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1.
Here we explored a novel and facile electrochemical route for the preparation of Zn1?xCdxO (x is atomic percentage of Cd) nanorods with controllable optical properties. The Zn1?xCdxO nanorods can be routinely obtained when the electrochemical deposition was carried out in solution of Zn(NO3)2 + Cd(NO3)2 + citric acid at ?1.0 V (vs SCE). EDS results demonstrated that Cd, Zn, and O elements existed in the deposits, and ternary Zn1?xCdxO compounds were obtained. XRD results showed that Zn1?xCdxO nanorods were pure ZnO wurtzite structures. HRTEM and SAED analyses confirmed that Zn1?xCdxO nanorods were single-crystalline. The optical properties of Zn1?xCdxO nanorods were investigated in this paper.  相似文献   

2.
(Mn, Co)-codoped ZnO nanorod arrays were successfully prepared on Cu substrates by electrochemical self-assembly in solution of 0.5 mol/l ZnCl2–0.01 mol/l MnCl2–0.01 mol/l CoCl2–0.1 mol/l KCl–0.05 mol/l tartaric acid at a temperature of 90 °C, and these nanorods were found to be oriented in the c-axis direction with wurtzite structure. Energy dispersive X-ray spectroscopy and x-ray diffraction show that the dopants Mn and Co are incorporated into the wurtzite-structure of ZnO. The concentrations of the dopants, and the orientations and densities of nanorods can easily be well controlled by the current densities of deposition or salt concentrations. Magnetization measurement indicates that the prepared (Mn, Co)-codoped ZnO nanorods with a coercivity of about 91 Oe and a saturation magnetization (Ms) of about 0.23 emu/g. The anisotropic magnetism for the (Mn, Co)-codoped ZnO nanorod arrays prepared in solution of 0.5 mol/l ZnCl2–0.01 mol/l MnCl2–0.01 mol/l CoCl2–0.1 mol/l KCl–0.05 mol/l tartaric acid with current density of 0.5 mA/cm2 was also investigated, and the crossover where the magnetic easy axis switches from parallel to perpendicular occurs at a calculated time of about 112 min. The anisotropic magnetism, depending on the rod geometry and density, can be explained in terms of a competition between self-demagnetization and magnetostatic coupling among the nanorods.  相似文献   

3.
Nano-crystalline zinc-substituted cobalt ferrite powders, Co1−xZnxFe2O4 (x = 0, 0.25, 0.5, 0.75 and 1), have been synthesized by the combustion route. The structural, morphological and magnetic properties of the products were determined and characterized in detail by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and vibrating sample magnetometer (VSM). X-ray analysis showed that the samples were cubic spinel. The increase in zinc concentration resulted in an increase in the lattice constant, unit cell volume, X-ray density, ionic radii, the distance between the magnetic ions and bond lengths on tetrahedral sites and octahedral sites of cubic spinel structure. Opposite behavior was observed for the average crystallite size of the as synthesized solids. The variation of saturation magnetization (Ms) value of the samples was studied. The maximum saturation magnetization value of the Coo.25Zn0.75Fe2O4 sample reached 76.87 emu/g. The high saturation magnetization of these samples suggests that this method is suitable for preparing high-quality nano-crystalline magnetic ferrites for practical applications.  相似文献   

4.
La0.76Sr0.19Mn1?xCoxOδ, LSMCox (0  x  1) perovskite oxides were synthesized by conventional ceramic route. The effect of Co substitution for Mn on the crystal structure, electrical conductivity and thermal expansion properties was investigated. XRD indicated rhombohedral symmetry for the studied compositions at 1673 K. The lattice parameters so determined showed significant reduction in cell volume, which is attributed to smaller ionic radii of Co3+ ions. The results of electrical conductivity data indicated that the conductivity mechanism is by thermally activated hopping of small polarons between localized states corresponding to Mn or Mn and Co sites of different valence value. The conductivity decreases at all temperatures up to 40 mol% Co substitution while the energy of activation increases. This is possibly due to an increase in Jahn–Teller distortion, at an extent higher than the increase of the concentration of charge carriers. Thermal expansion coefficient values in the series increase with increasing Co content which has been explained on the basis of the changes in the spin states of the Co ions and the consequent changes in the ionic size with temperature. Solution route synthesis produces fine-size particles with better properties, consequently one composition from the above having enhanced requisite properties, viz. La0.76Sr0.19Mn0.8Co0.2Oδ was synthesized by sol–gel route. The sol–gel synthesized compound had crystallite size of ~30 nm at 1173 K obtained using Scherrer's equation. Thus the potential of these compounds as cathodes for solid oxide fuel cells (SOFCs) have been evaluated.As Ce0.8RE0.2O2?δ (RE = Sm, Gd) are being investigated for their use as electrolytes in SOFCs, their mechanical compatibility as well as chemical compatibility with the potential cathode material from the above LSMCox series was also studied.  相似文献   

5.
《Vibrational Spectroscopy》2007,43(2):353-356
We present results of Raman scattering studies on LaMn1−xCoxO3+δ over a wide range of doping content (x = 0.1–0.75) and temperature range of 20–300 K. Powder X-ray diffraction patterns show that there is a structural change from orthorhombic to rhombohedral at x = 0.5 as x increases. Raman spectra of all LaMn1−xCoxO3+δ samples show peaks near 260, 500, and 650 cm−1. However, the Raman spectra are not drastically different from each other across the structural phase transition at x = 0.5. On the other hand, the peak frequencies of the modes near 260 and 500 cm−1 as functions of Co content (x) show slope changes at x = 0.5. The full-width at the half-maximum (FWHM) of the mode near 650 cm−1 as a function of Co content (x) shows minimum at x = 0.5. Normally, larger values of FWHM are expected at near x = 0.5, if the mode were affected by the structural disorder at the phase boundary. Therefore, it is likely due to lowest charge concentration at x = 0.5, which results in lowest screening effect. This is consistent with the fact that the intensity of the phonons is strongest at x = 0.5. As the temperature decreases, the two peaks near 500 and 650 cm−1 of different Co contents, related with octahedral distortions, are found to shift to lower frequencies unlike the usual temperature behavior. However, no abrupt change in the peak frequencies and the FWHM is observed across measured temperature range, regardless of the Co content.  相似文献   

6.
《Solid State Sciences》2007,9(9):869-873
Orthorhombic K2NiF4-type (Ca1+xSm1−x)CoO4 (0.00  x ≤0.15) with space group Bmab has been synthesized by the polymerized complex route. The cell parameters (a and b) decrease, while the cell parameter (c) increases with increasing Co4+ ion content. The global instability index (GII) indicates that the crystal stability of (Ca1+xSm1−x)CoO4 is not influenced by the Co4+ ion content. (Ca1+xSm1−x)CoO4 is a p-type semiconductor and exhibits hopping conductivity in the small-polaron model at low temperatures. The magnetic measurement indicates that (Ca1+xSm1−x)CoO4 shows paramagnetic behavior above 5 K, and that the spin state of both the Co3+ and Co4+ ions is low. The Co4+ ion acts as an acceptor, and the electron transfer becomes active through the Co3+–O–Co4+ path as the Co4+ ions increase.  相似文献   

7.
We report on the sol-gel synthesis of Zn1−xCrxO (x=0.0, 0.05, 0.10, 0.15 and 0.20) nanoparticles. These nanoparticles were characterized by using thermogravimetry/differential scanning calorimetry (TG/DSC), X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman and Photoluminescence (PL). Electronegativity of Cr ions (Cr3+) reduces the final decomposition temperature by 40 °C and activation energy of the reaction when Cr is doped into ZnO. Doping of higher Cr concentration (x≥0.10) into ZnO shows formation of secondary spinel (ZnCr2O4) phase along with the hexagonal (ZnO) and is revealed by XRD. Formation of secondary phase changes the activation energy of the reaction and thus the strain in ZnO lattice. In Raman spectra, additional Raman modes have been observed for Zn1−xCrxO nanoparticles, which can be assigned to the modes generated due to Cr doping. The Cr doping into ZnO is also supported by PL, in which vacancies are formed with Cr ion incorporation and emission band shifts towards higher wavelength.  相似文献   

8.
《Vibrational Spectroscopy》2007,43(2):387-394
The metal ion distributions at the two metal sites (hexaformate-coordinated Me1 sites and mixed-coordinated Me2 sites) in the title mixed crystals as determined by single crystal X-ray diffraction and double matrix infrared spectroscopic methods are presented and discussed. The mixed formates are isostructural with the end compounds (space group P21/c). The local metal ion concentrations as a function of the total metal ion concentrations exhibit a clear preference of Zn2+ ions to Me1 sites and the Mg2+ ions to Me2 sites.The analysis of the infrared spectra reveals that the spectral regions 2300–2500 cm−1 (νOD of matrix-isolated HDO molecules) and 1300–1400 cm−1 (symmetric COO stretching (ν2) and bending CH (ν5) modes) are mostly sensitive to the metal ion environment. The inclusion of Mg2+ and Zn2+ in the structures of Zn(HCOO)2·2H2O and Mg(HCOO)2·2H2O, respectively, leads to an appearance of new infrared bands corresponding to νOD of HDO molecules bonded to the incorporated ions (i.e. new hydrogen bonding systems MgOH2⋯OCHOZn and ZnOH2⋯OCHOMg are formed in the mixed formates). The respective new bands are observed at small concentrations of included Mg2+ ions (about 5 mol%, x = 0.05) and at considerably higher concentrations of included Zn2+ ions (about 30 mol%, x = 0.7). Contrarily, the ν2 and ν5 modes caused by the incorporated cations bonded to formate ions occur at x  0.3 and x  0.85 (Mg2+ ions in Zn(HCOO)2·2H2O and Zn2+ ions in Mg(HCOO)2·2H2O, respectively). Thus, the infrared spectroscopy experiments confirm the single crystal X-ray measurements that the Mg2+ ions are localized predominantly at Me2 sites and the Zn2+ ions at Me1 sites in the title mixed crystals. The pronounced preference of the Mg2+ ions to Me2 sites is owing to the strong affinity of these ions to water molecules.  相似文献   

9.
The whole range of solid solutions Li(Li(1−x)/3CoxMn(2−2x)/3)O2 (0  x  1) was firstly synthesized by an aqueous solution method using poly-vinyl alcohol as a synthetic agent to investigate their structure and electrochemical properties. X-ray diffraction results indicated that the synthesized solid solutions showed a single phase without any detectable impurity phase and have a hexagonal structure with some additional peaks caused by monoclinic distortion, especially in the solid solutions with a low Co amount. In the electrochemical examination, the solid solutions in the range between 0.2  x  0.9 showed higher discharge capacity and better cyclability than LiCoO2 (x = 1) on cycling between 2.0 and 4.6 V with 100 mA g−1 at 25 °C. For example, Li(Li0.2Co0.4Mn0.4)O2 (x = 0.4) exhibited a high discharge capacity of 180 mA h g−1 at the 50th cycle. By synthesizing the solid solution between Li2MnO3 and LiCoO2, the electrochemical properties of the end members were improved.  相似文献   

10.
In order to explain the relationship between physical change and electrochemical degradation of Co–Co3O4 coated Si, impedance spectroscopy on Co–Co3O4 coated Si was conducted at various states during charge or discharge. Nyquist plots during Li+ insertion (charge) showed a unique behavior that below 70 mV vs. Li/Li+, the more Li+’s were inserted into the electrode, the larger its comprehensive resistance was getting. During Li+ extraction (discharge), electrode resistance was decreased after going through 0.43 V vs Li/Li+. When these data were fitted with the ordinary equivalent circuit which is composed of electrolyte resistance, charge transfer resistance and contact resistance, there was an abrupt augmentation of charge transfer resistance below 70 mV vs. Li/Li+ during charge, whereas there was its drastic diminishment between 0.2 and 0.5 V vs. Li/Li+ during discharge. Because these potential regions are each related to amorphous LixSi-to-Li15Si4 transition and vice versa, it could be shown that the formation and decomposition of Li15Si4 is responsible for the electrochemical degradation of Co–Co3O4 coated Si.  相似文献   

11.
The Fe2(Sr2 ? xAx)FeO6.5 ? δ/2 systems have been investigated, by doping the iron rich 2201-type parent structure with Ba2+, La3+ and 5d10 post-transition cations. The syntheses have been carried out up to the limit of the 2201-type solid solutions, in order to test the role of the double iron layer Fe2O2.5 ? δ/2. The localisation of the charge carriers in these compounds is consistent with their strong antiferro-magnetism. The investigation was then carried out in the transition part of the diagram up to the formation of stable phases. The study of structural mechanisms was carried using high resolution electron microscopy (transmission and scanning transmission), electron diffraction and energy dispersive spectroscopy. Different non-stoichiometry mechanisms are observed, depending on the electronic structure and chemical properties of the doping elements. The specific behavior of the modulated double iron layer is discussed.  相似文献   

12.
The enthalpies of mixing of liquid (Co + Cu + Zr) alloys have been determined using the high-temperature isoperibolic calorimeter. The measurements have been performed along three sections (xCo/xCu = 3/1, 1/1, 1/3) with xZr = 0 to 0.55 at T = 1873 K. Over the investigated composition range, the partial mixing enthalpies of zirconium are negative. The limiting partial enthalpies of mixing of undercooled liquid zirconium in liquid (Co + Cu) alloys are (−138 ± 18) kJ · mol−1 (the section xCo/xCu = 3/1), (−155 ± 10) kJ · mol−1 (the section xCo/xCu = 1/1), and (−130 ± 22) kJ · mol−1 (the section xCo/xCu = 1/3). The integral mixing enthalpies are sign-changing. The isenthalpic curves have been plotted on the Gibbs triangle. The main features of the composition dependence of the integral mixing enthalpy of liquid ternary alloys are defined by the pair (Co + Zr) and (Cu + Zr) interactions.  相似文献   

13.
The Cr-doped zinc oxide (Zn1−xCrxO, 0≤x≤0.08) diluted magnetic semiconductors have been synthesized successfully by the sol-gel method. Investigations on magnetic, optical and structural properties of the produced samples have been done. Energy dispersive spectroscopy (EDS) shows the existence of Cr ion in the Cr-doped ZnO. The results of X-ray diffraction (XRD), the transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) indicate that the Cr ions are at least partially substitutionally incorporated into the crystal lattice of ZnO. The produced samples show good high-Tc (Curie temperature) ferromagnetism (FM) in Cr-doped ZnO nanoparticles with Cr concentration of less than 5 at%. The results of photoluminescence (PL) further testify that FM is an intrinsic property of the Cr-doped ZnO nanoparticles. And the occurrence of FM should mainly contribute to the Cr doping.  相似文献   

14.
The solid state interaction of the Zn1−xCoxO nominal system is investigated by means of diffusion couples and analysis of co-precipitated samples. The formation of a homogeneous Co:ZnO solid solution is found to be determined by the crystal structure from which CoII ions diffuse into the wurtzite lattice. No diffusion is observed whenever the CoO rock-salt structure is formed from the CoII precursor. On the contrary, the diffusion from the Co3O4 spinel phase is feasible but has a limited temperature range defined by the reduction at a high temperature of CoIII-CoII, since this process again leads to the formation of the rock-salt structure. However, when using a highly reactive and homogeneous co-precipitated starting powder, neither the spinel phase nor the rock-salt structure is formed, and a CoII:ZnO solid solution is obtained, which remains stable up to high temperatures.  相似文献   

15.
Isomorphously substituted (MeDM) and impregnated metal-containing MCM-41 (MeOx/IM) catalysts, in which Me = Co, Cu, Cr, Fe or Ni, have been prepared. Structural and textural characterizations of the catalysts were performed by means of X-ray diffraction (XRD), chemical analysis, Raman spectroscopy, electron paramagnetic resonance (EPR), N2 adsorption isotherms and temperature programmed reduction (TPR). Cu2+, Co2+, and Cr4+/Cr3+ species were found over the catalysts as cations incorporated in the MCM-41 structure (MeDM) or highly dispersed oxides on the surface (MeOx/IM). The MeDM catalysts exhibited a good performance in the dehydrogenation of ethylbenzene with CO2. However, MeOx/IM catalysts had a low performance in styrene production (activity less than 15 × 10?3 mmol h?1 and selectivity for styrene less than 80%) due to the high reducibility of the metals species. However, Ni2+ or Fe3+ coordinated with the MCM-41 framework, as well as NiOx and Fe2O3 extra-framework species, is continuously oxidized by the CO2 to maintain the active sites for dehydrogenating ethylbenzene. Deactivation studies on the FeDM sample showed that Fe3+ species produced active sp2 carbon compounds, which are removed by CO2; the referred sample is catalytically selective for styrene and stable over 24 h of reaction. In contrast, highly active Ni2+ and Ni0 species produced a large amount of polyaromatic carbonaceous deposits from styrene, as identified by TPO, TG and Raman spectroscopy. An acid–base mechanism is proposed to operate to adsorb ethylbenzene and abstract the β-hydrogen. CO2 plays a role in furnishing the lattice oxygen to maintain the Fe3+ active sites in the dehydrogenation of ethylbenzene to form styrene.  相似文献   

16.
Highly preferred orientation polycrystalline Zn1?xCoxO (x = 0, 0.03, 0.06, 0.09) thin films were prepared by improved sol–gel method on quartz glass substrates. The structural, optical and magnetic properties were investigated. The X-ray diffraction patterns show that all the samples have the same structure with one highly oriented c-axis (002) peak. None of the samples showed any signal of impurity phases. The c-axis lattice constant increased linearly with the increase in Co doping content, indicating that the doping of Co ions into the host lattice did not change the wurtzite structure of ZnO. UV–Vis transmittance spectroscopy showed that the average optical transmittance of the films is about 90 % in visible wavelength range. The optical band gap (Eg) decreased with increasing Co content. Also, the results of vibration sample magnetization ascertained the ferromagnetic behavior of Co-doped ZnO, having a Curie temperature higher than room temperature.  相似文献   

17.
《Polyhedron》2005,24(16-17):2607-2613
Equilibrium between low-spin [CoIII(SQ)(Cat)(N–N)] and high-spin [CoII(SQ)2(N–N)] redox isomers, where SQ is semiquinonate (charge: −1, spin: 1/2), Cat is catecholate (charge: −2, spin: 0) and N–N is chelating nitrogen donor ligand, respectively, is a representative valence tautomeric phenomenon. To elucidate independently the spin state of the cobalt ion and that of benzoquinone-derived ligands in the solid state, we measured 13C MAS NMR spectrum of 3,5-di-t-butyl-1,2-benzoquinone and 2H MAS NMR spectrum of deuterated 2,2′-bipyridine for [Co(3,5-di-t-butyl-1,2-benzoquinone)2(2,2′-bipyridine)] · x(C6H5CH3) and its deuterated analogue in a temperature range of 200–350 K. Irreversible change of an effective magnetic moment μeff of a virgin sample was observed around 370 K due to a partial loss of crystal solvent and a change of crystal structure, whereas the sample annealed at 390 K showed a crystal structure different from the reported one and a reversible change of μeff, which is ascribed to equilibrium between Co(III)-form (S = 1/2) and Co(II)-form (S = 3/2). Based on the shifts and the number of NMR peaks for the annealed sample, we concluded that (1) interconversion between redox isomers occurs faster than NMR time scale (>104 s−1) in the solid state, (2) intraconversion between SQ and Cat in Co(III)-form also occurs much faster than 5 × 104 s−1 even at 198 K and (3) electron spins on SQ ligands in Co(II)-form are quenched probably due to a strong antiferromagnetic coupling between the two SQ ligands. The enthalpy and the entropy of the interconversion were estimated to be 17 kJ/mol and 54 J/(K mol), respectively. For the virgin metastable phase, SQ and Cat were clearly distinguished by 13C MAS NMR spectrum. The solid-state high-resolution NMR spectrum is useful to detect independently the change of spin states of benzoquinone-derived radical and metal ion.  相似文献   

18.
Synthesis, crystal structures and magnetic properties of metal telluromolybdates MxM′1?xTeMoO6 (M, M′ = Mn, Co, Cd) have been investigated. Their crystal structures have two-dimensional arrays of M and M′ atoms. From the powder X-ray diffraction measurements, MnxCo1?xTeMoO6 adopt an orthorhombic structure throughout the composition range (x = 0.0–1.0). On the other hand, MnxCd1?xTeMoO6 and CoxCd1?xTeMoO6 adopt two types of structures corresponding to their end members (orthorhombic for Mn- or Co-rich solid solutions; tetragonal for Cd-rich ones). In the intermediate compositions, it was found that two phases coexist with different metal components. Magnetic properties of these solid solutions were investigated. All the MnxCo1?xTeMoO6 exhibits an antiferromagnetic transition at ~23 K. The antiferromagnetic transition was also observed in MnxCd1?xTeMoO6 and CoxCd1?xTeMoO6. However, the Néel temperature rapidly decreases with increasing the concentration of Cd and disappeared below x = 0.6, which is characteristic for two-dimensional magnetic system.  相似文献   

19.
Transition metal oxides with composite xLi2MnO3 ·  (1  x)LiMO2 rocksalt structures (M = Mn, Ni, Co) are of interest as a new generation of cathode materials for high energy density lithium-ion batteries. After electrochemical activation to 4.6 or 4.8 V (vs. Li0) at 50 °C, xLi2MnO3 · (1  x)LiMn0.33Ni0.33Co0.33O2 (x = 0.5, 0.7) electrodes deliver initial discharge capacities (>300 mAh/g) at a low current rate (0.05 mA/cm2) that exceed the theoretical values for lithiation back to the rocksalt stoichiometry (240–260 mAh/g), at least during the early charge/discharge cycles of the cells. Attention is drawn to previous reports of similar, but unaccounted and unexplained anomalous behavior of these types of electrode materials. Possible reasons for this anomalous capacity are suggested. Indications are that electrodes in which M = Mn, Ni and Co do not cycle with the same stability at 50 °C as those without cobalt.  相似文献   

20.
High aspect ratio cobalt doped ZnO nanowires showing strong photocatalytic activity and moderate ferromagnetic behaviour were successfully synthesized using a solvothermal method and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), vibrating sample magnetometry (VSM) and UV–visible absorption spectroscopy. The photocatalytic activities evaluated for visible light driven degradation of an aqueous methylene orange (MO) solution were higher than for Co doped ZnO nanoparticles at the same doping level and synthesized by the same synthesis route. The rate constant for MO visible light photocatalytic degradation was 1.9·10−3 min−1 in case of nanoparticles and 4.2·10−3 min−1 in case of nanowires. We observe strongly enhanced visible light photocatalytic activity for moderate Co doping levels, with an optimum at a composition of Zn0.95Co0.05O. The enhanced photocatalytic activities of Co doped ZnO nanowires were attributed to the combined effects of enhanced visible light absorption at the Co sites in ZnO nanowires, and improved separation efficiency of photogenerated charge carriers at optimal Co doping.  相似文献   

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