Electronic properties and vibrational spectra of (NH4)2M″(SO4)2·6H2O (M = Ni, Cu) Tutton's salt: DFT and experimental study.

The complex crystals of the family of the Tutton's salt have been investigated through the numerous experimental and theoretical studies to understand their physical properties and their potential technological applications. In spite of the more than 60 years of research, there are very few studies about the electronic properties of Tutton's salt. In our present work, we have calculated the stability, electronic properties and the first theoretical study of band structure of the three different crystals of the Tutton's salt, ammonium nickel sulfate hexahydrate ((NH4)2Ni(SO4)2·6H2O), ammonium nickel-copper sulfate hexahydrate ((NH4)2Ni0.5Cu0.5(SO4)2·6H2O) and ammonium copper sulfate hexahydrate ((NH4)2Ni(SO4)2·6H2O) with the help of periodic ab-initio calculations based on density functional theory (DFT). In addition to this, the internal Raman and FTIR modes of the ionic fragments [Ni(H2O)6]2+, [Cu(H2O)6]2+ NH4+ and SO42- of the sample crystals were obtained by employing the ab initio and the orientation of the molecular vibrations of the ionic fragments have been presented in picturized form. Furthermore, the Raman and FTIR spectroscopy of the sample crystals were measured in the range 100-4000 cm-1 and 400-4000 cm-1 respectively, and the internal vibrational modes obtained from experimental measurement have been compared with those obtained from DFT calculations.

Hydrotalcite-TiO2 magnetic iron oxide intercalated with the anionic surfactant dodecylsulfate in the photocatalytic degradation of methylene blue dye.

The new magnetic photocatalysts HT/TiO2/Fe and HT-DS/TiO2/Fe, modified with the anionic surfactant sodium dodecylsulfate (DS) were successfully synthesized in this work. Titanium dioxide (anatase) followed by iron oxide were deposited on the hydrotalcite support. Several catalyst samples were prepared with different amounts of titanium and iron. The photocatalysts were characterized by infrared and Raman spectroscopy, X-ray diffraction, scanning electron microscopy. Photocatalytic performance was analyzed by UV-visible radiation (filter cutoff, λ > 300 nm) of an aqueous solution (24 mg/L) of methylene blue (MB). The most efficient catalyst was obtained at an iron oxide:TiO2 molar ratio of 2:3. This catalyst showed high photocatalytic activity, removing 96% of the color and 61% of total organic carbon from the MB solution after 120 min. It was easily removed from solution after use because of its magnetic properties. The reuse of the HT-DS/TiO2/Fe23 catalyst was viable and the catalyst was structurally stable for at least four consecutive photocatalytic cycles.

Observation of strain-free rolled-up CVD graphene single layers: toward unstrained heterostructures.

Single layer graphene foils produced by chemical vapor deposition (CVD) are rolled with self-positioned layers of InGaAs/Cr forming compact multi-turn tubular structures that consist on successive graphene/metal/semiconductor heterojunctions on a radial superlattice. Using elasticity theory and Raman spectroscopy, we show that it is possible to produce homogeneously curved graphene with a curvature radius on the 600-1200 nm range. Additionally, the study of tubular structures also allows the extraction of values for the elastic constants of graphene that are in excellent agreement with elastic constants found in the literature. However, our process has the advantage of leading to a well-defined and nonlocal curvature. Since our curvature radius lies in a range between the large radius studied using mechanical bending and the reduced radius induced by atomic force microscopy experiments, we can figure out whether bending effects can be a majoritary driving force for modifications in graphene electronic status. From the results described in this work, one can assume that curvature effects solely do not modify the Raman signature of graphene and that strain phenomena observed previously may be ascribed to possible stretching due to the formation of local atomic bonds. This implies that the interactions of graphene with additional materials on heterostructures must be investigated in detail prior to the development of applications and devices.

Two-dimensional molecular crystals of phosphonic acids on graphene.

The synthesis and characterization of two-dimensional (2D) molecular crystals composed of long and linear phosphonic acids atop graphene is reported. Using scanning probe microscopy in combination with first-principles calculations, we show that these true 2D crystals are oriented along the graphene armchair direction only, thereby enabling an easy determination of graphene flake orientation. We have also compared the doping level of graphene flakes via Raman spectroscopy. The presence of the molecular crystal atop graphene induces a well-defined shift in the Fermi level, corresponding to hole doping, which is in agreement with our ab initio calculations.