding properties of the immobilized YADH enzyme were also studied by kinetic parameters, optimum operational pH, temperature, thermal stability and reusability. The immobilized YADH exhibits enhanced thermal stability as compared to the free enzyme over a wide range of temperature and pH, and showed good durability after recovery by magnetic separation for repeated use. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Design, synthesis and characterization of macrocyclic ligand based transition metal complexes of Ni(II), Cu(II) and Co(II) with their antimicrobial and antioxidant evaluation

    NASA Astrophysics Data System (ADS)

    Gull, Parveez; Malik, Manzoor Ahmad; Dar, Ovas Ahmad; Hashmi, Athar Adil

    2017-04-01

    Three new complexes Ni(II), Cu(II) and Co(II) were synthesized of macrocyclic ligand derived from 1, 4-dicarbonyl-phenyl-dihydrazide and O-phthalaldehyde in the ratio of 2:2. The synthesized compounds were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, FTIR, UV-Vis., Mass and 1H NMR spectral studies. The electronic spectra of the metal complexes indicate a six coordinate octahedral geometry of the central metal ion. These metal complexes and the ligand were evaluated for antimicrobial activity against bacteria (E. coli, B. subtilis, S. aureus) and fungi (A. niger, A. flavus, C. albicans) and compared against standard drugs chloramphenicol and nystatin respectively. In addition, the antioxidant activity of the compounds was also investigated through scavenging effect on DPPH radicals.

  6. Structural properties and optical characterization of flower-like Mg doped NiO

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Allaedini, Ghazaleh, E-mail: jiny-ghazaleh@yahoo.com; Tasirin, Siti Masrinda; Aminayi, Payam

    In this study, un-doped and Mg doped NiO nanoparticles have been synthesized through a simple sol-gel method. To investigate the effect of Mg-doping on the structure of NiO, the obtained nanoparticles were characterized using scanning electron microscopy (SEM). Flower/star like morphology was clearly observed in the SEM micrographs. The BET (Brunauer-Emmett-Teller) nitrogen absorption isotherm exhibits high specific surface area (∼37 m{sup 2} /g) for the Mg doped NiO nanoparticles. X-Ray diffraction (XRD) of the prepared Mg-NiO nanoparticles showed a face-centered cubic (f.c.c) structure, and the average particle size was estimated to be 32 nm using Scherrer’s formula. Energy Dispersive X-Ray (EDX)more » confirms that the NiO particles are successfully doped with Mg. Photoluminescence (PL) and UV-Vis optical absorption characteristics of the prepared nanoparticles have also been investigated in this study. The PL emission response showed a blue shift when NiO was doped with Mg, which is indicative of interstitial oxygen. The UV-Vis results demonstrate a band gap increase as NiO nanoparticles are doped with Mg.« less

  7. Microstructure and Tribological Properties of AlCoCrFeNiTi0.5 High-Entropy Alloy in Hydrogen Peroxide Solution

    NASA Astrophysics Data System (ADS)

    Yu, Y.; Liu, W. M.; Zhang, T. B.; Li, J. S.; Wang, J.; Kou, H. C.; Li, J.

    2014-01-01

    Microstructure and tribological properties of an AlCoCrFeNiTi0.5 high-entropy alloy in high-concentration hydrogen peroxide solution were investigated in this work. The results show that the sigma phase precipitates and the content of bcc2 decrease during the annealing process. Meanwhile, the complex construction of the interdendrite region changes into simple isolated-island shape, and much more spherical precipitates are formed. Those changes of microstructure during the annealing process lead to the increase of hardness of this alloy. In the testing conditions, the AlCoCrFeNiTi0.5 alloy shows smoother worn surfaces and steadier coefficient of friction curves than does the 1Cr18Ni9Ti stainless steel, and SiC ceramic preserves better wear resistance than ZrO2 ceramic. After annealing, the wear resistance of the AlCoCrFeNiTi0.5 alloy increases coupled with SiC counterface but decreases with ZrO2 counterface.

  8. Thermodynamic Characteristics of Reactions of the Formation of Complexes between Triglycine and Ni2+ Ions in Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Gorboletova, G. G.; Metlin, A. A.; Bychkova, S. A.

    2018-05-01

    Thermal effects of reactions of the formation of complexes between Ni(II) and triglycine are determined via direct calorimetry in aqueous solutions at 298.15 K and ionic strengths of 0.2, 0.5, and 1.0 (KNO3). Standard thermodynamic characteristics (Δr H°, Δr G°, Δr S°) of complexing processes in the investigated systems are calculated. The structures of triglycinate complexes NiL+, NiH-1L, NiL2, NiH-2L2- 2, NiL- 3, and NiH-3L4- 3 are introduced to compare the obtained values and data on the thermodynamics of triglycinate complexes of Ni(II).

  9. Tuning Ni-catalyzed CO 2 hydrogenation selectivity via Ni-ceria support interactions and Ni-Fe bimetallic formation

    DOE PAGES

    Winter, Lea R.; Gomez, Elaine; Yan, Binhang; ...

    2017-10-16

    CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less

  10. Co(II), Ni(II) and Cu(II) complexes of methyl-5-(Phenylthio) benzimidazole-2-carbamate: Molecular structures, spectral and DFT calculations

    NASA Astrophysics Data System (ADS)

    Mansour, Ahmed M.; El Bakry, Eslam M.; Abdel-Ghani, Nour T.

    2016-05-01

    [Co(FBZ)2(H2O)]·2NO3·0.5H2O (1), [Ni(FBZ)2X2]·zH2O (X = Cl​-, z = 0.5 (2) and X = CH3COO-, z = 1 (3)) and [Cu(FBZ)2(H2O) (NO3)]·NO3·1.5H2O (4) (FBZ = methyl-5-(Phenylthio) benzimidazole-2-carbamate; Fenbendazole) complexes were synthesized and characterized by elemental analysis, thermal, IR, EPR, UV-Vis, magnetic and conductance measurements. Geometry optimization, molecular electrostatic potential maps and natural bond orbital analysis were carried out at DFT/B3LYP/6-31G∗ level of theory. FBZ behaves as a neutral bidentate ligand via the pyridine-type nitrogen of the benzimidazole moiety and the carbamate group. Three-step ionization with pKa values of 3.38, 4.06 and 10.07 were reported for FBZ. The coordination of FBZ to the metal ions led to an increase in the antibacterial activity against the tested Staphylococcus aureus and Escherichia coli bacteria.

  11. Influence of valence electron concentration on Laves phases: Structures and phase stability of pseudo-binary MgZn 2-xPd x

    DOE PAGES

    Thimmaiah, Srinivasa; Miller, Gordon J.

    2015-06-03

    A series of pseudo-binary compounds MgZn 2-xPd x (0.15 ≤ x ≤ 1.0) were synthesized and structurally characterized to understand the role of valence electron concentration (vec) on the prototype Laves phase MgZn 2 with Pd-substitution. Three distinctive phase regions were observed with respect to Pd content, all exhibiting fundamental Laves phase structures: 0.1 ≤ x ≤ 0.3 (MgNi 2-type, hP24; MgZn 1.80Pd 0.20(2)), 0.4 ≤ x ≤ 0.6 (MgCu 2-type, cF24; MgZn 1.59Pd 0.41(2)), and 0.62 ≤ x ≤ 0.8 (MgZn 2-type, hP12: MgZn 1.37Pd 0.63(2)). Refinements from single-crystal X-ray diffraction indicated nearly statistical distributions of Pd and Znmore » atoms among the majority atom sites in these structures. Interestingly, the MgZn 2-type structure re-emerges in MgZn 2–xPd x at x ≈ 0.7 with the refined composition MgZn 1.37(2)Pd 0.63 and a c/a ratio of 1.59 compared to 1.64 for binary MgZn 2. Electronic structure calculations on a model “MgZn 1.25Pd 0.75” yielded a density of states (DOS) curve showing enhancement of a pseudogap at the Fermi level as a result of electronic stabilization due to the Pd addition. Moreover, integrated crystal orbital Hamilton population values show significant increases of orbital interactions for (Zn,Pd)–(Zn,Pd) atom pairs within the majority atom substructure, i.e., within the Kagomé nets as well as between a Kagomé net and an apical site, from binary MgZn 2 to the ternary “MgZn 1.25Pd 0.75”. Multi-centered bonding is evident from electron localization function plots for “MgZn 1.25Pd 0.75”, an outcome which is in accordance with analysis of other Laves phases.« less

  12. Evaluation of different approaches for improving the cycle life of MgNi-based electrodes for Ni-MH batteries

    NASA Astrophysics Data System (ADS)

    Rongeat, C.; Grosjean, M.-H.; Ruggeri, S.; Dehmas, M.; Bourlot, S.; Marcotte, S.; Roué, L.

    Several methods have been investigated to enhance the cycle life of amorphous MgNi used as the negative electrode for Ni-MH batteries. The first approach involves modifying its surface composition in different ways, including the electroless deposition of a chromate conversion coating, the addition of chromate salt or NaF into the electrolyte and the mechanical coating of the particles with various compounds (e.g. TiO 2). Another approach consists of developing (MgNi + AB 5) composite materials. However, the cycle life of these modified MgNi electrodes remains unsatisfactory. On the other hand, the modification of the bulk composition of the MgNi alloy with elements such as Ti and Al appears to be more effective. For instance, a Mg 0.9Ti 0.1NiAl 0.05 electrode retains 67% of its initial discharge capacity (404 mAh g -1) after 15 cycles compared to 29% for MgNi. The charging conditions also have a great influence on the electrode cycle life as demonstrated by the existence of a charge input threshold below which minor capacity decay occurs. In addition, the particle size has a major influence on the electrode performance. We have developed an optimized electrode constituted of Mg 0.9Ti 0.1NiAl 0.05 particles with the appropriate size (>150 μm) showing a capacity decay rate as low as ∼0.2% per cycle when charged at 300 mAh g -1.

  13. Carbonate mineral solubility at low temperatures in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system

    NASA Astrophysics Data System (ADS)

    Marion, Giles M.

    2001-06-01

    Carbonate minerals have played an important role in the geochemical evolution of Earth, and may have also played an important role in the geochemical evolution of Mars and Europa. Several models have been published in recent years that describe chloride and sulfate mineral solubilities in concentrated brines using the Pitzer equations. Few of these models are parameterized for subzero temperatures, and those that are do not include carbonate chemistry. The objectives of this work are to estimate Pitzer-equation bicarbonate-carbonate parameters and carbonate mineral solubility products and to incorporate them into the FREZCHEM model to predict carbonate mineral solubilities in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system at low temperatures (≤25°C) with a special focus on subzero temperatures. Most of the Pitzer-equation parameters and equilibrium constants are taken from the literature and extrapolated into the subzero temperature range. Solubility products for 14 sodium, potassium, magnesium, and calcium bicarbonate and carbonate minerals are included in the model. Most of the experimental data are at temperatures ≥ -8°C; only for the NaHCO 3-NaCl-H 2O and Na 2CO 3-NaCl-H 2O systems are there bicarbonate and carbonate data to temperatures as low as -21.6°C. In general, the fit of the model to the experimental data is good. For example, calculated eutectic temperatures and compositions for NaHCO 3, Na 2CO 3, and their mixtures with NaCl and Na 2SO 4 salts are in good agreement with experimental data to temperatures as low as -21.6°C. Application of the model to eight saline, alkaline carbonate waters give predicted pHs ranging from 9.2 to 10.2, in comparison with measured pHs that range from 8.7 to 10.2. The model suggests that the CaCO 3 mineral that precipitates during seawater freezing is probably calcite and not ikaite. The model demonstrates that a proposed salt assemblage for the icy surface of Europa consisting of highly hydrated MgSO 4

  14. Room-temperature ferromagnetic transitions and the temperature dependence of magnetic behaviors in FeCoNiCr-based high-entropy alloys

    NASA Astrophysics Data System (ADS)

    Na, Suok-Min; Yoo, Jin-Hyeong; Lambert, Paul K.; Jones, Nicholas J.

    2018-05-01

    High-entropy alloys (HEAs) containing multiple principle alloying elements exhibit unique properties so they are currently receiving great attention for developing innovative alloy designs. In FeCoNi-based HEAs, magnetic behaviors strongly depend on the addition of alloying elements, usually accompanied by structural changes. In this work, the effect of non-magnetic components on the ferromagnetic transition and magnetic behaviors in equiatomic FeCoNiCrX (X=Al, Ga, Mn and Sn) HEAs was investigated. Alloy ingots of nominal compositions of HEAs were prepared by arc melting and the button ingots were cut into discs for magnetic measurements as functions of magnetic field and temperature. The HEAs of FeCoNiCrMn and FeCoNiCrSn show typical paramagnetic behaviors, composed of solid solution FCC matrix, while the additions of Ga and Al in FeCoNiCr exhibit ferromagnetic behaviors, along with the coexistence of FCC and BCC phases due to spinodal decomposition. The partial phase transition in both HEAs with the additions of Ga and Al would enhance ferromagnetic properties due to the addition of the BCC phase. The saturation magnetization for the base alloy FeCoNiCr is 0.5 emu/g at the applied field of 20 kOe (TC = 104 K). For the HEAs of FeCoNiCrGa and FeCoNiCrAl, the saturation magnetization significantly increased to 38 emu/g (TC = 703 K) and 25 emu/g (TC = 277 K), respectively. To evaluate the possibility of solid solution FCC and BCC phases in FeCoNiCr-type HEAs, we introduced a parameter of valence electron concentration (VEC). The proposed rule for solid solution formation by the VEC was matched with FeCoNiCr-type HEAs.

  15. Microstructure and Antiwear Property of Laser Cladding Ni-Co Duplex Coating on Copper.

    PubMed

    Wang, Yiyong; Liang, Zhipeng; Zhang, Junwei; Ning, Zhe; Jin, Hui

    2016-07-28

    Ni-Co duplex coatings were cladded onto Cu to improve the antiwear properties of Cu products. Prior to laser cladding, n-Al₂O₃/Ni layers were introduced as interlayers between laser cladding coatings and Cu substrates to improve the laser absorptivity of these substrates and ensure defect-free laser cladding coatings. The structure and morphology of the coatings were characterized by scanning electron microscopy and optical microscopy, and the phases of the coatings were analyzed by X-ray diffraction. Their hardness was measured using a microhardness tester. Experimental results showed that defect-free composite coatings were obtained and that the coatings were metallurgically bonded to the substrates. The surface of the Ni-Co duplex coatings comprised a Co-based solid solution, Cr₇C₃, (Fe,Ni) 23 C₆, and other strengthening phases. The microhardness and wear resistance of the duplex coatings were significantly improved compared with the Cu substrates. The average microhardness of the cladded coatings was 845.6 HV, which was approximately 8.2 times greater than that of the Cu substrates (102.6 HV). The volume loss of the Cu substrates was approximately 7.5 times greater than that of the Ni-Co duplex coatings after 60 min of sliding wear testing. The high hardness of and lack of defects in the Ni-Co duplex coatings reduced the plastic deformation and adhesive wear of the Cu substrates, resulting in improved wear properties.

  16. Coexisting nanoscale inverse spinel and rock salt crystallographic phases in NiCo2O4 epitaxial thin films grown by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Sharona, H.; Loukya, B.; Bhat, U.; Sahu, R.; Vishal, B.; Silwal, P.; Gupta, A.; Datta, R.

    2017-12-01

    The origin of alternating wavy dark-bright stripe-like contrast in strain contrast transmission electron microscopy images of NiCo2O4 (NCO) epitaxial thin films grown by pulsed laser deposition has been investigated. The nanoscale stripe-like pattern is determined to be associated with coexisting rock salt (RS) and inverse spinel crystal phases. The presence of two different phases, not addressed in previous reports, is experimentally confirmed by both electron diffraction and high resolution transmission electron microscopy imaging. First principles based calculations, together with compressive strain present in the films, support the formation of such coexisting crystallographic phases in NCO. Similar microstructural patterns and RS structure are not observed in epitaxial films of two other oxides of the spinel family, namely, NiFe2O4 and CoFe2O4. A correlation between the coexisting structures and the macroscopic physical properties of NCO is discussed.

  17. Hot corrosion of Co-Cr, Co-Cr-Al, and Ni-Cr alloys in the temperature range of 700-750 deg C

    NASA Technical Reports Server (NTRS)

    Chiang, K. T.; Meier, G. H.

    1980-01-01

    The effect of SO3 pressure in the gas phase on the Na2SO4 induced hot corrosion of Co-Cr, Ni-Cr, and Co-Cr-Al alloys was studied in the temperature range 700 to 750 C. The degradation of the Co-Cr and Ni-Cr alloys was found to be associated with the formation of liquid mixed sulfates (CoSO4-Na2SO4 or NiSO4-Na2SO4) which provided a selective dissolution of the Co or Ni and a subsequent sulfidation oxidation mode of attack which prevented the maintenance of a protective Cr2O3 film. A clear mechanism was not developed for the degradation of Co-Cr-Al alloys. A pitting corrosion morphology was induced by a number of different mechanisms.

  18. Impact of Microcrack Generation and Surface Degradation on a Nickel-Rich Layered Li[Ni 0.9Co 0.05Mn 0.05]O 2 Cathode for Lithium-Ion Batteries

    DOE PAGES

    Sun, Ho-Hyun; Manthiram, Arumugam

    2017-09-13

    In this work, to address the growing demand for energy density, the Ni-rich layered [Ni 0.90Co 0.05Mn 0.05]O 2 cathode has been synthesized and its electrochemical performance in lithium-ion cells has been benchmarked against a lower-Ni content Li[Ni 0.6Co 0.2Mn 0.2]O 2 cathode. Li[Ni 0.90Co 0.05Mn 0.05]O 2 delivers a high discharge capacity of 227 mA h g -1 compared to a capacity of 189 mA h g -1 for Li[Ni 0.6Co 0.2Mn 0.2]O 2 when cycled up to a lower cutoff voltage of 4.3 V, making it an appealing candidate for electric vehicles. With an increase in the chargemore » cutoff voltage to 4.5 V, Li[Ni 0.90Co 0.05Mn 0.05]O 2 displays a capacity of 238 mA h g -1 compared to a capacity of 208 mA h g -1 for Li[Ni 0.6Co 0.2Mn 0.2]O 2. Although Li[Ni 0.90Co 0.05Mn 0.05]O 2 suffers during cycling from the usual rapid capacity fade in a manner similar to that of LiNiO 2, 87 and 81% of the initial capacity could still be retained after 100 cycles even after cycling to higher cutoff voltages of 4.3 and 4.5 V, respectively. A comparison of Li[Ni 0.90Co 0.05Mn 0.05]O 2 and Li[Ni 0.6Co 0.2Mn 0.2]O 2 reveals that the capacity fade of Li[Ni 0.90Co 0.05Mn 0.05]O 2 originates largely from the anisotropic volume change and subsequent microcrack propagation in the bulk and NiO-like rock salt impurity phase formation on the particle surface, which are exacerbated at 4.5 V. Lastly, future work with appropriate doping and surface modification could improve further the performance of Li[Ni 0.90Co 0.05Mn 0.05]O 2.« less

  19. Impact of Microcrack Generation and Surface Degradation on a Nickel-Rich Layered Li[Ni 0.9Co 0.05Mn 0.05]O 2 Cathode for Lithium-Ion Batteries

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sun, Ho-Hyun; Manthiram, Arumugam

    In this work, to address the growing demand for energy density, the Ni-rich layered [Ni 0.90Co 0.05Mn 0.05]O 2 cathode has been synthesized and its electrochemical performance in lithium-ion cells has been benchmarked against a lower-Ni content Li[Ni 0.6Co 0.2Mn 0.2]O 2 cathode. Li[Ni 0.90Co 0.05Mn 0.05]O 2 delivers a high discharge capacity of 227 mA h g -1 compared to a capacity of 189 mA h g -1 for Li[Ni 0.6Co 0.2Mn 0.2]O 2 when cycled up to a lower cutoff voltage of 4.3 V, making it an appealing candidate for electric vehicles. With an increase in the chargemore » cutoff voltage to 4.5 V, Li[Ni 0.90Co 0.05Mn 0.05]O 2 displays a capacity of 238 mA h g -1 compared to a capacity of 208 mA h g -1 for Li[Ni 0.6Co 0.2Mn 0.2]O 2. Although Li[Ni 0.90Co 0.05Mn 0.05]O 2 suffers during cycling from the usual rapid capacity fade in a manner similar to that of LiNiO 2, 87 and 81% of the initial capacity could still be retained after 100 cycles even after cycling to higher cutoff voltages of 4.3 and 4.5 V, respectively. A comparison of Li[Ni 0.90Co 0.05Mn 0.05]O 2 and Li[Ni 0.6Co 0.2Mn 0.2]O 2 reveals that the capacity fade of Li[Ni 0.90Co 0.05Mn 0.05]O 2 originates largely from the anisotropic volume change and subsequent microcrack propagation in the bulk and NiO-like rock salt impurity phase formation on the particle surface, which are exacerbated at 4.5 V. Lastly, future work with appropriate doping and surface modification could improve further the performance of Li[Ni 0.90Co 0.05Mn 0.05]O 2.« less

  20. Structural and magnetic properties of Ni-Zn and Ni-Zn-Co ferrites

    NASA Astrophysics Data System (ADS)

    Knyazev, A. V.; Zakharchuk, I.; Lähderanta, E.; Baidakov, K. V.; Knyazeva, S. S.; Ladenkov, I. V.

    2017-08-01

    Ni-Zn and Ni-Zn-Co ferrite powders with nominal compositions Ni0.5Zn0.5Fe2O4 and Ni0.5Zn0.3Co0.2Fe2O4 were prepared by the solid-state reaction synthesis with periodic regrinding during the calcination at 1073 K. The structure of Ni0.5Zn0.5Fe2O4 and Ni0.5Zn0.3Co0.2Fe2O4 was refined assuming space group F d-3m. Scanning electron microscopy revealed the average sizes of the crystalline ferrite particles are 130-630 nm for Ni0.5Zn0.5Fe2O4 and 140-350 nm for Ni0.5Zn0.3Co0.2Fe2O4. The room temperature saturation magnetizations are 59.7 emu/g for Ni0.5Zn0.5Fe2O4 and 57.1 emu/g for Ni0.5Zn0.3Co0.2Fe2O4. The coercivity of the samples is found to be much larger than that of bulk ferrites and increases with Co introduction. The Curie temperature tends to increase upon Zn substitution by Co, as well. The temperature dependences of magnetization measured using zero-field cooled and field cooled protocols exhibit large spin frustration and spin-glass-like behavior.

  1. Multiple resonance peaks of FeCo thin films with NiFe underlayer

    NASA Astrophysics Data System (ADS)

    Zhong, Xiaoxi; Soh, Wee Tee; Phuoc, Nguyen N.; Liu, Ying; Ong, C. K.

    2015-01-01

    Under zero external magnetic fields, single-layer FeCo thin films exhibit no ferromagnetic resonance (FMR) peaks, while multiple FMR peaks were obtained by growing FeCo thin films on NiFe underlayers with various thicknesses up to 50 nm. Comprehensive investigations of the dynamic magnetic properties and origin of the peaks were conducted through measurements of microwave permeability via a shorted microstrip perturbation technique. Through fitted values of saturation magnetization Ms, uniaxial anisotropy HKsta, and rotatable anisotropy HKrot extracted from the FMR experiments, it was found that two of the three resonance peaks originate from FeCo, and the third from NiFe. The two magnetic phases of FeCo grains are found to have different values of HKrot and explained by the exchange interaction between FeCo and NiFe grains.

  2. Solution and Gas-Phase H/D Exchange of Protein-Small-Molecule Complexes: Cex and Its Inhibitors

    NASA Astrophysics Data System (ADS)

    Kang, Yang; Terrier, Peran; Ding, Chuanfan; Douglas, D. J.

    2012-01-01

    The properties of noncovalent complexes of the enzyme exo-1,4-β-D-glycanase ("Cex") with three aza-sugar inhibitors, deoxynojirimycin (X2DNJ), isofagomine lactam (X2IL), and isofagomine (X2IF), have been studied with solution and gas-phase hydrogen deuterium exchange (H/Dx) and measurements of collision cross sections of gas-phase ions. In solution, complexes have lower H/Dx levels than free Cex because binding the inhibitors blocks some sites from H/Dx and reduces fluctuations of the protein. In mass spectra of complexes, abundant Cex ions are seen, which mostly are formed by dissociation of complexes in the ion sampling interface. Both complex ions and Cex ions formed from a solution containing complexes have lower cross sections than Cex ions from a solution of Cex alone. This suggests the Cex ions formed by dissociation "remember" their solution conformations. For a given charge, ions of the complexes have greater gas-phase H/Dx levels than ions of Cex. Unlike cross sections, H/Dx levels of the complexes do not correlate with the relative gas-phase binding strengths measured by MS/MS. Cex ions from solutions with or without inhibitors, which have different cross sections, show the same H/Dx level after 15 s, indicating the ions may fold or unfold on the seconds time scale of the H/Dx experiment. Thus, cross sections show that complexes have more compact conformations than free protein ions on the time scale of ca. 1 ms. The gas-phase H/Dx measurements show that at least some complexes retain different conformations from the Cex ions on a time scale of seconds.

  3. Importance of reduced sulfur for the equilibrium chemistry and kinetics of Fe(II), Co(II) and Ni(II) supplemented to semi-continuous stirred tank biogas reactors fed with stillage.

    PubMed

    Shakeri Yekta, Sepehr; Lindmark, Amanda; Skyllberg, Ulf; Danielsson, Asa; Svensson, Bo H

    2014-03-30

    The objective of the present study was to assess major chemical reactions and chemical forms contributing to solubility and speciation of Fe(II), Co(II), and Ni(II) during anaerobic digestion of sulfur (S)-rich stillage in semi-continuous stirred tank biogas reactors (SCSTR). These metals are essential supplements for efficient and stable performance of stillage-fed SCSTR. In particular, the influence of reduced inorganic and organic S species on kinetics and thermodynamics of the metals and their partitioning between aqueous and solid phases were investigated. Solid phase S speciation was determined by use of S K-edge X-ray absorption near-edge spectroscopy. Results demonstrated that the solubility and speciation of supplemented Fe were controlled by precipitation of FeS(s) and formation of the aqueous complexes of Fe-sulfide and Fe-thiol. The relatively high solubility of Co (∼ 20% of total Co content) was attributed to the formation of compounds other than Co-sulfide and Co-thiol, presumably of microbial origin. Nickel had lower solubility than Co and its speciation was regulated by interactions with FeS(s) (e.g. co-precipitation, adsorption, and ion substitution) in addition to precipitation/dissolution of discrete NiS(s) phase and formation of aqueous Ni-sulfide complexes. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Oxidation behavior of NiCoCrAlY coatings deposited by double-Glow plasma alloying

    NASA Astrophysics Data System (ADS)

    Cui, Shiyu; Miao, Qiang; Liang, Wenping; Li, Baiqiang

    2018-01-01

    The NiCoCrAlY coatings were deposited on the Inconel 718 alloy substrates by a novel method called double-glow plasma alloying (DG). The phases and microstructure of the coatings were investigated by X-ray diffraction analysis while their chemical composition was analyzed using scanning electron microscopy. The morphology of the NiCoCrAlY coatings was typical of coatings formed by DG, with their structure consisting of uniform submicron-sized grains. Further, the coatings showed high adhesion strength (critical load >46 N). In addition, the oxidation characteristics of the coatings and the substrate were examined at three different temperatures (850, 950, and 1050 °C) using a muffle furnace. The coatings showed a lower oxidation rate, which was approximately one-tenth of that of the substrate. Even after oxidation for 100 h, the Al2O3 phase was the primary phase in the surface coating (850 °C), with the thickness of the oxide film increasing to 0.65 μm at 950 °C. When the temperature was increased beyond 1050 °C, the elemental Al and Ni were consumed in the formation of the oxide scale, which underwent spallation at several locations. The oxidation products of Cr, which were produced in large amounts and had a prism-like structure, controlled the subsequent oxidation behavior at the surface.

  5. Multiple Supersonic Phase Fronts Launched at a Complex-Oxide Heterointerface

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Först, M.; Beyerlein, K. R.; Mankowsky, R.

    Selective optical excitation of a substrate lattice can drive phase changes across heterointerfaces. This phenomenon is a nonequilibrium analogue of static strain control in heterostructures and may lead to new applications in optically controlled phase change devices. Here, we make use of time-resolved nonresonant and resonant x-ray diffraction to clarify the underlying physics and to separate different microscopic degrees of freedom in space and time. We also measure the dynamics of the lattice and that of the charge disproportionation in NdNiO 3 , when an insulator-metal transition is driven by coherent lattice distortions in the LaAlO 3 substrate. We findmore » that charge redistribution propagates at supersonic speeds from the interface into the NdNiO 3 film, followed by a sonic lattice wave. Our results establish a hierarchy of events for ultrafast control at complex-oxide heterointerfaces, when combined with measurements of magnetic disordering and of the metal-insulator transition.« less

  6. Multiple Supersonic Phase Fronts Launched at a Complex-Oxide Heterointerface

    DOE PAGES

    Först, M.; Beyerlein, K. R.; Mankowsky, R.; ...

    2017-01-09

    Selective optical excitation of a substrate lattice can drive phase changes across heterointerfaces. This phenomenon is a nonequilibrium analogue of static strain control in heterostructures and may lead to new applications in optically controlled phase change devices. Here, we make use of time-resolved nonresonant and resonant x-ray diffraction to clarify the underlying physics and to separate different microscopic degrees of freedom in space and time. We also measure the dynamics of the lattice and that of the charge disproportionation in NdNiO 3 , when an insulator-metal transition is driven by coherent lattice distortions in the LaAlO 3 substrate. We findmore » that charge redistribution propagates at supersonic speeds from the interface into the NdNiO 3 film, followed by a sonic lattice wave. Our results establish a hierarchy of events for ultrafast control at complex-oxide heterointerfaces, when combined with measurements of magnetic disordering and of the metal-insulator transition.« less

  7. Electrodeposited Ni-Co films from electrolytes with different Co contents

    NASA Astrophysics Data System (ADS)

    Karpuz, Ali; Kockar, Hakan; Alper, Mursel; Karaagac, Oznur; Haciismailoglu, Murside

    2012-02-01

    The properties of electrodeposited Ni-Co films produced from electrolyte consisted of nickel sulfamate, cobalt sulfate and boric acid were investigated as a function of Co content in the films. The compositional analysis performed by an energy dispersive X-ray spectroscopy demonstrated that the Co content of the films increases as the cobalt sulfate concentration in the electrolyte increases. The anomalous codeposition behavior was observed for all concentrations. The crystal structure was analyzed using an X-ray diffraction technique. The face centered cubic (fcc) structure was observed in the films containing from 0 at.% Co to 58 at.% Co. For the higher atomic Co contents (64 at.% and 80 at.%), a mixed phase of dominantly fcc and hexagonal closed packed (hcp) structure was observed although the (10.0) and (10.1) hcp peaks had minor intensities in the patterns. Surface micrographs obtained from a scanning electron microscope revealed that the film surface has a rougher appearance as the Co content increases. Magnetic measurements showed that the saturation magnetization gradually increased with increasing Co content of the films. The coercivity, Hc can be controlled by the structural parameters such as average grain size and crystal structure. The results also indicated that the optimum film composition was 28-40 at.% Co since the lower Hc and higher magnetoresistance (MR) values with very smooth or slightly granular surfaces were achieved at this Co content. It is revealed that Co content has an important effect on structural, magnetic and MR properties of the Ni-Co films.

  8. Effect of synthesis route on the uptake of Ni and Cd by MgFe2O4 nanopowders

    NASA Astrophysics Data System (ADS)

    Al-Najar, B.; Khezami, L.; Judith Vijaya, J.; Lemine, O. M.; Bououdina, M.

    2017-01-01

    In this study, MgFe2O4 nanopowders were synthesized through two different methods, sol-gel method (SG) and modified sol-gel with Ammonia (MSG-A). The influence of synthesis route was investigated in terms of phase stability, pores size and surface area, magnetic properties and uptake of Ni and Cd metals from aqueous solution. Rietveld refinements of x-ray diffraction patterns confirmed the formation of single spinel phase for SG sample, while minor impurity was detected for SGM-A sample (few amount of MgO). The crystallite size was found to be sensitive to the preparation method; it ranges from 4 nm for SG to 15 nm for MSG-A. Magnetization experiment at room temperature showed ferromagnetic behavior with a saturation magnetization ( M s) ranging from 5.39 emu/g for SG to 9.93 emu/g for MSG-A. Preliminary results showed that SG and MSG-A samples are efficient adsorbent for Ni and Cd metal ions from aqueous solution. Maximum quantity of 62.67 and 61.2 mg of Ni(II) and 36.49 and 32.84 mg of Cd(II) was adsorbed per gram of MgFe2O4 synthesized by SG and MSG-A, respectively.

  9. Characterization of corrosion resistant on NiCoCr coating layer exposed to 5%NaCl

    NASA Astrophysics Data System (ADS)

    Sugiarti, E.; Sundawa, R.; Desiati, R. D.; Zaini, K. A.

    2018-03-01

    Highly corrosion resistant of carbon steel coated NiCoCr was applied in corrosive of marine environtment. Carbon steel coated NiCoCr was prepared by a two step technique of NiCo electro-deposition and Cr pack cementation. The samples were exposed to 5 wt.% NaCl for 48 and 168 hours. The microstructure and corrosion product were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The corrosion resistance of carbon steel coated NiCoCr was found to be better than that of carbon steel substrate without coating. The results showed the microstructure of 48 h corroded sample has duplex layer composed of inner α-(Ni,Co), α-Cr and outer Cr2O3, while a quite thin and continues protective oxide of Cr2O3 was observed in outer layer of 168 h corroded sample. The formation of oxide scale rich in Cr2O3 has contributed for the better corrosion resistance of carbon steel coated NiCoCr, whereas the formation of non protective oxide of iron might caused low corrosion resistance of carbon steel substrate.

  10. Oxoaporphine Metal Complexes (CoII, NiII, ZnII) with High Antitumor Activity by Inducing Mitochondria-Mediated Apoptosis and S-phase Arrest in HepG2

    PubMed Central

    Qin, Jiao-Lan; Shen, Wen-Ying; Chen, Zhen-Feng; Zhao, Li-Fang; Qin, Qi-Pin; Yu, Yan-Cheng; Liang, Hong

    2017-01-01

    Three new oxoaporphine Co(II), Ni(II) and Zn(II) complexes 1–3 have been synthesized and fully characterized. 1–3 have similar mononuclear structures with the metal and ligand ratio of 1:2. 1–3 exhibited higher cytotoxicity than the OD ligand and cisplatin against HepG2, T-24, BEL-7404, MGC80–3 and SK-OV-3/DDP cells, with IC50 value of 0.23−4.31 μM. Interestingly, 0.5 μM 1–3 significantly caused HepG2 arrest at S-phase, which was associated with the up-regulation of p53, p21, p27, Chk1 and Chk2 proteins, and decrease in cyclin A, CDK2, Cdc25A, PCNA proteins. In addition, 1–3 induced HepG2 apoptosis via a caspase-dependent mitochondrion pathway as evidenced by p53 activation, ROS production, Bax up-regulation and Bcl-2 down-regulation, mitochondrial dysfunction, cytochrome c release, caspase activation and PARP cleavage. Furthermore, 3 inhibited tumor growth in HepG2 xenograft model, and displayed more safety profile in vivo than cisplatin. PMID:28436418

  11. Formation of cation-anion complexes in the photochemical reaction of molybdenocene dihydrode with iron pentacarbonyl. Crystal structures of (Cp/sub 2/Mo(CO)H)/sup +/(Fe/sub 3/(CO)/sub 11/H)/sup -/ and (Cp/sub 2/Mo(CO)H)/sup +/(CoMo(CO)/sub 3/)/sup -/ (triclinic modification) (in Russian)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Antsyshkina, A.S.; Dikareva, L.M.; Porai-Koshits, M.A.

    1985-11-01

    The reaction of Cp/sub 2/MoH/sub 2/ with Fe(CO)/sub 5/ in boiling benzene under UV irradiation gives the ionic complexes (Cp/sub 2/Mo(CO)H)/sup +/(Fe/sub 3/(CO)/sub 11/H)/sup -/ (I) and (Cp/sub 2/Mo(CO)H)/sup +/(CpMo(CO)/sub 3/)/sup -/ (II), whose structures were established by x-ray diffraction analysis (Syntex P2/sub 1/ automatic diffractometer, lambda Mo K/sub ..cap alpha../, graphite monochromator, theta/2theta scan technique, full-matrix least-squares method, isotropic variant for I on the basis of 2112 reflections to % = 0.11 and anisotropic variant for II on the basis of 3770 values of hkl to R = 0.052). In complexes I and II the (CpMo(CO)H)/sup +/ fragment ismore » a tapered sandwich with an eclipsed conformation of the rings. In complex I the angle between the rings is 33.9/sup 0/, the mean Mo-C(C/sub 5/H/sub 5/) distance is 2.28(3) A, the mean Mo-C(CO) distance is 2.03(3) A, and the mean Mo-H distance is 1.78(10) A. The corresponding parameters in complex II are: 32.4/sup 0/, 2.296(7), 2.020(6), and 1.87(7) A. The anion in complex I is based on a triangular cluster of Fe atoms, in which one Fe-Fe distance is significantly shorter (2.488(5) A) than the other two (2.702(5) and 2.697(5) A). The Fe atoms forming the short bond are joined additionally by hydride (Fe-H = 2.14 A) and carbonyl (Fe-C = 1.90(3) and 1.93(3) A) Bridges. The remaining groups are terminal. A probable scheme for the process of the formation of complexes I and II has been discussed.« less

  12. Epitaxial Ni-Mn-Ga-Co thin films on PMN-PT substrates for multicaloric applications

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Schleicher, B., E-mail: b.schleicher@ifw-dresden.de; Niemann, R.; Schultz, L.

    2015-08-07

    Multicaloric stacks consisting of a magnetocaloric film on a piezoelectric substrate promise improved caloric properties as the transition temperature can be controlled by both magnetic and electric fields. We present epitaxially grown magnetocaloric Ni-Mn-Ga-Co thin films on ferroelectric Pb(Mg{sub 1/3}Nb{sub 2/3}){sub 0.72}Ti{sub 0.28}O{sub 3} substrates. Structure and microstructure of two samples, being in the austenitic and martensitic state at room temperature, are investigated by X-ray diffraction in two- and four-circle geometry and by atomic force microscopy. In addition, high temperature magnetometry was performed on the latter sample. The combination of these methods allows separating the influence of epitaxial growth andmore » martensitic transformation. A preferential alignment of twin boundaries is observed already in the as-deposited state, which indicates the presence of prestress, without applying an electric field to the substrate. A temperature-magnetic field phase diagram is presented, which demonstrates the inverse magnetocaloric effect of the epitaxial Ni-Mn-Ga-Co film.« less

  13. Porous microspheres of MgO-patched TiO2 for CO2 photoreduction with H2O vapor: temperature-dependent activity and stability.

    PubMed

    Liu, Lianjun; Zhao, Cunyu; Zhao, Huilei; Pitts, Daniel; Li, Ying

    2013-05-07

    A novel MgO-patched TiO2 microsphere photocatalyst demonstrated 10 times higher activity toward CO production from CO2 photoreduction with H2O vapor, when the reaction temperature increased from 50 to 150 °C. The catalytic performance of hybrid MgO-TiO2 was much more stable than TiO2, particularly at a higher temperature, likely due to easier desorption of reaction intermediates and the enhanced CO2 adsorption by MgO.

  14. Crystal structure and electrochemical properties of rare earth non-stoichiometric AB5-type alloy as negative electrode material in Ni-MH battery

    NASA Astrophysics Data System (ADS)

    Zhang, Xinbo; Chai, Yujun; Yin, Wenya; Zhao, Minshou

    2004-07-01

    The La 0.85Mg xNi 4.5Co 0.35Al 0.15 (0.05⩽ x⩽0.35) system compounds have been prepared by arc melting method under Ar atmosphere. X-ray diffraction (XRD) analysis reveals that the as-prepared alloys have different lattice parameters and cell volumes. The electrochemical properties of these alloys have been studied through the charge-discharge recycle testing at different temperatures and discharge currents. It is found that the La 0.85Mg 0.25Ni 4.5Co 0.35Al 0.15 alloy electrode is capable of performing high-rate discharge. Moreover, it has very excellent electrochemical properties as negative electrode materials in Ni-MH battery at low temperature, even at -40°C.

  15. Comprehensive structural and chemical (CO2, Fe/Fe Mg, H2O) investigations of Mg-Fe cordierite with micro Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Haefeker, U.; Kaindl, R.; Tropper, P.

    2012-04-01

    The Mg-Fe silicate cordierite with the idealized formula (Fe, Mg)2Al4Si5O18 occurs as a hexagonal and an orthorhombic polymorph with disordered/ordered Al-Si distribution on the tetrahedral sites. Most of the natural cordierites are fully ordered. Six-membered rings of (Si,Al)O4 are piled in the direction of the crystallographic c-axis and form channels, laterally and vertically linked by additional (Al, Si) tetrahedrons. Mg and Fe in varying fractions occupy the octahedrally coordinated M-sites. CO2 and H2O (and other volatiles) can be incorporated into the structural channels, thus cordierite can be used for paleofluid reconstruction. The vibration energies of incorporated volatiles, their interaction with the lattice and variations of certain lattice-vibration energies caused by the Mg-Fe exchange can be determined with Raman spectroscopy, allowing chemical quantifications and structural investigations. A method for the semi-quantitative determination of CO2-contents of natural cordierites by Kaindl et al. (2006) was optimized and enhanced by Haefeker et al. (2007). CO2 contents can be measured in single crystals and thin sections with an error of ± 0.05 - 0.09 wt.-%. Based on the Mg-Fe exchange with garnet, cordierite can be used as a geothermobarometer. Recent investigations of synthetic Mg-Fe cordierites with XFe = 0 - 1 have shown a linear downshift of six selected lattice peaks between 100 and 1250 cm-1 with the Mg-Fe contents. Correlation diagrams allow an estimation of the Mg-Fe contents in synthetic and natural samples. The experimental data are in good agreement with the results of quantum-mechanical calculations of the Raman spectra of Mg- and Fe cordierite (Kaindl et al., 2011) allowing the assignment of the peaks to specific vibrations of tetrahedral and octahedral sites. Natural Mg-Fe cordierites are mainly orthorhombic with a fully ordered Al/Si distribution on the tetrahedral sites. However, the disordered hexagonal polymorph is observed in many

  16. Characterization and corrosion behaviour of CoNi alloys obtained by mechanical alloying

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Olvera, S.; Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Química-Física Aplicada, 28049 Madrid; Sánchez-Marcos, J.

    2014-07-01

    CoNi alloys including Co{sub 30}Ni{sub 70}, Co{sub 50}Ni{sub 50} and Co{sub 70}Ni{sub 30} were prepared via mechanical alloying using Co and Ni powders. The crystallinity and short-range order were studied using X-ray diffraction and X-ray absorption spectroscopy. The results show that the milling process increases the number of vacancies, especially around the Co atoms, while the milling time decreases the crystalline size and enhances the crystallinity. X-ray photoelectron spectroscopy was used to characterise the chemical composition of the samples surface. The magnetic properties were analysed using zero-field cooling, field cooling and a magnetic hysteresis loops. The magnetic saturation moment ismore » approximately 1.05 μ{sub B}/atom; this value decreases with the mechanical alloying time, and it is proportional to the cobalt concentration. The polarization and impedance curves in different media (NaCl, H{sub 2}SO{sub 4} and NaOH) showed similar corrosion resistance values. The corrosion resistance increased in the order NaCl, H{sub 2}SO{sub 4} and NaOH. A good passivation layer was formed in NaOH due to the cobalt and nickel oxides on the particle surfaces. - Highlights: • Ni{sub x}Co{sub 100-x} alloys were synthesized by mechanical alloying • Milling time decrease size and enhances crystallinity. • Oxygen is not present in a significant percentage in bulk but is detected on the surface. • Magnetic saturation moment is 1.05 mB/atom and decrease with mechanical allowing time • Corrosion resistance is higher in NaOH than in NaCl or HCl solutions.« less

  17. The annealing temperature dependences of microstructures and magnetic properties in electro-chemical deposited CoNiFe thin films

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Suharyadi, Edi, E-mail: esuharyadi@ugm.ac.id; Riyanto, Agus; Abraha, Kamsul

    2016-04-19

    CoNiFe thin films with various compositions had been successfully fabricated using electro-chemical deposition method. The crystal structure of Co{sub 65}Ni{sub 15}Fe{sub 20}, Co{sub 62}Ni{sub 15}Fe{sub 23}, and Co{sub 55}Ni{sub 15}Fe{sub 30} thin films was fcc, bcc-fcc mix, and bcc, respectively. The difference crystal structure results the difference in magnetic properties. The saturation magnetic flux density (Bs) of Co{sub 65}Ni{sub 15}Fe{sub 20}, Co{sub 62}Ni{sub 15}Fe{sub 23}, and Co{sub 55}Ni{sub 15}Fe{sub 30} thin films was 1.89 T, 1.93 T, and 2.05 T, respectively. An optimal annealing temperature was determined for controlling the microstructure and magnetic properties of CoNiFe thin films. Depending onmore » annealing temperature, the ratio of bcc and fcc structure varied without changing the film composition. By annealing at temperature of T ≥ 350°C, the intensity ratio of X-ray diffraction peaks for bcc(110) to fcc(111) increased. The increase of phase ratio of bcc(110) to fcc(111) caused the increase of Bs, from 1.89 T to 1.95 T. Coercivity (Hc) also increased after annealing, from 2.6 Oe to 18.6 Oe for fcc phase thin films, from 2.0 Oe to 12.0 Oe for fcc-bcc mix phase thin films, and 7.8 Oe to 8 Oe for bcc phase thin films. The changing crystal structures during annealing process indicated that the thermal treatment at high temperature cause the changing crystallinity and atomic displacement. The TEM bright-field images with corresponding selected-area electron diffraction (SAED) patterns showed that there are strongly effects of thermal annealing on the size of fcc and bcc phase crystalline grain as described by size of individual spot and discontinuous rings. The size of crystalline grains increased by thermal annealing. The evolution of bcc and fcc structures of CoNiFe during annealing is though to be responsible for the change of magnetic properties.« less

  18. Porous Ni-Co-Mn oxides prisms for high performance electrochemical energy storage

    NASA Astrophysics Data System (ADS)

    Zhao, Jianbo; Li, Man; Li, Junru; Wei, Chengzhen; He, Yuyue; Huang, Yixuan; Li, Qiaoling

    2017-12-01

    Porous Ni-Co-Mn oxides prisms have been successfully synthesized via a facile route. The process involves the preparation of nickel-cobalt-manganese acetate hydroxide by a simple co-precipitation method and subsequently the thermal treatment. The as-synthesized Ni-Co-Mn oxides prisms had a large surface area (96.53 m2 g-1) and porous structure. As electrode materials for supercapacitors, porous Ni-Co-Mn oxides prisms showed a high specific capacitance of 1623.5 F g-1 at 1.0 A g-1. Moreover, the porous Ni-Co-Mn oxides prisms were also employed as positive electrode materials to assemble flexible solid-state asymmetric supercapacitors. The resulting flexible device had a maximum volumetric energy density (0.885 mW h cm-3) and power density (48.9 mW cm-3). Encouragingly, the flexible device exhibited good cycling stability with only about 2.2% loss after 5000 charge-discharge cycles and excellent mechanical stability. These results indicate that porous Ni-Co-Mn oxides prisms have the promising application in high performance electrochemical energy storage.

  19. Enhancement of C-H Oxidizing Ability in Co-O2  Complexes through an Isolated Heterobimetallic Oxo Intermediate.

    PubMed

    DeRosha, Daniel E; Mercado, Brandon Q; Lukat-Rodgers, Gudrun; Rodgers, Kenton R; Holland, Patrick L

    2017-03-13

    The characterization of intermediates formed through the reaction of transition-metal complexes with dioxygen (O 2 ) is important for understanding oxidation in biological and synthetic processes. Here, the reaction of the diketiminate-supported cobalt(I) complex L tBu Co with O 2 gives a rare example of a side-on dioxygen complex of cobalt. Structural, spectroscopic, and computational data are most consistent with its assignment as a cobalt(III)-peroxo complex. Treatment of L tBu Co(O 2 ) with low-valent Fe and Co diketiminate complexes affords isolable oxo species with M 2 O 2 "diamond" cores, including the first example of a crystallographically characterized heterobimetallic bis(μ-oxo) complex of two transition metals. The bimetallic species are capable of cleaving C-H bonds in the supporting ligands, and kinetic studies show that the Fe/Co heterobimetallic species activates C-H bonds much more rapidly than the Co/Co homobimetallic analogue. Thus heterobimetallic oxo intermediates provide a promising route for enhancing the rates of oxidation reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. The CO-H2 van der Waals complex and complex organic molecules in cold molecular clouds: A TMC-1C survey

    NASA Astrophysics Data System (ADS)

    Potapov, A.; Sánchez-Monge, Á.; Schilke, P.; Graf, U. U.; Möller, Th.; Schlemmer, S.

    2016-10-01

    Context. Almost 200 different species have been detected in the interstellar medium (ISM) during the last decades, revealing not only simple species but complex molecules with more than six atoms. Other exotic compounds, like the weakly-bound dimer (H2)2, have also been detected in astronomical sources like Jupiter. Aims: We aim to detect, for the first time, the CO-H2 van der Waals complex in the ISM, which could be a sensitive indicator for low temperatures if detected. Methods: We used the IRAM 30 m telescope, located in Pico Veleta (Spain), to search for the CO-H2 complex in a cold, dense core in TMC-1C (with a temperature of ~10 K). All the brightest CO-H2 transitions in the 3 mm (80-110 GHz) band were observed with a spectral resolution of 0.5-0.7 km s-1, reaching a rms noise level of ~2 mK. The simultaneous observation of a broad frequency band, 16 GHz, allowed us to conduct a serendipitous spectral line survey. Results: We did not detected any lines belonging to the CO-H2 complex. We set up a new, more stringent upper limit for its abundance to be [CO-H2]/[CO] ~ 5 × 10-6, while we expect the abundance of the complex to be in the range ~10-8-10-3. The spectral line survey has allowed us to detect 75 lines associated with 41 different species (including isotopologues). We detect a number of complex organic species, for example methyl cyanide (CH3CN), methanol (CH3OH), propyne (CH3CCH), and ketene (CH2CO), associated with cold gas (excitation temperatures ~7 K), confirming the presence of these complex species not only in warm objects but also in cold regimes. Based on observations carried out with the IRAM 30 m Telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany) and IGN (Spain).Reduced spectra (FITS files) are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/594/A117