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Understanding the complex chemistry of functional nanomaterials is of fundamental importance. Controlled synthesis and characterization at the atomic level is essential to gain deeper insight into the unique chemical reactivity exhibited by many nanomaterials. Cerium oxide nanoparticles have many industrial and commercial applications,resulting from very strong catalytic, pro-and anti-oxidant activity. However, the identity of the active species and the chemical mechanisms imparted by nanoceria remain elusive, impeding the further development of new applications. Here, we explore the behavior of cerium oxide nanoparticles of different sizes at different temperatures and trace the electronic structure changes by state-of-the-art soft and hard X-ray experiments combined with computational methods. We confirm the absence of the Ce(III) oxidation state at the surface of CeO2nanoparticles, even for particles as small as 2 nm. Synchrotron X-ray absorption experiments at Ce L3and M5edges, combined with X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and small angle X-ray scattering (SAXS) and theoretical calculations demonstrate that in addition to the nanoceria charge stability, the formation of hydroxyl groups at the surface profoundly affects the chemical performance of these nanomaterials, Comment: T. Plakhova et al, Nanoscale (2019)

The sorption of radionuclides by graphene oxides synthesized by different methods was studied through a combination of batch experiments with characterization by microscopic and spectroscopic techniques such as X-ray photoelectron spectroscopy (XPS), attenuated total reflection fourier-transform infrared spectroscopy (ATR-FTIR), high-energy resolution fluorescence detected X-Ray absorption spectroscopy (HERFD-XANES), extended X-ray absorption fine structure (EXAFS) and high resolution transmission electron microscopy (HRTEM).

This study focuses on heat and mass exchange processes in hydrate foam during its formation from methane bubbles in gas hydrate stability zone (GHSZ) of the Lake Baikal and following delivery of it in open container to the lake surface. The foam was formed as a result of methane bubble collection with a trap/container. The trap was inverted glass beaker of diameter of 70 mm and 360 mm long. Open bottom end of the beaker used as enter for bubbles ascended from the lakebed. At a depth of 1400 m all bubbles which fed to the trap were transformed here into solid hydrate foam. The sensitive thermometer was mounted in the middle of the trap and recorded the temperature inside trap. The fate of the bubbles in the trap was recorded by video-camera. During ascend within GHSZ with velocity of about 0.375 m/s we observed the continuous decrease of the temperature in the foam up to a level of negative magnitude in a depth interval of 1400 - 750 meters. Above 750 m temperature decrease was changed by small growth. However once the trap ascended above top boundary of GHSZ at a depth of 380 m, the temperature fell sharply. Falling to a negative values -0.25 oC, the temperature sharply stabilized and did not changed further until the trap reached the surface. The decreasing of the temperature during the ascent is due to the cooling of gas as a result of the performing of the work against the forces of hydrostatic pressure. The temperature drop at the boundary of the GHSZ is due to the absorption of heat by the decomposition of hydrate.

The paper is dedicated to the mechanics of the methane bubbles in the gas hydrate stability zone of the basin. Transformation of deep-water methane bubbles into solid hydrate was investigated in Lake Baikal in situ. Released from the bottom methane bubbles were caught by different traps with transparent walls. It was observed that when bubbles entered into internal space of the trap, the bubbles could be transformed into two different solid hydrate structures depending on ambient conditions. The first structure is hydrate granular matter consisted of solid fragments with sizes of order of 1 mm. The second structure is high porous solid foam consisted of solid bubbles with sizes of order of 5 mm. The formed granular matter did not change during trap lifting up to top border of gas hydrate stability zone, whereas free methane intensively released from solid foam sample during it lifting. It was concluded that the decrease of the depth of bubble sampling and the decrease of the bubble flux rate assist to formation of hydrate granular matter, whereas increase of the depth of bubble sampling and growth of bubble flux rate assist to conversation of bubbles into high porous solid hydrate foam., Comment: 29 pages, 17 figures