Synthesis of <Emphasis Type="Italic">N</Emphasis>-hydroxy-imidamide-functionalized graphene: an efficient metal-free electrocatalyst for oxygen reduction

Metal-free electrocatalysts for oxygen reduction reaction (ORR) are key to the development of efficient, durable, and low-cost alternatives to noble-metal-based electrocatalysts in fuel cell cathodes. In recent years, many efforts are directed to the metal-free catalyst based on heteroatom-doped graphene. In this work, we demonstrate that the graphene surface can be converted into the catalyst for the oxygen reduction by chemical functionalization. In this context, we first synthesized malononitrile-functionalized graphene oxide. Amidoximation of nitrile group and reduction in graphene oxide were then carried out by hydroxylamine in one step. The electrochemical behavior of functionalized graphene-modified electrode for the reduction in oxygen was studied. The results showed that the electrocatalyst fabricated by this method exhibited striking catalytic activities in alkaline solution. In alkaline solution, this catalyst showed a competitive activity to the commercial Pt catalyst via four-electron transfer pathway with better ORR selectivity and stability. In addition, this metal-free electrocatalyst exhibited tolerance to methanol crossover effect. Based on its outstanding performance, this functionalized graphene electrocatalyst showed the promising prospect of a metal-free catalyst for fuel cell with much lower cost than currently used Pt/C catalyst.     

A computational investigation of carbon-doped beryllium monoxide nanotubes

To investigate the influence of C-doping on the electrostatic structure properties in the frame work of density functional theory (DFT), we considered beryllium monoxide nanotubes (BeONTs), consisting of 60 Be and 60 O atoms. Full geometry optimizations are performed for all structures, i.e., all atoms are allowed to relax. Afterwards, the chemical shielding (CS) tensors are calculated for Be-9, O-17 and C-13 nuclei in the C-doped forms and also pristine models of the (10, 0) zigzag and (5, 5) armchair BeONTs. Formation energies indicate that C-doping of Be atom (CBe form) could be more favorable than C-doping of O atom (CO form) in both zigzag and armchair BeONTs. Gap energies and dipole moments detected the effects of dopant in the (5, 5) armchair models; however, those parameters did not indicate any significant changes in the C-doped (10, 0) zigzag BeONT models. The results show that the CS values for the Be and O atoms-contributed to the Be-C bonds or those atoms close to the C-doped region-in the CO form of BeONTs (zigzag and armchair) are changed. The same values only for the O atoms-contributed to the O-C bonds- in the CBe form of BeONTs (zigzag and armchair) are changed.     

An accurate pressure–velocity decoupling technique for semi‐implicit rotational projection methods

In this paper, an accurate semi‐implicit rotational projection method is introduced to solve the Navier–Stokes equations for incompressible flow simulations. The accuracy of the fractional step procedure is investigated for the standard finite‐difference method, and the discrete forms are presented with arbitrary orders or accuracy. In contrast to the previous semi‐implicit projection methods, herein, an alternative way is proposed to decouple pressure from the momentum equation by employing the principle form of the pressure Poisson equation. This equation is based on the divergence of the convective terms and incorporates the actual pressure in the simulations. As a result, the accuracy of the method is not affected by the common choice of the pseudo‐pressure in the previous methods. Also, the velocity correction step is redefined, and boundary conditions are introduced accordingly. Several numerical tests are conducted to assess the robustness of the method for second and fourth orders of accuracy. The results are compared with the solutions obtained from a typical high‐resolution fully explicit method and available benchmark reports. Herein, the numerical tests are consisting of simulations for the Taylor–Green vortex, lid‐driven square cavity, and vortex–wall interaction. It is shown that the present method can preserve the order of accuracy for both velocity and pressure fields in second‐order and high‐order simulations. Furthermore, a very good agreement is observed between the results of the present method and benchmark simulations. Copyright © 2016 John Wiley & Sons, Ltd.     

Silphox [POCl3−n (SiO2) n ] as a New,Efficient, and Heterogeneous Reagent for the Synthesis of Benzimidazole Derivatives Under Microwave Irradiation

Silphox [POCl_3-n(SiO₂)_n] efficiently catalyzes the condensation of benzene-1,2-diamine with mono and dicarboxylic acids under microwave irradiation to afford benzimidazole derivatives in high yields and short reaction times.     

The Oxidation of Thiocyanate to Polythiocyanic Acid Using Peroxydisulfate in Aqueous Solution

Abstract

The oxidation of thiocyanate to polythiocyanic acid by peroxydisulfate was carried out in an aqueous solution at room temperature. The primary step is the decomposition of peroxydisulfate into sulfate-free radicals. At room temperature in the presence of peroxydisulfate as a oxidizing agent, HSCN polymerizes to (HSCN)_n. The oxidation of thiocyanate in an aqueous solution is often complicated, but here we obtained the polythiocyanic acid as a major product. The products were characterized by elemental analysis, IR, UV- visible, H-NMR spectroscopy, and X-ray powder diffraction.     

Synthesis and Characterization of Organosoluble Poly(imide-ether)s with Bulky 2,3-Diaryl Imidazole Moiety: Study Physical,Thermal and Optical Properties

Two new symmetrical diamines were designed and synthesized having different functional groups such as a pair of phenyl ether linkages, 2,3-diaryl substituted imidazole rings and CF₃ groups as pendant, and characterized by FT-IR, ¹H and ¹³C-NMR spectroscopy and elemental analysis. A series of new fluorescent poly(imide-ether)s (PIEs) was prepared by polymerization of the diamines with commercial tetracarboxylic dianhydrides such as pyromellitic dianhydride and 3,3′,4,4′-benzophenone tetracarboxylic dianhydride. The resulting PIEs were amorphous and had intrinsic viscosity [η] in the range of 0.42–0.51 dL/g. The weight average molecular weights (Mw) of these polymers were measured by GPC and were in the range of 28658–35595 g/mol with molecular weight distribution (MWD) of 2.12–2.27. These polymers were readily soluble in a variety of organic solvents and formed low-colored and flexible thin films with cut-off wavelength (λ₀) in the range of 385–420 nm, and all PIEs films exhibited high optical transparency. They also possessed good thermal stability with 10% weight loss temperatures (T_10%) in the range 486–537°C in N₂. The glass transition temperatures (T_g) of PIEs are in the range 251–324°C. These polymers showed fluorescence emission in film and in solution at 459–476 nm with the quantum yields in the range 4–12%.     

Organically modified montmorillonite and chitosan–phosphotungstic acid complex nanocomposites as high performance membranes for fuel cell applications

Nanocomposite membranes based on polyelectrolyte complex (PEC) of chitosan/phosphotungstic acid (PWA) and different types of montmorillonite (MMT) were prepared as alternative membranes to Nafion for direct methanol fuel cell (DMFC) applications. Fourier transform infrared spectroscopy (FTIR) revealed an electrostatically fixed PWA within the PEC membranes, which avoids a decrease in proton conductivity at practical condition. Various amounts of pristine as well as organically modified MMT (OMMT) (MMT: Cloisite Na, OMMT: Cloisite 15A, and Cloisite 30B) were introduced to the PEC membranes to decrease in methanol permeability and, thus, enhance efficiency and power density of the cells. X-ray diffraction patterns of the nanocomposite membranes proved that MMT (or OMMT) layers were exfoliated in the membranes at loading weights of lower than 3 wt.%. Moreover, the proton conductivity and the methanol permeability as well as the water uptake behavior of the manufactured nanocomposite membranes were studied. According to the selectivity parameter, ratio of proton conductivity to methanol permeability, the PEC/2 wt.% MMT 30B was identified as the optimum composition. The DMFC performance tests were carried out at 70 °C and 5 M methanol feed and the optimum membrane showed higher maximum power density as well as acceptable durability compared to Nafion 117. The obtained results indicated that owing to the relatively high selectivity and power density, the optimum nanocomposite membrane could be considered as a promising polyelectrolyte membrane (PEM) for DMFC applications.