An N-pivot diglycolamide extractant (DGA-TREN) was synthesized for the first time and its complexation behaviour was studied towards trivalent lanthanide/actinide ions. The solvent extraction studies suggested a unique selectivity reversal in the extraction of trivalent actinides versus trivalent lanthanides which was observed performing extraction studies in an ionic liquid vis-à-vis a molecular diluent for a tripodal TREN-based diglycolamide ligand (DGA-TREN) vs. a tripodal diglycolamide ligand (T-DGA) which may have great significance in radioactive waste remediation. The nature of the bonding to Eu(3+) ion was investigated by EXAFS as well as by DFT calculations.
Surface modification of BaZrS3 nanocrystals for colloidal dispersions and field effect transistors. A rare example of solution processed chalcogenide perovskite thin films.
In this work, five types of MnO 2 nanostructres (nanowires, nanotubes, nanoparticles, nanorods, and nanoflowers) were synthesized with a fine control over their α-crystallographic form by hydrothermal method. The electrocatalytic activities of these materials were examined toward oxygen reduction reaction (ORR) in alkaline medium. Numerous characterizations were correlated with the observed activity by analyzing their crystal structure (TGA, XRD, TEM), material morphology (FE-SEM), porosity (BET), inherent structural nature (IR, Raman, ESR), surfaces (XPS), and electrochemical properties (Tafel, Koutecky−Levich plots and % of H 2 O 2 produced). Moreover, X-ray absorption near-edge structure (XANES) and the extended X-ray absorption fine structure (EXAFS) analysis were employed to study the structural information on the MnO 2 coordination number as well as interatomic distance. These combined results show that the electrocatalytic activities are significantly dependent on the nanoshapes and follow an order nanowire > nanorod > nanotube > nanoparticle > nanoflower. α-MnO 2 nanowires possess enhanced electrocatalytic activity compared to other shapes, even though the nanotubes possess a much higher BET surface area. In the ORR studies, α-MnO 2 nanowires displayed Tafel slope of 65 mV/decade, n-value of 3.5 and 3.6% of hydrogen peroxide production. The superior ORR activity was attributed to the fact that it possesses active sites composed with two shortened Mn− O bonds along with a Mn−Mn distance of 2.824 Å, which provides an optimum requirement for the adsorbed oxygen in a bridge mode favoring the direct 4 electron reduction. In accordance with the first principles based density functional theory (DFT), the enhancement in ORR activity is due to the less activation energy needed for the reaction by the (211) surface than all other surfaces.
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