Interaction of Co<Subscript>6</Subscript> cluster with γ-alumina surface: A quantum chemical study

The interaction of Co₆ cluster with partially dehydroxylated γ-alumina surface was studied by the DFT method. Hydrogen atoms of surface hydroxyl groups can be transferred to the metal particle to form partially oxidized cobalt states. The energy characteristics of hydrogen transfer were determined and changes in the electronic structure of supported Co₆ particles were characterized. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2194–2199, October, 2005.     

Quantum chemical investigation of the interaction of the Pt<Subscript>6</Subscript> cluster with oxides of different nature

The interaction of a Pt₆ nanoparticle with different oxide supports, viz., γ-Al₂O₃, FAU and MFI zeolites, was investigated using the density functional theory. The interaction with the basic oxygen anions of the lattice and with hydroxyl groups of the support affects the electronic structure of the metal particles. The transfer of H atoms of the hydroxyl groups to the metal particle suppresses the Brönsted acidity of the support, and the activation energy of proton transfer decreases with an increase in the acidity of the support. The potential energy profiles were calculated for the transfer processes, and changes in the electronic structures and charge distribution of the supported particles were outlined. The H atom transfer results in positive charging by the metal particles, whereas the interaction with basic sites leads to the appearance of electron-enriched metal clusters.     

Quantum chemical study of H<Subscript>2</Subscript> adsorption on Pd<Subscript>21</Subscript> cluster

Modeling of the interaction of an H₂ molecule with the surface of the Pd₂₁ cluster in different spin states was performed using the DFT/PBE scalar relativistic approximation. The spin multiplicity of the system significantly affects the mechanism of adsorption, its parameters, and migration of hydrogen atoms. The H atoms can migrate over the cluster surface with low barriers (1.6 kcal mol^–1). The complex with C _2v symmetry, wherein the H atoms occupy adjacent fcc sites, is the most energetically stable.     

Interaction of N<Subscript>2</Subscript> with the acid sites of oxides

Nitrogen adsorption on SiO₂, -Al₂O₃, TiO₂, and sulphated zircona (SO _2- ⁴ /ZrO₂) is studied by Fourier transform IR spectroscopy. Integrated absorption coefficients for the bands due to the N—N vibrations in nitrogen complexes with Brønsted and Lewis acid sites are determined. A general correlation between integrated absorption coefficients and the positions of N—N bands of nitrogen interacting with the above sites in zeolites and oxides is discussed. The orientation of a nitrogen molecule relative to Brønsted and Lewis acid sites is calculated ab initio using a 6-31G^** basis set.Translated from Kinetika i Kataliz, Vol. 46, No. 1, 2005, pp. 115–121.Original Russian Text Copyright © 2005 by Malyshev, Paukshtis, Malysheva.     

Solid-phase synthesis of intermetallic compounds Al<Subscript>13</Subscript>Co<Subscript>4</Subscript>, Al<Subscript>13</Subscript>Fe<Subscript>4</Subscript>, and Al<Subscript>13</Subscript>Co<Subscript>2</Subscript>Fe<Subscript>2</Subscript>

Intermetallic compounds Al₁₃Co₄, Al₁₃Fe₄, and Al₁₃Co₂Fe₂ were obtained by solid-phase synthesis in air at temperatures below 600°C using precursor metals subjected to mechanochemical preactivation. The phase composition of the synthesized aluminides and composites Al₁₃Co₄/SiO₂ and Al₁₃Fe₄/SiO₂ was analyzed.     

Relative Raman Intensities in C<Subscript>6</Subscript>H<Subscript>6</Subscript>, C<Subscript>6</Subscript>D<Subscript>6</Subscript>, and C<Subscript>6</Subscript>F<Subscript>6</Subscript>: A Comparison of Different Computational Methods

The accuracy of various computational methods (Hartree–Fock, MP2, CCSD, CAS-SCF, and several types of DFT) for predicting relative intensities in Raman spectra for C₆H₆, C₆D₆, and C₆F₆ was compared. The predicted relative intensities for ν₁ and ν₂ were compared with relative intensities measured by an FT-Raman spectrometer. While none of these methods excelled at this prediction, Hartree–Fock with a large basis set was most successful for C₆H₆ and C₆D₆, while PW91PW91 was the most successful for C₆F₆.     

Synthesis and characterization of Co<Subscript>0.8</Subscript>Zn<Subscript>0.2</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles

Cobalt zinc ferrite, Co_0.8Zn_0.2Fe₂O₄, nanoparticles have been synthesized via autocatalytic decomposition of the precursor, cobalt zinc ferrous fumarato hydrazinate. The X-ray powder diffraction of the ‘as prepared’ oxide confirms the formation of single phase nanocrystalline cobalt zinc ferrite nanoparticles. The thermal decomposition of the precursor has been studied by isothermal, thermogravimetric and differential thermal analysis. The precursor has also been characterized by FTIR, and chemical analysis and its chemical composition has been determined as Co_0.8Zn_0.2Fe₂(C₄H₂O₄)₃·6N₂H_4. The Curie temperature of the ‘as-prepared oxide’ was determined by AC susceptibility measurements.     

Geometry and electronic structure of a heterometallic cluster Mo<Subscript>2</Subscript>Mg<Subscript>2</Subscript> in different oxidation states of Mo: a DFT study

Reduction of tetranuclear heterometallic complex Mo₂Mg₂ was simulated using the B3LYP and PBE density functional methods. The results of geometry calculations of the initial complex [Mo^VIO₂Mg(MeOH)₂(OMe)₄]₂ and a partially reduced Mo^V complex are in good agreement with experimental data. The reduced Mo^III complex is characterized by a decrease in the binding energy of aqua ligands. Structural rearrangement of the complex with release of a coordination position at the Mo atoms requires small energy expenditure. One can assume that the reduction of the polynuclear complex causes overcrowding of its coordination sphere, which favors formation of dinitrogen complexes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–457, March, 2008.     

Vibrational dynamics of Co<Subscript>67</Subscript>Zr<Subscript>33</Subscript> semiconductor glassy alloy

The computation of vibrational dynamics of semiconductor Co₆₇Zr₃₃ glassy alloy has been reported for the first time that uses a different theoretical model potential formalism with Wills-Harrison (WH) form. Various local field correction functions are used to study the screening influence. The thermodynamic and elastic properties are also estimated from the elastic limits of the phonon dispersion curves (PDC). The dispersion frequency with respect to the wavenumber is found to be influenced by the dielectric screening due to the conduction electrons. Values obtained using the S-local field correction function and BS approach tend to be greater than other values calculated. The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 235–242, March–April, 2009.     

The synthesis and selected properties of Co<Subscript>2</Subscript>InV<Subscript>3</Subscript>O<Subscript>11</Subscript>

It has been demonstrated that Co₂V₂O₇ and InVO₄ react with each other forming a new compound of the Co₂InV₃O₁₁ formula, when their molar ratio is equal to 1:1, or among CoCO₃, In₂O₃ and V₂O₅, mixed at a molar ratio of 4:1:3. This compound melts incongruently at the temperature of 960±5°C, depositing crystals of InVO₄. It crystallizes in the triclinic system and the unit cell parameters amount to: a=0.6524(6) nm, b=0.6885(5) nm, c=1.0290(4) nm, α=96.5°, β=104.1°, γ=100.9°, Z=2. The phase equilibria being established in the Co₂V₂O₇–InVO₄ system over the whole components concentration range up to the solidus line were described.     

Synthesis and Electrocatalytic Properties of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanocrystallites with Various Morphologies

Co₃O₄ crystallites with particle, plate-, tube-, rod- and sheet-like morphologies were successfully prepared by the calcination of the corresponding precursors synthesized via a precipitation or hydrothermal procedure. The morphologies of the precursors and Co₃O₄ nano-tubes were detected by field emission scanning electron microscopy (FE-SEM). The as-obtained Co₃O₄ samples were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and special surface area measurement (BET). The electrocatalytic activity of p-nitrophenol reduction with the Co₃O₄ products decorated on a glassy carbon electrode (GCE) was tested, respectively, using cyclic voltammetry (CV) in a basic solution. The results indicated that p-nitrophenol was reduced with higher current density but almost at a constant potential on the Co₃O₄/GCE in contrast with that on a bare GCE at the same conditions. The highly catalytic activity of the as-prepared Co₃O₄ in a basic solution suggested their wide applications in environmental treatment or organic synthesis.     

Electrochemical dissolution of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> in acidic solutions

The cyclic voltammetry method was used to study the regularities of the electrochemical behavior of cobalt cobaltite in an acidic medium. It is shown that cathodic reduction of Co₃O₄ in the studied range of potentials of +1.0 to −0.8 V is a multistage process occurring according to the scheme:      

Towards high-performance cathode materials for lithium-ion batteries: Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-coated LiNi<Subscript>0.8</Subscript>Co<Subscript>0.15</Subscript>Zn<Subscript>0.05</Subscript>O<Subscript>2</Subscript>

Zn-doped LiNi_0.8Co_0.2O₂ exhibits impressive electrochemical performance but suffers limited cycling stability due to the relative large size of irregular and bare particle which is prepared by conventional solid-state method usually requiring high calcination temperature and prolonged calcination time. Here, submicron LiNi_0.8Co_0.15Zn_0.05O₂ as cathode material for lithium-ion batteries is synthesized by a facile sol-gel method, which followed by coating Al₂O₃ layer of about 15 nm to enhance its electrochemistry performance. The as-prepared Al₂O₃-coated LiNi_0.8Co_0.15Zn_0.05O₂ cathode delivers a highly reversible capacity of 182 mA h g^?1 and 94% capacity retention after 100 cycles at a current rate of 0.5 C, which is much superior to that of bare LiNi_0.8Co_0.15Zn_0.05O₂ cathode. The enhanced electrochemistry performance can be attributed to the Al₂O₃-coated protective layer, which prevents the direct contact between the LiNi_0.8Co_0.15Zn_0.05O₂ and electrolyte. The escalating trend of Li-ion diffusion coefficient estimated form electrochemical impedance spectroscopic (EIS) also indicate the enhanced structural stability of Al₂O₃-coated LiNi_0.8Co_0.15Zn_0.05O₂, which rationally illuminates the protection mechanism of the Al₂O₃-coated layer.     

Preparation and adsorption of magnetic Co<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript>-chitosan nanoparticles

In this paper, magnetic chitosan microspheres were prepared by the emulsification cross-linking technique, with glutaraldehyde as the cross-linking agent, liquid paraffin as the dispersant, and the Span-80 as emulsifier. The time of cross-linking and the ratio of Co_0.5Ni_0.5Fe₂O₄/chitosan were investigated. The morphology was studied by different instruments. The adsorption performance was investigated and the effects of initial concentration of methyl orange, the time of cross-linking, and the amount of adsorbent were discussed. It is found that the product has uniform morphology when the ratio of magnetic Co_0.5Ni_0.5Fe₂O₄/chitosan is 1 : 2 and the time of cross-linking is 5 h; At room temperature, magnetic Co_0.5Ni_0.5Fe₂O₄–chitosan has a good adsorption toward methyl orange when the magnetic Co_0.5Ni_0.5Fe₂O₄/chitosan dosage is 20 mg.     

Isomorphism in the KTaWO<Subscript>6</Subscript>-RbTaWO<Subscript>6</Subscript>-CsTaWO<Subscript>6</Subscript> system

Synthetic procedures have been developed and compounds of composition K _x Rb _y Cs _z TaWO₆ (x + y + z = 1) have been obtained. Their structure has been investigated by X-ray diffractometry. It has been shown that a continuous series of solid solutions is formed in the ternary system under study. Thermal decomposition of A^ITaWO₆ compounds (A^I = K, Rb, Cs) has been investigated by high-temperature X-ray diffractometry.     

Osmium thioselenochloride Os<Subscript>2</Subscript>S<Subscript>6</Subscript>Se<Subscript>2</Subscript>Cl<Subscript>8</Subscript>: Synthesis,cluster isolation,and structure

The quaternary thioselenochloride complex Os₂S₆Se₂Cl₈ (I) was obtained by a reaction of OsO₄ with a solution of Se in S₂Cl₂ at 100°C and identified by combination of X-ray diffraction (polycrystalline approach) and cluster framework isolation. A reaction of complex I with melted 4-cyanopyridine (4-CNPy) at 165°C gave the complex Os₂S₂Cl₄(4-CNPy)₄, which confirms the integrity of the binuclear cluster frame-work [Cl₂OsS₂OsCl₂] in complex I.     

Effect of Pd and rare earth oxides (La<Subscript>2</Subscript>O<Subscript>3</Subscript>, CeO<Subscript>2</Subscript>) on the properties of a Co<Subscript>3</Subscript>O<Subscript>4</Subscript>/cordierite catalyst in reduction of O<Subscript>2</Subscript> and no by hydrogen

We have established that introducing a promoter (Pd) and modifying additives (La₂O₃, CeO₂) into the composition of a Co₃O₄/cordierite catalyst leads to an increase in its activity and selectivity during reduction of oxygen by hydrogen in the presence of nitrogen(II) oxide.     

Phase formation in the FeVO<Subscript>4</Subscript>–Co<Subscript>3</Subscript>V<Subscript>2</Subscript>O<Subscript>8</Subscript> system

Phase relations in the solid state in the FeVO₄–Co₃V₂O₈ system, in the whole range of components concentration have been studied. It was found that the composition of the phase of the howardevansite type structure, formed in the investigated system, corresponds with the Co_2.616Fe_4.256V₆O₂₄ formula. The phase of the lyonsite type structure has a homogeneity range with the Co_3+1.5xFe_4–xV₆O₂₄ formula (0.476 formula (0.476<x<1.667). The melting temperature and the volume of the unit cell of the lyonsite type structure phase increases together with the rise of cobalt quantity contained in it. Basing on the results of the DTA and XRD measurements a phase diagram of the FeVO_4–Co₃V₂O₈ system up to the solidus line was constructed.     

Novel Visible-Light-Driven Photocatalyst Co<Subscript>3</Subscript>O<Subscript>4</Subscript>/FeWO<Subscript>4</Subscript> for Efficient Decomposition of Organic Pollutants

A highly efficient and visible light (λ ≥ 420 nm) responsive composite photocatalyst, Co₃O₄/FeWO₄ was prepared by simple impregnation method. The heterojunction semiconductors Co₃O₄/FeWO₄ demonstrated notably high photocatalytic activity over a wide range of composition than the individual component Co₃O₄ or FeWO₄ for the complete degradation of 1,4-dichlorobenzene (DCB) in aqueous phase under visible light irradiation. The photocatalytic activity of composite was optimized at 1/99 Co₃O₄/FeWO₄ composition. After 2 h of visible light irradiation 51% decomposition of 1,4-dichlorobenzene (DCB) was observed utilizing 1/99 Co₃O₄/FeWO₄ photocatalyst while the end members demonstrated a negligible degradation under the same experimental condition. The valence band (VB) and conduction band (CB) of Co₃O₄ is located above the VB and CB of FeWO₄, respectively. Both the semiconductors Co₃O₄ and FeWO₄ exhibit strong absorption over the wide range of visible light. The obviously enhanced photocatalytic performance of Co₃O₄/FeWO₄ composite has been discussed on the hole (h⁺) as well as electron (e^?) transfer mechanism between the VB and CB of individual semiconductors.     

Sn-doped Li<Subscript>1.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>O<Subscript>2</Subscript> cathode materials for lithium-ion batteries with enhanced electrochemical performance

Sn-doped Li-rich layered oxides of Li_1.2Mn_0.54-x Ni_0.13Co_0.13Sn _x O₂ have been synthesized via a sol-gel method, and their microstructure and electrochemical performance have been studied. The addition of Sn⁴⁺ ions has no distinct influence on the crystal structure of the materials. After doped with an appropriate amount of Sn⁴⁺, the electrochemical performance of Li_1.2Mn_0.54-x Ni_0.13Co_0.13Sn _x O₂ cathode materials is significantly enhanced. The optimal electrochemical performance is obtained at x = 0.01. The Li_1.2Mn_0.53Ni_0.13Co_0.13Sn_0.01O₂ electrode delivers a high initial discharge capacity of 268.9 mAh g^?1 with an initial coulombic efficiency of 76.5% and a reversible capacity of 199.8 mAh g^?1 at 0.1 C with capacity retention of 75.2% after 100 cycles. In addition, the Li_1.2Mn_0.53Ni_0.13Co_0.13Sn_0.01O₂ electrode exhibits the superior rate capability with discharge capacities of 239.8, 198.6, 164.4, 133.4, and 88.8 mAh g^?1 at 0.2, 0.5, 1, 2, and 5 C, respectively, which are much higher than those of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ (196.2, 153.5, 117.5, 92.7, and 43.8 mAh g^?1 at 0.2, 0.5, 1, 2, and 5 C, respectively). The substitution of Sn⁴⁺ for Mn⁴⁺ enlarges the Li⁺ diffusion channels due to its larger ionic radius compared to Mn⁴⁺ and enhances the structural stability of Li-rich oxides, leading to the improved electrochemical performance in the Sn-doped Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode materials.