MA(delta)Sb(2-delta) (M = Zr, Hf; A = Si, Ge): a new series of ternary antimonides and not "beta-ZrSb2"

The ternary antimonides ZrSi(delta)Sb(2-delta), HfGe(delta)Sb(2-delta), and ZrGe(delta)Sb(2-delta) were prepared by annealing of the elements in stoichiometric ratios below 800 degrees C. ZrSi(delta)Sb(2-delta) was earlier erroneously described as the binary "beta-ZrSb(2)", which does not exist as such, because the incorporation of tetrel atoms is necessary for the formation of this structure. ZrSi(delta)Sb(2-delta) has a small yet significant phase width with at least 0.066(7) < or = delta < or = 0.115(3), whereas the Ge analogues exist with larger tetrel concentration, i.e., ZrGe(0.211(5))Sb(1.789) and HfGe(0.205(6))Sb(1.795). The whole series of title compounds crystallizes in the Co(2)Si type (space group Pnma), with lattice dimensions of, e.g., for ZrGe(0.211(5))Sb(1.789), a = 730.4(1) pm, b = 395.13(6) pm, c = 957.6(2) pm, V = 0.27635(7) nm(3), Z = 4. The anionic substructure comprises infinite ribbons formed by the atom sites Q1 and Sb2, with Q1 being mixed occupied by Si or Ge and Sb atoms. These ribbons exhibit Q1-Q1 single bonds and Q1-Sb2 "half" bonds. Assuming the validity of the 8 - N rule, one can assign seven valence-electrons to Sb2 but only five to Q1, which might explain the preference of the tetrel atoms for the latter site.     

A simple approach to the synthesis of dialkyl 5-tert-butylamino-[2,2′]bifuranyl-3,4-dicarboxylates

Reaction of tert-butyl isocyanide with electron-deficient acetylenic esters in the presence of N¹-[(Z)-1-benzoyl-3-oxo-3-phenyl-1-propenyl]-2-(2-furyl)-2-oxoacetamide leads to dialkyl 5-tert-butylamino-[2,2′]bifuranyl-3,4-dicarboxylates in moderate yields.     

Red water treatment by photodegradation process in presence of modified TiO<Subscript>2</Subscript> nanoparticles and validation of treatment efficiency by MLR technique

An active photocatalyst under sunlight irradiation was proposed for treatment of red water of TNT production process. The nanoparticles of TiO₂/S_0.05,Zn_0.05 were prepared by the sol–gel method and were verified by XRD pattern, TEM image, EDXS analysis, BET analysis and DRS spectra. The proposed photocatalyst showed the surface area of 146 m² g^?1, anatase and rutile phases and band-gap energy of 2.92 eV. The prepared nanoparticles were used as photocatalyst in treatment of red water under UV lamp and sun irradiations. The photodegradation process was optimized in conditions of 5 g L^?1 of photocatalyst, irradiation time of 4 h and dilution times of 1000 of real samples. The treatment efficiency of 76 and 69 % and rate constants of 0.368 and 0.319 h^?1 were obtained under UV and sun irradiations, respectively. The multiple linear regression as a statistic technique was used for study of validation and verification of four factors of mole fraction of S dopant, the irradiation intensity of UV lamp, the dose of photocatalyst and dilution times on samples as predictor’s on the treatment efficiency of red water as the response variable. The output of MLR showed the obtained P values <0.05 in confidence level of 95 % for all of the variables. Thus, the null hypothesis is rejected, and a meaningful addition is observed in the model because changes in the predictor’s value are related to changes in the response variable.     

Experimental study of the neutron emission mechanisms in a Filippov-type plasma focus device

The results of an experimental investigation of neutron emission characteristics in the Filippov-type plasma focus facility Dena (90 kJ, 25 kV, 288 µF) with D₂ + %1 Kr as working gas are presented. From the experimental results, one can conclude that both thermonuclear and nonthermonuclear mechanisms are always present in neutron production, but their contributions to the total neutron yield are strongly dependent on the initial pressure and discharge voltage. It has been found that at constant discharge voltages and low pressures the beam—target interaction mechanism plays an important role in the neutron production and with increasing the pressure, its role decreases and the importance of thermonuclear mechanism increases. Also at constant pressures, the contribution of beam—target interaction mechanism in neutron production decreases with increasing the discharge energy. The value of the index in the empirical neutron yield scaling law Y_n I E^/2 was found to be about 3.82.     

Comparing the photocatalytic activity of N-doped and S-doped titanium dioxide nanoparticles for water splitting under sunlight radiation

The objective of this research is to compare the photocatalytic activity of nanoparticles of N-doped and S-doped titanium dioxide in water splitting by using sunlight radiation for hydrogen production. The sol–gel method was used for the preparation of nanoparticles of doped TiO₂ and the weight percent of doping element was 2, 4, 6 and 8. The prepared nanoparticles were identified by absorbance spectra of UV–Vis and FT-IR, TGA, XRD patterns, FE-SEM images and EDX spectra. The nanoparticles of S–\({\text{TiO}}_{2}\) indicated the lower band gap and lesser particle size versus N–\({\text{TiO}}_{2}\) nanoparticles. Nevertheless, the nanoparticles of N–\({\text{TiO}}_{2}\) showed the higher photocatalytic activity in hydrogen production process. The activity of doped samples with sulfur (S–\({\text{TiO}}_{2}\)) was reduced by the presence of sulfate anions, and the absorption of radiation in the samples surface was due to a decrease in the number of electron–hole pair in photocatalyst. The photocatalytic activity of N–\({\text{TiO}}_{2}\) was also increased with the increasing in weight fraction of N atoms, and the highest hydrogen production was obtained in 6 wt% of nitrogen.     

Stereoselective Solvent‐Free Synthesis of 4‐Hydroxy‐1,3‐thiazinane‐2‐thiones

An efficient solvent‐free one‐pot stereoselective synthesis of 4‐hydroxy‐1,3‐thiazinane‐2‐thione derivatives from the reaction of primary amines and carbon disulfide in the presence of α,β‐unsaturated aldehydes has been reported. The 4‐hydroxy‐1,3‐thiazinane‐2‐thione derivatives were easily converted to the related dehydrated or acetylated products.     

Polymerization of ethylene using a series of binuclear and a mononuclear Ni (II)‐based catalysts

A novel series of homo‐, bi‐, and mononuclear Ni(II)‐based catalysts (BNC_n n = 1–4, MNC₄) were used for ethylene polymerization. The optimum conditions for the catalyst BNC₄ (the highest catalytic activity) was obtained at [Al]/[Ni]=2000/1, T_p = 42 °C, and t_p = 20 min that was 1073 g PE/mmol Ni h. In theoretical study, steric and electronic effects of substituents and diimine backbone led to prominent influence on the catalyst behavior. The highest M_V was resulted from polymerization using BNC₄; however, the highest unsaturation content was obtained from BNC₁. GPC analysis showed a broad MWD (PDI = 17.8). BNC₁ and BNC₂ in similar structures showed broad peaks in DSC thermogram, while BNC₃ and BNC₄ with more electronic effects showed a peak along with a wide shoulder. Monomer pressure increasing showed enhancing in activity of the BNC₄, meanwhile a peak with shoulder to a single peak in DSC thermogram and uniformity in morphology of the resulted polymer were observed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3000–3011     

A novel dicationic ionic liquid as a highly effectual and dual-functional catalyst for the synthesis of 3-methyl-4-arylmethylene-isoxazole-5(4H)-ones

Research on Chemical Intermediates - A novel dicationic ionic liquid, N,N,N′,N′-tetramethyl-N,N′-bis(sulfo)ethane-1,2-diaminium mesylate [TMBSED][OMs]2), has been produced, and...