No abstract

For more than forty years, The Clay Minerals Society has dispensed a set of source clays which have enabled a large number of researchers to work on similar materials. Many of these source clays remained unchanged over the years but, conversely, other clays have gone out of stock and thus were replaced. This was the fate of montmorillonite STx-1a, which was replaced by STx-1b. Although STx-1a and STx-1b share many basic chemical and mineralogical features, some minor differences exist that can affect behavior. A baseline characterization of the source clay STx-1b, which was the objective of this study, was, therefore, necessary to provide researchers a tool useful not only for new investigation but also to compare new results obtained on STx-1b with literature data on STx-1a. This characterization was gained using traditional and advanced methods that included: 1) chemical composition (major and trace elements); 2) cation exchange capacity determination; 3) thermal analyses coupled with evolved gas mass spectrometry; 4) quantitative mineralogical characterization using powder X-ray diffraction and Rietveld- RIR (Reference Intensity Ratio) refinement; 5) X-ray absorption spectroscopy at the Fe K-edge; 6) diffuse reflectance ultraviolet-visible and infrared spectroscopies; and 7) 29Si, 27Al, and 1H magic-angle spinning nuclear magnetic resonance measurements. According to this multi-analytical approach, the chemical formula for STx-1b is [4](Si7.753Al0.247) [6](Al3.281Mg0.558Fe0.136Ti0.024Mn0.002) [12](Ca0.341Na0.039 K0.061)O20(OH)4.

The μ-oxo Fe(III)-phenanthroline complex [(OH)(Phen)FeOFe(Phen) (OH)] intercalated in montmorillonite provides a stable hybrid material. In this study, the ability and efficiency of this material to immobilize thiols in gas phase, acting as a trap at the solid-gas interface, were investigated. Aliphatic thiols containing both hydrophilic and hydrophobic end groups were chosen to test the selectivity of this gas trap. DR-UV-vis, IR, elemental analysis, thermal analysis and evolved gas mass spectrometry, X-ray powder diffraction, and X-ray absorption spectroscopy techniques were employed to characterize the hybrid material before and after thiol exposure and to provide information on the entrapping process. Thiol immobilization is very large, up to 21% w/w for heptanethiol. In addition, evidence was obtained that immobilization occurs through the formation of a covalent bond between the iron of the complex and the sulfur of the thiol. This provides an immobilization process characterized by a higher stability with respect to the methods based on physi-adsorption. Thiol immobilization resulted thermally reversible at least for 20 adsorption/desorption cycles. Unlike standard desulfurization processes like hydrotreating and catalytic oxidation which work at high temperatures and pressures, the present system is able to efficiently trap thiols at room temperature and pressure, thus saving energy. Furthermore, we found that the selectivity of thiol immobilization can be tuned acting on the amount of complex intercalated in montmorillonite. In particular, montmorillonite semisaturated with the complex captures both hydrophobic and hydrophilic thiols, while the saturated montmorillonite shows a strong selectivity toward the hydrophobic molecules.

We present a structural and magnetic study of La0.7Ca0.3MnO3 epitaxial films (the thickness ranges from 2.4 to 80 nm) on SrTiO3. Their structure, as obtained by x-ray diffraction, is orthorhombic with a 45° rotated 2×2 square lattice, referred to the SrTiO3 substrate, in the film plane. The 2.4 nm film adopts a different structure as evidenced by the extinction of particular diffraction peaks and supported by the behavior of the size of the in-plane structural domains. While no important structural changes are detected for the other films as the layer thickness is reduced, Tc decreases drastically while the remanent magnetization is constant. Tc follows the functional dependence of a mean field approximation for the limitation of the divergence of the spin–spin correlations by the film thickness.