Nickel(II) Schiff base complex supported on nano‐titanium dioxide: A novel straightforward route for preparation of supported Schiff base complexes applying 2,4‐toluenediisocyanate

For the first time, a novel, straightforward and inexpensive route for immobilization of metals in Schiff base complex form is reported applying 2,4‐toluenediisocyanate as a precursor of primary amine group. A nickel(II) Schiff base complex supported on nano‐TiO₂ was designed and synthesized as an effective heterogeneous nanocatalyst for organic reactions, and well characterized using various techniques such as Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, energy‐dispersive X‐ray analysis and thermogravimetric analysis. The catalytic efficiency of the complex was evaluated in selective oxidation of sulfide to sulfoxide by hydrogen peroxide as an oxidant under solvent‐free conditions at room temperature, which successfully resulted in high yield and high conversion of products. Effective factors including solvent type, oxidant and catalyst amount were also optimized. The catalyst shows outstanding reusability and could be impressively recovered for six consecutive cycles without significant change of its catalytic efficiency.     

低温燃烧法制备Mn-CeO_x催化剂及其NH_3-SCR脱硝性能

通过低温燃烧法(LCS)制备了不同金属硝酸盐与柠檬酸物质的量比的系列Mn-CeO_x(LCS)锰铈催化剂,将其与共沉淀法(CP)制备的Mn-CeO_x(CP)锰铈催化剂相对比,结合XRD、XPS、FESEM和H2-TPR等技术表征,对其NH_3-SCR脱硝催化性能进行了研究。结果表明,金属硝酸盐与柠檬酸的物质的量比是影响Mn-CeO_x(LCS)催化剂脱硝性能的重要因素。虽然两种催化剂中的锰氧化物组分均为无定型,但相较于Mn-CeO_x(CP),Mn-CeO_x(LCS)表面具有较高的锰含量与Oα/(Oα+Oβ)比,其脱硝催化性能也较高;同时,Mn-CeO_x(LCS)锰铈催化剂上有更多的多级孔,有利于气体在催化剂上的吸附和反应。硝酸盐与柠檬酸物质的量比为36∶22的Mn-CeO_x(LCS)锰铈催化剂在80-180℃下脱硝率可达75%-100%;即使通入SO2,180℃下的脱硝率仍可稳定于74%。     

Single crystal synthesis and magnetism of the BaLn2O4 family (Ln = lanthanide)

The series of compounds in the BaLn₂O₄ family (Ln = La–Lu, Y) has been synthesized for the first time in single crystalline form, using a molten metal flux. The series crystallizes in the CaV₂O₄ structure type with primitive orthorhombic symmetry (space group Pnma, #62), and a complete structural study of atomic positions, bonds, angles, and distortions across the lanthanide series is presented. With the exception of the Y, La, Eu, and Lu members, magnetic susceptibility measurements were performed between 2 K and 300 K. BaCe₂O₄ and BaYb₂O₄ display large crystal fields effects and suppression of magnetic ordering. All compounds show signs of magnetic frustration due to the trigonal arrangements of the trivalent lanthanide cations in the structure.     

17O and 33S nuclear magnetic shielding of sulfur trioxides from the experimental measurements and theoretical calculations

In a recent ¹⁷O NMR spectra of liquid sulfur trioxide, several unexpected peaks appeared with the temperature‐dependent integrated peak ratio. In order to interpret NMR spectra and assign peaks to possible molecular structures, the theoretical quantum mechanical density functional theory and Møller–Plesset second‐order perturbation theory calculations were performed. It is suggested that in the liquid sulfur trioxide, apart from monomeric SO₃, a significant amount of (SO₃)₃ cyclic trimers should appear. No theoretical data support hypothesis on (SO₃)₂ dimers formation. Copyright © 2014 John Wiley & Sons, Ltd.     

Structural distortion,charge modulation and local anisotropies in magnetite below the Verwey transition using resonant X‐ray scattering

The pattern of charge modulations and local anisotropies below the Verwey transition has been determined and quantified in high‐quality Fe₃O₄ single crystals and thin films grown on MgO by using resonant X‐ray scattering at the Fe K‐edge. The energy, polarization and azimuthal angle dependencies of an extensive set of reflections with potential sensitivity to charge or local anisotropy orderings have been analyzed to explore their origins. A charge disproportion on octahedral B sites of 0.20 ± 0.05 e^? with [0 0 1] and cubic periodicities has been confirmed, while no significant charge disproportion has been obtained with [0 0 1/2] cubic periodicity. Additional charge modulations in the monoclinic a–b plane are also present. In addition, the occurrence of new forbidden (1, 1, 0) and (0, 0, 2n + 1/2) cubic reflections that arise from the anisotropy of the local structure around different tetrahedral and octahedral Fe atoms is shown. This complex pattern of weak charge modulations and local anisotropies is fully compatible with the low‐temperature crystal structure refined in the non‐polar C2/c space group and disproves any bimodal charge disproportion of the octahedral Fe atoms.     

Porous Tungsten Oxide: Recent Advances in Design,Synthesis, and Applications

Tungsten oxide (WO₃) has received ever more attention and has been highly researched over the last decade due to its being a low-cost transition metal semiconductor with tunable, yet widely stable, band gaps. This minireview briefly highlights the challenges in the design and synthesis of porous WO₃ including methods, precursors, solvent effects, crystal phases, and surface activities of the porous WO₃ base material. These topics are explored while also drawing a connection of how the morphology and crystal phase affect the band gap. The shifts in band gap not only impact the optical properties of tungsten but also allow tuning to operate on different energy levels, which makes WO₃ highly desirable in many applications such as supercapacitors, batteries, solar cells, catalysts, sensors, smart windows, and bioapplications.     

Photoswitchable Composite Polymer Electrolytes Using Spiropyran-Immobilized Nanoporous Templates

Composite polymer electrolytes (CPEs) with smart, stimuli-responsive characteristics have gained considerable attention owing to their noninvasive manipulation and applications in future technologies. To address this potential, in this work, we demonstrate photoresponsive composite polymer electrolytes, consisting of gel polymer electrolyte (GPE) and spiropyran-immobilized nanoporous anodic aluminum oxide (SP-AAO) templates. Under UV irradiation, the close SP form isomerizes to the open merocyanine (MC) form, creating extremely polarized AAO surfaces; whereas, under visible light irradiation, the MC form reverts to the SP form, creating neutral surface conditions. The electrostatic interactions between ions and AAO surfaces are investigated by attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy. Moreover, the behavior of ionic conductivity of the GPE@SP-AAO is found to be consistent with the kinetics of isomerization tracked by UV-Vis spectroscopy. This work provides a promising platform for developing next-generation photoelectronic smart devices.