The formation of an active component in V-Mo-Nb-O catalysts of ethane oxidation and ammoxidation

Summary Genesis of an active component in V-Mo-Nb-O catalysts for the oxidation and ammoxidation of ethane was studied. It was shown that the mixing of aqueous solutions of initial reactants leads to the formation of MoV complexes in the solution and to sedimentation of a binary Nb-Mo compound. The latter serves as the basis for the formation of the catalyst active component phase (a triple V-Mo-Nb compound with a variable composition of Mo₅O₁₄-like structure) during the subsequent treatment in air at 400°C.     

ansa-Metallocene derivatives: VII. Synthesis and crystal structure of a chiral ansa-zirconocene derivative with ethylene-bridged tetrahydroindenyl ligands

The chiral ansa-zirconocene derivative ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-zirconium(IV) dichloride has been prepared by reaction of dilithiobis(indenyl)ethane with ZrCl₄ and subsequent hydrogenation. The product has been shown to be the 1-R,S rather than meso-metal-ring linkage stereoisomer by an X-ray determination of the molecular structure.     

Controlled Growth of Ag Nanocrystals in a H-Bonded Open Framework

A procedure that enabled rational access to the first example of hybrid material made of NPs grown within a H-bonded framework is reported. To avoid competitive reactions with the framework units, the metal precursor was chemically trapped in the porous structure and subsequently photo-reduced to afford the hybrid material Ag@SPA-2 , which consists of Ag NPs of nanometric sizes (<15 nm) homogeneously distributed in the crystals of the host material. In a subsequent step, taking advantage of the porous matrix the silver NPs have been transformed in situ to Ag₂S NP by simple infiltration of H₂S. The supramolecular network is shown to play an important role in stabilizing the inorganic nanomaterials and thus in controlling their growth.     

Relaxation processes in an aromatic polyamide-imide and composites on its basis with hydrosilicate nanoparticles

Features of the relaxation behavior of an aromatic polyamide-imide and a composite with nanotubes of magnesium silicate with the structure of chrysotile have been studied by dynamic mechanical analysis, dielectric spectroscopy, and differential scanning calorimetry. Two secondary relaxation (β₁ and β₂) transitions have been found, the activation energies of these processes have been determined, and the solvent effect on the cooperativeness degree has been studied. Changes in the value of the apparent activation energy of the β₁-process caused by the subsequent heating of polymeric and composite samples have been analyzed according to the Starkweather procedure. It has been shown that, as the solvent is released from the polyamide-imide film, the polymer exhibits increasing local mobility, which are predetermined by the structure of the molecular unit. Using the GAMESS software, we have assumed the most probable dimer conformations that correspond to two repeating units of the polyamide-imide molecule.     

XPS study of the oxidation of nanosize Ni/Si(100) films

The XPS (X-ray photoelectron spectroscopy) study of nickel oxide nanolayers obtained by magnetron sputtering of the metal and its subsequent oxidation in air at different temperatures (400°C and 1000°C) was performed. Silicon(100) was used as a substrate. Surface of the initial Ni/Si structure was shown to contain not only Ni metal, but also the NiO oxide. Annealing at 400°C results in a complete oxidation of the metal film. At a high-temperature annealing (1000°C), nickel interacts both with oxygen and silicon substrate to form NiSi silicide and a composite Ni-Si-O phase in transition layer. Electronconductivity of NiO films is determined by intercrystallite barriers. Activation energies of film electroconductivity in model gases (O₂, Ar, H₂) were found.     

Synthesis of rutile titanium dioxide from Russian raw materials

The conditions of the structure formation of rutile titanium dioxide from titanium dioxide (anatase) and titanium hydroxide isolated by thermolysis from the titanium compound (NH₄)₂TiO(SO₄)₂ · H₂O and by thermal hydrolysis of a titanium sulfate(IV) solution, respectively, were studied. It was shown that the mechanical activation of the studied powders causes, in addition to a decrease in the initial grain size, deep destructuring with the formation of the transition phase, which, in the process of the subsequent high-temperature treatment, functions as a matrix for the formation of rutile. The research results will be used for the development of a new variant of the technology for the synthesis of titanium dioxide, which is an important component of compositions for polymeric materials—in particular, the K-300-61 and K-153 adhesives.     

Designing a 0D/2D S-Scheme Heterojunction over Polymeric Carbon Nitride for Visible-Light Photocatalytic Inactivation of Bacteria

Constructing heterojunctions between two semiconductors with matched band structure is an effective strategy to acquire high-efficiency photocatalysts. The S-scheme heterojunction system has shown great potential in facilitating separation and transfer of photogenerated carriers, as well as acquiring strong photoredox ability. Herein, a 0D/2D S-Scheme heterojunction material involving CeO₂ quantum dots and polymeric carbon nitride (CeO₂/PCN) is designed and constructed by in situ wet chemistry with subsequent heat treatment. This S-scheme heterojunction material shows high-efficiency photocatalytic sterilization rate (88.1 %) towards Staphylococcus aureus (S. aureus) under visible-light irradiation (λ≥420 nm), which is 2.7 and 8.2 times that of pure CeO₂ (32.2 %) and PCN (10.7 %), respectively. Strong evidence of S-scheme charge transfer path is verified by theoretical calculations, in situ irradiated X-ray photoelectron spectroscopy, and electron paramagnetic resonance.     

Sol–gel derived nano-crystalline CaSnO3 as high capacity anode material for Li-ion batteries

CaSnO₃ with the distorted-perovskite structure was prepared by sol–gel and high temperature solid-state reaction and electrochemical properties were studied in cell with Li as counter electrode. The sol–gel method gave uniform nano-crystallites (200–300 nm) of CaSnO₃ and was shown to deliver a reversible capacity of 380 mAh/g (0.005–1.0 V; 60 mA/g) with good cycling stability up to 45 cycles. The observed capacity involved in the first-discharge and the reversible capacity values during subsequent charge–discharge cycles show that the electrochemical process in CaSnO₃ is similar to other Sn-containing mixed oxide systems, viz., an initial structural reduction with Sn-metal formation followed by reversible Li–Sn alloy formation. The performance with respect to the attainable capacity, its retention on charge–discharge cycling and rate capability is better than the previously reported best-performing bulk Sn-oxide or ATCO starting materials which reveals that the perovskite structure and Ca-ion play a beneficial role.     

Designing a 0D/2D S‐Scheme Heterojunction over Polymeric Carbon Nitride for Visible‐Light Photocatalytic Inactivation of Bacteria

Constructing heterojunctions between two semiconductors with matched band structure is an effective strategy to acquire high‐efficiency photocatalysts. The S‐scheme heterojunction system has shown great potential in facilitating separation and transfer of photogenerated carriers, as well as acquiring strong photoredox ability. Herein, a 0D/2D S‐Scheme heterojunction material involving CeO₂ quantum dots and polymeric carbon nitride (CeO₂/PCN) is designed and constructed by in situ wet chemistry with subsequent heat treatment. This S‐scheme heterojunction material shows high‐efficiency photocatalytic sterilization rate (88.1 %) towards Staphylococcus aureus (S. aureus) under visible‐light irradiation (λ≥420 nm), which is 2.7 and 8.2 times that of pure CeO₂ (32.2 %) and PCN (10.7 %), respectively. Strong evidence of S‐scheme charge transfer path is verified by theoretical calculations, in situ irradiated X‐ray photoelectron spectroscopy, and electron paramagnetic resonance.     

A bis 1,10-phenanthroline ligand leading to octahedral Ru(II) complexes containing a well-defined axis

A bis-chelating ligand (1), made of two 1,10-phenanthroline subunits connected with a p-(CH₂)₂C₆H₄(CH₂)₂- spacer through their 4 positions, has been prepared, using Skraup syntheses and reaction of the anion of 4-methyl-7-anisyl-1,10-phenanthroline with α,α’-dibromo-p-xylene. Complexation of 1 with Ru(CH₃CN)₄Cl₂ and subsequent reaction with 4,4’-dimethyl-2,2’-bipyridine afforded an octahedral Ru(II) tris-diimine complex, in which a well-defined axis running through the terminal anisyl substituents and the central metal has been created, as shown by an X-ray molecular structure analysis.     

Electron-impact promoted fragmentation of some substituted isoxazolidines

A series of substituted isoxazolidinylacetophenones (II to VI) have been shown to fragment subsequent to electron-impact in a generally predictable fashion. One characteristic fragmentation of all the compounds investigated was the loss of H₂O₂ from their respective molecular ions.     

Microwave plasmochemical synthesis of nanopowders in the system Pb-Zr-Ti-O

Conditions for building up the composition and structure of mixed Pb, Zr, and Ti oxides in a microwave plasma-chemical process were studied. As starting substances Pb(C₂H₅)₄, Ti(C₄H₉O)₄, and a 80% Zr(C₄H₉O)₄ solution in 2-propanol were used. To avoid stratification of the components the initial temperature of the flow should not exceed 1000°C. Under these conditions the crystallization of a complex structure requires a combination of a plasma-chemical synthesis with subsequent thermal treatment of the resulting powders. After the thermal treatment an average particle size of lead zirconate-titanate nanopowder was 120 nm.     

Struktur der Valenciaxanthine und Valenciachrome

Structure of the Valenciaxanthins and Valenciachromes Valenciaxanthin, a carotenoid first isolated from Californian Valencia orange juice in 1952/1954 by American scientists, was re-isolated from fresh Spanish ‘Navelinas’ and shown, by spectroscopical and chiroptical examination, to have the unexpected (9Z)-10′-apo-11′,12′-dihydroviolaxantin-10′-ol structure 6 . A further, very minor component represents the (all-E)-structure 7 . Therefore, the Valenciachromes are the furanoid rearrangement products of 6 and 7 and, thus, stereoisomers of the 10′-apo-11′,12′-dihydroauroxanthiiv 10′-ols 8 . Valenciaxanthin represents a modification of the common cleavage of carotenoids in higher plants according to the scheme C₄₀ → C₂₇ + C₁₃, insofar as the reduction step not only includes the aldehyde function but also the subsequent conjugated double bond.     

Internally dispersed synthesis of uniform silver nanoparticles via in situ reduction of [Ag(NH3)2]+ along natural microfibrillar substructures of cotton fiber

Silver nanoparticles (Ag NPs) are known to have efficient antimicrobial properties, but the direct application of Ag NPs onto the surface of textiles has shown to be ineffective and raise environmental concerns because Ag NPs leach out during washing. In this study, non-leaching and stable Ag-cotton nanocomposite fiber was produced by the in situ formation of Ag NPs inside the cotton fiber. The reported method is to introduce a nanofluidic system in alkali-swollen cotton fiber. Sequential flows of [Ag(NH₃)₂]⁺ and reductant aqueous fluids into the opened microfibrillar channels yielded a self-assembly of Ag ions on the deprotonated cellulose and subsequent nucleation and particle growth on the microfibrils. Transmission electron and field emission scanning electron microscopy images showed Ag NPs evenly dispersed throughout the entire cross-section of the fiber and their fixation onto the isolated secondary cell wall, respectively. Despite the rapid reduction reaction and the absence of a stabilizing agent, the successful formation of monodispersed Ag NPs (12 ± 3 nm) was attributed to the self-controlled function of the highly organized microfibrillar substructures, which regulated the transport and mixing of reactants. Incorporation of Ag NPs into the internal structure of the cotton fiber did not significantly influence the cotton crystalline structure.     

The Significance of Metal Coordination in Imidazole-Functionalized Metal–Organic Frameworks for Carbon Dioxide Utilization

The grafting of imidazole species onto coordinatively unsaturated sites within metal–organic framework MIL-101(Cr) enables enhanced CO₂ capture in close proximity to catalytic sites. The subsequent combination of CO₂ and epoxide binding sites, as shown through theoretical findings, significantly improves the rate of cyclic carbonate formation, producing a highly active CO₂ utilization catalyst. An array of spectroscopic investigations, in combination with theoretical calculations reveal the nature of the active sites and associated catalytic mechanism which validates the careful design of the hybrid MIL-101(Cr).     

A Robust (10,3)-a Network Containing Chiral Micropores in the AgI Coordination Polymer of a Bridging Ligand that Provides Three Bidentate Metal-Binding Sites

Framework integrity is retained when water molecules replace the nitromethane molecules in the coordination polymer [Ag(hat)ClO₄]⋅2 CH₃NO₂ (see picture for structure), which are arranged in a helical fashion within the chiral micropores of the three-dimensional [Ag(hat)⁺]_n network with a (10,3)-a topology. Remarkably, this is also the case after subsequent displacement of the water by nitromethane molecules. hat=1,4,5,8,9,12-hexaazatriphenylene.     

Studies of the degradation of organotin stabilizers in poly(vinyl chloride) during gamma irradiation

Organotin stabilizers of the type Bu₂SnX₂ (X = SCH₂CO₂C₈H₁₇ or O₂CCH?CHCO₂C₈H₁₇) present in poly(vinyl chloride) (PVC) and subjected to varying doses of gamma irradiation in the range 1–200 kGy (0.1–20 Mrad) are shown to suffer degradation with dealkylation to form monobutyltin trichloride and tin(IV) chloride, which have been characterized by a subsequent alkylation procedure followed by gas chromatographic analysis. The extent of degradation of the stabilizers on prolonged gamma irradiation is much more severe than during thermal degradation leading to comparable blackening of the polymer.     

Magnetic characteristics of iron-modified oxide layers on titanium

Iron-modified TiO₂ coatings on titanium exhibiting ferromagnetic properties are formed by combining plasma electrolytic oxidation (PEO) and impregnation with subsequent annealing. It is found that iron is contained in the composition of dispersed particles with sizes of 1–10 μm distributed over the surface of the coatings. It is shown that the coercive force of the coating on titanium samples is 20–70 Oe. The composition, structure, and magnetic properties of the samples with coatings prepared via direct PEO and by combining PEO and impregnation are compared. It is concluded that impregnation and annealing procedures can be used to impart ferromagnetic properties to PEO coatings with different compositions, e.g., protective coatings and coatings applied in catalysis or medicine.     

In situ growth of TiO2 in interlayers of expanded graphite for the fabrication of TiO2-graphene with enhanced photocatalytic activity

We present a facile route for the preparation of TiO₂–graphene composites by in situ growth of TiO₂ in the interlayer of inexpensive expanded graphite (EG) under solvothermal conditions. A vacuum‐assisted technique combined with the use of a surfactant (cetyltrimethylammonium bromide) plays a key role in the fabrication of such composites. Firstly, the vacuum environment promotes full infusion of the initial solution containing Ti(OBu)₄ and the surfactant into the interlayers of EG. Subsequently, numerous TiO₂ nanoparticles uniformly grow in situ in the interlayers with the help of the surfactant, which facilitates the exfoliation of EG under the solvothermal conditions in ethanol, eventually forming TiO₂–graphene composites. The as‐prepared samples have been characterized by Raman and FTIR spectroscopies, SEM, TEM, AFM, and thermogravimetic analysis. It is shown that a large number of TiO₂ nanoparticles homogeneously cover the surface of high‐quality graphene sheets. The graphene exhibits a multi‐layered structure (5–7 layers). Notably, the TiO₂–graphene composite (only 30 wt % of which is TiO₂) synthesized by subsequent thermal treatment at high temperature under nitrogen shows high photocatalytic activity in the degradation of phenol under visible and UV lights in comparison with bare Degussa P25. The enhanced photocatalytic performance is attributed to increased charge separation, improved light absorbance and light absorption width, and high adsorptivity for pollutants.     

(Sr2N)H: Untersuchungen zur Redox‐Intercalation von Wasserstoff in Sr2N

(Sr₂N)H: On the Redox-Intercalation of Hydrogen into Sr₂N Strontium-nitride-hydride is obtained as brown-yellow single phase powder by reaction of strontium-subnitride (Sr₂N) with hydrogen (200 bar, 620 K) and subsequent treatment under vacuum (10⁻⁶ bar, 870 K). The structure determination was carried out by a combination of X-ray and neutron diffraction experiments on a deuterated sample. The elemental composition of the ternary compound was confirmed by means of chemical analyses. (Sr₂N)D crystallizes in the space group with a = 381.91(2) pm and c = 1887.61(2) pm. Strontium (Sr²⁺) in the crystal structure of (Sr₂N)D is arranged with an only slightly distorted ccp-motif. Nitrogen (N³⁻) and deuterium (D⁻) occupy the octahedral voids of the Sr²⁺-matrix in an ordered manner resulting in an alternating sequence of layers (anti-α-NaFeO₂-type structure).