Structural,electronic, and mechanical properties of cubic TiO_2:A first-principles study

We present an analysis of structural, electronic, and mechanical properties of cubic titanium dioxide(TiO_2) using an all electron orthogonalzed linear combinations of atomic orbitals(OLCAO) basis set under the framework of density functional theory(DFT). The structural property, especially the lattice constant a, and the electronic properties such as the band diagram and density of states(DOS) are studied and analyzed. The mechanical properties such as bulk moduli, shear moduli, Young's Moduli, and Poison's ratio are also investigated thoroughly. The calculations are carried out on shear moduli and anisotropy factor for cubic TiO_2. The Vickers hardness is also tested for fluorite and pyrite cubic-structured TiO_2. Furthermore, the results are compared with the previous theoretical and experimental results. It is found that DFTbased simulation produces results which are approximation to experimental results, whereas the calculated elastic constants are better than the previous theoretical and experimental values.     

A Self-Healing Metal–Organic Hydrogel for an All-Solid Flexible Supercapacitor

A zinc containing metal–organic gel (Zn-MOG) with embedded free ions, which exhibits self-healing properties, has been synthesized for application in supercapacitors. The activated carbon-based flexible supercapacitor device with the MOG electrolyte has a broad potential window of 2.1 V, with high retention of specific capacitance compared to the traditional polyvinyl alcohol (PVA)-based gel. The Zn-MOG does not require an additional electrolyte. The sodium and sulphate ions embedded in the MOG are sufficient enough for the charge storage.     

Kinetics of catalyzed esterification of acetic acid with n-butanol using carbonized agro-waste

The objective of this research work was to investigate the kinetics of esterification of acetic acid with n-butanol through the variation of experimental parameters. The reaction mixture was catalyzed heterogeneously by a sulfonated catalyst in batch mode of operation. The catalyst was prepared from abundantly available agro-waste, Cajanus cajan husk by chemical activation process, which produces a carbon-based solid catalyst with high surface area. The catalyst was characterized by a Brunauer-Emmet-Teller surface analyzer and Fourier transform infrared spectroscopy to know the surface morphology. Process parameters such as contact time, reaction temperature, and catalyst loading, which can influence the extent of conversion of reactants, were studied. Furthermore, the kinetic investigation was also carried out to estimate the kinetic parameters for uncatalyzed and catalyzed reaction using the second-order pseudo-homogeneous (P-H), Eley-Rideal (E-R), and Langmuir-Hinshelwood (LH) kinetic models for this research work. The kinetic parameters such as activation energy, preexponential factor, and the thermodynamic parameters such as enthalpy and entropy were estimated for uncatalyzed and catalyzed reactions using these three models. The process conditions were optimized for catalyzed and uncatalyzed reactions to obtain the maximum product yield by minimizing root mean square error of each experimental data using the MS-excel solver tool. Thus, this study reveals the high potential of an agro-waste, Cajanus cajan husk as raw material for the synthesis of catalyst. The results show that the E-R model is more appropriate for predicting the dynamic data of an esterification reaction, as the forward rate of reaction estimated using the E-R model are more modified than P-H and L-H models.     

Langmuir wave phase-mixing in warm electron-positron-dusty plasmas

An analytical study on nonlinear evolution of Langmuir waves in warm electron-positron-dusty plasmas is presented. The massive dust grains of either positively or negatively charged are assumed to form a fixed charge neutralizing background. A perturbative analysis of the fluid-Maxwell's equations confirms that the excited Langmuir waves phase-mix and eventually break, even at arbitrarily low amplitudes. It is shown that the nature of the dust-charge as well as the amount of dust grains can significantly influence the Langmuir wave phase-mixing process. The phase-mixing time is also found to increase with the temperature.     

Formation of bamboo-shaped carbon nanotubes on carbon black in a fluidized bed

For the first time, bamboo-shaped multiwalled carbon nanotubes, having diameter of the order of 50 nm, have been grown on carbon black in a fluidized bed in bulk amount. The activation energy for the synthesis of the product was found out to be around 33 kJ/mol in the temperature range of 700−900 °C. The carbon nanotubes were separated from the carbon black by preferential oxidation of the later, the temperature of which was determined by thermogravimetry. The transmission electron microscopy revealed different features of the nanotubes such as “Y” junction, bend, and catalyst filling inside the nanotubes. Small angle neutron scattering was performed on the nanotubes synthesized at different temperatures. The data were fitted into a suitable model in order to find out the average diameter, which decreases with increase in synthesis temperature. The Monte Carlo simulation predicts the same behavior. Based on the above observations, a possible growth mechanism has been predicted. The oscillation in carbon saturation value inside the catalyst in the fluidized bed has been indicated as the responsible factor for the bamboo-shaped structure.     

Association reaction between SiH3 and H2O2: a computational study of the reaction mechanism and kinetics

The association reaction between silyl radical (SiH₃) and H₂O₂ has been studied in detail using high-level composite ab initio CBS-QB3 and G4MP2 methods. The global hybrid meta-GGA M06 and M06-2X density functionals in conjunction with 6-311++G(d,p) basis set have also been applied. To understand the kinetics, variational transition-state theory calculation is performed on the first association step, and successive unimolecular reactions are subjected to Rice–Ramsperger–Kassel–Marcus calculations to predict the reaction rate constants and product branching ratios. The bimolecular rate constant for SiH₃–H₂O₂ association in the temperature range 250–600 K, k(T) = 6.89 × 10^?13 T ^?0.163exp(?0.22/RT) cm³ molecule^?1 s^?1 agrees well with the current literature. The OH production channel, which was experimentally found to be a minor one, is confirmed by the rate constants and branching ratios. Also, the correlation between our theoretical work and experimental literature is established. The production of SiO via secondary reactions is calculated to be one of the major reaction channels from highly stabilized adducts. The H-loss pathway, i.e., SiH₂(OH)₂ + H, is the major decomposition channel followed by secondary dissociation leading to SiO.     

Magnesium Methoxide-Assisted Synthesis of 2,4,6-Triaryl Pyridines

A new three-component reaction of chalcones, ketones, and ammonia assisted by magnesium methoxide is described. The corresponding 2,4,6-triaryl pyridines (Kröhnke pyridines) are formed in fair to good yields (34–76%) within 3 h. The method also provides a facile way to synthesize 2(6)-difluoromethyl pyridines via an interesting mechanism.     

Size‐Selective Encapsulation of Hydrophobic Guests by Self‐Assembled M4L6 Cobalt and Nickel Cages

Subtle differences in metal–ligand bond lengths between a series of [M₄L₆]^4? tetrahedral cages, where M=Fe^II, Co^II, or Ni^II, were observed to result in substantial differences in affinity for hydrophobic guests in water. Changing the metal ion from iron(II) to cobalt(II) or nickel(II) increases the size of the interior cavity of the cage and allows encapsulation of larger guest molecules. NMR spectroscopy was used to study the recognition properties of the iron(II) and cobalt(II) cages towards small hydrophobic guests in water, and single‐crystal X‐ray diffraction was used to study the solid‐state complexes of the iron(II) and nickel(II) cages.