Ce-exchange capacity of zeolite L in different cationic forms: a structural investigation

Cerium exchange by microporous materials, such as zeolites, has important applications in different fields, for example, rare earth element recovery from waste or catalytic processes. This work investigated the Ce-exchange capacity of zeolite L in three different cationic forms (the as-synthesized K form and Naand NH4-exchanged ones) from a highly concentrated solution. Chemical analyses and structural investigations allowed determination of the mechanisms involved in the exchanges and give new insights into the interactions occurring between the cations and the zeolite framework. Different cation sites are involved: (i) K present in the original LTL in the cancrinite cage (site KB) cannot be exchanged; (ii) the cations in KD (in the 12-membered ring channel) are always exchanged; while (iii) site KC (in the eight-membered ring channel) is involved only when K+ is substituted by NH4+, thus promoting a higher exchange rate for NH4+ -> K+ than for Na+ -> K+. In the Ce-exchanged samples, a new site occupied by Ce appears in the centre of the main channel, accompanied by an increase in the number of and a rearrangement of H2O molecules. In terms of Ce exchange, the three cationic forms behave similarly, from both the chemical and structural point of view (exchanged Ce ranges from 38 to 42% of the pristine cation amount). Beyond the intrinsic structural properties of the zeolite L framework, the Ce exchange seems thus also governed by the water coordination sphere of the cation. Complete Ce recovery from zeolite pores was achieved

Breathing Metal–Organic Framework Based on Flexible Inorganic Building Units

Five novel bismuth carboxylate coordination polymers were synthesized from biphenyl-3,4\u2032,5-tricarboxylic acid (H3BPT) and [1,1\u2032:4\u2032,1\u2032\u2032]terphenyl-3,3\u2032\u2032,5,5\u2032\u2032-tetracarboxylic acid (H4TPTC). One of the phases, [Bi(BPT)]\ub72MeOH (denoted SU-100, as synthesized), is the first example, to the best of our knowledge, of a reversibly flexible bismuth-based metal\u2013organic framework. The material exhibits continuous changes to its unit cell parameters and pore shape depending on the solvent it is immersed in and the dryness of the sample. Typically, in breathing carboxylate-based MOFs, flexibility occurs through tilting of the organic linkers without significantly altering the coordination environment around the cation. In contrast to this, the continuous breathing mechanism in SU-100 involves significant changes to bond angles within the Bi2O12 inorganic building unit (IBU). The flexibility of the IBU of SU-100 reflects the nondiscrete coordination geometry of the bismuth cation. A disproportionate increase in the solvent accessible void volume was observed when compared to the expansion of the unit cell volume of SU-100. Additionally, activated SU-100 (SU-100-HT) exhibits a large increase in unit cell volume, yet has the smallest void volume of all the studied samples

The “Historical Materials BAG”: A New Facilitated Access to Synchrotron X-ray Diffraction Analyses for Cultural Heritage Materials at the European Synchrotron Radiation Facility

The European Synchrotron Radiation Facility (ESRF) has recently commissioned the new Extremely Brilliant Source (EBS). The gain in brightness as well as the continuous development of beamline instruments boosts the beamline performances, in particular in terms of accelerated data acquisition. This has motivated the development of new access modes as an alternative to standard proposals for access to beamtime, in particular via the “block allocation group” (BAG) mode. Here, we present the recently implemented “historical materials BAG”: a community proposal giving to 10 European institutes the opportunity for guaranteed beamtime at two X-ray powder diffraction (XRPD) beamlines—ID13, for 2D high lateral resolution XRPD mapping, and ID22 for high angular resolution XRPD bulk analyses—with a particular focus on applications to cultural heritage. The capabilities offered by these instruments, the specific hardware and software developments to facilitate and speed-up data acquisition and data processing are detailed, and the first results from this new access are illustrated with recent applications to pigments, paintings, ceramics and wood

Robust estimation of bacterial cell count from optical density

Optical density (OD) is widely used to estimate the density of cells in liquid culture, but cannot be compared between instruments without a standardized calibration protocol and is challenging to relate to actual cell count. We address this with an interlaboratory study comparing three simple, low-cost, and highly accessible OD calibration protocols across 244 laboratories, applied to eight strains of constitutive GFP-expressing E. coli. Based on our results, we recommend calibrating OD to estimated cell count using serial dilution of silica microspheres, which produces highly precise calibration (95.5% of residuals <1.2-fold), is easily assessed for quality control, also assesses instrument effective linear range, and can be combined with fluorescence calibration to obtain units of Molecules of Equivalent Fluorescein (MEFL) per cell, allowing direct comparison and data fusion with flow cytometry measurements: in our study, fluorescence per cell measurements showed only a 1.07-fold mean difference between plate reader and flow cytometry data

Complementary use of monochromatic and white-beam X-ray micro-diffraction for the investigation of ancient materials

Archaeological artefacts are often heterogeneous materials where several phases coexist in a wide grain size distribution. Most of the time, retrieving structure information at the micrometre scale is of great importance for these materials. Particularly, the organization of different phases at the micrometre scale is closely related to optical or mechanical properties, manufacturing processes, functionalities in ancient times and long-term conservation. Between classic X-ray powder diffraction with a millimetre beam and transmission electron microscopy, a gap exists and structure and phase information at the micrometre scale are missing. Using a micrometre-size synchrotron X-ray beam, a hybrid approach combining both monochromatic powder micro-diffraction and Laue single-crystal micro-diffraction was deployed to obtain information from nanometre-and micrometre-size phases, respectively. Therefore providing a way to bridge the aforementioned gap, this unique methodology was applied to three different types of ancient materials that all show a strong heterogeneity. In Roman terra sigillata, the specific distribution of nanocrystalline hematite is mainly responsible for the deep-red tone of the slip, while the distribution of micrometre-size quartz in ceramic bodies reflects the change of manufacturing process between pre-sigillata and high-quality sigillata periods. In the second example, we investigated the modifications occurring in Neolithic and geological flints after a heating process. By separating the diffracted signal coming from the nano-and the micrometre scale, we observed a domain size increase for nanocrystalline quartz in geological flints and a relaxation of the residual strain in larger detritic quartz. Finally, through the study of a Roman iron nail, we showed that the carburation process to strengthen the steel was mainly a surface process that formed 10-20μm size domains of single-crystal ferrite and nanocrystalline cementite

Quantitative microstructural imaging by scanning Laue x-ray micro- and nanodiffraction

Local crystal structure, crystal orientation, and crystal deformation can all be probed by Laue diffraction using a submicron x-ray beam. This technique, employed at a synchrotron facility, is particularly suitable for fast mapping the mechanical and microstructural properties of inhomogeneous multiphase polycrystalline samples, as well as imperfect epitaxial films or crystals. As synchrotron Laue x-ray microdiffraction enters its 20th year of existence and new synchrotron nanoprobe facilities are being built and commissioned around the world, we take the opportunity to overview current capabilities as well as the latest technical developments. Fast data collection provided by state-of-the-art area detectors and fully automated pattern indexing algorithms optimized for speed make it possible to map large portions of a sample with fine step size and obtain quantitative images of its microstructure in near real time. We extrapolate how the technique is anticipated to evolve in the near future and its potential emerging applications at a free-electron laser facility