Experimental and Theoretical Study on Crown Ether-Appended-Fe(III) Porphyrin Complexes and Catalytic Oxidation Cyclohexene with O2.

Modifying non-precious metal porphyrins at the meso-position is sufficient to further improve the ability to activate O2 and the selectivity of the corresponding redox products. In this study, a crown ether-appended Fe(III) porphyrin complex (FeTC4PCl) was formed by replacing Fe(III) porphyrin (FeTPPCl) at the meso-position. The reactions of FeTPPCl and FeTC4PCl catalysed by O2 oxidation of cyclohexene under different conditions were studied, and three main products, 2-cyclohexen-1-ol (1), 2-cyclohexen-1-one (2), and 7-oxabicyclo[4.1.0]heptane (3), were obtained. The effects of reaction temperature, reaction time, and the addition of axial coordination compounds on the reactions were investigated. The conversion of cyclohexene reached 94% at 70 °C after 12 h, and the selectivity toward product 1 was 73%. The geometrical structure optimization, molecular orbital energy level analysis, atomic charge, spin density, and density of orbital states analysis of FeTPPCl, FeTC4PCl, as well as the oxygenated complexes (Fe-O2)TCPPCl and (Fe-O2)TC4PCl formed after adsorption of O2, were carried out using the DFT method. The results of thermodynamic quantity variation with reaction temperature and Gibbs free energy variation were also analysed. Finally, based on experimental and theoretical analysis, the mechanism of the cyclohexene oxidation reaction with FeTC4PCl as a catalyst and O2 as an oxidant was deduced, and the reaction mechanism was obtained as a free radical chain reaction process.

On-chip mid-IR octave-tunable Raman soliton laser.

Photonic chip-based continuously tunable lasers are widely recognized as an indispensable component for photonic integrated circuits (PICs). Specifically, mid-infrared (mid-IR) laser sources are of paramount importance in applications such as photonic sensing and spectroscopy. In this article, we theoretically investigate the propagation dynamics of mid-IR Raman soliton in Ge28Sb12Se60 chalcogenide glass waveguide. By carefully engineer the waveguide dispersion and nonlinear interaction, we propose a suspended chalcogenide glass waveguide device that allows an octave-tuning, from 1.96 µm to 3.98 µm, Raman soliton source. The threshold pump energy is in the low pico-Joule range. Our result provides a solution to continuously tunable on-chip mid-IR ultrafast laser sources.

Influence Mechanism of Cu Layer Thickness on Photoelectric Properties of IWO/Cu/IWO Films.

Transparent conductive IWO/Cu/IWO (W-doped In2O3) films were deposited on quartz substrates by magnetron sputtering of IWO and Cu in the Ar atmosphere. The X-ray diffraction (XRD) patterns identified the cubic iron-manganese ore crystal structure of the IWO layers. The influence of the thickness of the intermediate ultra-thin Cu layers on the optical and electrical properties of the multilayer films was analyzed. As the Cu layer thickness increases from 4 to 10 nm, the multilayer resistivity gradually decreases to 4.5 × 10-4 Ω·cm, and the optical transmittance in the mid-infrared range increases first and then decreases with a maximum of 72%, which serves as an excellent candidate for the mid-infrared transparent electrode.

Cellular Automata Modeling of Ostwald Ripening and Rayleigh Instability.

A cellular automata (CA) approach to modeling both Ostwald ripening and Rayleigh instability was developed. Curvature-driven phase interface migration was implemented to CA model, and novel CA rules were introduced to ensure the conservation of phase volume fraction of nearly equilibrium two-phase system. For transient Ostwald ripening, it is shown that the temporal growth exponent m is evolving with time and non-integer temporal exponents between 2 and 3 are predicted. The varying temporal growth exponent m is related to the particle size distributions (PSDs) evolution. With an initial wide PSD, it becomes narrowed toward steady state. With an initial narrow PSD, it becomes widened at first and then narrowed toward steady state. For Rayleigh instability, two cases (one with sinusoidal perturbation on the surface of the long cylinder, and the other with grain boundaries in the interior of the long cylinder) were simulated, and the breakup of the long cylinder was shown for both cases. In the end, a system containing long cylinders with interior grain boundaries was simulated, which demonstrated the integration of Rayleigh instability and Ostwald ripening relating to the spheroidization of the lamellar structure.