Thermochemistry of 3D and 2D Rare Earth Oxychlorides (REOCls).

The thermodynamic stability of rare earth (RE) materials plays a key role in the design of separation and recycling processes for RE elements. Thermodynamic stability is fundamentally influenced by the lanthanide contraction, as observed in the systematic reduction of unit cell volumes with increasing atomic number. RE materials are found in the form of solids having primary bonds in three dimensions (3D materials) as well as ones with primary bonds in two dimensions (2D materials) whose layers are held together by weak van der Waals (vdW) forces. While studies of synthesis, structure, and physical properties of 2D RE materials are numerous, no systematic research has compared their thermodynamic stability to that of 3D materials. In the present work, RE oxychlorides (REOCls), which display a structural transition from a 3D-polyhedral network (PbFCl-type) to a vdW-bonded layered one (SmSI-type) as the RE size decreases, were all synthesized by the flux method. High-temperature oxide melt solution calorimetry was used to determine their formation enthalpies to enable Born-Haber cycles to calculate lattice energies. Our results indicate that REOCl compounds are thermodynamically stable when compared to their binary oxides and chlorides. The lattice energies of 3D REOCls increase with decreasing RE size yet are insensitive to unit cell volumes for 2D REOCls. This is caused by interatomic interactions parallel and perpendicular to layers in the SmSI-type REOCls, causing a different structure response to the lanthanide contraction than 3D RE materials.

Good Reporting Practice for Thermophysical and Thermochemical Property Measurements (IUPAC Technical Report).

Scientific projects frequently involve measurements of thermophysical, thermochemical, and other related properties of chemical compounds and materials. These measured property data have significant potential value for the scientific community, but incomplete and inaccurate reporting often hampers their utilization. The present IUPAC Technical Report summarizes the needs of chemical engineers and researchers as consumers of these data and shows how publishing practices can improve information transfer. In the Report, general principles of Good Reporting Practice are developed together with examples illustrating typical cases of reporting issues. Adoption of these principles will improve the quality, reproducibility, and usefulness of experimental data, bring a better level of consistency to results, and increase the efficiency and impact of research. Closely related to Good Reporting Practice, basic elements of Good Research Practice are also introduced with a goal to reduce the number of ambiguities and unresolved problems within the thermophysical property data domain.

Bioadsorption of Rare Earth Elements through Cell Surface Display of Lanthanide Binding Tags.

With the increasing demand for rare earth elements (REEs) in many emerging clean energy technologies, there is an urgent need for the development of new approaches for efficient REE extraction and recovery. As a step toward this goal, we genetically engineered the aerobic bacterium Caulobacter crescentus for REE adsorption through high-density cell surface display of lanthanide binding tags (LBTs) on its S-layer. The LBT-displayed strains exhibited enhanced adsorption of REEs compared to cells lacking LBT, high specificity for REEs, and an adsorption preference for REEs with small atomic radii. Adsorbed Tb(3+) could be effectively recovered using citrate, consistent with thermodynamic speciation calculations that predicted strong complexation of Tb(3+) by citrate. No reduction in Tb(3+) adsorption capacity was observed following citrate elution, enabling consecutive adsorption/desorption cycles. The LBT-displayed strain was effective for extracting REEs from the acid leachate of core samples collected at a prospective rare earth mine. Our collective results demonstrate a rapid, efficient, and reversible process for REE adsorption with potential industrial application for REE enrichment and separation.

Effects of Simulated Rare Earth Recycling Wastewaters on Biological Nitrification.

Increasing rare earth element (REE) supplies by recycling and expanded ore processing will result in generation of new wastewaters. In some cases, disposal to a sewage treatment plant may be favored, but plant performance must be maintained. To assess the potential effects of such wastewaters on biological treatment, model nitrifying organisms Nitrosomonas europaea and Nitrobacter winogradskyi were exposed to simulated wastewaters containing varying levels of yttrium or europium (10, 50, and 100 ppm), and the extractant tributyl phosphate (TBP, at 0.1 g/L). Y and Eu additions at 50 and 100 ppm inhibited N. europaea, even when virtually all of the REE was insoluble. Provision of TBP with Eu increased N. europaea inhibition, although TBP alone did not substantially alter activity. For N. winogradskyi cultures, Eu or Y additions at all tested levels induced significant inhibition, and nitrification shut down completely with TBP addition. REE solubility was calculated using the previously developed MSE (Mixed-Solvent Electrolyte) thermodynamic model. The model calculations reveal a strong pH dependence of solubility, typically controlled by the precipitation of REE hydroxides but also likely affected by the formation of unknown phosphate phases, which determined aqueous concentrations experienced by the microorganisms.

Insights into the interplay of Lewis and Brønsted acid catalysts in glucose and fructose conversion to 5-(hydroxymethyl)furfural and levulinic acid in aqueous media.

5-(Hydroxymethyl)furfural (HMF) and levulinic acid production from glucose in a cascade of reactions using a Lewis acid (CrCl3) catalyst together with a Brønsted acid (HCl) catalyst in aqueous media is investigated. It is shown that CrCl3 is an active Lewis acid catalyst in glucose isomerization to fructose, and the combined Lewis and Brønsted acid catalysts perform the isomerization and dehydration/rehydration reactions. A CrCl3 speciation model in conjunction with kinetics results indicates that the hydrolyzed Cr(III) complex [Cr(H2O)5OH](2+) is the most active Cr species in glucose isomerization and probably acts as a Lewis acid-Brønsted base bifunctional site. Extended X-ray absorption fine structure spectroscopy and Car-Parrinello molecular dynamics simulations indicate a strong interaction between the Cr cation and the glucose molecule whereby some water molecules are displaced from the first coordination sphere of Cr by the glucose to enable ring-opening and isomerization of glucose. Additionally, complex interactions between the two catalysts are revealed: Brønsted acidity retards aldose-to-ketose isomerization by decreasing the equilibrium concentration of [Cr(H2O)5OH](2+). In contrast, Lewis acidity increases the overall rate of consumption of fructose and HMF compared to Brønsted acid catalysis by promoting side reactions. Even in the absence of HCl, hydrolysis of Cr(III) decreases the solution pH, and this intrinsic Brønsted acidity drives the dehydration and rehydration reactions. Yields of 46% levulinic acid in a single phase and 59% HMF in a biphasic system have been achieved at moderate temperatures by combining CrCl3 and HCl.