Incorporating solvent effects in DFT: insights from cation exchange in faujasites.

Zeolites are versatile materials renowned for their extra-framework cation exchange capabilities, with applications spanning diverse fields, including nuclear waste treatment. While detailed experimental characterization offers valuable insight, density functional theory (DFT) proves particularly adept at investigating ion exchange in zeolites, owing to its atomic and electronic resolution. However, the prevalent occurrence of zeolitic ion exchange in aqueous environments poses a challenge to conventional DFT modeling, traditionally conducted in a vacuum.

Capture Instead of Release: Defect-Modulated Radionuclide Leaching Kinetics in Metal-Organic Frameworks.

Comparison of defect-controlled leaching-kinetics modulation of metal-organic frameworks (MOFs) and porous functionalized silica-based materials was performed on the example of a radionuclide and radionuclide surrogate for the first time, revealing an unprecedented readsorption phenomenon. On a series of zirconium-based MOFs as model systems, we demonstrated the ability to capture and retain >99% of the transuranic Am radionuclide after 1 week of storage. We report the possibility of tailoring radionuclide release kinetics in MOFs through framework defects as a function of postsynthetically installed organic ligands including cation-chelating crown ether-based linkers.

Hafnium Oxide Nanostructured Thin Films: Electrophoretic Deposition Process and DUV Photolithography Patterning.

In the frame of the nanoarchitectonic concept, the objective of this study was to develop simple and easy methods to ensure the preparation of polymorphic HfO2 thin film materials (<200 nm) having the best balance of patterning potential, reproducibility and stability to be used in optical, sensing or electronic fields. The nanostructured HfO2 thin films with micropatterns or continuous morphologies were synthesized by two different methods, i.e.

In-Situ Synthesis and Characterization of Nanocomposites in the Si-Ti-N and Si-Ti-C Systems.

The pyrolysis (1000 °C) of a liquid poly(vinylmethyl--methyl)silazane modified by tetrakis(dimethylamido)titanium in flowing ammonia, nitrogen and argon followed by the annealing (1000-1800 °C) of as-pyrolyzed ceramic powders have been investigated in detail. We first provide a comprehensive mechanistic study of the polymer-to-ceramic conversion based on TG experiments coupled with in-situ mass spectrometry and ex-situ solid-state NMR and FTIR spectroscopies of both the chemically modified polymer and the pyrolysis intermediates. The pyrolysis leads to X-ray amorphous materials with chemical bonding and ceramic yields controlled by the nature of the atmosphere.

Tailored Perovskite Waste Forms for Plutonium Trapping.

Perovskite ceramics have been extensively studied as host matrixes for radionuclide entrapment for nuclear waste disposal. As an expansion of these investigations, cerium, neodymium, and plutonium were incorporated into a perovskite phase, ACuFeTiO (A = Nd, Ce, Pu), using sol-gel methods under oxidizing and reducing atmospheres. The targeted materials contained varying levels of Ce and Nd on the A site, yielding potential compositions of NdCe CuFeTiO ( x = 0, 0.

[AgM(TeO)]SO (M = Ce or Th): A New Purely Inorganic d/f-Heterometallic Cationic Material.

Two new isotypic d/f-heterometallic purely inorganic cationic materials, [AgM(TeO)]SO (M = Ce or Th), were synthesized using the metal oxides (MO and TeO), silver nitrate, and sulfuric acid under mild hydrothermal conditions. The prepared materials were characterized via single-crystal X-ray diffraction, which revealed that the materials possess a 3D framework of corner-sharing TeO units. The tellurite framework creates four unique pores, three of which are occupied by the M and Ag metal centers.

Uncovering the Origin of Divergence in the CsM(CrO) (M = La, Pr, Nd, Sm, Eu; Am) Family through Examination of the Chemical Bonding in a Molecular Cluster and by Band Structure Analysis.

A series of f-block chromates, CsM(CrO) (M = La, Pr, Nd, Sm, Eu; Am), were prepared revealing notable differences between the Am derivatives and their lanthanide analogs. While all compounds form similar layered structures, the americium compound exhibits polymorphism and adopts both a structure isomorphous with the early lanthanides as well as one that possesses lower symmetry. Both polymorphs are dark red and possess band gaps that are smaller than the Ln compounds.

Nanocomposites through the Chemistry of Single-Source Precursors: Understanding the Role of Chemistry behind the Design of Monolith-Type Nanostructured Titanium Nitride/Silicon Nitride.

Monolith-type titanium nitride/silicon nitride nanocomposites, denoted as TiN/Si N , have been prepared by a reaction of polysilazanes with a titanium amide precursor, warm pressing of the resultant polytitanosilazanes, and subsequent pyrolysis of the green bodies at 1400 °C. Initially, a series of polytitanosilazanes was synthesized and the role of the chemistry behind their synthesis was studied in detail by using solid-state NMR spectroscopy, elemental analysis, and molecular-weight measurements. The intimate relationship between the chemistry and the processability of these precursors is discussed.

In situ controlled growth of titanium nitride in amorphous silicon nitride: a general route toward bulk nitride nanocomposites with very high hardness.

Bulk nanocomposites possessing very high hardness in which TiN nanocrystallites are homogeneously embedded in an amorphous Si3N4 matrix are produced from perhydropolysilazane and tetrakisdimethylaminotitanium. That is, a low-molecular-weight TiN molecule is mixed in controlled molar ratio with a polymeric Si3N4 precursor; further processing, including ammonolysis, warm pressing, and controlled nanocrystal growth, yields nanocomposites with the desired properties.