Graphitized carbon materials for electrosynthesis of Н<Subscript>2</Subscript>О<Subscript>2</Subscript> from О<Subscript>2</Subscript> in gas-diffusion electrodes

New graphitized carbon materials: technical carbon N220, С140, and СН85 (Omsktekhuglerod) were studied as catalysts of electrosynthesis of alkaline solutions of hydrogen peroxide from oxygen in gasdiffusion electrodes (GDEs). The kinetic parameters of oxygen reduction in alkaline solution and the capacity of gas-diffusion electrodes based on technical carbon N220, С140, and СН85 were determined. Data on the kinetics of hydrogen peroxide accumulation were obtained at different current densities. The fraction of current γ spent on the reduction of oxygen to hydrogen peroxide was determined. The rate constants of hydrogen peroxide decomposition under the given conditions were calculated.     

Kinetics of electroreduction of S<Subscript>2</Subscript>O<Stack><Subscript>8</Subscript><Superscript>2−</Superscript></Stack> anions on mechanically renewable silver electrode

The kinetics of electroreduction of peroxodisulfate anions on a mechanically renewed silver electrode is studied by voltammetric and impedance methods. Impedance diagrams obtained in the region of negatively charged metal surface are successfully modeled by the equivalent circuit formed by the solution resistance and also the reaction resistance connected in parallel with the constant-phase element substituted for the double layer capacitance. The analysis of experimental data carried out in terms of this circuit and their comparison with the literature data makes it possible to assume that the reduction kinetics of S₂O ₈ ^2? anions on this electrode can be adequately described in the framework of the phenomenological theory of slow discharge. The reasons for deviation of the literature data on the kinetics of this reaction on polycrystalline Ag electrode from the relationships following from the slow discharge theory are put forward and substantiated.     

Thermogravimetric analysis of wheatleyite Na<Subscript>2</Subscript>Cu<Superscript>2+</Superscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>·2H<Subscript>2</Subscript>O

Evidence for the existence of primitive life forms such as lichens and fungi can be based upon the formation of oxalates. These oxalates form as a film like deposit on rocks and other host matrices. The anhydrous oxalate mineral moolooite CuC₂O₄ as the natural copper(II) oxalate mineral is a classic example. Another example of a natural oxalate is the mineral wheatleyite Na₂Cu²⁺(C₂O₄)₂·2H₂O. High resolution thermogravimetry coupled to evolved gas mass spectrometry shows decomposition of wheatleyite at 255°C. Two higher temperature mass losses are observed at 324 and 349°C. Higher temperature mass losses are observed at 819, 833 and 857°C. These mass losses as confirmed by mass spectrometry are attributed to the decomposition of tennerite CuO. In comparison the thermal decomposition of moolooite takes place at 260°C. Evolved gas mass spectrometry for moolooite shows the gas lost at this temperature is carbon dioxide. No water evolution was observed, thus indicating the moolooite is the anhydrous copper(II) oxalate as compared to the synthetic compound which is the dihydrate.     

Two crystalline modifications of Pd<Subscript>2</Subscript>(μ-ac)<Subscript>2</Subscript>(acac)<Subscript>2</Subscript>

Crystal structures of two modifications of a binuclear Pd₂(μ-ac)₂(acac)₂ complex are studied at 150 K and 297 K (ac = acetate; acac = acetylacetonate). It is demonstrated that in both cases, the packing of the complexes can be considered as pseudohexagonal, the molecules forming infinite chains by interactions between chelate rings with the shortest contacts Pd...C _γ ～ 3.3 Å.     

Crystal structure of Cs[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)] · H<Subscript>2</Subscript>O

Single crystals of Cs[(UO₂)₂(C₂O₄)₂(OH)] · H₂O were synthesized and structurally studied using X-ray diffraction. The compound crystallizes in monoclinic space group P2₁/m, Z = 2, with the unit cell parameters a = 5.5032(4) Å, b = 13.5577(8) Å, c = 9.5859(8) Å, β = 97.012(3)°, V = 709.86(9) ų, R = 0.0444. The main building units of crystals are [(UO₂)₂(C₂O₄)₂(OH)]^? layers of the A₂K ₂ ⁰² M² (A = UO ₂ ²⁺ , K⁰² = C₂O ₄ ^2? , and M² = OH^?) crystal-chemical family. Uranium-containing layers are linked into a three-dimensional framework via electrostatic interactions with outer-sphere cations and hydrogen bonds with water molecules.     

Neutron diffraction study of Rb<Subscript>2</Subscript>UO<Subscript>2</Subscript>(SeO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 2D<Subscript>2</Subscript>O

A powder of deuterated rubidium diselenatouranylate dihydrate Rb₂UO₂(SeO₄)₂ · 2D₂O has been studied by neutron diffraction. The compound is orthorhombic, space group Pna2₁, with the following unit cell parameters: a = 13.654(2) Å, b = 11.863(2) Å, c = 7.625(1) Å, Z = 4, R _F = 3.77, R _I = 6.12, and χ² = 2.21. Basic structure units are [UO₂(SeO₄)₂ · D₂O]^2? layers belonging to the AB ₂ ² M¹ crystal-chemical group (A = UO ₂ ²⁺ , B² = SeO ₄ ^2? , M¹ = D₂O) of uranyl complexes. The hydrogen atoms if the water molecules involved in the layer form intralayer hydrogen bonds with the terminal oxygen atoms of selenate ions. The outer-sphere water molecules are coordinated to the rubidium ions and are involved in hydrogen bonding with oxygen atoms of neighboring [UO₂(SeO₄)₂ · D₂O]^2? layers.     

Electrosynthesis of Н<Subscript>2</Subscript>О<Subscript>2</Subscript> from О<Subscript>2</Subscript> in a Gas-Diffusion Electrode Based on Mesostructured Carbon CMK-3

Mesostructured carbon CMK-3 (Carbon Mesostructured by KAIST) synthesized by the template method is studied as the electrocatalyst for electrosynthesis of Н₂О₂ from О₂ in a gas-diffusion electrode (GDE) in alkaline and acidic solutions. The texture characteristics of the original material and its mixture with hydrophobizer (polytetrafluoroethylene) are studied by the method of low-temperature nitrogen adsorption. The rate constants for hydrogen peroxide decomposition on these materials in alkaline and acidic solutions are calculated. Kinetic parameters of oxygen reduction in alkaline and acidic solutions are determined as well as the capacitance of gas-diffusion electrodes based on mesocarbon. The selectivity of the electrocatalyst is estimated by finding the current fracture γ consumed in oxygen reduction to hydrogen peroxide. Data on the kinetics of hydrogen peroxide accumulation during electrosynthesis of Н₂О₂ from О₂ are obtained. The acidic solution of hydrogen peroxide with the concentration more than 3 M is obtained with the current efficiency higher than 80%.     

Electrosynthesis of Н<Subscript>2</Subscript>О<Subscript>2</Subscript> from О<Subscript>2</Subscript> in Gas Diffusion Electrodes Based on Black СН600

Furnace black СН600 was studied as a catalyst for electrosynthesis of Н₂О₂ from О₂ in a gas diffusion electrode in alkaline and acidic solutions. The texture properties of the starting black СН600 and gas diffusion electrodes (GDEs) based on it were determined by the low-temperature nitrogen adsorption (LTNA) method. The rate constants of Н₂О₂ decomposition on black and its mixtures with fluoroplast-4D in acidic and alkaline solutions of electrolyte were calculated. The process selectivity γ (the current fraction spent on the two-electron reduction of oxygen), kinetic parameters of oxygen reduction, and double-layer capacity of the СН600-based GDE were determined. Data on the kinetics of hydrogen peroxide accumulation during electrosynthesis from oxygen in СН600-based GDE in acidic and alkaline solutions were obtained.     

Preparation of nano-SO<Stack><Subscript>4</Subscript><Superscript>2−</Superscript></Stack>/TiO<Subscript>2</Subscript> catalyst and its application in esterification of sebacic acid with 2-ethyl hexanol

A pure anatase phase nano-SO₄²⁻ /TiO₂ catalysts were synthesized and their catalytic activities were tested. Nano-SO₄²⁻/TiO₂ shows high activity and effective re-usable when used as basic catalysts for the synthesis of dioctyl sebacate.     

Synthesis and structure of the [Co(NioxH)<Subscript>2</Subscript>(Thio)<Subscript>2</Subscript>]<Subscript>2</Subscript>SO<Subscript>4</Subscript>·2H<Subscript>2</Subscript>O complex compound

A new Co(III) complex of 1,2-cyclohexanedionedioxime and thiocarbamide with an SO ₄ ^2? anion and solvation water molecules in the outer sphere has been synthesized and its structure has been defined. Orthorhombic crystals, a = 11.659(2) Å, b = 26.448(5) Å, c = 30.142(6) Å, V = 9295(3) Å ³, Z = 8, d_calc = 1.599 g/cm³, space group Pbca; final R index is 0.0578 for 8221 reflections with I > 2σ(I). In the octahedral Co(III) complex, two 1,2-cyclohexanedionedioxime residues lie in the equatorial plane, while two thiocarbamide molecules are in the axial plane. Intramolecular bonds: N-H…O and O-H…O type hydrogen bonds and π-π interactions that stabilize the complex cations. In crystal, the components are linked by N-H…O and O-H…O hydrogen bonds into a 3D framework.     

Crystal structure of Ba<Subscript>3</Subscript>[UO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>(NCS)]<Subscript>2</Subscript> · 9H<Subscript>2</Subscript>O

Single crystals of Ba₃[UO₂(C₂O₄)₂(NCS)]₂ · 9H₂O are synthesized and studied by X-ray diffraction. The crystals are orthorhombic, space group Fddd, Z = 16, and the unit cell parameters are a = 16.253(3) Å, b = 22.245(3) Å, c = 39.031(6) Å. The main crystal structural units are mononuclear complex groups [UO₂(C₂O₄)₂NCS]^3? of the crystal-chemical family (AB ₂ ⁰¹ M¹ (A = UO ₂ ²⁺ , B⁰¹ = C₂O ₄ ^2? , M¹ = NCS^?) of the uranyl complexes linked into a three-dimensional framework by electrostatic interactions and hydrogen bonds involving oxalate ions and water molecules.     

Influence of ion size on the stability of chloroplumbates containing PbCl<Stack><Subscript>5</Subscript><Superscript>−</Superscript></Stack> or PbCl<Stack><Subscript>6</Subscript><Superscript>2−</Superscript></Stack>

The enthalpies of formation of PbCl₄, PbCl₅⁻ and PbCl₆²⁻, originating from quantum mechanics, have enabled the thermodynamic behaviour of these ions with respect to Cl-detachment to be assessed. The stability of salts containing PbCl₅⁻ and PbCl₆²⁻ as a function of the dimensions of these anions and complementary cations was studied using an approach combining the Kapustinskii-Yatsimirskii equation with basic thermochemical relationships. It was found that hexachloroplumbates of monovalent metal cations will not dissociate into metal chlorides and PbCl₄, provided the complementary cations are suitably large in size. Hexachloroplumbates of divalent metal cations have not yet been synthesised since no known metal cations attain the requisite large size. Such salts will not dissociate if the divalent metal cations are able to complex suitably large electron-donating ligands. The pentachloroplumbates of both monovalent and divalent metal cations are unstable, since no known metal cations have appropriately large ionic radii. The approach adopted appears to be useful for the examination of the thermal behaviour, stability and reactivity of chloroplumbates.     

Crystal structure and thermal properties of [Au(en)<Subscript>2</Subscript>]<Subscript>2</Subscript>[Cu(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>]<Subscript>3</Subscript>·8H<Subscript>2</Subscript>O

The crystal structure of a double complex salt of the composition [Au(en)₂]₂[Cu(C₂O₄)₂]₃·8H₂O (en = ethylenediamine) at 150 K is determined by single crystal X-ray diffraction. The crystal data for C₂₀H₄₈Au₂Cu₃N₈O₃₂ are: a = 9.1761(3) Å, b = 16.9749(6) Å, c = 13.4475(5) Å, β = 104.333(1)°, V = 2029.43(12) ų, P2₁/c space group, Z = 2, d _x = 2.450 g/cm³. It is demonstrated that the thermal decomposition of the double complex salt in a helium or hydrogen atmosphere affords the solid solution Au_0.4Cu_0.6.     

A theoretical study on the dynamics of the gas phase reaction of NH<Subscript>2</Subscript>(<Superscript>2</Superscript>B<Subscript>1</Subscript>) with HO<Subscript>2</Subscript>(<Superscript>2</Superscript>A″)

Quasi-classical trajectory calculations and stochastic one-dimensional chemical master equation simulation methods are used to study the dynamics of the reaction of amidogen radical [NH₂(²B₁)] with hydroperoxyl radical [HO₂(²A″)] on the lowest singlet electronic state. The title complex reaction takes place on a multi-well multichannel potential energy surface consisting of three deep potential wells and one van der Waals complex. In quasi-classical trajectory calculations a new analytical potential energy surface based on CCSD(T)/aug-cc-pVTZ//MPW1K/6-31+G(d,p) ab initio method was driven and used to study the dynamics of the title reaction. In quasi-classical trajectory calculations, the reactive cross sections and reaction probabilities are determined for 200–2000 K relative translational energies to calculate the rate constants. The same ab initio method was used to have the necessary data for solving the one-dimensional chemical master equation to calculate the rate constants of different channels. In solving the master equation, the Lennard-Jones potential model was used to form the collision between the collider gases. The fractional populations of different intermediates and products in the early stages of the reaction were examined to determine the role of the energized intermediates and the van der Waals complex on the dynamics of the title reaction. Although the calculated total rate constants from both methods are in good agreement with the reported experimental values in the literature, the quasi-classical trajectory simulation predicts the formation of NH₂O + OH as the major channel in the title reaction in accordance with the previous studies (Sumathi and Peyerimhoff, Chem. Phys. Lett., 263:742–748, 1996), while the stochastic master equation simulation predicts the formation of HNO + H₂O as the major products.     

Conformational isomerism of the seven-membered heterocycle in a single crystal of [η<Superscript>2</Superscript>-Ph<Subscript>2</Subscript>P(O)(CH<Subscript>2</Subscript>)<Subscript>2</Subscript>C(O)NМе<Subscript>2</Subscript>]TiF<Subscript>4</Subscript> adduct

The crystal structure of TiF₄[(Ph₂P(O)CH₂CH₂C(O)NMe₂)] chelate (I) was studied by X-ray crystallography, which revealed four crystallographically independent complex molecules of similar structure (1–4). It was found that the molecules are only slightly different in the bond lengths between the coordinated atoms and the central titanium ion and considerably different in the geometry of the seven-membered TiOPCCCO chelate ring. The geometry of the chelate rings was found to be almost identical in each pair of complexes 1, 2 (A) and 3, 4 (B), and a conclusion was drawn on the presence of two conformational isomers (A and B) of the chelate complex. Quantum chemical calculations of the relative thermodynamic stability of molecules 1–4 were performed, and their geometry optimization led to one theoretical structure. The comparison of the chelate ring geometry in the theoretical structure and in conformers A and B revealed that the conformation of the theoretical chelate ring coincides with that of conformer A.     

Oxidation of Adamantane with H<Subscript>2</Subscript>O<Subscript>2</Subscript>–CF<Subscript>3</Subscript>COCF<Subscript>3</Subscript> · 1.5 H<Subscript>2</Subscript>O in the Presence of VO(acac)<Subscript>2</Subscript>

The system hydrogen peroxide–hexafluoroacetone sesquihydrate effectively oxidizes adamantane in the presence of VO(acac)₂ to afford 64% of adamantan-1-ol in tert-butyl alcohol or 76% of adamantan-2-one in a mixture of acetic acid with pyridine.     

Diagram of the PbF<Subscript>2</Subscript>–SnF<Subscript>2</Subscript> system

A phase diagram of the PbF₂–SnF₂ system has been studied by differential thermal analysis and X-ray powder diffraction. The system forms Pb_1–хSn_хF₂ (х ≤ 0.33) solid solution and three compounds. Pb₂SnF₆ decomposes in solid state by a peritectoid reaction at 350°С; Pb₃Sn₂F₁₀ and PbSnF₄ melt by peritectic reactions at 565 and 380°С, respectively. The eutectic coordinates are 180°С, 90 mol % SnF₂.     

Crystal Structure of Neptunium(V) Acetate [(NpO<Subscript>2</Subscript>)<Subscript>2</Subscript>(OOCCH<Subscript>3</Subscript>)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)] ⋅ 2H<Subscript>2</Subscript>O

A new neptunium(V) complex [(NpO₂)₂(CH₃COO)₂(H₂O)] ? 2H₂O was synthesized and its crystal structure was determined. The unit cell parameters are: a = 24.007(10) Å, b = 6.779(3) Å, c = 8.076(3) Å, space group Pnma, Z = 4, V = 1314.2(9) ų, R = 0.049, wR(F²) = 0.105. The crystal structure of the compound is composed of neutral [(NpO₂)₂(CH₃COO)₂(H₂O)] layers and molecules of the water of crystallization. Each of the crystallographically independent neptunoyl ions performs a bidentate function thus forming a composite system of cation-cation bonds.     

Non-isothermal kinetics of thermal decomposition of NH<Subscript>4</Subscript>ZrH(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>·H<Subscript>2</Subscript>O

Nanocrystalline NH₄ZrH(PO₄)₂·H₂O was synthesized by solid-state reaction at low heat using ZrOCl₂·8H₂O and (NH₄)₂HPO₄ as raw materials. X-ray powder diffraction analysis showed that NH₄ZrH(PO₄)₂·H₂O was a layered compound with an interlayer distance of 1.148 nm. The thermal decomposition of NH₄ZrH(PO₄)₂·H₂O experienced four steps, which involves the dehydration of the crystal water molecule, deamination, intramolecular dehydration of the protonated phosphate groups, and the formation of orthorhombic ZrP₂O₇. In the DTA curve, the three endothermic peaks and an exothermic peak, respectively, corresponding to the first three steps' mass losses of NH₄ZrH(PO₄)₂·H₂O and crystallization of ZrP₂O₇ were observed. Based on Flynn–Wall–Ozawa equation and Kissinger equation, the average values of the activation energies associated with the NH₄ZrH(PO₄)₂·H₂O thermal decomposition and crystallization of ZrP₂O₇ were determined to be 56.720 ± 13.1, 106.55 ± 6.28, 129.25 ± 4.32, and 521.90 kJ mol⁻¹, respectively. Dehydration of the crystal water of NH₄ZrH(PO₄)₂·H₂O could be due to multi-step reaction mechanisms: deamination of NH₄ZrH(PO₄)₂ and intramolecular dehydration of the protonated phosphate groups from Zr(HPO₄)₂ are simple reaction mechanisms.