Synthesis and electrochemical properties of nanostructured LiAl x Mn2 − x O4 − y Br y particles

Nanostructured LiAl _x Mn_2 − x O_4 − y Br _y particles were synthesized successfully by annealing the mixed precursors, which were prepared by room-temperature solid-state coordination method using lithium acetate, manganese acetate, lithium bromide, aluminum nitrate, citric acid, and polyethylene glycol 400 as starting materials. X-ray diffractometer patterns indicated that the particles of the as-synthesized samples are well-crystallized pure spinel phase. Transmission electron microscopy images showed that the LiAl _x Mn_2 − x O_4 − y Br _y samples consist of small-sized nanoparticles. The results of galvanostatic cycling tests revealed that the initial discharge capacity of LiAl_0.05Mn_1.95O_3.95Br_0.05 is 119 mAh g⁻¹; after the 100th cycle, its discharge capacity still remains at 92 mAh g⁻¹. The introduction of Al and Br in LiMn₂O₄ bring a synergetic effect and is quite effective in increasing the capacity and elevating cycling performance.     

High temperature characterization of the YBa2Cu3O9−y phase

We report the high temperature behaviour of single-phase YBa₂Cu₃O_{9 − y}. This compound reveals superconductivity above 90 K. We performed high temperature (20–960 °C) resistivity measurements, differential thermal analysis and thermogravimetric analysis investigations.It was found that substantial oxygen depletion occurred above 420°C. The oxygen content changed reversibly with temperature at ambient pressure. The second-order-like transition around 650 °C, observed by differential thermal analysis, is an orthorhombic-tetragonal rearrangement of the lattice. These results are important for optimizing the processing conditions of this new class of high T_c superconducting compounds.     

Thermodynamics of BaCa(1 + y)/3Nb(2 − y)/3O3 − δ·xH2O proton-conducting perovskites

Journal of Thermal Analysis and Calorimetry - Complex perovskites BaCa(1?+?y)/3Nb(2???y)/3O3???δ (y?=?0, 0.18 and 0.5) with...     

μ-XAFS of a single particle of a practical NiO(x)/Ce2Zr2O(y) catalyst

μ-XAFS analysis using an X-ray μ-beam (1000 nm (h) × 800 nm (v)) was successfully carried out on a single particle of a practical catalyst NiO(x)/Ce(2)Zr(2)O(y) (0 ≤x≤ 1, 7 ≤y≤ 8). The oxidation state and local coordination structure of the NiO(x)/Ce(2)Zr(2)O(y) particle were characterized by Ni K-edge μ-XANES and μ-EXAFS, which showed the catalytically active and inactive phases of a single catalyst particle.     

Electrochemical study of spinel oxide systems with nominal compositions Ni1− x Cu x Co2O4 and NiCo2− y Cu y O4

Studies on the electrochemical behaviour of Ni_{1− x} Cu _x Co₂O₄ (x ≤ 0.75) and NiCo_{2− y} Cu _y O₄ (y ≤ 0.30) electrodes in 5 mol dm⁻³ KOH aqueous solutions are presented. The oxide layers have been prepared by thermal decomposition of aqueous nitrate solutions on nickel supports at 623 K. Powder samples were also prepared by thermal decomposition under the same conditions. The powder samples and the oxide layers were characterised by X-ray powder diffraction. The influence of the copper content on the voltammetric response of the electrodes and activity towards oxygen evolution reaction is analysed and correlated with the surface composition of the electrodes by means of X-ray photoelectron spectroscopy data. The analysis of the results reveals that the presence of Cu affects the electrode behaviour and its influence depends on which cation has been replaced. Received: 22 February 1999 / Accepted: 26 October 1999     

The formation of the Ba(CuOx)1−y(CO3)y

Carbocuprate compounds are generally described as multiple perovskites with CO ₃ ² - and Cu-O alternating layers containing Ba and/or Sr; they have gained an unexpected importance in the high temperature superconductivity field, because many compounds with transition temperature above 100 K belong to this class of materials.We have started a systematic study on phase formation and stabilisation in the Ba-Cu-C-O system in the temperature range 20-600°C, by using thermal analysis techniques. Starting from a BaCO₃-BaO₂-CuO mixture (311 mol), a new phase isomorphic with BaCO₃ formed after heat treatment above 390°C in air. TG, DSC, EGA and high temperature XRD were employed to follow the complex interaction of the reactants with the atmosphere and the formation of the new phase.     

Ceometries,Energetics and Spectroscopic Properties of Oxygen Clusters Oxy (x=2～6, y=-2～2)

The geometries, energetics and spectroscopic properties of oxygen clusters, Oxy(x=2~6, y=-2~2), were investigated at the B3LYP/6-311G (d, p) level. The CASSCF calculations were carried out for the ground and excited states of3O2and2O2+. The total energy is3O2(3Σg-)<2O2-(2Πgi)<1O2(1Δg)<1O2-2(1Σg+)<2O2+(2Πg)<1O2+2(1Σg+). The relative energy of the active doublet anion of oxygen molecule,2O2-(2Πgi), is only 28 kJ/mol higher than the triplet neutral oxygen molecule,3O2(3Σg-). The calculated O-O vibrational frequencies all are in good agreement with the experimental values. They are 1577 (1580), 1139 (1090), 1563 (1484), 627 (615~545) and 1993 (1905) cm-1, where the O-O vibrational frequency values in parentheses are experimental values, for3O2(3Σg-),2O2-(2Πgi),1O2(1Δg),1O2-2(1Σg+) and2O2+(2Πg), respectively. Moreover, the O-O vibrational frequency of1O2+2(1Σg+) was computed as 2368 cm-1which has not been reported before at both experimental and theoretical levels. Both bent and linear geometries of O3were studied. The bent-types of O3are more favorable than the linear-type in energy. Three types of structure for oxygen trimers are calculated at the B3LYP/6-311G (d, p) level. They are the structure-I with an obtuse angle of O-O-O,the structure-II with an acute angle of O-O-O, and the structure-III of linear type. For a bent-type structure of O3species (structure-I), the total enegy is2O3-(2B1)<1O3(1A1)<3O3(3B2)<1O3-2(1A1)<2O3+(2A1). The optimization of geometry at B3LYP/6-311G (d, p) level indicated that the species of2O3-(2B1) with 1.3573 of O-O bond length and 115.6584o of O-O-O bond anger is the ground state of O3. The total energy of O4species and their ions is2O4-(Cs,2A′, bend-type)<2O4-(C2v,2A2,face-centered triangle-type)<2O4-(D∞h,2Σg, linear-type)<1O4(Cs,1A′, bend-type)<1O4(D∞h,1Σg, linear-type)<1O4(D4h,1A1g, square-type)<1O4(C2v,1A1, face-centered triangle-type)<2O4-(D4h,1A1g, square-type)<2O4+(D∞h,2Σg, linear-type)<2O4+(Cs,1A′, bend-type). The species with the lowest relative energy is an anion,2O4-(Cs,2A′, bendtype), with chair form geometry and characteristic vibronic frequencies of 1179 and 1349 cm-1. The relative energy of1O5(C2v,1A1) with coplanar-triangle-bicone geometry is the lowest among the O5species and their ions, which may be a resonance structure with1O5(C2v,1A1) of A type. Their characteristic vibronic frequency is 1302 cm-1. The relative energy of the O6species and their ions with hexagon geometry is lower than one with linear geometry. Their infrared vi-bronic intensity may be weak and unobservable but the Raman vibronic intensity may be strong and observable based on their symmetry.     

Classification of VxOyq Clusters by △=2y+q-5x

Vanadium oxide clusters V_xO_y^q (x≤8, q=0,±1) are classified according to the oxidation index (△=2y+q-5x) of each cluster. Density functional calculations indicate that clusters with the same oxidation index tend to have similar bonding characters, electronic structures, and reactivities. This general rule leads to the findings of new possible ground state struc-tures for V₂O₆ and V₃O₆⁺ clusters. This successful application of the classification method on vanadium oxide clusters proves that this method is very effective in studying the bonding properties of early transition metal oxide clusters.     

Relationship between oxygen content and superconductivity of Tl0.5Pb0.5Sr2CuOy(y≈5)

The electronic energy band structures of the Tl_0.5Pb_0.5Sr₂Cu0_y (y5) superconductor were calculated and the effect of the oxygen content on its electronic structures was studied in the present paper. The results show that the oxygen content has a great influence on its electronic structures. The moderate oxygen content causes the number of bands near the Fermi surface to increase and results in a sudden change in the densities of states at the Fermi level E _f. The influence of the oxygen content on the electronic structures is mainly due to the peroxide pairs in the unit cell. The lower or higher oxygen content results in the decrease in the number of bands near E _f and the densities of states at E _f, which is of no advantage to superconductivity.     

Effect of Silver Nanoparticles on the Sorption Characteristics of La1 − xAgxMnO3 ± y

The effect silver nanoparticles have on the sorption characteristics of perovskite lanthanum manganite relative to methanol, benzene, and hexane vapors is studied by means of gravimetric equilibrium interval sorption. The state of silver particles is investigated using spectroscopic tools. Sorption data are compared to the catalytic activity in deep oxidation reactions of organic compounds over lanthanum manganite-based catalysts.

     

Zn_(2-x)GeO_(4-x-3y)N_(2y)催化剂的制备、表征及可见光催化性能

通过氮化Zn2GeO4制备了Zn2-xGeO4-x-3yN2y催化剂,其带边吸收由400nm的紫外光区扩展到600nm的可见光区。光催化产氧性能的结果表明,氮化温度为800℃时,制备的催化剂具有最大活性。不同助催化剂对产氧活性的影响研究表明,担载助催化剂能大大提高产氧活性,其中担载Co2O3的产氧活性可达未担载的3.8倍。     

Kinetics of decomposition of the liquid phase of the ternary system LiOH-H2O2-H2O in the presence of the solid phase of Li2O2 · H2O

The kinetics of decomposition of hydrogen peroxide in the liquid phase of the ternary system LiOH-H₂O₂-H₂O was studied in the presence the solid phase of Li₂O₂·H₂O and without it. The main kinetic parameters of the processes studied were determined.     

Comparison of corn starch-assisted sol–gel and combustion methods to prepare LiMn x Co y Ni z O2 compounds

In a novel attempt to exploit corn starch as gelling agent (in sol–gel method) and combustible fuel (in solution-assisted combustion method), high-capacity LiMn_0.4Ni_0.4Co_0.2O₂ and LiMn_1/3Ni_1/3Co_1/3O₂ cathode materials have been prepared and a comparison of electrochemical performance of the same has been made. Among the two compounds chosen for the study, LiMn_1/3Ni_1/3Co_1/3O₂ exhibits better physical and electrochemical properties. Particularly, LiMn_1/3Ni_1/3Co_1/3O₂ cathode synthesized using corn starch-assisted combustion method exhibits an appreciable capacity of 176 mAh g^?1, excellent capacity retention of 93 % up to 100 cycles and susceptible to rate capability test up to 1 C rate, thus qualifying the same for high-capacity and high-rate lithium battery applications. The study demonstrates the possibility of exploiting corn starch as gelling agent and as a combustible fuel in synthesizing lithium intercalating oxide compounds with improved electrochemical behaviour.     

Magnetic susceptibility of La1–уCе y AlO3 solid solutions

Russian Journal of General Chemistry - Magnetic properties of the La1–уCе y AlO3 solid solutions (y = 0.02–0.20) were studied by the magnetic dilution method....     

Preparation and crystal structure of members of the solid solution phase Ba5Ru2−xAl1+x−yCuyO11 with x=0.378, y=0.085 and x=0.5, y=0

Single crystals of the new phase Ba₅Ru_2−xAl_1+x−yCu_yO₁₁ (x=0.378, y=0.085) have been grown from a powder mixture of BaCO₃, RuO₂ and CuO in an alumina crucible. The new compound crystallizes isostructurally to Ba₅Ir₂AlO₁₁. The crystal structure was determined by X-ray single-crystal diffraction technique and refined to a composition of Ba₅Ru_1.622(8)Al_1.29(1)Cu_0.085(6)O₁₁ (orthorhombic, Pnma (No. 62), a=18.615(4) Å, b=5.771(1) Å, c=11.098(2) Å, Z=4, R₁=0.048, wR₂=0.075). The composition of the new compound obtained from crystal structure refinement is in good agreement with the result of electron probe microanalysis using wavelength-dispersive X-ray spectroscopy. Octahedra [RuO₆] are connected via faces forming pairs. The central positions of the octahedra pairs are statistically occupied by Ru and Al atoms. These octahedra pairs are interconnected to one-dimensional chains extending along [010] via tetrahedra [Al_1−yCu_yO₄]. Isotypic Ba₅Ru_1.5Al_1.5O₁₁ is a further member of the solid solution with the lattice parameters a=18.6654(5) Å, b=5.7736(1) Å, c=11.0693(3) Å according to Rietveld refinement on a microcrystalline sample.     

Determination of the stability constants of Pb–(DIPSO)x–(OH)y and Pb–(AMPSO)x–(OH)y systems

In this work, complexation between lead ion and the ligands 3-[N,N-bis(2-hydroxyethyl)amino]-2-hydroxypropanesulfonic acid (DIPSO) and N-(1,1-dimethyl-2-hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (AMPSO), which are commercial pH buffers, is presented. Both ligands form complexes with lead in their pH buffer range (between pH 6.5 and 8.5 for DIPSO and between pH 8.0 and 9.0 for AMPSO). The final models and the overall stability constants, which are reported here, were determined by direct current polarography and glass electrode potentiometry [only for the Pb–(DIPSO)_x–(OH)_y system] at 25.0 °C and 0.1 M KNO₃ ionic strength. For the Pb–(DIPSO)_x–(OH)_y system, the proposed final model contains PbL, PbL₂, PbL₂(OH), and PbL₂(OH)₂ with stability constants, as log β, of 3.4 ± 0.1, 6.35 ± 0.15, 12.8 ± 0.2, and 18.0 ± 0.3, respectively. For the Pb–(AMPSO)_x–(OH)_y system, the species observed are PbL, PbL(OH), and PbL(OH)₂ with stability constants, as log β, of 2.9 ± 0.5, 9.4 ± 0.1, and 14.5 ± 0.2, respectively. For AMPSO, the possible adsorption of the ligand at the mercury electrode surface was evaluated by alternating current polarography through calculation of the capacitance of the double layer.     

Osmotic and activity coefficients of {yNaH2PO4+(1−y)Na2SO4}(aq) at the temperature 298.15 K

The osmotic coefficients of the mixed electrolyte solution {yNaH₂PO₄+(1−y)Na₂SO₄}(aq) have been measured by the isopiestic method, at the temperature T=298.15 K. The activity coefficients of NaH₂PO₄ and Na₂SO₄ were calculated by Scatchard's neutral-electrolyte method and by Pitzer and Kim's treatment for mixed-electrolyte solutions. The Scatchard interaction parameters are used for calculation of the excess Gibbs energy as a function of ionic strength and ionic-strength fraction of NaH₂PO₄. Also, the Zdanovskii's rule of linearity is tested.     

Spectroscopic Study of the Interaction of Bu_2SnCl_2 with EHPG

A number of Sn (Ⅳ)complexes have been synthesized since 1980 and tested its anticancer activity1. The simplest complex Bu2SnCl2 has activity to P388 tumor cells. Several metal complexes such as Ru-ind (trans-indazolium (bisindazole) tetrachloro- ruthenate (Ⅲ)) had used transferrin as a drug delivery system, the complexes still exhibit high antitumor activity and lower toxicity2. We use EHPG as a model ligand3 to study the interaction between Bu2SnCl2 and EHPG. EHPGAt first, we stud…     

Solvent-Free Acetylation of Thiols Under Catalysis of MgBr2·OEt2

Solvent-free protection of aromatic and aliphatic thiols with acetic anhydride was performed at room temperature under trace quantities of magnesium bromide ethyl etherate, affording rapid formation of various thiol esters in excellent yields.