Is degradation of dyes even possible without using photocatalysts? - a detailed comparative study.

Herein, catalyst-free, eco-friendly, photo-triggered, self-degradation of malachite green (MG) and crystal violet (CV) dyes in comparison to photocatalytic degradation were investigated. To the best of our knowledge, this is the first systematic study to demonstrate the reactive oxygen species (ROS), electron (e-) and hole (h+) generation ability of dyes to initiate self-degradation in the presence of direct solar energy (a free source of UV radiation) and UV light (254 and 365 nm). Various experimental conditions, e.g., different dye concentrations, pH, vessel-materials (borosilicate glass and quartz) were optimized to achieve the optimum degradation outcomes. The degradation kinetics of dyes suggested the applicability of second-order-kinetics to all kinds of applied light sources. Investigation of the thermodynamic approach reveals that the self-degradation procedure was endothermic, with activation energies of 46.89 and 52.96 kJ mol-1, respectively, for MG and CV. The self-degradation mechanism was further corroborated by the quantum calculations, while the formation of final degraded products for dye-degradations was established on the basis of mass spectroscopy and total organic carbon (TOC) analysis. The computed emission energies for MG and CV advocate that the excitation energy occurs due to the sole-attribution electron excitation from the Highest Occupied Molecular Orbital (HOMO) to the Lowest Unoccupied Molecular Orbital (LUMO). The close energy difference between the hydroxyl anions and the dyes also facilitates the creation of the hydroxyl radical. In a similar manner, the excited electrons from the aforementioned dyes may readily be transferred to triplet molecular oxygen, which makes it possible to generate super oxide. The radical generated in the process facilitates the self-degradation of the dyes.

Direct Oxidative Azo Coupling of Anilines Using a Self-Assembled Flower-like CuCo2O4 Material as a Catalyst under Aerobic Conditions.

Herein, we report the synthesis of a self-assembled flower-like CuCo2O4 material by the oxalate decomposition method. The crystalline structure and morphology of the material have been analyzed by powder X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray measurement techniques. The self-assembled flower-like CuCo2O4 material showed remarkable catalytic activity in the direct aerobic oxidative azo coupling of anilines under oxidant and other additive-free reaction conditions. The mechanistic insight of CuCo2O4 in the oxidative azo coupling reaction has been established by density functional theory calculations, which disclosed that the absorption and dissociation of areal oxygen preferentially take place at the Cu site and dissociation of aniline takes place at the Co site. Thus, the Cu and Co sites of CuCo2O4 exert a cooperative effect on the direct oxidative azo coupling reactions through the selective activation of anilines and aerobic oxygen. The CuCo2O4 material was recovered from the reaction mixture and reused for at least eight runs without appreciable loss of catalytic activity.

Recovery of combustibles from electrostatic precipitator discharge.

Coal is the main fuel for the direct reduced iron (DRI) plants of India, which are one of the major sources of fly ash generation. The generation of fly ash and its disposal has raised concern because of the environmental impacts. In the present study, two different fly ash samples were investigated to explore the scope of recovery of combustibles. One did not show any recovery potential. The second sample indicated that about 40% of material could be recovered, with 35% fixed carbon and 10,841 kJ kg(-1) gross calorific value. This can be used as a fuel blend in standard fluidised bed combustion boilers efficiently burning inferior coal. A process flowsheet has been suggested for the recovery purpose. It was estimated that for a small 0.2 million tonnes per year (Mtpy) capacity DRI plant, approximately 3.4 ha of land could thus annually be saved from dumping of the generated fly ash, while recovering 1.83 MW of electrical energy.

Charge-transfer complex formation in gelation: the role of solvent molecules with different electron-donating capacities.

A naphthalenediimide (NDI)-based synthetic peptide molecule forms gels in a particular solvent mixture (chloroform/aromatic hydrocarbon, 4:1) through charge-transfer (CT) complex formation; this is evident from the corresponding absorbance and fluorescence spectra at room temperature. Various aromatic hydrocarbon based solvents, including benzene, toluene, xylene (ortho, meta and para) and mesitylene, have been used for the formation of the CT complex. The role of different solvent molecules with varying electron-donation capacities in the formation of CT complexes has been established through spectroscopic and computational studies.

Color polymorphism: understanding the diverse solid-state packing and color in dimethyl-3,6-dichloro-2,5-dihydroxyterephthalate.

Dimethyl-3,6-dichloro-2,5-dihydroxyterephthalate (MCHT) is known to exist in three differently packed crystals having three different colors, namely yellow (Y), light yellow (LY), and white (W). Apart from the difference in their color, the molecules in the crystals also differ in their intramolecular O-H⋅⋅⋅O and O-H⋅⋅⋅Cl hydrogen bonds. Time-dependent DFT calculations reveal the role of the various types of hydrogen bonds in controlling the color of the polymorphs. Mechanistic pathways that lead to such transformations in the crystal are elucidated by solid-state dispersion-corrected DFT studies. Relative stabilities of the various polymorphs rationalize the experimentally observed transformations between them. Calculations reveal that the minimum-energy pathway for the conversion of the Y form to a W form is through stepwise disrotatory motion of the two -OH groups through a hybrid intermediate having one intramolecular OH⋅⋅⋅O and one O-H⋅⋅⋅Cl bond. The LY form is shown to exist on the higher-energy pathway involving a concerted Y→W transformation.

Note: Neutron shutter for Kolkata superconducting cyclotron.

In particle accelerator facilities, experimental areas are isolated from active accelerator area with thick concrete walls. A neutron shutter is used to isolate the experimental areas from the active accelerator area in the beam line. These shutters are provided primarily to reduce the secondary radiations like neutrons in the experimental areas to permissible limit when the primary beam is blocked in the accelerator area. The reduced radiation level in the experimental areas makes the experimental areas accessible. The shutters should allow the primary beam to pass to the experimental caves when they retracted from the beam line. A new neutron shutter has been designed and fabricated. This shutter incorporates compact features with considerable reduction in length, surface area and volume. The attenuation of secondary radiations is evaluated using Monte-Carlo radiation transport code FLUKA. It is found that the features of the shutter are sufficiently good enough to reduce the diffused secondary radiations well within the permissible levels.