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1.
Electronic states of CeO2, Ce1????em>x Pt x O2????em>δ , and Ce1????em>x????em>y Ti y Pt x O2????em>δ electrodes have been investigated by X-ray photoelectron spectroscopy as a function of applied potential for oxygen evolution and formic acid and methanol oxidation. Ionically dispersed platinum in Ce1????em>x Pt x O2????em>δ and Ce1????em>x????em>y Ti y Pt x O2????em>δ is active toward these reactions compared with CeO2 alone. Higher electrocatalytic activity of Pt2+ ions in CeO2 and Ce1????em>x Ti x O2 compared with the same amount of Pt0 in Pt/C is attributed to Pt2+ ion interaction with CeO2 and Ce1????em>x Ti x O2 to activate the lattice oxygen of the support oxide. Utilization of this activated lattice oxygen has been demonstrated in terms of high oxygen evolution in acid medium with these catalysts. Further, ionic platinum in CeO2 and Ce1????em>x Ti x O2 does not suffer from CO poisoning effect unlike Pt0 in Pt/C due to participation of activated lattice oxygen which oxidizes the intermediate CO to CO2. Hence, higher activity is observed toward formic acid and methanol oxidation compared with same amount of Pt metal in Pt/C.  相似文献   

2.
Continuous variation method in UV revealed that methyl N-acetylaminoacrylate (MNA) and SnCl4 formed the 1:1 complex. The copolymerization of MNA with styrene in tetrahydrofuran was carried out at 50 °C in the presence of SnCl4. The resulting monomer reactivity ratios decreased with an increasing concentration of SnCl4 added. This finding suggests that SnCl4 participates in the propagation step of the copolymerization. Therefore, the copolymerization was analyzed by assuming terpolymerization of free MNA (M1), complexed MNA (M2), and styrene (M3). The absolute copolymerization parameters were obtained as follows: k11/k12=0.165, k11/k13=3.04, k22/k21=0.32, k22/k23=0.103, k33/k31=0.058, k33/k32=0.001, Q1=6.03, e1=0.52, Q2=88.57, and e2=2.23. The complexed MNA is more reactive to polymer radicals with free MNA and styrene as the terminal unit than the free MNA. Very small values of k22/k23 and k33/k32 suggests that the copolymerization of the complexed MNA and styrene proceeds alternatingly.  相似文献   

3.
Quasi-one-dimensional (1D) solid solutions Ti1 ? x Fe x (OCH2CH2O)2 ? x/2 (0 < x ≤ 0.1) with the structure of anatase were prepared by heating the glycolate Ti1 ? x Fe x (OCH2CH2O)2 ? x/2 in an atmosphere of air at a temperature of >450°C. The conditions of formation and the properties of the new glycolate Ti3Fe2(OCH2CH2O)9 were described. It was found that the synthesized Ti1 ? x Fe x O2 ? 2x/2 solid solutions exhibit photocatalytic activity in the reaction of hydroquinone oxidation in an aqueous solution on irradiation with UV light. A correlation between the rate of oxidation of hydroquinone and the concentration of iron in the catalyst was established. A procedure for the preparation of titanium dioxide with the structure of anatase doped with iron and carbon (Ti1 ? x Fe x O(2 ? x/2) ? yCy) and also composites on its basis, which contain an excess amount of carbon, was proposed.  相似文献   

4.
Magnetic and electron transport properties of four series of manganates of the composition La0.5−xLnxSr0.5MnO3 (Ln=Pr, Nd, Gd and Y) have been investigated to examine how the ferromagnetic metallic nature of the parent La compound changes over to antiferromagnetic insulating behavior, with change in Ln and x due to the associated changes in the A-site cation radius as well as the size disorder. When Ln=Pr and Nd, there is a transition from the tetragonal I4/mcm structure to the orthorhombic Immm and Imma structures at x=0.2 and 0.35, respectively. There is a gradual evolution of the properties from those of La0.5Sr0.5MnO3 to those of Pr0.5Sr0.5MnO3 or Nd0.5Sr0.5MnO3 with increase in x. Thus, when x>0.2 and >0.35, respectively, the Pr- and Nd-substituted manganates show ferromagnetic transitions followed by antiferromagnetic transitions at low temperatures, with the ferromagnetic TC decreasing with increasing x. The Gd and Y series of compounds are all orthorhombic and show a decrease in TC with the increase in x, the ferromagnetism disappearing at high x. At a value of x corresponding to the A-site cation radius of Pr0.5Sr0.5MnO3, the Gd and Y series of compounds exhibit ferromagnetism in the 250-300 K region and undergo an antiferromagnetic transition on cooling. The TCTN gap is sensitive to the disorder arising from the size mismatch.  相似文献   

5.
The crystal structures of Bi2.5Na0.5Ta2O9 and Bi2.5Nam-1.5NbmO3m+3 (m=3,4) have been investigated by the Rietveld analysis of their neutron powder diffraction patterns (λ=1.470 Å). These compounds belong to the Aurivillius phase family and are built up by (Bi2O2)2+ fluorite layers and (Am-1BmO3m+1)2- (m=2-4) pseudo-perovskite slabs. Bi2.5Na0.5Ta2O9 (m=2) and Bi2.5Na2.5Nb4O15 (m=4) crystallize in the orthorhombic space group A21am, Z=4, with lattice constants of a=5.4763(4), b=5.4478(4), c=24.9710 (15) and a=5.5095(5), b=5.4783(5), c=40.553(3) Å, respectively. Bi2.5Na1.5Nb3O12 (m=3) has been refined in the orthorhombic space group B2cb, Z=4, with the unit-cell parameters a=5.5024(7), b=5.4622(7), and c=32.735(4) Å. In comparison with its isostructural Nb analogue, the structure of Bi2.5Na0.5Ta2O9 is less distorted and bond valence sum calculations indicate that the Ta-O bonds are somewhat stronger than the Nb-O bonds. The cell parameters a and b increase with increasing m for the compounds Bi2.5Nam-1.5NbmO3m+3 (m=2-4), causing a greater strain in the structure. Electron microscopy studies verify that the intergrowth of mixed perovskite layers, caused by stacking faults, also increases with increasing m.  相似文献   

6.
The structure and magnetic properties of the RCo5Ga7 (R=Y, Tb, Dy, Ho and Er) compounds with the ScFe6Ga6-type structure have been studied. The stability of RCo5Ga7 is closely related with the ratio of the metal radii RRE/R(Co,Ga). With RRE/R(Co,Ga)?1.36, the compounds can be stabilized in the ScFe6Ga6-type structure. The lattice of RCo5Ga7 shrinks as the atomic order of R increases, and it is consistent with the lanthanide contraction. The structure analysis based on X-ray diffraction patterns reveals that in the orthorhombic RCo5Ga7 (Immm), R occupies the 2a site, and Co enters into the 8k and the 4h sites, and Ga is at the 4e, 4f, 4g, 4h and 8k sites. The interatomic distances and the coordination numbers of RCo5Ga7 are provided from the refinement results. The short interatomic distance (less than 2.480 Å) between the Co ions results in the negative magnetic interaction, which does not favor ferromagnetic ordering. The magnetic moment of YCo5Ga7 is absent, and RCo5Ga7 (R=Tb, Dy, Ho and Er) may have long-range magnetic ordering with the paramagnetic Curie temperature lower than 5 K.  相似文献   

7.
At constant temperature (isothermal) maintained throughout in the capacitive discharge technique, the measured absorbance at any time t due to concentration of analyte atoms can be given by: absorbance = p[A]0{k1/(k1?k2)}[exp(?k2t)-exp(?k1t)], where p is a function of the oscillator strength (a constant) and the efficiency with which the analyte atoms are produced, [A]0 is the initial concentration of the analyte atoms, k1 and k2 are first-order rate constants for formation and decay of analyte atoms, respectively. This technique yields k1?k2 and k1t?k2t; and so the above equation reduces to: absorbance ?p[A]0, resulting in large enhancement in sensitivity. In the case of lead, the immediate precursor of the gaseous lead monomer is the gaseous lead dimer, which is partly lost by diffusion of the lead dimer with a first-order rate constant, k3. The kinetic parameters k1, k2 and k3 have been evaluated, and the values of k1 at different temperatures used to draw the Arrhenius plots, from which activation energies of the rate-determining steps have been determined. The activation energies have been used to elucidate atomization mechanisms by extensive correlation of the experimental energy values with the literature values.  相似文献   

8.
The influence of Bi3+ on the structural and magnetic properties of the rare-earth-containing perovskites REFe0.5Mn0.5O3 (RE=La,Nd) was studied, and the limit of bismuth substitution was determined to be x≤0.5 in BixRE1−xFe0.5Mn0.5O3+δ (RE=La,Nd) at ambient pressure. Crystal structures in both La and Nd series were determined to be GdFeO3-type Pnma with the exception of the Bi0.3La0.7Fe0.5Mn0.5O3 sample, which is monoclinic I2/a in the abb tilt scheme. The samples undergo a transition to G-type antiferromagnetic order along with a weak ferromagnetic component, mixed with cluster-glass type behavior. The substitution of bismuth into the lattice results in a drop in TN relative to the lanthanide end-members. Long range ordering temperatures TN in the range 240-255 K were observed, with a significantly lower ordered magnetic moment in the case of lanthanum (M∼1.7-1.9 μB) than in the case of neodymium (M∼2.1 μB).  相似文献   

9.
The phase diagram and metal distribution of the (CrxTi1?x)3Se4 system were studied by X-ray, neutron diffraction, and DTA measurements. The metal distribution of MM2X4 with the Cr3S4-type structure, which was estimated from the composition dependence of lattice parameters in the solid solution (MxM1?x)3X4 system, was in good agreement with results from other measurements such as neutron diffraction and Mössbauer effect.  相似文献   

10.
Nine novel sulfate-type hybrid surfactants, CmF2m+1C6H4CH(OSO3Na)CnH2n+1 (FmPHnOS: m=4, 6, 8; n=3, 5, 7; C6H4: p-phenylene), with a benzene ring in their molecules were synthesized. Alkanoyl chlorides were allowed to react with iodobenzene in the presence of aluminum chloride to give the corresponding aromatic ketones. The reaction of the ketones with perfluoroalkyl iodides yielded 1-[4-(perfluoroalkyl)phenyl]-1-alkanones as intermediates. The intermediates were allowed to react with methanol in tetrahydrofuran in the presence of sodium borohydride to yield 1-[4-(perfluoroalkyl)phenyl]-1-alkanols. The desired hybrid surfactants were obtained by the reaction of 1-[4-(perfluoroalkyl)phenyl-1-alkanols with sulfur trioxide/pyridine complex in pyridine and by the subsequent neutralization of the products with sodium hydroxide solution. When compared with the conventional hybrid surfactants, CmF2m+1C6H4COCH(SO3Na)CnH2n+1 (FmHnS: m=4, 6; n=2, 4, 6; C6H4: p-phenylene), the new hybrid surfactants thus synthesized were found to have a comparable ability to lower the surface tension of water and a high hydrophilicity. The cmc of FmPHnOS obeyed Kleven’s rule and their occupied areas per molecule increased with increasing m and n with the values between 0.66 and 1.05 nm2. The aggregation number for FmPHnOS micelles ranged from 6 to 45 and the hydrodynamic radius of the micelles was in the range of 1.4-3.1 nm.  相似文献   

11.
We have investigated the magnetic and dielectric properties of YbFe2−xMnxO4 (0?x?1), which is an Fe-site-substituted system of new multiferroic oxides RFe2O4 (R=Y, Ho-Lu). X-ray diffraction measurements show that a solid solution is formed between YbFe2O4 (x=0) and YbFeMnO4 (x=1) for 0?x?1, whereas only compounds with x=1 (i.e., RM1M2O4; M1 and M2=trivalent and divalent cations, respectively) have been known for the Fe-site substitution in RFe2O4. The valence of the Mn ion is determined to be ∼2+, consistently with the suppression of low-temperature magnetization by the Mn substitution. The magnetic transition temperature (TN) and the dielectric constant (ε′) decrease monotonically with increasing x. This result plausibly confirms that the magnetic and dielectric properties in oxides isostructural with RFe2O4 are governed by the electron transfer between Fe-site ions, unlike ordinary ferroelectrics and dielectrics, in which the ionic displacement plays a key role. The possibility for application is briefly discussed as well.  相似文献   

12.
Optical rotatory dispersion and circular dichroism studies have allowed the determination of the changes in configuration at the molybdenum center upon displacement of carbonyl and iodide in neomenthylcyclopentadienyl—Mo(allyl)(NO)X systems. Displacement of carbonyl by iodide occurs with retention of configuration. Replacement of iodide with benzenesulfonate followed by replacement of the sulfonate with iodide occurs stereospecifically with net retention of configuration. In the case of cyclopentadienylMo(cyclooctenyl)(NO)I, the enantiomers were separated via a spontaneous resolution through crystallization of the complex in the space group P212121. These studies have allowed the correlation not only of the absolute configuration at the metal center with CD studies, but also have established that a long wavelength optically active transition at approximately 400 nm can be correlated with endo-exo isomerism. Comparison of the rates of interconversion suggest that endo to exo isomerization occurs via a clockwise rotation of the allyl in the (R)-isomer. Crystallographic details: (—)-(S)-(NMCp)Mo(allyl)(NO)I crystallizes in the space group P212121 with a 7.221(1), b 12.686(7), c 21.603(7) Å, Z = 4, V = 1979(2) Å3; R1 = 0.039, R2 = 0.046; (—)-(S)-(Cp)Mo(cyclooctenyl)(NO)I crystallizes in the space group P212121 with a 8.466(1), b 10.449(2), c 16.372(2) Å, Z = 4, V = 1448.3(6), R1 = 0.038, and R2 = 0.046.  相似文献   

13.
The (1?x)CsHSO4-xKH2PO4 system was studied in a wide range of compositions (x = 0.05?0.97). Mixed salts with different crystal structures and different transport, thermodynamic, and thermal properties were shown to form. In these mixed (1?x)CsHSO4-xKH2PO4 compounds (x = 0.05?0.5), solid solutions formed on the basis of the compound with a crystal structure Cs3(HSO4)2(H2PO4) (C2/c). As the content of KH2PO4 increased further, another compound with a crystal structure, CsH5(PO4)2 (P21/c), formed and existed up to x = 0.95. At x ≥ 0.7, KH2PO4 existed as an individual phase along with CsH5(PO4)2; its content increased considerably at x ≥ 0.9. The low conductivities and high activation energies of (1?x)CsHSO4-xKH2PO4 at x = 0.6?0.95 were close to those for CsH5(PO4)2. The compounds with x = 0.5–0.9 showed low thermal stability corresponding to the individual CsH5(PO4)2 phase.  相似文献   

14.
The effect of substitution of the cation Cr by Ti in Cr5Te8 has been investigated with respect to its crystal structure, magnetic properties, and electronic structure. The compounds Cr5−xTixTe8 (x=0, 0.5, 1, 1.5, 1.85, 2, 3, 4, 5) were synthesized at elevated temperatures followed by slow cooling the samples to room temperature. The crystal structures have been refined with X-ray powder diffraction data with the Rietveld method. Three structural modifications are identified: monoclinic with space group F2/m for Cr5−xTixTe8 (x=0, 0.5, 1, 1.5, 1.85), trigonal supercell with space group P-3m1 for Cr5−xTixTe8 (x=2, 3), and trigonal basic cell with space group P-3m1 for Cr5−xTixTe8 (x=4, 5). The structures of all these phases are related to the NiAs structure with full and deficient metal layers stacking alternatively along the c-axis.The irreversibility in the field-cooled/zero-field-cooled magnetization with low field depends strongly on the Ti concentration x. Four types of magnetic states are distinguished: re-entrant ferromagnet for m-Cr5Te8, cluster-glass for m-Cr4.5Ti0.5Te8 and m-Cr4TiTe8, antiferromagnetic for m-Cr3.5Ti1.5Te8, and spin-glass for tr-Cr3Ti2Te8, tr-Cr2Ti3Te8, and Cr0.25TiTe2.Accompanying spin polarized scalar-relativistic Korringa-Kohn-Rostoker band-structure calculations strongly support the observation that the crystallographic sites in the full metal layers are preferentially occupied and predict that Ti atoms have the preference to occupy the full metal layers. These compounds are predicted metallic. Results for the spin-resolved DOS and magnetic moments on each crystallographic sites are presented.  相似文献   

15.
The chemical stability of perovskite-type La1−xCaxCrO3−δ (x=0.1, 0.2, 0.3) in high oxygen partial pressure, PO2, was investigated with three methods: thermogravimetry, XRD analysis, and thermodynamic calculation. The second phase, CaCrO4 was observed by XRD analysis on the powder equilibrated in high PO2. Thermogravimetry under fixed temperatures sensitively detected the segregation of the second phase in the form of oxygen incorporation, because oxidation of chromium ion accompanies the segregation. The second phase tended to appear in high PO2 and at low temperature. The single-phase regions of La1−xCaxCrO3−δ obtained from the two experimental methods well agreed with each other. The results of thermodynamic calculation on the assumption of ideality of the solid solution also agreed with the experimental results. These results suggested the sufficient chemical stability of La1−xCaxCrO3−δ in high PO2 concerning the application to an interconnector of high-temperature solid oxide fuel cells; for example, La0.7Ca0.3CrO3−δ is stable at 1273 K in air.  相似文献   

16.
Large single crystals from RENi2-xP2 (RE=La, Ce, Pr) were synthesized from the pure elements using Sn as a metal flux, and their structures were established by X-ray crystallography. The title compounds were confirmed to crystallize in the body-centered tetragonal ThCr2Si2 structure type (space group I4/mmm (No. 139); Pearson's symbol tI10), but with a significant homogeneity range with respect to the transition metal. Systematic synthetic work, coupled with accurate structure refinements indicated strong correlation between the degree of Ni-deficiency and the reaction conditions. According to the temperature dependent dc magnetization measurements, LaNi2-xP2 (x=0.30(1)), as expected, is Pauli-like paramagnetic in the studied temperature regime, while the Ce-analog CeNi2-xP2 (x=0.28(1)) shows the characteristics of a mixed valent Ce3+/Ce4+ system with a possible Kondo temperature scale on the order of 1000 K. For three different PrNi2-xP2 (x?0.5) samples, the temperature and field dependence of the magnetization indicated typical local moment 4f-magnetism and a stable Pr3+ ground state, with subtle variations of TC as a function of the concentration of Ni defects. Field-dependent heat capacity data for CeNi2-xP2 (x=0.28(1)) and PrNi2-xP2 (x=0.53(1)) are discussed as well.  相似文献   

17.
In a series of norbornanes, benzonorbornenes, and norbornenes, the vicinal cis couplings 3Jexo,exo and 3Jendo,endo are determined. A trend is recognized in which Jexo,exo steadily decreases in this series while Jendo,endo remains relatively constant; in norbornenes Jexo,exo and Jendo,endo are about the same. These observations are understood by means of theoretical calculations performed for representative compounds of the series. This study indicates that interactions of the C7-methylene bridge with the bonds of the C2C3 ethylene bridge are responsible for the nonequivalence of Jexo,exo and Jendo,endo in norbornanes, and that in norbornenes interaction of the olefin functionality with bonds of the ethylene bridge is responsible for bridging Jexo,exo back fortuitously close to Jendo,endo.  相似文献   

18.
A new palladium-bidentate complex [m-C6H4(CH2ImMe)2(PdCl2)] (III) was prepared in two steps. In the first step, [m-C6H4(CH2ImMeAgCl)2] (II) (Im = imidazole moiety) was obtained by reacting imidazolium salt [m-C6H4(CH2ImMe)2]Cl2 (I) (prepared by quaternisation of Nmethylimidazole with 1,3-bis(chloromethyl)benzene) and Ag2O in CH2Cl2. In the next step, treatment of (II) with Pd(CH3CN)2Cl2 afforded complex III which was evaluated for its catalytic activity for C-C bond-formation reactions by examining the coupling reaction of 3-iodoanisole with phenylacetylene in the Sonogashira reaction. In addition, 3-methoxybiphenyls were obtained with good to excellent yields by Suzuki coupling reactions of 3-iodoanisole with phenylboronic acids or phenylborates salts in the presence of this complex.  相似文献   

19.
New cation-deficient solid solutions of Ca3–1.5xYbx0.5xB2SiO8 (x = 0–0.4) based on Ca3B2SiO8 borosilicate were synthesized. It was found that solid solutions in the range 0 ≤ x < 0.125 are structurally similar to the low-temperature monoclinic β-Ca3B2SiO8, whereas those of the range 0.187 < x < 0.4 are similar to the high-temperature orthorhombic α-Ca3B2SiO8. The crystal structures of solid solutions with x = 0.2 and 0.3 were determined from single crystal X-ray diffraction data and refined in the orthorhombic space group Pnma to Robs = 0.051 and 0.057, respectively. Thermal expansion of the samples with x = 0.1, 0.3 was investigated using powder high-temperature X-ray diffraction in the temperature range of 20–800 °C. Photoluminescence spectra of Ca3–1.5xYbx0.5xB2SiO8 consist of the intra-configurational 2F5/22F7/2 transitions inside of Yb3+ ions with a maximum at 975 nm.  相似文献   

20.
The influence of Zn-doping on the crystal structure and magnetic properties of the spin ladder compounds La2Cu2O5 (4-leg) and La8Cu7O19 (5-leg) have been investigated. The La2(Cu1−xZnx)2O5 and La8(Cu1−xZnx)7O19 solid solutions were obtained as single phases with x=0-0.1 via the solid-state reaction method in the temperature range between 1005-1010 °C and 1015-1030 °C in oxygen and air atmospheres, respectively. The lattice parameters a and c of the monoclinic crystal structures as well as the unit cell volume V increase with increasing x, while b and β decrease for both series. The magnetic susceptibilities χ of both series show a very similar behavior on temperature as well as on Zn-doping, which is supposed to be due to the similar Cu-O coordination in both La2Cu2O5 and La8Cu7O19. For low Zn-doping (x?0.04), a spin-chain like behavior is found. This quasi-one-dimensional behavior is strongly suppressed in both series for x?0.04. Here, the maximum (characteristic for spin chains) in χ(T) disappears and χ(T) decreases monotonically with increasing temperature.  相似文献   

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