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The reduction of Pt content in the cathode for proton exchange membrane fuel cells is highly desirable to lower their costs. However, lowering the Pt loading of the cathodic electrode leads to high voltage losses. These voltage losses are known to originate from the mass transport resistance of O 2 through the platinum–ionomer interface, the location of the Pt particle with respect to the carbon support and the supports’ structures. In this study, we present a new Pt catalyst/support design that substantially reduces local oxygen-related mass transport resistance. The use of chemically modified carbon supports with tailored porosity enabled controlled deposition of Pt nanoparticles on the outer and inner surface of the support particles. This resulted in an unprecedented uniform coverage of the ionomer over the high surface-area carbon supports, especially under dry operating conditions. Consequently, the present catalyst design exhibits previously unachieved fuel cell power densities in addition to high stability under voltage cycling. Thanks to the Coulombic interaction between the ionomer and N groups on the carbon support, homogeneous ionomer distribution and reproducibility during ink manufacturing process is ensured. Reducing Pt content in cathodes for proton exchange membrane fuel cells is crucial to lower costs but results in high voltage losses. A Pt catalyst/support design that substantially reduces local oxygen-related mass transport resistance is reported.

In this work the flexural rigidity of individual large diameter multi-walled carbon nanotubes (MWCNTs) was investigated. The bending modulus were obtained by detecting the resonance frequencies of mechanically excited cantilevered carbon nanotubes using the so-called dynamic scanning electron microscopy technique, and applying the Euler–Bernoulli beam theory. For the nanotubes studied, we determined a modulus of up to 160 GPa. This agrees with values reported by other authors for MWCNTs produced by catalytic chemical vapor deposition, however, it is 6-8 times smaller than values reported for single and multi-walled carbon nanotubes produced by arc-discharge synthesis. Toxicological studies with carbon nanotubes have been showing that inhaled airborne nanofibers that reach the deep airways of the respiratory system may lead to serious, asbestos-like lung diseases. These studies suggested that their toxicity critically depends on the fiber flexural rigidity, with high rigidity causing cell lesions. To complement the correlation between observed toxicological effects and fiber rigidities, reliable and routinely applicable measurement techniques for the flexural rigidity of nanofibers are required.

Atmospheric pressure plasma jets (APPJ) are widely used in industry for surface cleaning and chemical modification. In the recent past, they have gained more scientific attention especially in the processing of carbon nanomaterials. In this work, a novel power generation technique was applied to realize the stable discharge in N2 (10 vol.% H2) forming gas in ambient conditions. This APPJ was used to reduce solution-processed graphene oxide (GO) thin films and the result was compared with an established and optimized reduction process in a low–pressure capacitively coupled (CCP) radiofrequency (RF) hydrogen (H2) plasma. The reduced GO (rGO) films were investigated by Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Effective deoxygenation of GO was observed after a quick 2 s treatment by AAPJ. Further deoxygenation at longer exposure times was found to proceed with the expense of GO–structure integrity. By adding acetylene gas into the same APPJ, carbon nanomaterials on various substrates were synthesized. The carbon materials were characterized by Raman spectroscopy, scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) analyses. Fullerene-like particles and graphitic carbon with short carbon nanotubes were detected on Si and Ag surfaces, respectively. We demonstrate that the APPJ tool has obvious potential for the versatile processing of carbon nanomaterials.

The Volyn biota, fossilized organisms with a minimum age of 1.5 Ga, were found in cavities in granitic pegmatites from the Korosten Pluton, NW Ukrainian shield. Fossilization was due to an influx of hydrothermal fluorine-rich waters, which silicified the outermost part of the organisms, thus preserving the 3D morphology. Details of the morphology (investigated by scanning electron microscopy) show that the majority of the specimens are filamentous, of a large variety with diameters ranging from ∼ 10 to ∼ 200 µm, thin filaments with typical branching and thick filaments with ball-shaped outgrowths and dented surface. Filaments can be straight or conical, curvilinear, or strongly curved, up to millimeters in length, some with a central channel. Some filaments show indications of segmentation and are grown as sessile organisms onto substrate; others show both intact ends, indicating a non-sessile, free-living lifestyle. Objects with flaky morphology and agglutinating filaments are interpreted as fossil biofilms. Other objects are hollow and show a large variety of forms; spherical objects are scarce. Infrared spectroscopy indicates the presence of chitosan in one filament type, electron microprobe analysis of nanometer-sized inclusions in filaments identified the presence of Bi(Te,S) minerals, and both observations are compatible with the interpretation as fungi-like organisms. Stable C- and N-isotope data of bulk samples are in the range of −31 ‰ to −47 ‰ δ13C and of +3 ‰ to +10 ‰ δ15N, indicating possible methanogens as part of the subsurface microecosystem. The Volyn biota indicate that at 1.5 Ga complex forms of life existed in the continental deep biosphere, well above the microscopic level, including fungi-like organisms resembling eukaryotes.

The Volyn pegmatites from Volodarsk-Volynskyi in the Zhytomyr Oblast, NW Ukraine, are associated with granites genetically related to the Paleoproterozoic Korosten pluton. Their late-stage evolution is characterized by the formation of opal-cemented breccia. A polymineralic pseudomorph after beryl within the breccia includes bertrandite (±euclase) + F-muscovite (with tobelite component) + buddingtonite + organic matter (OM) + opal (+ traces of K-feldspar, albite, columbite, FeS2, barite, REE-minerals). Sector-zoned and platy to fibrous buddingtonite has variable (K+Na)- vs. NH4-contents (electron microprobe analyses) and some H2O or H3O+, as indicated by microscope infrared spectroscopy. We suggest that ammonium was produced by decay of OM, which is partly preserved in the pseudomorph. Energy-dispersive electron microprobe data of the OM show with increasing O-decreasing C-N-content due to degassing; the OM contains the high field strength elements Zr (≤7 at%), Y (≤3 at%), Sc (≤0.8 at%), REE (≤0.3 at%), Th (≤0.2 at%), and U (≤1.25 at%), which increase with increasing O-content. Transmission electron microscopy of the OM confirms the presence of N; Zr, Si, and O (with other HFSE) are concentrated in nanometer-sized areas and at the transition from OM to opal in nanometer-sized platy Zr-Si-O crystals. C-rich areas are amorphous but show poorly developed lattice fringes. OM is present in the pseudomorph also as brown pigmentation of opal and in pegmatitic beryl from Volyn as a component in late stage fluid inclusions, identified by C-H vibrational bands in infrared spectra. Stable isotope investigations of C and N of buddingtonite, black opal and kerite (fibrous OM known from the literature to occur in the Volyn pegmatites and interpreted as microfossils) indicate a biogenic origin of the OM. We propose that OM in the pseudomorph is condensed kerite, which achieved the high concentrations of high field strength elements via fluid-pegmatite interaction. Although no age determination of minerals in the pseudomorph is available, textural arguments and phase equilibria indicate its formation in a late stage of the pegmatite evolution, at P-T conditions below ∼100 MPa/150 °C. We favor a conceptual model for the formation of the Volyn buddingtonite in analogy to Phanerozoic occurrences of buddingtonite, where over and around the shallow anorthosite-granite Korosten pluton hydrothermal convection cells introduced N-bearing hydrocarbons and its precursors into the cooling igneous rocks. Due to the elevated temperature, the OM disintegrated into degassing volatile and non-volatile residual components analogous to petroleum maturation. Organic N, released as NH4, was then incorporated into buddingtonite.

We report on Precambrian microfossils from igneous rocks of the Volyn pegmatite district, associated with the Paleoproterozoic Korosten pluton, northwestern Ukraine. The fossils were recovered from meter-sized miarolitic cavities and show a well-preserved 3D morphology, mostly filamentous but with a large variety of types and also in irregular, flaky shapes reminiscent of former biofilms, as well as rare spherical objects. Based on literature data, pyrolysis experiments, and reflected light microscopy results, the organic matter (OM) is characterized as (oxy-)kerite. Further investigations with microscopic techniques, including scanning and transmission electron microscopy, and electron microprobe analysis show that fossilization likely occurred during a hydrothermal, post-pegmatitic event by silicification dominantly in the outermost 1–2 µm of the microfossils. The hydrothermal fluid, derived from the pegmatitic environment, was enriched in SiF4, Al, Ca, Na, K, Cl, and S. The OM shows O enrichment in which N and S content is low, indicating simultaneous N and S loss during anaerobic oxidation. Mineralization with Al silicates starts at the rim of the microfossils, continuing in its outer parts into identifiable encrustations and intergrowths of clay minerals, feldspar, Ca sulfate, Ca phosphate, Fe sulfide, and fluorite. Breccias, formed during collapse of some the miarolitic cavities, contain decaying OM, which released high concentrations of dissolved NH4+, responsible for the late-stage formation of tobelite-rich muscovite and buddingtonite. The age of the fossils can be restricted to the time between the pegmatite formation, at ∼1.760 Ga, and the breccia formation at ∼1.49 Ga. As the geological environment for the growth of the microorganisms and fossilization, we assume a geyser system in which the essential biological components C, N, S, and P for growth of the organisms in the miarolitic cavities were derived from microorganisms at the surface. Fossilization was induced by magmatic SiF4-rich fluids. The Volyn occurrence is a distinct and uncommon example of Precambrian fossils, and the results underline the importance of cavities in granitic rocks as a possible habitat for microorganisms preserved in the deep biosphere.

In the framework of the German R&D joint project CLEAN (CO₂ large-scale enhanced gas recovery in the Altmark natural gas field), Rotliegend reservoir sandstones of the Altensalzwedel block in the Altmark area (Saxony-Anhalt, central Germany) have been studied to characterise litho- and diagenetic facies, mineral content, geochemical composition, and petrophysical properties. These sands have been deposited in a playa environment dominated by aeolian dunes, dry to wet sand flats and fluvial channel fills. The sediments exhibit distinct mineralogical, geochemical, and petrophysical features related to litho- and diagenetic facies types. In sandstones of the damp to wet sandflats, their pristine red colours are preserved and porosity and permeability are only low. Rocks of the aeolian environment and most of the channel fill deposits are preferentially bleached and exhibit moderate to high porosity and permeability. Although geochemical element whole rock content in these rocks is very similar, element correlations are different. Variations in porosity and permeability are mainly due to calcite and anhydrite dissolution and differences in clay coatings with Fe-bearing illitic-chloritic composition exposed to the pore space. Moreover, mineral dissolution patterns as well as compositions (of clays and carbonate) and morphotypes of authigenic minerals (chlorite, illite) are different in red and bleached rocks. Comparison of the geochemical composition and mineralogical features of diagenetically altered sandstones and samples exposed to CO₂-bearing fluids in laboratory batch experiments exhibit similar character. Experiments prove an increase in wettability and water binding capacity during CO₂ impact.