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Mesoporous carbon/iron carbide hybrid materials with surface areas reaching 800 m(2) g(-1) were synthesized via an exotemplating route using monolithic mesoporous silica as template and the ionic liquid 1-butyl-3-methylimidazolium tetrachloridoferrate(III) [Bmim][FeCl4] as carbon and iron source. After heat treatment (750 degrees C under argon) of the [Bmim][FeCl4] precursor confined within the silica matrix, the silica exotemplate was removed with HF leaving the mesoporous C/Fe3C hybrid behind. The surface areas and the pore sizes depend on the exotemplate and the surface areas a significantly larger than any other surface area reported for C/Fe3C hybrid materials so far. The approach is thus a prototype for the synthesis of high-surface area iron carbide-based hybrid materials with potential application in catalysis.
A facile one-pot synthesis for preparing thermosensitive, luminescent gold nanodots with diameters of 1-2 nm is presented. The influence of the alkyl chain length of the surface ligands (alkyl thiols) on the optical properties of the gold nanodots was investigated. The synthesized gold nanodots show strong thermosensitive photoluminescence. A photoluminescence quantum yield of 16.6% was observed at room temperature, which could be improved to a value of 28.6% when cooling the gold nanodot solutions to -7 degrees C. The synthesized thermosensitive, luminescent gold nanodots are interesting candidates for optoelectronic devices, medical imaging, sensing, or security labels.
The sensing potential of CuO nanoparticles synthesized via. precipitation from a water/ionic liquid precursor (ILP) mixture was investigated. The particles have a moderate surface area of 66 m(2)/g after synthesis, which decreases upon thermal treatment to below 5 m(2)/g. Transmission electron microscopy confirms crystal growth upon annealing, likely due to sintering effects. The as-synthesized particles can be used for ethanol sensing. The respective sensors show fast response and recovery times of below 10 s and responses greater than 2.3 at 100 ppm of ethanol at 200 degrees C, which is higher than any CuO-based ethanol sensor described so far.
Orbitolinids are larger foraminifera widespread in Lower Cretaceous shallow-water carbonates of the Tethyan realm. They are among the most important fossil groups used for Biostratigraphy. Despite this and although the structural features of the group have been described in detail, very little is known about the composition of their agglutinated test and the process by which they selected foreign grains. In this study, the test of Orbitolina d'Orbigny, 1850 (subgenus Mesorbitolina Schroeder, 1962) from Aptian shallow-water carbonate deposits of southern Italy has been studied in detail. We combine petrographic techniques (optical microscope and SEM) with energy-dispersive x-ray spectrometry (EDS), electron probe microanalyzer (EPMA), X-ray diffraction and Raman spectroscopy analyses.
The results show that the test of Mesorbitolina is composed of carbonate and non-carbonate agglutinated grains with the latter distributed across the test with a specific pattern, moving from the marginal to the central zone. In the marginal zone, non-carbonate grains are found only in the epidermis and along the septa which are composed of quartz, with smaller amounts of illite/muscovite and K-feldspar grains. In the central zone of the test, non-carbonate grains are distributed in two ways. Coarse grains of quartz and K-feldspar are abundant and randomly placed in the endoskeleton embedded in a mosaic of minute carbonate grains. Flat grains, mainly of illite/muscovite constitute the external part of the septa. Our observations indicate that Mesorbitolina did select and place agglutinated grains across its test, mainly according to their shape, whereas it did not select particles according to grain size. The distribution of agglutinated particles according to their mineralogical composition shows some contradictory evidence and therefore, at the moment, grain selection in function of mineralogy cannot be completely confirmed or ruled out. Analogies in the test composition of Mesorbitolina specimens from coeval deposits from different areas of southern Italy indicate that the features of their agglutinated test are typical characters of the genus Mesorbitolina. However, it is still unclear what advantage was obtained by the foraminifer by the described test features.
The Garzn Complex of the Garzn Massif in SW Colombia is composed of the Vergel Granulite Unit (VG) and the Las Margaritas Migmatite Unit (LMM). Previous studies reveal peak temperature conditions for the VG of about 740 A degrees C. The present study considers the remarkable exsolution phenomena in feldspars and pyroxenes and titanium-in-quartz thermometry. Recalculated ternary feldspar compositions indicate temperatures around 900-1,000 A degrees C just at or above the ultra-high temperature-metamorphism (UHTM) boundary of granulites. The calculated temperatures range of exsolved ortho- and clinopyroxenes also supports the existence of an UHTM event. In addition, titanium-in-quartz thermometry points towards ultra-high temperatures. It is the first known UHTM crustal segment in the northern part of South America. Although a mean geothermal gradient of ca 38 A degrees C km(-1) could imply additional heat supply in the lower crust controlling this extreme of peak metamorphism, an alternative model is suggested. The formation of the Vergel Granulite Unit is supposed to be formed in a continental back-arc environment with a thinned and weakened crust behind a magmatic arc (Guapotn-Mancagua Gneiss) followed by collision. In contrast, rocks of the adjacent Las Margaritas Migmatite Unit display "normal" granulite facies temperatures and are formed in a colder lower crust outside the arc, preserved by the Guapotn-Mancagu Gneiss. Back-arc formation was followed by inversion and thickening of the basin. The three units that form the modern-day Garzn Massif, were juxtaposed upon each other during collision (at ca. 1,000 Ma) and exhumation. The collision leading to the deformation of the studied area is part of the Grenville orogeny leading to the amalgamation of Rodinia.
We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-14, IFP=imidazolate framework Potsdam) that form one-dimensional, microporous hexagonal channels. Varying R in the 2-substitued linker (R=Me (IFP-1), Cl (IFP-2), Br (IFP-3), Et (IFP-4)) allowed the channel diameter (4.01.7 angstrom), the polarisability and functionality of the channel walls to be tuned. Frameworks IFP-2, IFP-3 and IFP-4 are isostructural to previously reported IFP-1. The structures of IFP-2 and IFP-3 were solved by X-ray crystallographic analyses. The structure of IFP-4 was determined by a combination of PXRD and structure modelling and was confirmed by IR spectroscopy and 1H MAS and 13C CP-MAS NMR spectroscopy. All IFPs showed high thermal stability (345400?degrees C); IFP-1 and IFP-4 were stable in boiling water for 7 d. A detailed porosity analysis was performed on the basis of adsorption measurements by using various gases. The potential of the materials to undergo specific interactions with CO2 was investigated by measuring the isosteric heats of adsorption. The capacity to adsorb CH4 (at 298 K), CO2 (at 298 K) and H2 (at 77 K) at high pressure were also investigated. In situ IR spectroscopy showed that CO2 is physisorbed on IFP-14 under dry conditions and that both CO2 and H2O are physisorbed on IFP-1 under moist conditions.