Effect of Cesium and Phosphate Addition to Mo/V/W Mixed Oxide Catalysts for the Gas Phase Oxidation of Methacrolein to Methacrylic Acid

The present study investigates modified Mo/V/W mixed oxides as a possible alternative for state of the art heteropoly acid catalysts (HPA) in the partial oxidation of methacrolein (MAC) to methacrylic acid (MAA). Even though HPAs show an excellent activity and MAA selectivity, their long-term stability is unsatisfying, rendering the catalyst inoperable after runtimes of roughly 6 months. Mo/V/W mixed oxides consisting of M1 and a hexagonal (Mo,V,W)O$_{x}$-phase (h-phase) in varying proportions were modified by impregnation with aqueous solutions containing cesium and phosphate ions. All samples were characterized with respect to specific surface area, crystallinity, elemental and phase composition. The catalytic performance in the oxidation of MAC to MAA was investigated using a continuously operated reaction unit with tubular fixed bed reactor. Impregnation with cesium and phosphate ions and subsequent heating triggers the transformation of the mixed oxide into a Keggin-type HPA, whereby the h-phase is more reactive than M1. The transformation into HPA is accompanied by a change in the catalytic properties, i.e., the selectivity to MAA is considerably improved. Compared to HPA synthesized directly, however, the HPA samples obtained by transformation of mixed oxides exhibit no advantages, be it with respect to activity, MAA selectivity or stability

Pseudopeptidic ligands: exploring the self-assembly of isopthaloylbisglycine (H2IBG) and divalent metal ions

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Facile template-free synthesis of multifunctional 3D cellular carbon from edible rice paper

Edible rice paper wrapper is found to be an interesting precursor of a porous and light-weight carbon material. During pyrolysis, material samples show significant differences in length change, displaying typical 20–25% shrinking in the in-plane directions, and strongly expanding (up to 500%) across their out-of-plane direction. This results in a template-free synthesis of a 3D network of cellular carbon material. The out-of-plane expansion also allows for fabrication of 3D shapes of cellular carbon material from the 2D precursor. The rice paper derived carbon material features a hierarchical porosity, resulting in a specific surface area ranging from 6 m(2) g(−1) to 239 m(2) g(−1) depending on the synthesis temperature. The carbon material has a density of 0.02–0.03 g cm(−3), and a higher modulus-density ratio than reported for other cellular carbon materials. It is mechanically stiff and exhibits excellent fire-resistant properties

Elimination of Domain Boundaries Accelerates Diffusion in MOFs by an Order of Magnitude: Monolithic Metal‐Organic Framework Thin Films Epitaxially Grown on Si(111) Substrates

Many properties of the emerging class of metal-organic frameworks (MOFs) depend crucially on defect concentrations, as in case of other solids. In order to provide reference systems with nearly perfect structure and low defect density, a procedure to grow MOFs epitaxially on cm-sized Si(111) single crystals is developed. The crystalline metal-organic thin films are in high registry with the substrate\u27s crystal lattice, as demonstrated by synchrotron-based grazing incidence X-ray diffraction (GI-XRD) experiments. The corresponding reduction of MOF defect density is shown to have striking effects on the properties of these porous frameworks. The most pronounced difference concerns mass transport. An increase in the diffusion coefficient of guest molecules by one order of magnitude relative to the same MOF materials with normal defect densities is observed

Cation diffusion patterns across the magneto-structural transition in Fe7S8

Migration of atoms in solids during diffusion-dependent reactions is relatively fast and generally not directly recordable in experiments. Here we present an experimental framework that includes fast differential scanning calorimetry to resolve cation-migration paths in crystalline solids using the reversible magneto-structural transition of 4C to 1C pyrrhotite as a testbed. The transition between these two polymorphic Fe7S8 phases at about 600 K is a diffusive process of vacancies, respectively of Fe in octahedral interstitial sites within a hexagonal close-packed lattice of sulfur, and it coincides with the Curie temperature of 4C pyrrhotite. The Fe cations migrate along three kinds of diffusion paths, and their enthalpy contributions to the total reaction enthalpy are taken to define the diffusion patterns in the endothermic reaction and the exothermic back-reaction, respectively. Our experimental findings provide insight into the potential of diffusion patterns to disentangle ordering mechanisms in solids.ISSN:1463-9084ISSN:1463-907