RESUMEN
Under varying hydrostatic pressures ranging from 0 to 150 GPa, first-principles calculations were conducted to investigate the structural, electronic, bonding, optical, elastic, and mechanical characteristics of the Lead (Pb)-free halide perovskite FrCaCl3 using both the GGA and hybrid HSE06 parameterized density functional theory (DFT). Since the FrCaCl3 cubic perovskite has not yet been synthesized experimentally, its structural and thermodynamic stabilities are confirmed by the Goldschmidt tolerance factor, the octahedral factor, and the formation energy. The induction of pressure has caused a simultaneous decrease in both the lattice parameters and the electronic band gap. Applying the hybrid HSE06 potential refines the accuracy of the band gap, with values decreasing from 5.705 to 2.618 eV from 0 to 150 GPa pressure, suggesting improved optoelectronic attributes. Employing pressure facilitates the formation of stronger chemical bonds characterized by reduced bond lengths. The investigation of optical functions demonstrates that with increased pressure ranging to 150 GPa, the optical conductivity along with the absorption coefficient is oriented towards the low-energy region. The FrCaCl3 perovskite has the prospect to be used in X-ray imaging and other fields of nuclear medicine and diagnostics as it contains the radioactive element Francium (Fr). Additionally, it is found via the study of mechanical characteristics that FrCaCl3 is mechanically stable under various applied pressure, and adding pressure makes it more ductile as well as more anisotropic.
RESUMEN
Dehydrogenation chemistry has long been established as a fundamental aspect of organic synthesis, commonly encountered in carbonyl compounds. Transition metal catalysis revolutionized it, with strategies like transfer-dehydrogenation, single electron transfer and C-H activation. These approaches, extended to multiple dehydrogenations, can lead to aromatization. Dehydrogenative transformations of aliphatic carboxylic acids pose challenges, yet engineered ligands and metal catalysis can initiate dehydrogenation via C-H activation, though outcomes vary based on substrate structures. Herein, we have developed a catalytic system enabling cyclohexane carboxylic acids to undergo multifold C-H activation to furnish olefinated arenes, bypassing lactone formation. This showcases unique reactivity in aliphatic carboxylic acids, involving tandem dehydrogenation-olefination-decarboxylation-aromatization sequences, validated by control experiments and key intermediate isolation. For cyclopentane carboxylic acids, reluctant to aromatization, the catalytic system facilitates controlled dehydrogenation, providing difunctionalized cyclopentenes through tandem dehydrogenation-olefination-decarboxylation-allylic acyloxylation sequences. This transformation expands carboxylic acids into diverse molecular entities with wide applications, underscoring its importance.
RESUMEN
This study reports the formation of Er-doped nanocrystalline cobalt ferrite with the formula CoFe2-x Er x O4 (0.0 ≤ x ≤ 0.10) from nontoxic metal precursors Co(NO3)2·6H2O, Fe(NO3)3·9H2O, and Er(NO3)3·5H2O through an easy and economical sol-gel route in which citric acid is served as the chelating agent. The as-prepared powder was annealed at 700 °C for 3 h in ambient air to get the required spinel structure. The annealed samples were subjected to structural and magnetic characterization. The X-ray diffraction (XRD) data of the samples confirmed the cubic spinel structure formation. The average crystallite size evaluated from XRD data increased from 21 to 34 nm with the substitution of Er due to the larger atomic size of Er3+ than Fe3+. Moreover, the crystallite size obtained from XRD data are well matched with the particle size measured from transmission electron microscopy images. The lattice parameters obtained from XRD data agree well with the values estimated from theoretical cation distribution and Rietveld refinement calculation. The hysteresis curve exhibits the particles are soft ferromagnetic and the coercivity increased from 54.7 to 76.6 kA/m with maximum saturation magnetization, M s = 61 emug-1 for 0.10 Er content. The squareness ratios were found to be less than 0.5, which indicates the single-domain nature of our particles. The blocking temperature measured from field cooled-zero field cooled curves is T B > 350 K for all the samples, which is much higher than the room temperature (300 K). The enhancement of saturation magnetization and coercivity has been explained based on the crystallite size, anisotropy constant, and cation distribution. Thus, the structural and magnetic properties of CoFe2O4 nanoparticles (NPs) can be tuned by Er incorporation and these NPs can be applied in different soft magnetic devices.