The effects of the conditions of formation of Ag-Co zeolite supported systems on their activity in the oxidation of carbon monoxide

The activity of Ag-Co zeolite catalysts in the oxidation of CO was studied. The peculiarities of the formation of Ag-Co-NaX systems with different active metal ratios were studied. The temperatures of hydrogen absorption maxima in the H₂ temperature-programmed reduction spectra of Ag-Co-NaX systems with different Ag/Co ratios correlated with the catalytic activity in the oxidation of CO. Different valence states of silver (Ag⁺, Ag⁰) and cobalt (Co³⁺, Co²⁺) were observed by X-ray photoelectron spectroscopy. It was found that the mutual influence of these states in the surface layer of Ag-Co zeolite catalysts affected their activity.     

Synthesis,structural and multinuclear natural abundance (<Superscript>13</Superscript>C, <Superscript>31</Superscript>P, <Superscript>195</Superscript>Pt) CP/MAS NMR studies of crystalline O,O′-dialkyldithiophosphate platinum(II) complexes

Platinum(II) O,O′-dicyclohexyl dithiophosphate [Pt{S₂P(O-cyclo-C₆H₁₁)₂}₂] (I) and platinum(II) O,O′-diisopropyl dithiophosphate [Pt{S₂P(O-iso-C₃H₇)₂}₂] (II) complexes were obtained and studied by solidstate ¹³C, ³¹P, and ¹⁹⁵Pt CP/MAS NMR spectroscopy. The dithiophosphate (Dtph) ligands in molecular structure I were found to be coordinated by platinum in S,S′-bidentate fashion to form the planar chromophore [PtS₄] (single-crystal X-ray diffraction data). For complex II, a new α-form (α-II) was obtained and identified by ³¹P MAS NMR spectroscopy. The ³¹P chemical shift anisotropy δ_aniso and the asymmetry parameter η of the ³¹P chemical shift tensor were calculated from the whole MAS spectra.     

Photoinduced grafting polymerization onto the surface with the use of radiation of high-power ultraviolet light-emitting diodes

The photoinduced grafting polymerization of acrylic acid onto the surface of a polypropylene film under the action of radiation with a wavelength of 365 nm and an intensity of 8–193 mW/cm² emitted by high-power UV light-emitting diodes is studied. Grafting is performed from a thin layer of the aqueous solution of the monomer onto the surface containing a photoinitiator (benzophenone) deposited from a solution in a volatile solvent. The amount of graft polymer is determined with the use of ATR FTIR spectroscopy. At an intensity of UV radiation of 193 mW/cm², the time of attainment of grafting-polymerization saturation is decreased by a factor of 6 relative to this time at an intensity of 8 mW/cm², typical for emitters based on mercury lamps. The rate of grafting polymerization in the studied UV-radiation-intensity range grows in proportion to the square root of intensity.     

Acoustic emission monitoring of damaging of fiberglass

The results of studies on determining the nucleation moment of microcracks in fiberglass are presented on the basis of a full-strength glassfiber mat and vinyl ether binder by the acoustic emission method in uniaxial tension. The research was carried out by continuous monotonic loading of samples under uniaxial tension until failure with simultaneous recording of the parameters of acoustic emission signal. Qualitative dependences of the parameters of acoustic emission signals on the stress value in the sample are revealed. It is found that, at a stress value of about 40% of the ultimate strength of material (about 420 MPa), microfracture processes—cracking of the polymer matrix—begin.     

Formation of supramolecular complexes in reactions of adduct formation of zinc diethyldithiocarbamate with morpholine. Molecular structures and thermal properties

A supramolecular compound of the general formula [Zn{NH(CH₂)₄O} {S₂CN(C₂H₅)₂}₂]₄ · NH(CH₂)₄O · C₂H₄{N(CH₂)₄O}₂ (I) was obtained and examined by X-ray diffraction analysis and thermography. According to X-ray diffraction data, the crystal lattice of compound I shows an unusual alternation of two independent centrosymmetric supramolecular complexes [Zn{NH(CH₂)₄O} {S₂CN(C₂H₅)₂}₂]₂ · C₂H₄{N(CH₂)₄O}₂ (Ia) and [Zn{NH(CH₂)₄O} {S₂CN(C₂H₅)₂}₂]₂ · NH(CH₂)₄O (Ib). Either complex includes two molecules of an adduct of bis(diethyldithiocarbamato)zinc with morpholine and outer-sphere molecules of 1,2-dimorpholinoethane or morpholine. Adduct molecules are structurally nonequivalent in pairs and linked with solvate molecules by hydrogen bonds. The calculated geometries of the zinc polyhedra are intermediate between trigonal bipyramid and tetragonal pyramid. Thermal decomposition of supramolecular compound I proceeds through desorption of the outer-sphere and coordinated organic molecules; in the final step, defragmentation of the dithiocarbamate part gives zinc sulfide.     

Platinum(II) O,O′-diisobutyl dithiophosphate: Synthesis,structure, thermal properties,and solid-state <Superscript>13</Superscript>C, <Superscript>31</Superscript>P,and <Superscript>195</Superscript>Pt CP/MAS NMR spectra. Model of the structural state of platinum in cooperite

The complex bis(O,O′-diisobutyl dithiophosphato)platinum(II) (I) was obtained and characterized by solid-state ¹³C, ³¹P, and ¹⁹⁵Pt CP/MAS NMR spectroscopy. In complex I, the dithiophosphate fragments are structurally equivalent with a predominantly orthorhombic tensor of the ³¹P chemical shift (η = 0.73). The tensor of the ¹⁹⁵Pt chemical shift approximates to an axially symmetric one (for δ_zz> δ_xx and δ_yy), which suggests the existence of square chromophores [PtS₄], as in cooperite (natural PtS). The crystal and molecular structures of complex I were determined from X-ray diffraction data. The Pt atom coordinates two Dtph ligands in a S,S′-anisobidentate fashion (the Pt-S bonds are nonequivalent: 2.315 and 2.329 Å) to form two four-membered chelate rings [PtS₂P] with platinum as a spiro atom. The P-S bond length (1.997 and 1.986 Å), which is intermediate between the idealized lengths of the single and double phosphorus-sulfur bonds, suggests the delocalization of the π-electron density in the structural fragments PS₂. In complex I, the electron shielding of the platinum nucleus in the direction perpendicular to the plane of the chromophore [PtS₄] was found to be noticeably higher than that in cooperite. The thermal properties of complex I were examined by combined DSC-TG thermal analysis. The intermediate product of the thermolysis of complex I was platinum(II) dithiometaphosphate [Pt(S₂PO)₂] and the final thermolysis product was PtS.     

Development of m-plane GaN anisotropic film properties during MOVPE growth on LiAlO2 substrates

The anisotropic film properties of m-plane GaN deposited by metal organic vapour phase epitaxy (MOVPE) on LiAlO₂ substrates are investigated. To study the development of layer properties during epitaxy, the total film thickness is varied between 0.2 and 1.7 μm. A surface roughening is observed caused by the increased size of hillock-like features. Additionally, small steps which are perfectly aligned in (1 1 −2 0) planes appear for samples with a thickness of ∼0.5 μm and above. Simultaneously, the X-ray rocking curve (XRC) full width at half maximum (FWHM) values become strongly dependent on incident X-ray beam direction beyond this critical thickness. Anisotropic in-plane compressive strain is initially present and gradually relaxes mainly in the [1 1 −2 0] direction when growing thicker films. Low-temperature photoluminescence (PL) spectra are dominated by the GaN near-band-edge peak and show only weak signal related to basal plane stacking faults (BSF). The measured background electron concentration is reduced from ∼10²⁰ to ∼10¹⁹ cm⁻³ for film thicknesses of 0.2 μm and ∼1 μm while the electron mobilities rise from ∼20 to ∼130 cm²/V s. The mobilities are significantly higher in [0 0 0 1] direction which we explain by the presence of extended planar defects in the prismatic plane. Such defects are assumed to be also the cause for the observed surface steps and anisotropic XRC broadening.     

Chiral ditopic receptors. Application to palladium-catalyzed allylic alkylation

Chiral pyridinooxazoline, quinolinooxazoline, bis(oxazolino)pyridine (pybox), and bisoxazoline (box) derivatives containing crown ether residues were prepared. Some of the ligands were assessed in substrate binding studies and in palladium catalyzed allylic alkylations.     

Photoluminescence and Raman scattering in spatially inhomogeneous heteroepitaxial InGaN layers

Spatial inhomogeneities of the indium distribution in In _x Ga_1–x N epitaxial layers grown on sapphire substrate with a GaN buffer layer were investigated using photoluminescence (PL) in addition to confocal scanning Raman spectroscopy (RS) and PL. Broad emission bands from In-enriched InGaN nanoclusters (700–900 nm) and from the volume outside the clusters (about 460 nm) were observed in PL spectra of an epitaxial InGaN layer with an average In content of 25.7%. It was established that larger micro-PL intensities corresponded to energetically shallower clusters. The observed broadly asymmetric A₁(LO) RS band of InGaN confirmed that the In concentration in the layer was highly variable. Modeling the LO phonon band by two Lorentzian curves gave an average In concentration of 21% in the volume outside the clusters and 37% in the nanoclusters, which was considerably higher than the average concentration in the layer and agreed well with their PL band positions.