Hematites Precipitated in Alkaline Precursors: Comparison of Structural and Textural Properties for Methane Oxidation.

Hematite (α-Fe2O3) catalysts prepared using the precipitation methods was found to be highly effective, and therefore, it was studied with methane (CH4), showing an excellent stable performance below 500 °C. This study investigates hematite nanoparticles (NPs) obtained by precipitation in water from the precursor of ferric chloride hexahydrate using precipitating agents NaOH or NH4OH at maintained pH 11 and calcined up to 500 °C for the catalytic oxidation of low concentrations of CH4 (5% by volume in air) at 500 °C to compare their structural state in a CH4 reducing environment. The conversion (%) of CH4 values decreasing with time was discussed according to the course of different transformation of goethite and hydrohematites NPs precursors to magnetite and the structural state of the calcined hydrohematites. The phase composition, the size and morphology of nanocrystallites, thermal transformation of precipitates and the specific surface area of the NPs were characterized in detail by X-ray powder diffraction, transmission electron microscopy, infrared spectroscopy, thermal TG/DTA analysis and nitrogen physisorption measurements. The results support the finding that after goethite dehydration, transformation to hydrohematite due to structurally incorporated water and vacancies is different from hydrohematite α-Fe2O3. The surface area SBET of Fe2O3_NH-70 precipitate composed of protohematite was larger by about 53 m2/g in comparison with Fe2O3_Na-70 precipitate composed of goethite. The oxidation of methane was positively influenced by the hydrohematites of the smaller particle size and the largest lattice volume containing structurally incorporated water and vacancies.

Extreme biomimetics: Preservation of molecular detail in centimeter-scale samples of biological meshes laid down by sponges.

Fabrication of biomimetic materials and scaffolds is usually a micro- or even nanoscale process; however, most testing and all manufacturing require larger-scale synthesis of nanoscale features. Here, we propose the utilization of naturally prefabricated three-dimensional (3D) spongin scaffolds that preserve molecular detail across centimeter-scale samples. The fine-scale structure of this collagenous resource is stable at temperatures of up to 1200°C and can produce up to 4 × 10-cm-large 3D microfibrous and nanoporous turbostratic graphite. Our findings highlight the fact that this turbostratic graphite is exceptional at preserving the nanostructural features typical for triple-helix collagen. The resulting carbon sponge resembles the shape and unique microarchitecture of the original spongin scaffold. Copper electroplating of the obtained composite leads to a hybrid material with excellent catalytic performance with respect to the reduction of p-nitrophenol in both freshwater and marine environments.

Functionalization of organically modified silica with gold nanoparticles in the presence of lignosulfonate.

It is shown that lignosulfonate (LS) can be used as an effective reducing agent for gold ions and simultaneously as a stabilizing agent for gold nanoparticles (AuNPs). When organically modified silica is introduced to the reaction mixture, most of the AuNPs grow on the surface of the silica due to hydrophobic interactions between LS and organic layers covering the solid particles. It was also found that the structure of the organic layer is crucial for the effective deposition of gold nanoparticles onto silica spheres in terms of particle size and gold content in the final SiO2-LS-AuNPs composites. Due to the hydrophobicity of the modified silica it was necessary to carry out the modification in mixed organic/aqueous solvent. The polarity of the organic co-solvent was found to have an effect on the size of the deposited Au-NPs and their quantity. The physical appearance of the obtained hybrids was analyzed by colorimetry, and their structure and composition were evaluated using transmission electron microscopy (TEM). Additionally dispersive and thermal properties were examined by dynamic light scattering (DLS) and thermogravimetry (TG), respectively. The obtained multifunctional hybrid materials exhibits remarkable catalytic activity for the reduction of C.I. Basic Blue 9 (Methylene Blue) by borohydride.

An extreme biomimetic approach: hydrothermal synthesis of ß-chitin/ZnO nanostructured composites.

ß-Chitinous scaffolds isolated from the skeleton of marine cephalopod Sepia officinalis were used as a template for the in vitro formation of ZnO under conditions (70 °C) which are extreme for biological materials. Novel ß-chitin/ZnO film-like composites were prepared for the first time by hydrothermal synthesis, and were thoroughly characterized using numerous analytical methods including Raman spectroscopy, HR-TEM and XRD. We demonstrate the growth of hexagonal ZnO nanocrystals on the ß-chitin substrate. Our chitin/ZnO composites presented in this work show antibacterial properties against Gram positive bacteria and can be employed for development of inorganic-organic wound dressing materials.

Interface phenomena in (super)hard nitride nanocomposites: from coatings to bulk materials.

Mechanical properties of nanocomposites usually surpass the mechanical properties of their micro-structured and single-crystalline counterparts. This is mainly due to an extremely high density of internal interfaces in nanocomposites like grain, crystallite and phase boundaries. When compared to diamond, carbides and borides, nitrides are of interest because of their high temperature oxidation resistance and compatibility with iron containing alloys. This tutorial review classifies the contributions of various internal interfaces to the hardness of the nanocomposites, and appreciates the outstanding role of partially coherent phase boundaries in the hardness enhancement. With selected examples of transition metal nitrides containing aluminium and silicon as well as of boron nitrides, it is explained how the nanocomposites with partially coherent phase boundaries and thus with enhanced hardness can be synthesised. As the possible ways of the formation of coherent phase boundaries, the local epitaxial growth of phases with limited mutual solubility, the production of supersaturated solid solutions followed by the segregation of elements during the spinodal decomposition and the incomplete phase transformation are discussed. The most important techniques, used for synthesis of nitride nanocomposites, like CVD, PVD, precursor-based methods, mechanical alloying and high-pressure-high-temperature synthesis are briefly reviewed. Besides, a short overview on hardness definitions and hardness measurements is included.