During nuclear waste disposal process, radioactive iodine as a fission product can be released. The widespread implementation of sustainable nuclear energy thus requires the development of efficient iodine stores that have simultaneously high capacity, stability and more importantly, storage density (and hence minimized system volume). Here, we report high I2 adsorption in a series of robust porous metal–organic materials, MFM-300(M) (M = Al, Sc, Fe, In). MFM-300(Sc) exhibits fully reversible I2 uptake of 1.54 g g–1, and its structure remains completely unperturbed upon inclusion/removal of I2. Direct observation and quantification of the adsorption, binding domains and dynamics of guest I2 molecules within these hosts have been achieved using XPS, TGA-MS, high resolution synchrotron X-ray diffraction, pair distribution function analysis, Raman, terahertz and neutron spectroscopy, coupled with density functional theory modeling. These complementary techniques reveal a comprehensive understanding of the host–I2 and I2–I2 binding interactions at a molecular level. The initial binding site of I2 in MFM-300(Sc), I2I, is located near the bridging hydroxyl group of the [ScO4(OH)2] moiety [I2I···H–O = 2.263(9) Å] with an occupancy of 0.268. I2II is located interstitially between two phenyl rings of neighboring ligand molecules [I2II···phenyl ring = 3.378(9) and 4.228(5) Å]. I2II is 4.565(2) Å from the hydroxyl group with an occupancy of 0.208. Significantly, at high I2 loading an unprecedented self-aggregation of I2 molecules into triple-helical chains within the confined nanovoids has been observed at crystallographic resolution, leading to a highly efficient packing of I2 molecules with an exceptional I2 storage density of 3.08 g cm–3 in MFM-300(Sc).

In contrast to synthetic materials, materials produced by organisms are formed in ambient conditions and with a limited selection of elements. Nevertheless, living organisms reveal elegant strategies for achieving specific functions, ranging from skeletal support to mastication, from sensors and defensive tools to optical function. Using state-of-the-art characterization techniques, we present a biostrategy for strengthening and toughening the otherwise brittle calcite optical lenses found in the brittlestar This intriguing process uses coherent nanoprecipitates to induce compressive stresses on the host matrix, functionally resembling the Guinier-Preston zones known in classical metallurgy. We believe that these calcitic nanoparticles, being rich in magnesium, segregate during or just after transformation from amorphous to crystalline phase, similarly to segregation behavior from a supersaturated quenched alloy.

The thermal transformation, stability field, and reaction kinetics of serpentine minerals (antigorite, chrysotile, and lizardite) have been studied to draw a comprehensive model for their dehydroxylation and recrystallization reactions. In situ X‑ray powder diffraction (XRPD) and kinetic studies were combined with transmission electron microscopy (TEM) observations to describe the mechanisms of dehydroxylation and later high-temperature crystallization. During dehydroxylation, a metastable transition phase with a characteristic peak around 9 Å was observed in antigorite and, to a minor extent, in lizardite. Rietveld refinements confirmed that the 9 Å phase actually possesses a talc-like structure. The appearance of this phase is controlled by structure and kinetic factors.\ud The kinetic parameters and reaction mechanism for lizardite and antigorite dehydroxylation in air at ambient pressure were calculated using the Avrami models and compared to those of chrysotile. For both lizardite and antigorite, the kinetics of dehydroxylation is controlled by diffusion. Apparent activation energy of the reaction in the temperature range 612–708 °C was 221 and 255 kJ/mol for lizardite and antigorite, respectively. The reaction sequences of chrysotile, lizardite, and antigorite leading to the formation of stable high-temperature products (i.e., forsterite and enstatite) are described taking into account previous topotactic and dissolution-recrystallization models.\ud Keywords: Main serpentine minerals, dehydroxylation, reaction kinetics, Avrami, metastable phase

No abstract

The high‐resolution powder diffraction beamline at ESRF (ID22), built with a dual‐undulator source on the 6 GeV storage ring, combines a wide continuous range of incident energy (6–80 keV) with high brightness, offering the possibility to carry out high‐flux high‐resolution powder diffraction measurements. In routine operation, a bank of nine scintillation detectors is scanned vertically to measure the diffracted intensity versus 2gθ, each detector being preceded by an Si 111 analyser crystal. Although the current detector system has operated successfully for the past 20 years, recent developments in detector technology could be exploited to improve the overall performance. With this in mind, as a test, a two‐dimensional Pilatus3 X CdTe 300 K‐W pixel detector has been mounted on the arm of the diffractometer, replacing the nine scintillator detectors. At each nominal 2gθ value, a two‐dimensional image is recorded showing nine distinct regions corresponding to the diffraction signals passing via each of the analyser crystals. This arrangement offers new flexibility in terms of data handling and processing, with the possibility to optimize both peak shape and statistics, to remove parasitic effects, and to gain spatial resolution information. Combining the high efficiency of a hybrid photon‐counting area detector with the high angular resolution given by analyser crystals is an effective approach to improving the overall performance of high‐resolution powder diffraction.