Synthesis, structural analysis, electrochemical and magnetic properties of tetrachloroferrate ionic liquids

Eight ionic liquids have been synthesized with the tetrachloroferrate anion and varying cations with the general formula of [RA]+[FeCl4]− (R = –CH3, –CH2C6H5; A = pyridine, benzimidazole, trimethylamine, triphenylphosphine). They were characterized using spectroscopic techniques such as FT-IR, ESI-MS, Raman, and AAS along with single-crystal XRD to validate their structural motifs. The ionic conductivity, electrochemical and magnetic properties were determined to assess their possible uses in synthesis, separation, magnetic and transportation technologies, and high-energy capacitors. The diffusion coefficient value for these compounds was calculated to be around 7.55 × 10−8 cm2 s−1 and the heterogeneous rate constant value is about 3.60 × 10−3 cm s−1, which quantitatively complemented not only quasi reversibility but also moderately fast electron transfer processes. The effective magnetic moment values for the ionic liquids were determined to be similar to that expected from the spin-only approximation

Geometric analysis and formability of the cubic A2BX6 vacancy ordered double perovskite structure

A geometric analysis of the cubic A2BX6 structure commonly formed by metal halides is presented. Using the “hard-sphere” approximation, where the ions are represented by spheres of a fixed radius, we derive four limiting models that each constrain the distances between constituent ions in different ways. We compare the lattice parameters predicted by these four models with experimental data from the Inorganic Crystal Structure Database (ICSD). For the fluorides, the maintenance of the AX bond length at the sum of the A and X radii gives the best approximation of the lattice parameter, leading to structures with widely separated BX6 octahedra. For the heavier halides, a balance between forming an A-site cavity of the correct size and maintaining suitable anion–anion distances determines the lattice parameter. It is found that in many A2BX6 compounds of heavier halides, the neighboring octahedra show very significant anion–anion overlap. We use these models to predict a compound with A-site rattling and use density functional theory (DFT) to confirm this prediction. Finally, we use the geometric models to derive formability criteria for vacancy-ordered double perovskites

Anion Distribution, Structural Distortion, and Symmetry-Driven Optical Band Gap Bowing in Mixed Halide Cs₂SnX₆ Vacancy Ordered Double Perovskites

Mixed anion compounds in the Fm-3m vacancy ordered perovskite structure were synthesised and characterised experimentally and computationally with a focus on compounds where A = Cs+. Pure anion Cs2SnX6 compounds were formed with X = Cl, Br and I using a room temperature solution phase method. Mixed anion compounds were formed as solid solutions of Cs2SnCl6 and Cs2SnBr6 and a second series from Cs2SnBr6 and Cs2SnI6. Single phase structures formed across the entirety of both composition series, with no evidence of long range anion ordering observed by diffraction. A distortion of the cubic A2BX6 structure was identified in which the spacing of the BX6 octahedra changes to accommodate the A site cation without reduction of overall symmetry. Optical band gap values varied with anion composition between 4.89 eV in Cs2SnCl6 to 1.35 eV in Cs2SnI6, but proved highly non-linear with changes in composition. In mixed halide compounds it was found that lower energy optical transitions appeared that were not present in the pure halide compounds, and this could be attributed to lowering of the local symmetry within the tin halide octahedra. The electronic structure was characterised by photoemission spectroscopy, and Raman spectroscopy revealed vibrational modes in the mixed halide compounds that could be assigned to particular mixed halide octahedra. This analysis was used to determine the distribution of octahedra types in mixed anion compounds, which was found to be consistent with a near-random distribution of halide anions throughout the structure, although some deviations from random halide distribution were noted in mixed iodide-bromide compounds, where the larger iodide anions preferentially adopted trans configurations

Intelligent Multifunctional VO2/SiO2/TiO2 Coatings for Self-Cleaning, Energy-Saving Window Panels

Monoclinic vanadium(IV) oxide (VO2) has received much attention for applications as intelligent solar control coatings, with the potential to reduce the need for both heating and air conditioning loads within building infrastructure. Chemical vapor deposition, a high-throughput industrially scalable method, is an ideal technology for the deposition of VO2 thin films on window panels. However, these films suffer from poor adhesion and are chemically susceptible to attack. In addition, the VO2 films with optimum solar modulation are unfortunately translucent, restraining their commercial use in energy-efficient fenestration. In this work, multifunctional, robust, layered VO2/SiO2/TiO2 films were quickly deposited on glass substrates using atmospheric-pressure chemical vapor deposition and fully characterized using structural, vibrational spectroscopy, and electron microscopy techniques. The VO2/SiO2/TiO2 thin films were designed to exhibit excellent solar modulation properties as well as high transparency and resistance to abrasion, compared to single VO2 films of the same thickness. The films also showed self-cleaning properties comparable to those of commercial Pilkington Activ glass, as demonstrated here during the photodegradation of a model organic pollutant (stearic acid). The SiO2 acted as a barrier layer, preventing the diffusion of Ti4+ ions into the VO2 layer but it also promoted the optical properties and allowed for superior thermochromic behavior when compared to single VO2 films. The system was modeled to determine the effect of the individual components on the properties of the overall material. It was found that the deposition of the SiO2/TiO2 overlayer resulted in a dramatic improvement of visible-light transmission (∼30% increase when compared to single-layer analogues) while also doubling the solar modulation of the material

The diet of a small group of extralimital giraffe

Giraffe are extralimital in the Eastern Cape Province, South Africa where recent local introductions have persisted despite limited research into their impact on the indigenous flora. The diet of 15 giraffe at the Shamwari Game Reserve was recorded by direct observation during summer (March/April) and winter (July/August) 2001, quantifying diet by frequency of occurrence (individual records scored and expressed as a percentage of the total). Preference indices were also calculated. Habitat use was measured by the number of hours giraffe fed in different habitats. The diet comprised of 14 plant species, the most important species being Rhus longispina (47.9%), Acacia karroo (25.7%) and Euclea undulata (17.6%). Importance of R. longispina, A. karroo and Tarchonanthus camphoratus fluctuated seasonally. Rhus longispina was more important in winter with a corresponding decrease in feeding on A. karroo. Tarchonanthus camphoratus was only consumed during summer. Acacia karroo thickets (previously disturbed areas) were utilized most (summer 12 h; winter 9 h), with alternative habitats utilized more often in winter than in summer. We suggest that the seasonal fluctuation in the importance of R. longispina & A. karroo reflects the deciduous nature of A. karroo

Bio-nanotechnology application in wastewater treatment

The nanoparticles have received high interest in the field of medicine and water purification, however, the nanomaterials produced by chemical and physical methods are considered hazardous, expensive, and leave behind harmful substances to the environment. This chapter aimed to focus on green-synthesized nanoparticles and their medical applications. Moreover, the chapter highlighted the applicability of the metallic nanoparticles (MNPs) in the inactivation of microbial cells due to their high surface and small particle size. Modifying nanomaterials produced by green-methods is safe, inexpensive, and easy. Therefore, the control and modification of nanoparticles and their properties were also discussed

Quaternary glacial history of the Mediterranean mountains

Glacial and periglacial landforms are widespread in the mountains of the Mediterranean region. The evidence for glacial and periglacial activity has been studied for over 120 years and it is possible to identify three phases of development in this area of research. First, a pioneer phase characterized by initial descriptive observations of glacial landforms; second, a mapping phase whereby the detailed distribution of glacial landforms and sediments have been depicted on geomorphological maps; and, third, an advanced phase characterized by detailed understanding of the geochronology of glacial sequences using radiometric dating alongside detailed sedimentological and stratigraphical analyses. It is only relatively recently that studies of glaciated mountain terrains in the Mediterranean region have reached an advanced phase and it is now clear from radiometric dating programmes that the Mediterranean mountains have been glaciated during multiple glacial cycles. The most extensive phases of glaciation appear to have occurred during the Middle Pleistocene. This represents a major shift from earlier work whereby many glacial sequences were assumed to have formed during the last cold stage. Glacial and periglacial deposits from multiple Quaternary cold stages constitute a valuable palaeoclimatic record. This is especially so in the Mediterranean mountains, since mountain glaciers in this latitudinal zone would have been particularly sensitive to changes in the global climate system. © 2006 Edward Arnold (Publishers) Ltd