Metallic ruthenium nanoparticles (Ru NPs) are formed on the glassy carbon electrode (GC) at electrodeposition potential of -0.75 V, as observed from X-ray photoelectron spectroscopy. Thus formed Ru NPs have the arsenite selective surface and conducting core that is ideally suited for designing a highly sensitive and reproducible response generating matrix for the arsenite detection at an ultratrace concentration in aqueous matrices. Contrary to this, arsenate ions sorb via chemical interactions on the ruthenium oxide (RuO2 and RuO3) NPs formed at -0.25 V, but not on the Ru NPs. For exploring a possibility of the quantification of arsenite in the ultratrace concentration range, the Ru NPs have been deposited on the GC by a potentiostatic pulse method of electrodeposition at optimized -0.75 V for 1000 s. Arsenite preconcentrates onto the Ru surface just by dipping the RuNPs/GC into the arsenite solution as it interacts chemically with Ru NPs. Electrochemical impedance spectroscopy of As(III) loaded RuNPs/GC shows a linear increase in the charge transfer resistance with an increase in As(III) conc. Using a differential pulse voltammetric technique, arsenite is oxidized to arsenate leading to its quantitative determination without any interference of Cu(2+) ions that are normally encountered in the water systems. Thus, the use of RuNPs/GC eliminates the need for a preconcentration step in stripping voltammetry, which requires optimization of the parameters like preconcentration potential, time, stirring, inferences, and so on. The RuNPs/GC based differential pulse voltammetric (DPV) technique can determine the concentration of arsenite in a few min with a detection limit of 0.1 ppb and 5.4% reproducibility. The sensitivity of 2.38 nA ppb(-1) obtained in the present work for As(III) quantification is considerably better than that reported in the literature, with a similar detection limit and mild conditions (pH = 2). The RuNPs/GC based DPV has been evaluated for its analytical performance using the lake water, ground water, and seawater samples spiked with known amounts of As(III).

A simple way of catching a big fat element: plutonium from radioactive waste by a task specific ionic liquid.

Studies have been carried out to understand the specific role of the alkali charge compensator on the luminescence properties of an alkali ion (Li, Na, and K) codoped SrWO:Eu phosphor. The oxidation state of the europium ion was found to be +3 on the basis of X-ray absorption near edge structure (XANES) measurements. This is the first report of its kind where opposite effects of Li ion and Na/K ions on photoluminescence intensity have been observed. Li ion codoping enhanced the photoluminescence intensity from SrWO:Eu phosphor while Na/K ion codoping did not. On the other hand, the luminescence lifetime is maximum for the Na ion codoped sample and minimum for the Li ion codoped sample. The results could be explained successfully using time-resolved luminescence, positron annihilation lifetime spectroscopy (PALS), and extended X-ray absorption fine structure (EXAFS) spectroscopy measurements. Changes in the Eu-O bond length and Debye-Waller Factor (σ) upon Li/Na/K codoping were monitored through EXAFS measurements. PALS also highlighted the fact that Li codoping is not contributing to reduction in the cation vacancies and might be occupying interstitial sites rather than lattice positions due to its very small size. On europium doping there is lowering in symmetry of SrO polyhedra from S to C, which is reflected in an intense electric dipole transition in comparison to the magnetic dipole transition. This is also corroborated using trends in Judd-Ofelt parameters. The results have shown that the luminescence lifetime is better when the vacancy concentration is lower as induced by Na and K codoping, while the emission intensity is higher in the samples when distortion around Eu is reduced as induced by Li codoping.

Understanding the speciation of metal ions in heterogeneous hydrogen-bonded deep eutectic solvents (DES) has immense importance for their wide range of applications in green technology, environmental remediation, and nuclear industry. Unfortunately, the fundamental nature of the interaction between DES and actinide ions is almost completely unknown. In the present work, we outline the speciation, solvation mechanism, and redox chemistry of uranyl ion (UO2 2+) in DES consisting of choline chloride (ChCl) and urea as the hydrogen-bond donor. Electrochemical and spectroscopic techniques along with molecular dynamics (MD) simulations have provided a microscopic insight into the solvation and speciation of the UO2 2+ ion in DES and also on associated changes in physical composition of the DES. The hydrogen-bonded structure of DES plays an important role in the redox behavior of the UO2 2+ ion because of its strong complexation with DES components. X-ray absorption spectroscopy and MD simulations showed strong covalent interactions of uranyl ions with the constituents of DES, which led to rearrangement of the hydrogen-bonding network in it without formation of any clusters or aggregations. This, in turn, stabilizes the most unstable pentavalent uranium (UO2 +) in the DES. MD analysis also highlights the fact that the number of H-bonds is reduced in the presence of uranyl nitrate irrespective of the presence of water with respect to pristine reline, which suggests high stability of the formed complexed species. The effect of added water up to 20 v/v % on speciation is insignificant for DES, but the presence of water influences the redox chemistry of UO2 2+ ions considerably. The fundamental findings of the present work would have far reaching consequences on understanding DES, particularly for application in the field of nuclear fuel reprocessing.

Pure and Eu(3+) doped β-Ag2MoO4 were synthesized using a co-precipitation method at room temperature. The as prepared compounds were characterized systematically using X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, cyclic voltammetry (CV) and positron annihilation lifetime spectroscopy (PALS). It is observed that pure β-Ag2MoO4 gives blue (445 nm) and green (550 nm) emission when irradiated with UV light. The origin of the green band was qualitatively explained from density functional theory (DFT) calculations using a suitable distortion model. It was observed that on doping europium ions, efficient energy transfer from molybdate to europium takes place. The excitation spectrum depicting f-f transitions (particularly 395 nm and 465 nm peaks) is much more intense than the CTB showing that Eu(3+) ions can be effectively excited by near UV-light. Based on DFT calculations it is proposed that due to the occurrence of Eu(3+) d-states in the conduction band (CB) as well as the strong contribution of Eu(3+) d-states to the impurity level present in the vicinity of the Fermi level, the host (β-Ag2MoO4) to dopant (Eu(3+)) energy transfer is preferable. β-Ag2MoO4 is also explored as a potential candidate for electrocatalysis of the oxygen reduction reaction (ORR). It was observed that the doping of europium ions in β-Ag2MoO4 enhances the electrocatalytic activity toward the ORR. The presence of a large concentration of cation vacancies and large surface defects as suggested by positron annihilation lifetime spectroscopy (PALS) seem to be aiding the ORR.