Ultrafine 5 nm ceria isotropic nanoparticles were prepared using the rapid chemical precipitation approach from cerium(III) nitrate and ammonium hydroxide aqueous solutions. The as-prepared nanoparticles were shown to contain predominantly Ce(IV) species. The solubility of nanocrystalline CeO2 at several pH values was determined using ICP-MS and radioactive tracer methods. Phase composition of the ceria samples remained unchanged upon partial dissolution, while the shape of the particles changed dramatically, yielding nanorods under neutral pH conditions. According to X-ray absorption spectroscopy investigation of the supernatant, Ce(III) was the main cerium species in solution at pH < 4. Based on the results obtained, a reductive dissolution model was used for data interpretation. According to this model, the solubility product for ceria nanoparticles was determined to be log Ksp = −59.3 ± 0.3 in 0.01 M NaClO4. Taken together, our results show that the pH dependence of ceria anti- and pro-oxidant activity can be related to the dissolution of CeO2 in aqueous media.
Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr2+, Fe3+, Nd3+, and Am3+, from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity.
X-ray absorption experiments at Ce L3 and M5 edges and theoretical calculations demonstrate that in addition to the nanoceria charge stability, the formation of hydroxyl groups at the surface affects the chemical performance of nanomaterials.
18 November 2020 in Chemistry – A European Journal
Oh, now I see! The precipitates formed during ThIV hydrolysis are ThO2 nanoparticles, which in their initial stages of formation are a mixture of ultra‐small nanoparticles and Th hexamer clusters. This new structural insight is made possible by the combined use of two synchrotron techniques: HEXS and XANES in HERFD mode, which probe short‐ and medium‐range order in the sample under study. More information can be found in the Full Paper by L. Amidani et al. (DOI: 10.1002/chem.202003360).
We report a full characterization of PuO2nanoparticles at the atomic level and probe their local and electronic structure by a variety of methods available at the synchrotron and theoretical approaches.
29 April 2019 in Physical Chemistry Chemical Physics