Preparation of polycrystalline Ti-Al-O films by magnetron sputtering ion plating: constitution, structure and morphology

Ti-Al-O layers were deposited on Si-<100> wafers at 500 °C by means of reactive magnetron sputtering ion plating (R-MSIP). An Al-target was sputtered in rf-mode and a Ti-target in dc-mode simultaneously by an oxygen/argon plasma. The influence of the Al- and Ti-sputter powers on composition, structure, and morphology of the Ti-Al-O layers and the binding states of the components were investigated. The analysis with EPMA, XPS, AES and TEM yielded the following results: Ti-Al-O coatings with different Ti, Al, and O contents in the range of TiO₂ to Al₂O₃ were grown. TEM structure analysis revealed: the pure TiO₂ film consisted of the tetragonal phases rutile and anatase; the two structures were found in the titanium-rich Ti-Al-O film, too, but with significant smaller lattice constants. The aluminium-rich Ti-Al-O film displayed the same cubic structure of γ-Al₂O₃ as determined for the pure Al₂O₃ film, but the lattice constant is significant lower. Evaluation of the TEM pattern of the film with a Ti/Al ratio of 0.8 indicates a hexagonal structure with lattice constants similar to those of κ′-Al₂O₃. All films are nanocrystalline and not textured. Received: 24 June 1996 / Revised: 27 December 1996 / Accepted: 4 January 1997     

Derivatives (Cu/CuO,Cu/Cu2O,and CuS) of Cu superstructures reduced by biomass reductants

Metallic Cu is considered as the promising functional material owing to its high conductivity and harmlessness. Here, metallic Cu which presents a unique interconnected and continuous structure (Cu superstructure) is prepared using Magnolia grandiflora leaves as the biomass reductant, a green process which avoided the release of harmful gases and massive energy consumption. What's more, Cu/CuO, Cu/Cu₂O, and CuS nanosheets with different sizes were fabricated using Cu superstructure as the substrate via facile methods, and the morphology is regulated by controlling the relevant factors. The electrochemical sensors based on the three derivations were fabricated to study the sensing performance of glucose. The unique structure of nanosheets encapsulating Cu superstructure guarantees the excellent conductivity of Cu/CuO and Cu/Cu₂O composites. Moreover, the electrochemical stability is improved owing to the nanosheet protective layer. Although no metallic Cu was maintained in CuS, the integrated multilayer nanosheets endow CuS with short channels for fast interlayer electronic transmission and with structural stability.     

Ni(II), Pd(II), Cu(II) And Zn(II) complexes with N-(2-Pyridyl)Carbonylaniline (L), Syntheses and X-Ray Crystal structures of [Cu(L)2(H2O)2](No3)2, [Cu(L)2(H2O)2](Clo4)2 and [Zn(L)2(H2O)2](Clo4)2

Reaction of the N-(2-pyridyl)carbonylaniline ligand (L) with Cu(NO₃)₂, Cu(ClO₄)₂, Zn(ClO₄)₂, Ni(NO₃)₂ and PdCl₂ gives complexes with stoichiometry [Cu(L)₂(H₂O)₂](NO₃)₂, [Cu(L)₂(H₂O)₂](ClO₄)₂, [Zn(L)₂(H₂O)₂] (ClO₄)_2, [Ni(L)₂(H₂O)Cl](NO₃) and PdLCl₂. The new complexes were characterized by elemental analyses and infrared spectra. The crystal structures of [Cu(L)₂(H₂O)₂](NO₃)₂, [Cu(L)₂(H₂O)₂](ClO₄)₂, and [Zn(L)₂(H₂O)₂](ClO₄)₂ were determined by X-ray crystallography. The cation complexes [M(L)₂(H₂O)₂] contain copper(II) and zinc(II) with distorted octahedral geometry with two N-(2-pyridyl)carbonylaniline (L) ligands occupying the equatorial sites. The hexa-coordinated metal atoms are bonded to two pyridinic nitrogens, two carbonyl oxygens and two water molecules occupying the axial sites. Both the coordinated water molecules and uncoordinated amide NH groups of the N-(2-pyridyl)carbonylaniline (L) ligands are involved in hydrogen bonding, resulting in infinite hydrogen-bonded chains running in one and two-dimensions.     

Inorganic-organic hybrids formed by P,P'-diphenylmethylenediphosphinate, pcp2-, with the Cu2+ ion. X-ray crystal structures of [Cu(pcp)(H2O)2] x H2O and [Cu(pcp)(bipy)(H2O)

Weakly coordinated [Cu(pcp)(H2O)n] complexes are formed in aqueous solution, at room temperature, by interaction of P,P'-diphenylmethylene diphosphinic acid (H2pcp) with copper(II) ions. However, heating of the solutions gives rise to the formation of two extended metal-oxygen networks of formulas [Cu(pcp)(H2O)2] x H2O, 1, and [Cu(pcp)(H2O)2], 2. In the presence of 2,2'-bipyridyl (bipy) the diamine derivative [Cu(pcp)(bipy)(H2O)], 4, has been isolated. Complex 1 easily loses water to form a monohydrated derivative [Cu(pcp)H2O], 3, whereas 2 is completely dehydrated after prolonged heating at 150 degrees C, under vacuum. The compounds 1 and 2 have substantially different solid-state structures as shown by X-ray powder diffraction spectra, IR spectra, and thermogravimetric analyses. Consistently, the two complexes cannot be directly interconverted and present different dehydration pathways. Rehydration of these materials in both cases allows quantitative formation of 1. X-ray analysis established that the structure of 1 consists of a corrugated two-dimensional layered polymeric array, where infinite zigzag chains of Cu centers and bridging phenylphosphinate ligands are linked together through strong hydrogen-bonding interactions; the structure of 4 consists of monodimensional polymers, where the hydrogen-bonding interactions play an essential bridging role in the extended architecture. In both structures the metal center displays a five-coordinate environment with approximate square pyramidal geometry, with the pcp ligand acting as bidentate and monodentate in 1 and solely as bidentate in 4. In 1 the coordination sphere is completed through water molecules; in 4, through water and diamine ligands. The thermogravimetric analyses of the complexes are compared with those of the related hybrids [M(pcp)(H2O)3] x H2O, where M = Mn, Co, or Ni, confirming that noncoordinated water molecules also play a basic role in determining the molecular packing.     

[Cu_3(hssal)_2(phen)_2(H_2O)_4]配合物的合成、性质和作为前驱体合成CuO的研究

用配体磺基水杨酸,1,10菲罗啉和CuCO3·Cu(OH)2·H2O反应合成了配合物[Cu3(hssal)2(phen)2(H2O)4]·2CH3OH(1)(H3hssal:磺基水杨酸;phen:1,10菲罗啉),用单晶X-射线衍射、元素分析和红外光谱对该配合物进行了表征。研究了1的固体荧光和热稳定性,并用它作为前驱体合成了CuO微晶粒子,用粉末XRD和SEM对合成的CuO进行了表征和形貌研究。     

Layer-engineering of high-Tc superconductors: (Cu,Mo)Sr2(Ce,Y)4Cu2O13+delta with a quadruple-fluorite-layer block between CuO2 planes

Among high-Tc superconductive copper oxides, there have been known phases that contain fluorite-structured layers as an additional "blocking block" between adjacent CuO2 planes. Here, we report that even a phase with the CuO2 planes separated by a 12-A thick quadruple-fluorite-layer block can be synthesized in a single phase and strongly oxygenated form to exhibit superconductivity with a Tc value as high as 55 K. The new phase is the fourth member of the (Cu,Mo)Sr2(Ce,Y)sCu2O(5+2s+delta) or (Cu,Mo)-12s2 homologous series. Comparison with the previously known s = 1, 2, and 3 members of the series reveals the amazing conclusion that Tc remains essentially unaffected upon inserting additional fluorite-structured layers between the two CuO2 planes as long as the hole-doping level of the planes is kept constant.     

Preparation,characterization and reactions of tris(2-chloroethoxy)iron(III), Fe(OC2H4Cl)3

Summary Tris(2-chloroethoxy)iron(III) has been prepared and exists as a 11 electrolyte in nitrobenzene, methanol and dimethyl-sulphoxide. Cryoscopic data suggest that it ionises into two species in nitrobenzene. The complex, with a variety of ligands containing C=O, S=O, P=O and As=O groups, forms adducts which have been characterized by their i.r. spectra, molar conductances, molecular weights and magnetic moments. Magnetic susceptibility measurements are in accord with the existence of antiferromagnetic interactions between iron atoms.     

Preparation and characterization of the Na4UO2(O2)3·8H2O complex

The Na₄UO₂(O₂)₃·8H₂O complex was prepared from aqueous systems and its crystallographic and chemical structural conformation characterized. IR spectroscopy and X-ray diffraction were used for analyzing the solid crystal extracted with ethanol to determine the anionic compositon. Composition of the solid phase did not depend on the molar ratio of the reactants or on the pH of the medium, but only upon the absolute concentrations of uranium and alkali. It was observed that the temperature significantly influenced the crystal structure of the product and that a limit to the UO₂ concentration existed for inducing the production of a mixture of soluble and insoluble species.     

Preparation and characterization of copper sulfide nanoparticles from symmetrical [(Bu)2NC(S)NC(O)C6H3(3,5-NO2)2]2Cu(II) and [(Bu)2NC(S)NC(O)C6H4(4-NO2)]2Cu(II) complexes by thermolysis

Trigonal copper sulfide nanoparticles were synthesized from symmetrical [(Bu)₂NC(S)NC(O)C₆H₃(3,5-NO₂)₂]₂Cu(II) and [(Bu)₂NC(S)NC(O)C₆H₄(4-NO₂)]₂Cu(II) complexes by thermolysis in the presence of surfactant oleylamine. The symmetrical copper complexes were synthesized by reaction of copper(II) acetate with N-(3,5-dinitrobenzoyl)-N′,N′-dibutylthiourea and N-(4-nitrobenzoyl)-N′,N′-dibutylthiourea. The symmetrical copper complexes were characterized by FT-IR spectroscopy, elemental analysis, and mass spectrometry (MS-APCI). The single-crystal X-ray structure of [(Bu)₂NC(S)NC(O)C₆H₄(4-NO₂)]₂Cu(II) has been determined from single-crystal X-ray diffraction data. These metal complexes have been used as single source precursors for the preparation of copper sulfide nanoparticles. The deposited copper sulfide nanoparticles were characterized by X-ray powder diffraction and transmission electron microscopy.     

Thermal, spectral and magnetic characterization of Co(II), Ni(II) AND Cu(II) 4-chloro-2-nitrobenzoates

Physico-chemical properties of 4-chloro-2-nitrobenzoates of Co(II), Ni(II), and Cu(II) were studied. The complexes were obtained as mono- and trihydrates with a metal ion to ligand ratio of 1:2. All analysed 4-chloro-2-nitrobenzoates are polycrystalline compounds with colours depending on the central ions: pink for Co(II), green for Ni(II), and blue for Cu(II) complexes. Their thermal decomposition was studied only in the range of 293–523 K, because it was found that on heating in air above 523 K 4-chloro-2-nitrobenzoates decompose explosively. Hydrated complexes lose crystallization water molecules in one step and anhydrous compounds are formed. The final products of their decomposition are the oxides of the respective transition metals. From the results it appears that during dehydration process no transformation of nitro group to nitrite takes place. The solubilities of analysed complexes in water at 293 K are of the order of 10^–4–10^–2 mol dm^–3. The magnetic moment values of Co²⁺, Ni²⁺ and Cu²⁺ ions in 4-chloro-2-nitrobenzoates experimentally determined at 76–303 K change from 3.89 to 4.82 μ_B for Co(II) complex, from 2.25 to 2.98 μ_B for Ni(II) 4-chloro-2-nitrobenzoate, and from 0.27 to 1.44 μ_B for Cu(II) complex. 4-chloro-2-nitrobenzoates of Co(II), and Ni(II) follow the Curie–Weiss law. Complex of Cu(II) forms dimer.     

Das erste Alkali-Erdalkali-Oxocuprat(II,III): NaBa2Cu22+Cu3+O6

The first Alkaline Alkaline-Earth Oxocuprate (II, III): NaBa₂Cu₂²⁺Cu³⁺O₆ The compound NaBa₂Cu₃O₆ was prepared by heating of Na₂O₂, BaO₂, Cu₂O in closed Ag-tubes. X-ray single crystal investigations led to orthorhombic symmetry, space group D-Fmmm; a = 8.4229; b = 11.4418; c = 14.4063 Å; Z = 8. Cu²⁺ and Cu³⁺ show square planar polygones of four and Na⁺ trigonal prisms of six O^2?. The two barium point positions show coordination numbers C.N. = 8 and 6 + 4. The crystal structure is discussed.     

Influence of γ-Irradiation on the Thermal Decomposition Of (BaC2O4+CuO) Mixture

Influence of γ-irradiation, 0.1–0.75 MGy on the thermal decomposition of (BaC₂O₄+CuO, 10 mol%) mixture has been studied between the temperature range 678-718 K. It is evident from ‘α-f’ plots that decomposition of both unirradiated and irradiated mixtures follows: (i) initial gas evolution (initial puff of gas), (ii) acceleratory and (iii) decay periods. Irradiation promotes the initial gas evolution (α₁), decreases the fractional decomposition (α), the effect being higher at lower doses, without altering the nature of the isotherms. But these effects increase with increasing radiation dose. Analysis of the kinetic data in the light of theories of various kinetic models are found to be well fitted to Prout-Tompkins, Avrami-Erofeyev and contracting square mechanisms. It is found that irradiation diminishes the rate of reaction of both the periods and decreases the energy of activation of the acceleratory stage without affecting the same in the decay period. Plausible mechanism of decomposition and the effect of γ-irradiation thereon has been discussed in detail.     

Spin dimer analysis of the spin exchange interactions in paramelaconite Cu(4)O(3) and its analogue Ag(2)Cu(2)O(3) and the spin ordering of the Cu(2)O(3) spin lattice leading to their magnetic phase transitions

The magnetic structures of the Cu(2)O(3) spin lattices present in Cu(4)O(3) and Ag(2)Cu(2)O(3) were analyzed by studying their spin exchange interactions on the basis of spin dimer analysis. Calculations of spin exchange parameters were calibrated by studying LiCuVO(4) whose intrachain and interchain antiferromagnetic spin exchange parameters are known experimentally. The magnetic phase transition of Cu(4)O(3) at 42.3 K doubles the unit cell along each crystallographic direction. The spin arrangements of the Cu(2)O(3) lattice consistent with this experimental observation are different from conventional antiferromagnetic ordering. Our analysis indicates that spin fluctuation should occur in Cu(4)O(3), low-dimensional magnetism should be more important than magnetic frustration in Cu(4)O(3), and Ag(2)Cu(2)O(3) and Cu(4)O(3) should have similar structural and magnetic properties.     

4:2钼、钨过氧配合物的制备、结构及其氧化还原分解行为

本文作者曾在用过钨酸分解法制备钨酸的过程中发现, 溶液中W与O2^2^-之比始终为2:1, 这一事实说明溶液中有2:1金属过氧配合物形成, 2:1铂过氧络合物[Mo4O12(O2)2]^4^-文献上已有记载, 但类似的钨配合物尚未见报道。本文制备了这二种配合物, 对比它们的红外和Raman光谱, 并用循环伏安法, 恒电位电解法探讨它们的氧化还原分解体系。     

Synthesis, characterization and thermal behavior of 4-chloromethyl-2-(2-hydroxybenzilidenehydrazino) thiazole and its complexes with Cr(III), Co(II), Ni(II) and Cu(II)

A new ligand, 4-chloromethyl-2-(2-hydroxybenzilidenehydrazino) thiazole, has been synthesized from dicholoroacetone and 2-hydroxybenzylidenethiosemicarbazon. Metal complexes of the ligand were prepared from acetate salts of Co(II), Cu(II), Ni(II) and chloride of Cr(III) in dry acetone. Characterization of the ligand and its complexes was made by microanalyses, FT-IR, 13C, 1H NMR and UV-vis spectroscopy, magnetic susceptibility and thermogravimetric analysis. In the light of these results, it was suggested that two ligands coordinate to each metal atom by hydroxyl oxygen, imino nitrogen and thiazole ring nitrogen to form high spin octahedral complexes with Cr(III), Co(II), Ni(II) and Cu(II).     

Combination of lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions. 3. Structure and characterization of [Cu(enMe)2]2{[Cu(enMe)2(H2O)]2[Cu6(enMe)2(B-a-SiW9O34)2]}.4H2O

A novel sandwich-type polyoxometalate incorporating a unique hybrid hexanuclear copper cluster, [Cu(enMe)2]2{[Cu(enMe)2(H2O)]2[Cu6(enMe)2(B-a-SiW9O34)2]}.4H2O (1, enMe=1,2-diaminopropane), has been hydrothermally synthesized and structurally characterized by the elemental analyses, IR spectroscopy, TG analysis, magnetic properties, and single-crystal X-ray diffraction analysis. Crystal data for 1: triclinic, P; a=12.5105(2), b=14.3710(2), c=17.2687(2) A; alpha=98.834(1), beta=110.744(1), gamma=104.711(1) degrees; V=2704.57(7) A3; rho=3.646 g/cm3; Z=1. X-ray crystallographic study shows that the molecular structure of 1 contains 10 copper ions: Six of them form an unprecedented inorganic-organic hybrid Cu6 cluster via edge-sharing combination of two CuO6 octahedra, two CuO5, and two CuO3N2 square pyramids and are encapsulated between two {B-a-SiW9O34} units. Two of them form two [Cu(enMe)2(H2O)]2+ complexes and further attach to the two {B-a-SiW9O34} units via two Cu-O=W bridges, acting as a decorated role. The remaining two form isolated [Cu(enMe)2]2+ complexes playing roles of charge-compensation and space-fillers. Magnetization measurement reveals that the hexanuclear copper cluster exhibits overall ferromagnetic interactions.     

The mechanism of proton exchange: guided ion beam studies of the reactions, H(H2O)n+ (n=1-4)+D2O and D(D2O)n+ (n=1-4)+H2O

Reactions of protonated water clusters, H(H(2)O)(n) (+) (n=1-4) with D(2)O and their "mirror" reactions, D(D(2)O)(n) (+) (n=1-4) with H(2)O, are studied using guided-ion beam mass spectrometry. Absolute reaction cross sections are determined as a function of collision energy from thermal energy to over 10 eV. At low collision energies, we observe reactions in which H(2)O and D(2)O molecules are interchanged and reactions where H-D exchange has occurred. As the collision energy is increased, the H-D exchange products decrease and the water exchange products become dominant. At high collision energies, processes in which one or more water molecules are lost from the reactant ions become important, with simple collision-induced dissociation processes, i.e., those without H-D exchange, being dominant. Threshold energies of endothermic channels are measured and used to determine binding energies of the proton bound complexes, which are consistent with those determined by thermal equilibrium measurements and previous collision-induced dissociation studies. A kinetic scheme that relies only on the ratio of isomerization and dissociation rate constants successfully accounts for the kinetic energy dependence observed in the branching ratios for H-D and water exchange products in all systems. Rice-Ramsperger-Kassel-Marcus theory and ab initio calculations confirm the feasibility and establish the details of this kinetic model.