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. This study seeks to enhance zeolite modeling by systematically evaluating predictive differences across varying degrees of aqueous solvent inclusion. Specifically focusing on monovalent cation exchange in Na-X zeolites, we explore diverse modeling approaches. These range from simple dehydrated systems (representing bare reference states in vacuum) to more sophisticated models that incorporate aqueous solvent effects through explicit water molecules and/or a dielectric medium. Through comparative analysis of DFT and semi-empirical DFT approaches, along with their validation against experimental results, our findings underscore the necessity to concurrently consider explicit and implicit solvent effects for accurate prediction of zeolitic ionic exchange.

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 241Am 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. Based on comprehensive analysis using spectroscopy (EXAFS, UV-vis, FTIR, and NMR), X-ray crystallography (single crystal and powder), and theoretical calculations (nine kinetics models and structure simulations), we demonstrated the synergy of radionuclide integration methods, topological restrictions, postsynthetic scaffold modification, and defect engineering. This combination is inaccessible in any other material and highlights the advantages of using well-defined frameworks for gaining fundamental knowledge necessary for the advancement of actinide-based material development, providing a pathway for addressing upcoming challenges in the nuclear waste administration sector.

Effects of Impregnated Amidophosphonate Ligand Concentration on the Uranium Extraction Behavior of Mesoporous Silica.

A series of solid-phase uranium extractants were prepared by post-synthesis impregnation of a mesoporous silica support previously functionalized with octyl chains by direct silanization. Five materials were synthesized with 0, 0.2, 0.3, 0.4 and 0.5 mmol of the amidophosphonate ligand DEHCEBP per gram of functionalized solid, and the effect of the ligand concentration on the uranium extraction efficiency and selectivity of the materials was investigated. Nitrogen adsorption-desorption data show that with increasing ligand loadings, the specific surface area and average pore volume decrease as the amidophosphonate ligand fills first the micropores and then the mesopores of the support. Acidic uranium solutions with a high sulfate content were used to replicate the conditions in ore treatment leaching solutions. Considering the extraction kinetics, the equilibration time was found to increase with the ligand concentration, which can be explained by the clogging of micropores and the multilayer arrangement of the DEHCEBP molecules in the materials with their highest ligand contents. The fact that the equilibrium ligand/uranium ratio is about 2 mol/mol regardless of the ligand concentration in the material suggests that all the ligand molecules remain accessible for extraction. The maximum uranium extraction capacities ranged from 30 mg∙g-1 at 0.2 mmol∙g-1 DEHCEBP to 54 mg∙g-1 in the material with 0.5 mmol∙g-1 DEHCEBP. These materials could therefore potentially be used as solid-phase uranium extractants in acidic solutions with high sulfate concentrations.

Clarifying the in-situ cytotoxic potential of electronic waste plastics.

Plastics in waste electronics (E-plastics) account for approximately 20% of the entire global electronic waste (E-waste) stream. Most of the E-plastics are not recycled as the presence of toxic additives (e.g. heavy metals, brominated flame retardants (BFRs), antimony, etc.) have associated environmental and health concerns. However, the majority of the studies are focused on quantitative assessment of the toxic constituents in E-plastics, while empirical information regarding the potential toxic effects in humans is largely lacking. To gain a deeper appreciation into the toxicological profile of E-plastics, in situ time-dependent exposures of 6 different human cell lines to a panel of 8 representative E-plastics recovered from liquid crystal displays (LCD), keyboards, screen frames, and wire insulators were conducted. Although several hazardous elements (e.g. Pb, As, Sb, Zn, Cu, etc) were detected at concentrations that far exceed the limit values permitted by the Restriction of Hazardous Substances Directive and EU Directives in the panel E-plastics, in-depth analysis of the 144 unique cell viability data points and live-dead staining experiments suggest that the acute and sub-chronic toxic effects of E-plastics in direct contact with human cells are negligible. These observations agreed with the inductively coupled plasma-optical emission spectrometry data, which revealed that leaching of these toxic additives into the biological milieu is not sufficiently high to trigger a cytotoxic response up to a continuous culture period of 2 weeks. The novel insights gained from this study are posited to further clarify the uncertainty associated with the safety and circular economy implementation of E-plastics.

On-line spectroscopic study of brominated flame retardant extraction in supercritical CO2.

Removal of brominated flame retardants (BFRs) from polymers before disposal or recycling will alleviate negative environmental effects and ensure safe usage of recycled products. Extraction of BFRs in supercritical CO2 is appealing but also presents challenges to industries due to limited solubility and lack of kinetic studies. For a more comprehensive evaluation of supercritical extraction potentialities, we (i) developed an on-line pressure apparatus that is compatible with both the FTIR and UV-vis spectrometers to enable kinetic and thermodynamic studies; (ii) studied kinetic extraction involving three conventional and two novel BFRs as well as three typical polymeric matrix. Solubilities were determined using the gravimetric method or X-ray fluorescence. FTIR exhibited a superior applicability compared to UV-vis in the following BFR extraction's time-dependency binary and ternary systems. We observed that faster stirring speed, higher temperature, and finer particle size can accelerate the overall extraction kinetics. In binary systems, it took less than 2 h to achieve equilibrium for each BFR at 60 °C, 25 MPa and 1000 rpm. In the presence of polymeric matrix, slower extraction kinetics were observed due to the occurrence of competitive dissolution and molecular diffusion within the matrix. Mathematical models derived from irreversible desorption and Fick's diffusion laws fitted well with the observed extraction kinetics of BFRs, thus enabling us to identify the rate-determining step. The high solubilization rate coefficients that we measured for BFRs revealed that the dynamic extraction process in up-scaling design could compensate for the low solubility with flowing supercritical CO2.

Crystal structure of dicaesium strontium hexa-cyanidoferrate(II), Cs2Sr[Fe(CN)6], from laboratory X-ray powder data.

Ferrocyanides with general formula A I xB II y [Fe(CN)6], where A and B are cations, are thought to accept many substitutions on the A and B positions. In this communication, the synthesis and crystal structure of Cs2Sr[Fe(CN)6] are reported. The latter was obtained from K2Ba[Fe(CN)6] particles, put in contact with caesium and strontium ions. Hence, a simultaneous ion-exchange mechanism (Cs for K, Sr for Ba) occurs to yield Cs2Sr[Fe(CN)6]. The synthesis protocol shows that K2BaFe(CN)6 particles can be used for the simultaneous trapping of radioactive caesium and strontium nuclides in water streams. Cs2Sr[Fe(CN)6] adopts the cryolite structure type and is isotypic with the known compound Cs2Na[Mn(CN)6] [dicaesium sodium hexa-cyanidomanganate(III)]. The octa-hedrally coordinated Sr and Fe sites both are located on inversion centres, and the eightfold-coordinated Cs site on a general position.

High Internal Phase Emulsions Stabilized by a Zeolite-Surfactant Combination in a Composition-Dependent Manner.

As a step toward synthesizing zeolite-based porous materials, this study demonstrates for the first time the feasibility of stabilizing oil-in-water (O/W) high internal phase emulsions (HIPEs) using a cationic surfactant (tetradecyltrimethylammonium bromide, TTAB) and "homemade" submicronic Linde type A zeolite particles. The zeolite particles are hydrophilic and therefore do not attach to dodecane-water interfaces, but surface tension measurements and electrochemical data show that their surface can be activated by the electrostatic and subsequent hydrophobic adsorption of TTAB. Comparing the adsorption isotherm of TTAB and zeta potential of the particles with the droplet sizes and rheological properties of the emulsion shows that the stabilization mechanism depends on the TTAB/zeolite weight ratio. At low TTAB/zeolite weight ratios (≤0.2 wt %), gel-like O/W Pickering HIPEs form, but at intermediate TTAB concentrations, the zeolite particles become more hydrophobic, leading to phase inversion and the stabilization of W/O emulsions. At high TTAB/zeolite weight ratios (>1.25 wt %), a second phase inversion occurs and creamy O/W HIPEs form through a different stabilization mechanism. In this case indeed, the zeolite particles are fully covered by a bilayer of TTAB and remain dispersed in the aqueous phase with no adsorption to the dodecane-water interface. The emulsion is stabilized by electrostatic repulsion between the highly positively charged zeolite particles and the cationic surfactant adsorbed at the dodecane-water interface.

Hybrid colloidal suspensions tailored as gels to remove radioactive bitumen stains.

Vacuumable gels have been developed in the nuclear industry to decontaminate solid surfaces with little or no mechanical operations and without producing any liquid effluents. These gels can be spread on the contaminated surface and rapidly trap the radio-contaminants by sorption after corroding the substrate down to several tens of microns if necessary. The gel then dries and eventually fractures into a non-powdery solid that is easily removable by brushing or vacuum cleaning. This process was initially developed for the nuclear decontamination of metallic surfaces but innovative formulations are being developed for wide range of applications. This paper introduces two such formulations designed to remove sticky organic layers, bitumen in this study. We show that adding an organic bio-solvent, limonene, allows bitumen layers to be dissolved, absorbed in the liquid state into the gel matrix, and then removed from the substrate as solid waste after drying. Substituting an organic co-solvent (ethanol) for some of the limonene improves the overall efficiency of the process by decreasing the drying time of the gel and limiting the diffusion of the dissolved bitumen without affecting the dissolving power of the gel. Finally, the performance of these gels is demonstrated for the removal of nuclear contaminated (137Cs) bitumen stains.

Remediation of 137Cs-contaminated concrete rubble by supercritical CO2 extraction.

The removal of cesium contamination is a critical issue for the recycling of concrete rubble in most decommissioning operations. The high solvent strength and diffusivity of supercritical CO2 make it an attractive choice as vector for extractant system in this context. Experimental extraction runs have been carried out in a radioactive environment on rubble contaminated with 137Cs. The best extraction system was found to be CalixOctyl (25,27-Bis(1-octyloxy)calix[4]arene-crown-6, 1,3-alternate) with pentadecafluorooctanoic acid as a modifier. The effects of various operating parameters were investigated, namely the coarseness of rubble, the temperature of supercritical CO2, the residual water and initial cesium concentrations, and the amounts of extractant and modifier used. The yields from direct extraction were low (<30%), because of the virtually irreversible sorption of Cs in concrete. The best extraction yield of ∼55% was achieved by leaching concrete rubble with nitric acid prior to supercritical CO2 extraction.

Sorption pH dependance of strontium/calcium by sodium nonatitanate.

Sodium nonatitanate powder is a layered material containing some potential exchangeable sodium ions between layers. In this work, sorption mechanism of this material has been studied and modeled at the solid-liquid interface. In particular, the ion-exchange mechanism is up to now not entirely known and especially the role of the pH on sorption properties. To investigate this latter, the solid is first equilibrated with inert acidic and base (nitric acid and triethylamine) for which the co-ions nitrate and triethylammonium do not penetrate the solid. The exchange between proton or divalent ions (strontium or calcium), and the sodium initially located in the sodium nonatitanate, is characterized through capillary ionic chromatography and conductivity experiments. To understand and explain the sorption properties, we modeled the equilibrium constant of different exchange reactions as a function of the solution pH. The equilibrium constants of the strontium/sodium and the calcium/sodium exchange have been obtained. We have shown the important role of the pH on the sorption rate of the strontium and moreover the hydrolysis rate of the sodium nonatitanate is calculated. We found that one eighth of sodium is spontaneously hydrolysed in aqueous phase whereas seven-eighths are exchanged by different divalent cations (strontium or calcium). Strontium and calcium exhibit similar exchange curves and competition with the proton adsorbed is modeled with global equilibrium constant. The prediction is in agreement with the conductivity experiments and the global extraction isotherms.

Molecular iodine adsorption within Hofmann-type structures M(L)[M'(CN)4] (M = Ni, Co; M' = Ni, Pd, Pt): impact of their composition.

A series of thermally stable Hofmann-type clathrate structures with the general formula M(pz)[M'(CN)4], where M and M' are bivalent metal ions M(II) = Ni(II), Co(II), M(II)' = Ni(II), Pd(II), Pt(II), and pz is the pyrazine bidentate ligand, was synthesized and investigated for the efficient entrapment of iodine (I2) in solution and in the gas phase. Iodine-containing clathrates thus prepared were analysed to determine the saturation capacity, thermal stability, guest-induced structural changes of the clathrate's lattice and the nature of the confined iodine according to the chemical composition of the host structure. An efficient confinement of about 1 I2 per unit cell is observed for the series of clathrates with the Ni(II) and Pd(II) ions in the square planar position whatever the bivalent metal ion in the octahedral position. Specific responses in the lattice adjustment are detected for Co(II) in the octahedral and Pd(II) in the square planar positions.

Strontium selectivity in sodium nonatitanate Na 4Ti9O20·xH2O.

We study the extraction of strontium by sodium nonatitanate powder from nitrate strontium and acetate sodium mixture. Experiments show that adsorption is quantitative. The excess Gibbs free energy has been modeled by various models (ideal, 2D Coulomb, regular solution model) for the solid phase. We find that the free energy of the solid phase is controlled by short-range interactions rather than long-ranged Coulombic forces. The selectivity is the consequence of a competition between the liquid and solid phases: both phases prefer strontium rather than sodium but the solid contribution is predominant.

Iodine capture by Hofmann-Type clathrate Ni(II)(pz)[Ni(II)(CN)4].

The thermally stable Hofmann-type clathrate framework Ni(II)(pz)[Ni(II)(CN)4] (pz = pyrazine) was investigated for the efficient and reversible sorption of iodine (I2) in the gaseous phase and in solution with a maximum adsorption capacity of 1 mol of I2 per 1 mol of Ni(II)(pz)[Ni(II)(CN)4] in solution.

Surface Diels-Alder reactions as an effective method to synthesize functional carbon materials.

The post-synthesis chemical modification of various porous carbon materials with unsaturated organic compounds is reported. By this method, amine, alcohol, carboxylate, and sulfonic acid functional groups can be easily incorporated into the materials. Different carbonaceous materials with surface areas ranging from 240 to 1500 m(2)g(-1) and pore sizes between 3.0 and 7.0 nm have been studied. The resulting materials were analyzed by elemental analysis, nitrogen sorption, FTIR spectroscopy, zeta-potential measurements, thermogravimetric analysis, photoelectron spectroscopy, and small-angle X-ray scattering. These analyses indicated that the degree of functionalization is dependent on the nature of the dienophile (reactivity, steric hindrance) and the porosity of the carbon material. As possible applications, the functionalized carbonaceous materials were studied as catalysts in the Knoevenagel reaction and as adsorbents for Pb(2+) from aqueous solution.