Increasing the activity of copper exchanged mordenite in the direct isothermal conversion of methane to methanol by Pt and Pd doping.

PtCu- and PdCu-mordenite allow for isothermal reaction at 200 °C for the stepwise methane to methanol conversion with comparably high yields. In contrast to traditional Cu-zeolites, these materials are more reactive under isothermal conditions than after high temperature activation.

A three-dimensional view of structural changes caused by deactivation of fluid catalytic cracking catalysts.

Since its commercial introduction three-quarters of a century ago, fluid catalytic cracking has been one of the most important conversion processes in the petroleum industry. In this process, porous composites composed of zeolite and clay crack the heavy fractions in crude oil into transportation fuel and petrochemical feedstocks. Yet, over time the catalytic activity of these composite particles decreases. Here, we report on ptychographic tomography, diffraction, and fluorescence tomography, as well as electron microscopy measurements, which elucidate the structural changes that lead to catalyst deactivation. In combination, these measurements reveal zeolite amorphization and distinct structural changes on the particle exterior as the driving forces behind catalyst deactivation. Amorphization of zeolites, in particular, close to the particle exterior, results in a reduction of catalytic capacity. A concretion of the outermost particle layer into a dense amorphous silica-alumina shell further reduces the mass transport to the active sites within the composite.Catalyst deactivation in fluid catalytic cracking processes is unavoidably associated with structural changes. Here, the authors visualize the deactivation of zeolite catalysts by ptychography and other imaging techniques, showing pronounced amorphization of the outer layer of the catalyst particles.

Selective sensing of isoprene by Ti-doped ZnO for breath diagnostics.

Exhaled isoprene could enable non-invasive monitoring of cholesterol-lowering therapies. Here, we report an isoprene-selective sensor at high relative humidity (RH) for the first time (to our knowledge). It is made of nanostructured, chemo-resistive Ti-doped ZnO particles (10-20 nm crystal size) produced by flame spray pyrolysis (FSP) and directly deposited in one step onto compact sensor substrates forming highly porous films. The constituent particles consist of stable Ti-doped ZnO solid solutions for Ti levels up to 10 mol% apparently by substitutional incorporation of Ti4+ into the ZnO wurtzite lattice and dominant presence at the particle surface. These Ti4+ point defects strongly enhance the isoprene sensitivity (>15 times higher than pure ZnO) and turn ZnO isoprene-selective, while also improving its thermal stability. In situ infrared spectroscopy confirms that Ti4+ intensifies the surface interaction of Ti-doped ZnO with isoprene by providing additional sites for chemisorbed hydroxyl species. In fact, at an optimal Ti content of 2.5 mol%, this sensor shows superior isoprene responses compared to acetone, NH3 and ethanol at 90% RH. Most notably, breath-relevant isoprene concentrations can be detected accurately down to 5 ppb with high (>10) signal-to-noise ratio. As a result, an inexpensive isoprene detector has been developed that could be easily incorporated into a portable breath analyzer for non-invasive monitoring of metabolic disorders (e.g. cholesterol).

Atomically dispersed rhodium on a support: the influence of a metal precursor and a support.

The influence of the support type and the metal precursor on the dispersion of rhodium after calcination and reduction was determined. The combination of electron microscopy and X-ray absorption analysis allowed the quantification of the amount of atomically dispersed rhodium in the samples. Higher amounts of atomically dispersed rhodium atoms are obtained when metal impregnation is performed with a rhodium acetate precursor in comparison to a rhodium chloride precursor over supports of the same composition. The stability of rhodium is improved with the addition of promoters; the co-presence of samaria and ceria in the support and metal impregnation with a rhodium acetate precursor leads to the highest amount of atomically dispersed rhodium remaining after reductive treatment at 773 K.

DNA protection against ultraviolet irradiation by encapsulation in a multilayered SiO2/TiO2 assembly.

DNA is protected against UV-induced damage by encapsulation in a core-shell-shell particulate construct. The DNA is hermetically sealed in SiO2 particles coated with TiO2. The TiO2 coating acts as a physical sunscreen and prevents high energy photons from damaging the nucleic acids. DNA can be recovered unharmed from the protection system with fluoride comprising buffers, and then directly analyzed using biochemical standard techniques (quantitative PCR, gel electrophoresis and Sanger sequencing). The coatings increase the DNA UV resistance by 42 times, which is equivalent to the increase in UV resistance obtained by bacteria during sporulation. The attenuation coefficient of the 20 nm titania layer is 1.8 106 cm-1 at 254 nm UV irradiation and optical attenuation is largely attributed to light scattering on the titania surface.

Phase-contrast imaging in aberration-corrected scanning transmission electron microscopy.

Although the presence of phase-contrast information in bright field images recorded with a scanning transmission electron microscope (STEM) has been known for a long time, its systematic exploitation for the structural characterization of materials began only with the availability of aberration-corrected microscopes that allow sufficiently large illumination angles. Today, phase-contrast STEM (PC-STEM) imaging represents an increasingly important alternative to the well-established HRTEM method. In both methods, the image contrast is coherently generated and thus depends not only on illumination and collection angles but on defocus and specimen thickness as well. By PC-STEM, a projection of the crystal potential is obtained in thin areas, with the scattering sites being represented either with dark or bright contrast at two different defocus values which are both close to Gaussian defocus. This imaging behavior can be further investigated by image simulations performed with standard HRTEM simulation software based on the principle of reciprocity. As examples for the application of this method, PC-STEM results obtained on metal nanoparticles and dodecagonal quasicrystals dd-(Ta,V)1.6Te are discussed.

Development and optimization of iron- and zinc-containing nanostructured powders for nutritional applications.

Reducing the size of low-solubility iron (Fe)-containing compounds to nanoscale has the potential to improve their bioavailability. Because Fe and zinc (Zn) deficiencies often coexist in populations, combined Fe/Zn-containing nanostructured compounds may be useful for nutritional applications. Such compounds are developed here and their solubility in dilute acid, a reliable indicator of iron bioavailability in humans, and sensory qualities in sensitive food matrices are investigated. Phosphates and oxides of Fe and atomically mixed Fe/Zn-containing (primarily ZnFe2O4) nanostructured powders were produced by flame spray pyrolysis (FSP). Chemical composition and surface area were systematically controlled by varying precursor concentration and feed rate during powder synthesis to increase solubility to the level of ferrous sulfate at maximum Fe and Zn content. Solubility of the nanostructured compounds was dependent on their particle size and crystallinity. The new nanostructured powders produced minimal color changes when added to dairy products containing chocolate or fruit compared to the changes produced when ferrous sulfate or ferrous fumarate were added to these foods. Flame-made Fe- and Fe/Zn-containing nanostructured powders have solubilities comparable to ferrous and Zn sulfate but may produce fewer color changes when added to difficult-to-fortify foods. Thus, these powders are promising for food fortification and other nutritional applications.

Advanced piezoresistance of extended metal-insulator core-shell nanoparticle assemblies.

Assembled metal-insulator nanoparticles with a core-shell geometry provide access to materials containing a large number (>10(6)) of tunneling barriers. We demonstrate the production of ceramic coated metal nanoparticles exhibiting an exceptional pressure-sensitive conductivity. We further show that graphene bi- and trilayers on 20 nm copper nanoparticles are insulating in such a core-shell geometry and show a similar pressure-dependent conductivity. This demonstrates that core-shell metal-insulator assemblies offer a route to alternative sensing materials.

Solid-gas reactions of complex oxides inside an environmental high-resolution transmission electron microscope.

In a gas reaction cell (GRC), installed in a high-resolution transmission electron microscope (HRTEM) (JEOL 4000EX), samples can be manipulated in an ambient atmosphere (p<50mbar). This experimental setup permits not only the observation of solid-gas reactions in situ at close to the atomic level but also the induction of structural modifications under the influence of a plasma, generated by the ionization of gas particles by an intense electron beam. Solid state reactions of non-stoichiometric niobium oxides and niobium tungsten oxides with different gases (O2, H2 and He) have been carried out inside this controlled environment transmission electron microscope (CETEM), and this has led to reaction products with novel structures which are not accessible by conventional solid state synthesis methods. Monoclinic and orthorhombic Nb(12)O(29) crystallize in block structures comprising [3x4] blocks. The oxidation of the monoclinic phase occurs via a three step mechanism: firstly, a lamellar defect of composition Nb(11)O(27) is formed. Empty rectangular channels in this defect provide the diffusion paths in the subsequent oxidation. In the second step, microdomains of the Nb(22)O(54) phase are generated as an intermediate state of the oxidation process. The structure of the final product Nb(10)O(25), which consists of [3x3] blocks and tetrahedral coordinated sites, is isostructural to PNb(9)O(25). Microdomains of this apparently metastable phase appear as a product of the Nb(22)O(54) oxidation. The oxidation reaction of Nb(12)O(29) was found to be a reversible process: the reduction of the oxidation product with H(2) results in the formation of the starting Nb(12)O(29) structure. On the other hand, the block structure of Nb(12)O(29) has been destroyed by a direct treatment of the sample with H(2) while NbO in a cubic rock salt structure is produced. This in situ technique has also been applied to niobium tungsten oxides which constitute the solid solution series Nb(8-n)W9(+n)O47 with 0< or =n< or =4. All of these phases crystallize in the threefold tetragonal tungsten bronze (TTB) superstructure of Nb(8)W(9)O(47) (n=0). In the main reaction, these phases decompose in a gas plasma (O2, H2 or He, p=20mbar) into WO(3-x), which evaporates and solidifies again near the irradiated crystallite, and (Nb,W)(24)O(64), which crystallizes in a 2a superstructure of the TTB type observed here for the first time in the system Nb-W-O. Nb(8)W(9)O(47), Nb(7)W(10)O(47) and Nb(6)W(11)O(47) always react in this way, independent of the applied gas. On the other hand, the treatment of Nb(5)W(12)O(47) (n=3) and Nb(4)W(13)O(47) (n=4) in an oxygen atmosphere often caused a different reaction: these phases have been oxidized and a heavily disordered bronze-type structure has been formed. The oxygen excess in these products is largely accommodated in segregated domains of WO(3).

A simple and fast TEM preparation method utilizing the pre-orientation in plate-like, needle-shaped and tubular materials

In order to observe anisotropically grown crystalline materials perpendicular to a certain preferred orientation, a standard cross-sectional TEM preparation method has been modified. The material is embedded in an organic epoxy resin between two Si-wafers. Plates, needles and tubes lay flat inside the resulting sandwich, which is then cut into slices perpendicular to the wafers. The slices are thinned by mechanical abrading and, finally, by ion milling. Crystals located near the central hole are electron-transparent, and their orientation often allows for an observation along the desired direction. The usefulness of this procedure is demonstrated on the examples of high-Tc superconductors and vanadium oxide nanotubes.

Redox-Active Nanotubes of Vanadium Oxide.

Unlike many small carbon nanotubes, VOx nanotubes (shown on the right) are obtained as the main product of a direct chemical synthesis at relatively low temperatures. The multiwalled material contains template molecules between the individual shells, which by a simple cation exchange can be removed without destruction of the tubes.

Preparation by ion milling and TEM investigation of embedded needle-shaped crystals of H-Nb2O5.

A method for preparing needle-shaped and platelike crystals for electron microscopical investigation was elaborated. Crystals of H-Nb2O5 were embedded in a synthetic resin and disks were cut off perpendicular to the desired direction of observation. The thickness of the sample was reduced by planar grinding and then by using a dimple grinder and furthermore by ion milling with argon ions. With the precision ion milling system small crystal areas were selected and subsequently irradiated. The TEM investigations showed that the desired crystallographic orientation was reached and that the crystal structure has been preserved. The contrast of highly resolved images was reduced by an amorphous surface layer which was not removable.