Oxidation of Deactivated Cage Substrates in the System H2SO4–HNO3

Russian Journal of Organic Chemistry - The kinetics of oxidation of 16 carboxylic acid esters of the adamantane series in the system H2SO4–HNO3 have been studied, and the effective rate...     

NaBrO3/NaHSO4 · H2O as a Versatile Reagent System for the Oxidation of Benzylic Alcohols and Aldehydes

The oxidation of benzylic alcohols and aldehydes by NaBrO₃ is efficiently promoted in the presence of NaHSO₄ · H₂O. All reactions were performed under mild and completely heterogeneous conditions in good to high yields.     

CoFe2O4–SiO2–SO3H nanocomposite as a magnetically recoverable catalyst for oxidative bromination of alkynes

A hybrid catalyst has been prepared by incorporating sulfonic acid onto cobalt ferrite magnetic nanoparticles. The catalyst was successfully applied for rapid (20?min) synthesis of α,α-dibromoketones directly from alkynes and NBS. The reaction works well in the presence of 10?wt% of the catalyst at room temperature to produce the desired products in high yield. The catalyst could be recovered using an external magnet and reused without appreciable change in activity.     

Preparation and characterization of zein/chitosan complex for encapsulation of α-tocopherol, and its in vitro controlled release study

Chitosan (CS) nanoparticles coated with zein has been newly demonstrated as a promising encapsulation and delivery system for hydrophilic nutrient with enhanced bioactivities in our previous study. In this study, a hydrophobic nutrient, α-tocopherol (TOC), was successfully encapsulated into zein/CS complex. The fabrication parameters, including zein concentration, zein/CS weight ratio, and TOC loading percentage, were systematically investigated. The physicochemical and structural analysis showed that the electrostatic interactions and hydrogen bonds were major forces responsible for complex formation. The scanning electron microscopy study revealed the spherical nature with smooth surface of complex. TOC encapsulation was also evidenced by differential scanning calorimetry. The particle size and zeta potential of the complex varied from 200 to 800 nm and +22.8 to +40.9 mV, respectively. The kinetic release profile of the TOC showed burst effect followed by slow release. Compared with zein nanoparticles, zein/CS complex provided better protection of TOC release against gastrointestinal conditions, due to CS coatings. Zein/CS complex is believed to be a promising delivery system for supplementation or treatment of hydrophobic nutrients or drugs.     

Liquid–liquid equilibria in the system H3PO4–KCl–H2O–tri-n-butyl phosphate: experiments and modelling

The liquid–liquid equilibria of the system H₃PO₄–KCl–H₂O–TBP was studied experimentally in the concentration range 0–6 mol/kg. The obtained data were modelled using the Pitzer equation for the aqueous phase and the Sergievskii–Dannus relationship for the organic phase. A fairly good agreement was observed between the model and the experimental data.     

Magnetic core–shell Fe3O4@C-SO3H nanoparticle catalyst for hydrolysis of cellulose

Catalytic hydrolysis of cellulose over solid acid catalysts is one of efficient pathways for the conversion of biomass into fuels and chemicals. High catalytic activity and easy separation from reaction media are two important factors for evaluating the performance of the solid acid catalysts for the cellulose hydrolysis. In this study, we report a core–shell Fe₃O₄@C-SO₃H nanoparticle with a magnetic Fe₃O₄ core encapsulated in a sulfonated carbon shell, as recyclable catalyst for the hydrolysis of cellulose. The sulfonated carbon shell shows a good activity, presenting 48.6 % cellulose conversion with 52.1 % glucose selectivity under the moderate conditions of 140 °C after 12 h reaction. Importantly, the magnetic Fe₃O₄ core makes the catalysts easily separated from reaction mixtures by using the externally applied magnetic field. In addition, the Fe₃O₄@C-SO₃H nanoparticle catalyst shows a high stability in the activity and magnetization during recycling tests, suggesting it a promising solid acid catalyst for the hydrolysis of cellulose.     

Kinetics and mechanism of 1-phenyl-5-methyltetrazole nitration in HNO3–H2SO4 system

Russian Journal of Organic Chemistry - At nitration of 1-phenyl-5-methyltetrazole with nitric acid in aqueous solutions of sulfuric acid of 84–96% concentration a mixture forms of...     

Fe2O3–Al2O3 oxygen carrier materials for chemical looping combustion,a redox thermodynamic and thermogravimetric evaluation in the presence of H2S

Journal of Thermal Analysis and Calorimetry - Alumina-supported Fe2O3 oxygen carrier material (OCM) system is among the most promising OCM systems for solid and gaseous fuel CLC. This work utilizes...     

The synthesis and crystal structure of a hydrated magnesium phosphate Mg3(PO4)2·4H2O

The synthesis and crystal structure of a novel hydrated magnesium phosphate is described. The crystal structure was solved from powder X-ray diffraction data. Mg₃(PO₄)₂·4H₂O crystallizes in the orthorhombic space group Cmc2₁ (No. 36) with a=8.41087(9) Å, b=17.3850(2) Å, c=12.8034(1) Å, V=1872.15(4) ų and Z=8. The structure consists of sheets stacked along [010], which are linked by edge sharing octahedral Mg₂O₆(H₂O)₄ dimers. Within the sheets there are infinite edge-sharing chains of Mg octahedra along [100]. The compound has been further characterized by ³¹P MAS NMR spectroscopy and thermogravimetric analysis. The crystal structure of two dehydrated variants existing around 200 (Mg₃(PO₄)₂·2.5H₂O) and 275 °C (Mg₃(PO₄)₂·2H₂O) remain unknown.     

Tetranuclear CuII Cluster as the Ten Node Building Unit for the Construction of a Metal–Organic Framework for Efficient C2H2/CO2 Separation

Rational design of high nuclear copper cluster-based metal–organic frameworks has not been established yet. Herein, we report a novel MOF ( FJU-112 ) with the ten-connected tetranuclear copper cluster [Cu₄(PO₃)₂(μ₂-H₂O)₂(CO₂)₄] as the node which was capped by the deprotonated organic ligand of H₄L (3,5-Dicarboxyphenylphosphonic acid). With BPE (1,2-Bis(4-pyridyl)ethane) as the pore partitioner, the pore spaces in the structure of FJU-112 were divided into several smaller cages and smaller windows for efficient gas adsorption and separation. FJU-112 exhibits a high separation performance for the C₂H₂/CO₂ separation, which were established by the temperature-dependent sorption isotherms and further confirmed by the lab-scale dynamic breakthrough experiments. The grand canonical Monte Carlo simulations (GCMC) studies show that its high C₂H₂/CO₂ separation performance is contributed to the strong π-complexation interactions between the C₂H₂ molecules and framework pore surfaces, leading to its more C₂H₂ uptakes over CO₂ molecules.     

Synthesis of novel ZnAl2O4/Al2O3 nanocomposite by sol–gel method and its application as adsorbent

Journal of Sol-Gel Science and Technology - In this research, ZnAl2O4/Al2O3 nanocomposites with different ZnAl2O4 (30, 50, and 70?wt.%) were successfully prepared in one step by sol–gel...     

Preparation of CdS–TiO2/Fe3O4 photocatalyst and its photocatalytic properties

The CdS modified TiO₂/Fe₃O₄ photocatalysts were prepared by sol–gel and immersion methods. The morphological, structural and optical properties of as-prepared samples were characterized by X-ray diffraction (XRD), UV–Vis absorption spectra, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The TEM observation showed that the surface of magnetite particles (Fe₃O₄) were coated by CdS–TiO₂ layer as loose clusters, and average diameter of composites particles was about 250 nm. UV–Vis absorption spectra indicated that CdS–TiO₂/Fe₃O₄ composites had pronounced red-shift compared with that of TiO₂/Fe₃O₄. The CdS–TiO₂/Fe₃O₄ composites exhibit higher photocatalytic activity than pure TiO₂ and TiO₂/Fe₃O₄ for the degradation of Reactive Brilliant Red X-3B dye (X-3B) aqueous solution under simulated sunlight, and the optimum content of CdS is 1.0 % (mol ratio of CdS to TiO₂). In addition, a gradual loss of photocatalytic activity can be observed in reusability test of CdS–TiO₂/Fe₃O₄ composites, and degradation of X-3B reached still to 78.9 % after five runs.     

Phase formation along the PO 4 3− /Zr = 1.5–2.0 section of the ZrO(NO3)2-KF-H3PO4-H2O) system

The phase composition of precipitates at 20°C along the PO ₄ ^3? /Zr = 1.5–2.0 section at KF/Zr = 1–5 (mol/mol) of the ZrO(NO₃)₂-H₃PO₄-KF-H₂O system has been investigated. Phases in these precipitates have been identified by X-ray powder diffraction, crystal-optical, chemical, and thermal analyses and by IR spectroscopy. The previously known potassium zirconates K₃ZrF₇ and K₂ZrF₆ have been revealed, and crystalline fluorophosphate zirconate K₃Zr₃F₃(HPO₄)₃(PO₄)₂ and a phosphate nitrate of unknown formula have been obtained for the first time.     

Critical temperatures,pressures, and densities for the mixtures CO2–C3H8, CO2–nC4H10, C2H6–C3H8, and C3H8–nC4H10

A simple method is developed to estimate mixture critical temperatures (T_c), pressures (P_c), and densities (ρ_c) as a function of overall composition (X) from near critical region experimental coexistence data. This three-step method is applied to four mixtures, CO₂–C₃H₈, CO₂–nC₄H₁₀, C₂H₆–C₃H₈, and C₃H₈–nC₄H₁₀. Isothermal liquid–vapor coexistence data, which includes temperature, vapor pressure, coexisting densities (ρ^ℓ and ρ^v), and coexisting compositions for the more volatile component (x₁^v and x₁^ℓ) are used. In the first step, the difference of the saturated liquid and vapor densities (ρ^ℓ−ρ^v) is fitted to an empirical function in ((P_c−P)/P_c) to obtain P_c. Then P/P_c and ((ρ^ℓ+ρ^v)/2ρ_c) are simultaneously fitted to functions of a polynomial in (X₁−(x₁^v+x₁^ℓ)/2) yielding estimates of ρ_c and X₁. Finally, the discrete estimated critical data points are fitted with an equation to provide a continuous representation of the critical lines. The method is successfully tested for the mixtures, CO₂–C₃H₈ and CO₂–nC₄H₁₀, for which there is a reasonable amount of isothermal data. The procedure is then applied to the mixtures, C₂H₆–C₃H₈ and C₃H₈–nC₄H₁₀, for which there are sparse data. For all four mixtures, the critical temperature line, T_c vs. X₁, matches literature values within ±0.5%. The critical pressure line, P_c vs. X₁, and critical density line, ρ_c vs. X₁, match literature values, in general, within ±2%.     

Calculations for the vibration frequencies of the OH⋯O bond in KH2PO4 by a semiempirical method

The frequencies of the stretching vibration and the bending vibration of the OH⋯O bond in potassium dihydrogen phosphate have been calculated by means of two semiempirical formulae with three parameters. The calculated results can give satisfactory explanation for the experimental spectra of the potassium dihydrogen phosphate crystal. The parameters used in the calculations may be related to the chemical bonding and the charge distribution about the two oxygen atoms of the OH⋯O bond system.