Helium mass flow through a solid-superfluid-solid junction.

We report the results of flow experiments in which two chambers containing solid ^{4}He are connected by a superfluid Vycor channel. At low temperatures and pressures, mechanically squeezing the solid in one chamber produced a pressure increase in the second chamber, a measure of mass transport through our solid-superfluid-solid junction. This pressure response is very similar to the flow seen in recent experiments at the University of Massachusetts: it began around 600 mK, increased as the temperature was reduced, then decreased dramatically at a temperature, T_{d}, which depended on the ^{3}He impurity concentration. Our experiments indicate that the flow is limited by mass transfer across the solid-liquid interface near the Vycor ends, where the ^{3}He collects at low temperature, rather than by flow paths within the solid ^{4}He.

Cooperative dehydrogenation of N-heterocycles using a carbon nanotube-rhodium nanohybrid.

Rhodium nanoparticles were anchored on carbon nanotubes and the resulting nanohybrid was studied as co-catalyst, along with tert-butylcatechol, for the dehydrogenation of various N-heterocycles. The co-catalytic system operates in high yields, under the mildest conditions reported so far, and can be applied to a wide variety of secondary amine-containing scaffolds.

New insight on the simultaneous H2 and HNO2 production in concentrated HNO3 aqueous solutions under alpha radiation.

Knowledge of hydrogen and nitrous acid yields (G(H2) and G(HNO2)) from α radiolysis of nitric acid solutions is of critical importance for the technological aspects of reprocessing of spent nuclear fuel (SNF). This study provides critical information on the G values for external alpha irradiation of concentrated HNO3 solutions. An investigation-specifically developed experimental setup allows performing this investigation without encountering issues related to extreme high local doses. In situ monitoring of the UV-visible induced absorption in irradiated HNO3 solutions permitted quantification of HNO2 production, and mass spectrometry was used to quantify H2. The influence of the dose rate and HNO3 concentration was investigated, and the primary yields of these two species were determined. It was found that dose rate increase leads to diminished production of HNO2 and H2, while HNO3 concentration increase leads to increased HNO2 formation and reduced H2 production. The values of the primary yields of these two species were determined and compared to the literature reported values. While the determined values show similar trends as those reported, this study provides accurate radiolytic yields for H2 and HNO2 that are radioelement-independent compared to the α radiolysis using radioisotope/HNO3 mixtures and provides the basis for perfecting numerical codes used for simulating the radiolytic processes associated with SNF reprocessing.

Ruthenium-catalyzed hydrogen isotope exchange of C(sp3)-H bonds directed by a sulfur atom.

We present here the first example of C(sp3)-H activation directed by a sulfur atom. Based on this transformation catalyzed by Ru/C, we have developed a hydrogen isotope exchange reaction for the deuterium and tritium labelling of thioether substructures in complex molecules.

Radiolysis as a solution for accelerated ageing studies of electrolytes in Lithium-ion batteries.

Diethyl carbonate and dimethyl carbonate are prototype examples of eco-friendly solvents used in lithium-ion batteries. Nevertheless, their degradation products affect both the battery performance and its safety. Therefore, it is of paramount importance to understand the reaction mechanisms involved in the ageing processes. Among those, redox processes are likely to play a critical role. Here we show that radiolysis is an ideal tool to generate the electrolytes degradation products. The major gases detected after irradiation (H2, CH4, C2H6, CO and CO2) are identified and quantified. Moreover, the chemical compounds formed in the liquid phase are characterized by different mass spectrometry techniques. Reaction mechanisms are then proposed. The detected products are consistent with those of the cycling of Li-based cells. This demonstrates that radiolysis is a versatile and very helpful tool to better understand the phenomena occurring in lithium-ion batteries.

Electrolytes Ageing in Lithium-ion Batteries: A Mechanistic Study from Picosecond to Long Timescales.

The ageing phenomena occurring in various diethyl carbonate/LiPF6 solutions are studied using gamma and pulse radiolysis as a tool to generate similar species as the ones occurring in electrolysis of Li-ion batteries (LIBs). According to picosecond pulse radiolysis experiments, the reaction of the electron with (Li(+), PF6(-)) is ultrafast, leading to the formation of fluoride anions that can then precipitate into LiF(s). Moreover, direct radiation-matter interaction with the salt produces reactive fluorine atoms forming HF(g) and C2H5F(g). The strong Lewis acid PF5 is also formed. This species then forms various R(1)R(2)R(3) P=O molecules, where R is mainly -F, -OH, and -OC2H5. Substitution reactions take place and oligomers are slowly formed. Similar results were obtained in the ageing of an electrochemical cell filled with the same model solution. This study demonstrates that radiolysis enables a description of the reactivity in LIBs from the picosecond timescale until a few days.