Nitrogen-Doped Graphene Monolith Catalysts for Oxidative Dehydrogenation of Propane

It’s of paramount importance to develop renewable nanocarbon materials to replace conventional precious metal catalysts in alkane dehydrogenation reactions. Graphene-based materials with high surface area have great potential for light alkane dehydrogenation. However, the powder-like state of the graphene-based materials seriously limits their potential industrial applications. In the present work, a new synthetic route is designed to fabricate nitrogen-doped graphene-based monolith catalysts for oxidative dehydrogenation of propane. The synthetic strategy combines the hydrothermal-aerogel and the post thermo-treatment procedures with urea and graphene as precursors. The structural characterization and kinetic analysis show that the monolithic catalyst well maintains the structural advantages of graphene with relatively high surface area and excellent thermal stability. The homogeneous distributed nitrogen species can effectively improve the yield of propylene (5.3% vs. 1.9%) and lower the activation energy (62.6 kJ mol−1 vs. 80.1 kJ mol−1) in oxidative dehydrogenation of propane reaction comparing with un-doped graphene monolith. An optimized doping amount at 1:1 weight content of the graphene to urea precursors could exhibit the best catalytic performance. The present work paves the way for developing novel and efficient nitrogen-doped graphene monolithic catalysts for oxidative dehydrogenation reactions of propane.

In Situ Synchrotron X-ray Diffraction Studies of Hydrogen-Desorption Properties of 2LiBH4–Mg2FeH6 Composite

Adding a secondary complex metal hydride can either kinetically or thermodynamically facilitate dehydrogenation reactions. Adding Mg2FeH6 to LiBH4 is energetically favoured, since FeB and MgB2 are formed as stable intermediate compounds during dehydrogenation reactions. Such “hydride destabilisation” enhances H2-release thermodynamics from H2-storage materials. Samples of the LiBH4 and Mg2FeH6 with a 2:1 molar ratio were mixed and decomposed under three different conditions (dynamic decomposition under vacuum, dynamic decomposition under a hydrogen atmosphere, and isothermal decomposition). In situ synchrotron X-ray diffraction results revealed the influence of decomposition conditions on the selected reaction path. Dynamic decomposition of Mg2FeH6–LiBH4 under vacuum, or isothermal decomposition at low temperatures, was found to induce pure decomposition of LiBH4, whilst mixed decomposition of LiBH4 + Mg and formation of MgB2 were achieved via high-temperature isothermal dehydrogenation.

Crosslinking Behavior of UV-Cured Polyorganosilazane as Polymer-Derived Ceramic Precursor in Ambient and Nitrogen Atmosphere

Polymer-derived ceramics (PDCs) based on silicon precursor represent an outstanding material for ceramic coatings thanks to their extraordinary versatile processibility. A promising example of a silicone precursor, polyorganosilazane (Durazane 1800), was studied concerning its crosslinking behavior by mixing it with three different photoinitiators, and curing it by two different UV-LED sources under both nitrogen and ambient atmosphere. The chemical conversion during polymerization and pyrolysis was monitored by FTIR spectroscopy. Pyrolysis was performed in a nitrogen atmosphere at 950 °C. The results demonstrate that polyorganosilazane can be cured by the energy-efficient UV-LED source at room temperature in nitrogen and ambient atmosphere. In nitrogen atmosphere, already common reactions for polysilazanes, including polyaddition of the vinyl group, dehydrogenation reactions, hydrosilylation, and transamination reaction, are responsible for crosslinking. Meanwhile, in ambient atmosphere, hydrolysis and polycondensation reactions occur next to the aforementioned reactions. In addition, the type of photoinitiator has an influence on the conversion of the reactive bonds and the chemical composition of the resulting ceramic. Furthermore, thermogravimetric analysis (TGA) was conducted in order to measure the ceramic yield of the cured samples as well as to study their decomposition. The ceramic yield was observed in the range of 72 to 78% depending on the composition and the curing atmosphere. The curing atmosphere significantly impacts the chemical composition of the resulting ceramics. Depending on the chosen atmosphere, either silicon carbonitride (SiCN) or a partially oxidized SiCN(O) can be produced.

Structural Characterization of Thermally Stabilized Poly(acrylonitrile) Fibers by Means of X-ray Diffraction, FT-IR Spectroscopy, and TGA Analysis

The structure and effects of thermally stabilized PAN original fibers were characterized utilizing a mixture of volume density, color change observations, flame tests, X-ray diffraction (XRD), infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA) measurements. The results obtained from the analysis of XRD work showed the conversion of the original molecular structure from a highly laterally ordered condition to a disordered amorphous structure. The experimental results acquired from FT-IR analysis indicated rapid and concurrent aromatization and dehydrogenation reactions assisted by the formation of oxygen-containing functional groups. TGA analysis showed a carbon yield of 72% at 1000 °C. The application and use of NH4Br pretreatment are expected to increase the productivity of carbon fiber processing at lowered cost by significantly reducing the processing time necessary for the successful completion of thermal stabilization reactions.