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1.
A phase diagram is constructed for the Sc2S3–Cu2S system. The system forms two incongruently melting complex sulfides: hexagonal CuScS2 (1Cu2S: 1Sc2S3): a = 0.3734 nm, c = 0.6102 nm, space group P3m1, Тm = 1635 K, ΔHm = 1670 kJ/mol; and cubic CuSc3S5 (1Cu2S: 3Sc2S3), a = 1.0481 nm, space group Fd3m, Тm = 1835 K. In the 45–62 mol % Cu2S solid solution (ss) range, there is a singular point corresponding to the composition of compound CuScS2 (50 mol % Cu2S). The Sc2S3-based solubility at 1070 K is 14 mol % Cu2S. In the γ-Cu2S-based solid solution range, there is a peritectic point at 7 mol % Sc2S3, 1423 K.  相似文献   

2.
Possibility of forming the solid phase of copper(I) and (II) sulfides in ammonia and acetate solutions at pH values exceeding 10 was demonstrated by calculation with the use of thiocarbamide. Mirror-like nanocrystalline layers of exclusively monovalent copper sulfide Cu2S of stoichiometric composition with thicknesses of up to 110 ± 10 nm were formed on glass-ceramic substrates at 298–343 K via chemical deposition from solutions of both kinds due to the reducing properties of thiocarbamide. The films produced from the acetate system are more uniform and are constituted by globules (~10 nm) forming agglomerates up to 80–150 nm in diameter. According to X-ray diffraction data, they are crystallized in the chalcocite structure (space group P21/c) with crystal lattice constants a = 1.5307(5) Å, b = 1.1908(5) Å, c = 1.3485(6) Å, and β = 116.60(1)°.  相似文献   

3.
Binuclear copper(II) complexes with acyldihydrazones of 1,3- or 1,4 benzenedicarboxylic acid and 5-methyl- or 5-bromo-2-hydroxyacetophenone in which coordination polyhedra are connected by an aromatic bridge have been synthesized and studied. The structure of the copper(II) complex with diacylhydrazone of isophthalic acid and 2-hydroxy-5-methylacetophenone (H4L) of composition [Cu2L · 3Py] was studied by X-ray diffraction. The crystals are monoclinic: a = 12.1996(12) Å, b = 17.7295(17) Å, c = 17.9339(17) Å, β = 109.7450(10)°, space group P21/n, Z = 4. The complex is of the “dimer of dimers” type and contains two binuclear subunits that bind together into a centrosymmetric dimer owing to the coordination of the copper cation to the phenoxyl oxygen atom of a neighboring binuclear molecule to form the Cu2O2 moiety, in which the copper atoms are 3.409 Å apart. The distance between the copper(II) cations in the binuclear subunit is 8.56 atoms (2N + O) of the doubly deprotonated acylhydrazone moiety and the nitrogen atom of the pyridine molecule. One of the copper cation is additionally coordinated to an extra pyridine molecule so that its coordination sphere is completed to a tetragonal pyramid. The second copper atom is involved in additional interaction with the phenoxyl oxygen atom of the neighboring molecule. The EPR spectra of solutions of the binuclear complexes show an isotropic signal of four HFS lines (g o = 2.065–2.143, a Cu = 52.1–66.5 × 10?4 cm?1) typical of mononuclear copper(II) complexes.  相似文献   

4.
Binuclear copper(II) complexes with acyldihydrazones of benzenedicarboxylic acid and trifluoroacetylacetone have been synthesized and studied. The structure of the copper(II) complex with diacylhydrazone of 1,3-benzenedicarboxylic acid (H4L) of composition [Cu2L · 2LPy] has been studied by X-ray diffraction. The crystals are triclinic: a = 9.2298(4) Å, b = 11.8510(6) Å, c = 13.8314(7) Å, α = 90.780(3)°, β = 96.124(3)°, γ = 99.264(3)°, space group \(P\bar 1\), Z = 2. The number of symmetry-unrelated reflections with I > 2σ(I) 5941; R = 0.0357, R w = 0.0589. The complex contains two equivalent copper atoms at a distance of 9.56 Å from each other in the square-planar coordination environment. The high-temperature EPR spectra of the complexes show a signal of seven HFS lines indicating the coupling of unpaired electrons to two equivalent copper nuclei (g = 2.113?2.116, a Cu = 37.0?37.2 × 10?4 cm?1).  相似文献   

5.
The O?H bond dissociation energy (D O?H) has been determined for eight alkylseleno-substituted phenols, one alkyltelluro-substituted phenol, and one alkyltelluro-substituted pyridinol. D O?H has been estimated by the intersecting-parabolas method from kinetic data using five reference compounds: α-tocopherol (D O?H = 330.0 kJ/mol), 3,5-di-tert-butyl-4-methoxyphenol (D O?H = 347.6 kJ/mol), 4-methylphenol (D O?H = 361.6 kJ/mol), 2,6-di-tert-butyl-4-methylthiophenol (D O?H = 336.3 kJ/mol), and 2,6-di-ter-tbutyl-4-methylphenol (D O?H = 338.0 kJ/mol). The following D O?H values (kJ/mol) have been obtained: 335.9 for 2,5,7,8-tetramethyl-2-phytyl-6-hydroxy-3,4-dihydro-2H-1-benzoselenopyran, 342.6 for 2-methyl-5-hydroxy-2,3-dihydrobenzoselenophene, 333.5 for 2,4,6,7-tetramethyl-5-hydroxy-2,3-dihydrobenzoselenophene, 339.4 for 2-tert-butyl-4-methoxy-6-octylselenophenol, 357.9 for dodecyl 3-(4-hydroxyphenyl) propyl selenide, 348.5 for dodecyl 3-(3,5-dimethyl-4-hydroxyphenyl)propyl selenide, 350.9 for dodecyl 3-(3-tert-butyl-4-hydroxyphenyl)propyl selenide, 338.0 for dodecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propyl selenide, 343.0 for 2,6-di-tert-butyl-4-(tellurobutyl-4′-phenoxy)phenol, and 338.8 for 6-octyltelluro-3-pyridinol. The stabilization energies of phenoxyl radicals containing R substituents (X = O, S, Se, Te) have been compared.  相似文献   

6.
The structure and EPR spectra of copper(II) complexes with bis(salicylidene)hydrozones of N-benzoyl-L-aspartic and N-benzoyl-L-glutamic acids have been described. The compounds have been studied by chemical and thermal analyses, IR spectroscopy, and EPR spectroscopy. The molecular and crystal structure of the copper(II) complex with bis(salicylidene)hydrozone of N-benzoyl-L-aspartic acid (H4L) of composition [Cu2L · 2Py] · 2CH3OH · H2O has been determined by X-ray single-crystal diffraction. The crystals are monoclinic: a = 10.3316(7) Å, b = 16.7552(9) Å,c = 11.0137(6) Å, β = 105.758(3)°, space group P21, Z = 2. The complex has a polymeric structure composed of alternating copper-containing binuclear fragments bound to each other either via phenoxy bridges or via an aliphatic spacer (the Cu…Cu distances are 3.471 Å and 8.939 Å, respectively). The EPR spectra of the solutions of the complexes under study shows an isotropic signal comprising seven HFS lines due to two equivalent copper nuclei with the spin Hamiltonian parameters g = 2.115–2.122 and a Cu = (36.1–36.9) × 10?4 cm?1, which indicates the reaization of weak exchange coupling of the paramagnetic centers.  相似文献   

7.
A trinuclear copper(II) complex of trimesic acid salicylidene hydrazone (H6L) having the composition [Cu3L · 4Py] · CH3OH was synthesized and characterized. By X-ray crystallography, the crystals are triclinic: a = 11.7940(4) Å, b = 13.7241(5) Å, c = 15.8993(6) Å, α = 107.4120(10)°, β = 94.2900(10)°, γ = 105.5650(10)°, space group \(P\bar 1\), Z = 2. The number of symmetrically unique reflections having I > 2σ(I) is 7636, R = 0.0465, and R w = 0.1198. The newly prepared complex contains, in its unit cell, two [Cu3L · 4Py] molecules which are linked to form a dimer on account of phenoxo bridges (the Cu-O bond length is 2.555 the Cu…Cu distance is 3.348 Separations between them are 9.414, 9.371, and 9.667 of temperature is satisfactorily fitted in terms of a triangular cluster model (?2J = 2.2 cm?1) with extra intermolecular interactions (zJ′ = 0.4 cm?1). EPR spectra of solutions at 360–380 K feature a poorly resolved HFS, whose modeling gives a satisfactory result with allowance for the interaction of unpaired electrons with three equivalent copper nuclei (g = 2.098; a Cu = 25.8 × 10?4 cm?1).  相似文献   

8.
A tetragonal (123) phase of composition CdBa2Cu2WO8 with the complete and selective substitution of tungsten atoms for copper in the Cu(1) positions is synthesized from CdWO4 and BaCuO2 at 800°C in flowing oxygen. The percentage of the (123) phase in the sample is at least 90%; the unit cell parameters are a = b = 0.4151(3) nm, c = 1.2537(8) nm. The X-ray diffraction pattern shows a superstructure with all three of the unit cell parameters being doubled.  相似文献   

9.
The process of reduction of divalent copper ions with tert-butylamine borane in dilute aqueous solutions of poly(N-vinylpyrrolidone) is investigated. The influence of polymer molecular mass on properties of the resultant Cu2O sols is studied. It is shown that Cu2O nanoparticles with an average diameter of 6–8 nm independent of polymer molecular mass and a relatively narrow size distribution of particles are formed in the systems under study. The contour length of macromolecules and the hydrodynamic diameter of a poly(N-vinylpyrrolidone) macromolecular coil are compared with the diameter of Cu2O particles. Poly(N-vinylpyrrolidone) with M ≥ 1 × 104 can be used to produce Cu2O nanoparticles. Poly(N-vinylpyrrolidone) with M > 4 × 104 should be used for the formation of long-living Cu2O sols.  相似文献   

10.
The crystal and molecular structure of tris(m-chlorophenyl)phosphine selenide, C18H12Cl3PSe (I), was investigated by X-ray diffraction (XRD) analysis. The trigonal rhombohedral structure of I (space group \(R\overline 3 c\), a = 14.110(2) Å, c = 32.360(4) Å, Z = 12) was solved by direct methods and refined by least squares in an anisotropic approximation (R = 0.029) for 1319 averaged measured reflections (CAD-4 automatic diffractometer, λCuKα).  相似文献   

11.
A Cu1O1.7 oxide film containing a large amout of superstoichiometric oxygen was obtained by low-temperature oxidation of metallic copper in the oxygen plasma. An STM study of the film structure showed that ~10 nm planar copper oxide nanocrystallites with particles packed parallel to the starting metal surface. In an XPS study, the spectral characteristics of the Cu2p and O1s lines indicated that particles with a CuO lattice formed (E bnd(Cu2p 3/2) = 933.3 eV and a shake-up satellite, E bnd(O1s) = 529.3 eV). The additional superstoichiometric oxygen is localized at the sites of contact of nanoparticles in the interunit space and is characterized by a state with the binding energy E bnd(O1s) = 531.2 eV. Due to the formation of a nanostructure in the films during low-temperature plasma oxidation, the resulting copper oxide has a much lower thermal stability than crystalline oxide CuO.  相似文献   

12.
The binuclear copper(II) complexes with acyldihydrazones formed by 1,4-cyclohexanedicarboxylic acid and salicylaldehyde or 2-hydroxyacetophenone were synthesized and studied. The structure of the complex with 1,4-cyclohexanedicarboxylic acid bis(salicylidene)hydrazone (H4L1) [Cu2L1(Py)2] was studied by X-ray diffraction. The crystals are triclinic: a = 8.1852(4) Å, b = 8.5157(5) Å, c = 11.6553(7) Å, α = 80.678(3)°, β = 70.041(4)°, γ = 74.803(3)°. Space group \(P\bar 1\), Z = 1. The number of symmetrically independent reflections with I > 2(σ(I)) is 2245, R = 0.0395; R w = 0.0917. The complex contains two equivalent copper atoms located at a 10.772 Å distance from each other. The coordination polyhedra have a square geometry and are involved in the intermolecular π/π-stacking. The EPR spectra of solutions of the binuclear complexes show an isotropic signal of seven HFS lines (g = 2.113–2.118, A Cu ≈ 38 G), indicating interaction between the unpaired electrons and the two equivalent copper nuclei. The possible exchange interaction channels were analyzed.  相似文献   

13.
A Sm–Sm2Se3 phase diagram has been studied from 1000 K until melting. This system forms three congruently melting compounds: SmSe (ST NaCl, a = 0.6200 nm, Tm = (2400 ± 50) K, and H = 2750 MPa), Sm3Se4 (ST Th3P4, a = 0.8925 nm, Tm = (2250 ± 30) K, and H = 3350 MPa), and Sm2Se3 (ST Th3P4, a = 0.8815 nm, Tm = (2150 ± 40) K, and H = 5300 MPa). There are eutectics between Sm and SmSe phases and between SmSe and Sm3Se4 phases at 2.5 at % Se, 1300 K and at 54.5 at % Se, 2100 K, respectively. Within the extent of Sm2+ Sm23+ Se4–Sm23+Se3 solid solution (ST Th3P4), the experimentally determined percentages of Sm2+ ions correspond with the values calculated from the formula compositions of samples. The bandgap width for SmSe1.45 and SmSe1.48 phases is ΔE = (1.90 ± 0.05) eV.  相似文献   

14.
Existence boundaries, structure, and transport parameters of ultrafine powders were studied in Bi4V2 ? x Fe x O11 ? x (BIFEVOX) solid solutions. The details of synthesis of the solid solutions via liquid precursors are analyzed comparatively. In general, BIFEVOX formation via liquid precursors is similar to phase formation in solid-phase synthesis. With low iron levels (x = 0.05–0.1), solid solutions are formed in the monoclinic α phase (space group C2/m) The compositions with x = 0.125 and 0.15 are mixtures of α- and β phases. In the range 0.2 < x < 0.7, the Bi4V2 ? x Fe x O11 ? x solid solution has the structure of the γ phase of Bi4V2O11 (space group I4/mmm). The β phase in the system in question has a very narrow existence range in the vicinity of x = 0.175. The average particle sizes of the powders prepared by various methods are within 0.5–3 μm. In the powders prepared via liquid precursors, however, the distribution peak shifts toward smaller sizes, to 0.3–1 μm. Mechanical activation conserves the structure of the γ phase of BIFEVOX, and unit cell parameters change only insignificantly; however, the crystal lattice is slightly distorted. The electrical conductivity of BIFEVOX was studied as a function of temperature, preparation technology, and composition using impedance spectroscopy. Equivalent circuits of cells were analyzed. The conductivity of samples prepared by solution technology is always higher than for samples prepared by the solid-phase process. Features of electrical conductivity versus temperature for various phases are noted. All transitions on the conductivity curves match the features of linear thermal expansion curves. Compositions with doping levels x= 0.1–0.3 have the highest total conductivities.  相似文献   

15.
Some earlier synthesized copper selenide (Cu x Se) layers formed on the surface of polyamide 6 by sorption-diffusion method using potassium selenotrithionate (K2SeS2O6) as precursor of selenium were characterized by the XRD, XPS and SEM methods. According to the results of the SEM studies, the most uniform Cu x Se layers form at the 2.5 h polyamide seleniumized duration at the temperature of 60°C. The thickness of layers, which dependeds on the duration of seleniumization, changed in the range of 0.8–3.2 µm. The XRD patterns of not previously studied Cu x Se layers showed their phase composition of six copper selenides: Cu2Se, two phases of CuSe2, Cu3Se2, berzellianite, Cu2-x Se, and bellidoite Cu2Se. Analysis of the XRD and XPS data shows that the macrostructure and composition of the CuxSe layers depend on the conditions of formation of these layers.   相似文献   

16.
A new mixed-ligand one-dimensional copper(II) coordination polymer [Cu(en)(sal)Cl] n where en = ethylenediamine(C2H8N2) and Hsal = 2-hydroxybenzoic acid (salicylic acid; C7H6O3) is synthesized and characterized by FTIR spectroscopy and single crystal X-ray diffraction. The structure contains Cu2+ ions in two different distorted octahedral coordination environments: an axially extended CuN4Cl2 moiety arising from a pair of bidentate en ligands and a CuO4Cl2 moiety arising from a pair of asymmetrically coordinated sal anions. The chloride ions bridge the copper ions into a zigzag chain propagating in [001]. The structure is consolidated by N–H???O and N–H???Cl hydrogen bonds which generate a layered network. Crystal data: C9H13ClCuN2O3, M r = 296.20, monoclinic, P21/c, a = 13.9179(10) Å, b = 10.4900(8) Å, c = 8.5181(6) Å, β = 105.518(4)°, V = 1198.30(15) Å3, Z = 4, R(F) = 0.026, w R(F 2) = 0.068.  相似文献   

17.
The catalytic properties of a series of copper chromite ferrite samples with the composition CuCr2–xFexO4 (where x = 0–2) and a spinel-type structure in reactions with reducing (water gas shift reaction, WGSR) and oxidizing (the oxidation of hydrogen) reaction atmospheres were studied. The samples were obtained by the thermal decomposition of mixed hydroxo compounds. The distribution of Cu2+ ions in the tetrahedral and octahedral crystallographic positions of spinel, which depends on the Cr3+/Fe3+ ratio, affects the apparent activation energy (Ea) in both of the reactions. In WGSR, Ea is ~33 kJ/mol for CuCr2O4, in which Cu2+ ions mainly occupy tetrahedral positions, whereas Ea ≈ 100 kJ/mol for CuFe2O4, in which Cu2+ ions mainly occupy octahedral positions. In the reaction of hydrogen oxidation, Ea is ~71 kJ/mol for CuCr2O4 or ~42 kJ/mol for CuFe2O4. The value of Ea for the mixed chromite ferrites changes with the replacement of chromium ions by iron ions and, hence, with a ratio between the amounts of copper ions in the tetrahedral and octahedral oxygen positions of spinel.  相似文献   

18.
A novel Cu(II) complex Cu2(Endc)2(Bipy)2 has been synthesized by the reaction of Cu(NO3)2 · 3H2O, Endc (endo-norbornene-cis-5,6-dicarboxylic acid), and Bipy (2,2-bipyridine) at room temperature. Elemental analysis, IR spectra, and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. Crystal data for this complex: triclinic, P \(\bar 1\) with a = 9.0373(10), b = 10.1637(11), c = 10.5574(12) Å, α = 65.78(1)°, β = 72.32(2)°, β = 73.23(2)°, Z = 1, V = 827.46(16) Å3, ρ c = 2.160 g/cm3, F(000) = 410.0, R = 0.0483 and wR = 0.0958 independent reflections for 4468 observed ones (I > 2 σ(I)).The Cu2+ ion is coordinated by two nitrogen atoms from the Bipy molecule and three oxygen atoms from two Endc, giving a distorted squarepyramidal coordination geometry. Two neighboring Cu2+ ions are bridged by a pair of bimonodentate carboxyl groups of different Endc acids, giving a centrosymmetrical binuclear structure which a Cu…Cu distance of 3.2946 Å. The photoluminescence properties of the complex were studied at room temperature. The complex displays an obvious photoluminescent emission upon excitation at 390 nm in the solid state.  相似文献   

19.
Phase equilibria in the systems SrS-Cu2S-Ln2S3 (Ln = La or Nd) have been studied along the isothermal section at 1050 K and vertical sections CuLnS2-SrS and Cu2S-SrLnCuS3, which are partially quasibinary joins. Compounds SrLnCuS3 with Ln = La or Nd have been synthesized for the first time. They crystallize in orthorhombic space group Pnma, the BaLaCuS3 structure type, with the following unit cell parameters: for SrLaCuS3, a = 1.1157(2) nm, b = 0.41003(6) nm, c = 1.1545(2) nm; for SrNdCuS3, a = 1.1083(1) nm, b = 0.40887(7) nm, c = 1.1477(2) nm. Noticeable homogeneity regions for SrLnCuS3 are not found. The compounds melt congruently by the reaction SrLnCuS3 ? SrS + L at 1365 K for SrLaCuS3 and 1400 K for SrNdCuS3. The tie-lines at 1050 K in the systems SrS-Cu2S-Ln2S3 radiate from SrLnCuS3 toward phases SrS, Cu2S, CuLnS2, and SrLn2S4, lying between the phases CuLnS2 and compositions from the γ-Ln2S3-SrLn2S4 solid-solution field. Eutectics are formed between the compounds CuLaS2 and SrLaCuS3 at 21.0 mol % SrS, T = 1345 K; between the compounds CuNdS2 and SrNdCuS3 at 31.0 mol % SrS, T = 1310 K; and between the phases Cu2S and SrLnCuS3 at 14.0 mol % SrLaCuS3, T = 1075 K and 8.0 mol % SrNdCuS3, T = 1055 K.  相似文献   

20.
Phase equilibria in the isothermal (970 K) and polythermal LaCuS2–EuS, Cu2S–EuLaCuS3, LaCuS2–EuLa2S4, and EuLaCuS3–EuLa2S4 sections of the Cu2S–La2S3–EuS system have been studied. EuLaCuS3 (annealing at 1170 K) is of orthorhombic system, space group Pnma, a = 8.1366(1) Å, b = 4.0586(1) Å, c = 15.9822(2) Å, is isostructural to Ba2MnS3, and incongruently melts by the reaction EuLaCuS3cryst (0.50 EuS; 0.50 LaCuS2) ? 0.22 EuS SS (0.89 EuS; 0.11 LaCuS2) + 0.78 liq (0.39 EuS; 0.61 LaCuS2); ΔН = 52 J/g. The Cu2S–La2S3–EuS system has been found to contain five major subordinate triangles. At 970 K, tie-lines lie between EuLaCuS3 and the Cu2S, EuS, LaCuS2, and EuLa2S4 phases and between the LaCuS2 phase and the γ-La2S3–EuLa2S4 solid solution. Eutectics are formed between LaCuS2 and EuLaCuS3 at 26.0 mol % of EuS and T = 1373 K and between EuLaCuS3 and EuLa2S4 at 29.0 mol % of EuLa2S4 and T = 1533 K.  相似文献   

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