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The synthesis, structure, and photocatalytic water splitting performance of two new titania (TiO2)/gold(Au)/Bombyx mori silk hybrid materials are reported. All materials are monoliths with diameters of up to ca. 4.5 cm. The materials are macroscopically homogeneous and porous with surface areas between 170 and 210 m(2)/g. The diameter of the TiO2 nanoparticles (NPs) - mainly anatase with a minor fraction of brookite - and the Au NPs are on the order of 5 and 7-18 nm, respectively. Addition of poly(ethylene oxide) to the reaction mixture enables pore size tuning, thus providing access to different materials with different photocatalytic activities. Water splitting experiments using a sunlight simulator and a Xe lamp show that the new hybrid materials are effective water splitting catalysts and produce up to 30 mmol of hydrogen per 24 h. Overall the article demonstrates that the combination of a renewable and robust scaffold such as B. mori silk with a photoactive material provides a promising approach to new monolithic photocatalysts that can easily be recycled and show great potential for application in lightweight devices for green fuel production.
The synthesis, structure, and photocatalytic water splitting performance of two new titania (TiO 2 )/gold(Au)/Bombyx mori silk hybrid materials are reported. All materials are monoliths with diameters of up to ca. 4.5 cm. The materials are macroscopically homogeneous and porous with surface areas between 170 and 210 m 2/g. The diameter of the TiO 2 nanoparticles (NPs) – mainly anatase with a minor fraction of brookite – and the Au NPs are on the order of 5 and 7–18 nm, respectively. Addition of poly(ethylene oxide) to the reaction mixture enables pore size tuning, thus providing access to different materials with different photocatalytic activities. Water splitting experiments using a sunlight simulator and a Xe lamp show that the new hybrid materials are effective water splitting catalysts and produce up to 30 mmol of hydrogen per 24 h. Overall the article demonstrates that the combination of a renewable and robust scaffold such as B. mori silk with a photoactive material provides a promising approach to new monolithic photocatalysts that can easily be recycled and show great potential for application in lightweight devices for green fuel production.
This study is focused on the analysis of volcanic deposits that crop out at the middle portion of the Las Planchadas range, northern part of the Famatina System in Argentina. These volcanic rocks are records of an Ordovician effusive basaltic volcanism that took place under subaqueous marine conditions. Along the study area crop out an Arenigian volcanic and volcaniclastic rocks succession with massive and autoclastic lavas, hyaloclastites of basaltic composition and volcaniclastic sandstones and mudstones. Large volumes of the volcanic deposits were strongly affected by fragmentation processes during their subaqueous emplacement and in situ accumulated as basaltic breccias. The same volcanic-volcaniclastic association crops out to the south of the Las Planchadas range, forming a basaltic belt with similar characteristics. The geochemical features of the basalts are compatible with depleted mid-ocean ridge basalt (MORB)-like source for the magma, with contribution of subducted related components such as water rich marine hemipelagic sediments, compatible with a back arc geotectonic setting developed along the northern part of the Famatina System during the Arenigian.
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.
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.
Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.
Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.
The central European Bohemian Massif has undergone over two centuries of scientific investigation which has made it a pivotal area for the development and testing of modern geological theories. The discovery of melt inclusions in high-grade rocks, either crystallized as nanogranitoids or as glassy inclusions, prompted the re-evaluation of the area with an ‘inclusionist’ eye. Melt inclusions have been identified in a wide range of rocks, including felsic/perpotassic granulites, migmatites, eclogites and garnet clinopyroxenites, all the result of melting events albeit over a wide range of pressure/temperature conditions (800–1000°C/0.5–5 GPa). This contribution provides an overview of such inclusions and discusses the qualitative and quantitative constraints they provide for melting processes, and the nature of melts and fluids involved in these processes. In particular, data on trace-element signatures of melt inclusions trapped at mantle depths are presented and discussed. Moreover, experimental re-homogenization of nanogranitoids provided microstructural criteria allowing assessment of the conditions at which melt and host are mutually stable during melting. Overall this work aims to provide guidelines and suggestions for petrologists wishing to explore the fascinating field of melt inclusions in metamorphic terranes worldwide, based on the newest discoveries from the still-enigmatic Bohemian Massif.
Pseudotachylyte veins frequently associated with mylonites and ultramylonites occur within migmatitic paragneisses, metamonzodiorites, as well as felsic and mafic granulites at the base of the section of the Hercynian lower crust exposed in Calabria (Southern Italy). The crustal section is tectonically superposed on lower grade units. Ultramylonites and pseudotachylytes are particularly well developed in migmatitic paragneisses, whereas sparse fault-related pseudotachylytes and thin mylonite/ultramylonite bands occur in granulite-facies rocks. The presence of sillimanite and clinopyroxene in ultramylonites and mylonites indicates that relatively high-temperature conditions preceded the formation of pseudotachylytes. We have analysed pseudotachylytes from different rock types to ascertain their deep crustal origin and to better understand the relationships between brittle and ductile processes during deformation of the deeper crust. Different protoliths were selected to test how lithology controls pseudotachylyte composition and textures. In migmatites and felsic granulites, euhedral or cauliflower-shaped garnets directly crystallized from pseudotachylyte melts of near andesitic composition. This indicates that pseudotachylytes originated at deep crustal conditions (> 0.75 GPa). In mafic protoliths, quenched needle-to-feather-shaped high-alumina orthopyroxene occurs in contact with newly crystallized plagioclase. The pyroxene crystallizes in garnet-free and garnet-bearing veins. The simultaneous growth of orthopyroxene and plagioclase as well as almandine, suggests lower crustal origin, with pressures in excess of 0.85 GPa. The existence of melts of different composition in the same vein indicates the stepwise, non-equilibrium conditions of frictional melting. Melt formed and intruded into pre-existing anisotropies. In mafic granulites, brittle faulting is localized in a previously formed thin high-temperature mylonite bands. migmatitic gneisses are deformed into ultramylonite domains characterized by s-c fabric. Small grain size and fluids lowered the effective stress on the c planes favouring a seismic event and the consequent melt generation. Microstructures and ductile deformation of pseudotachylytes suggest continuous ductile flow punctuated by episodes of high-strain rate, leading to seismic events and melting.