Effect of potassium for cesium replacement in atomic level structure of potassium cobalt hexacyanoferrate(II)

Potassium cobalt hexacyanoferrate(II) [K2CoFe(CN)(6)] is an extremely selective ion exchanger for cesium ions. To examine the atomic level background for the selectivity a computational structural study using DFT modelling was carried out for K2CoFe(CN)(6) and for products where Cs has replaced K in the elemental cube cages closest to the surface. In the K-form compound the potassium ions are not in the center of the Co-Fe-CN elementary cube cages closest to the surface but locate about 140 pm from the cube center towards the surface. When cesium ions are exchanged to these potassium ions they locate much deeper from the surface, being only about 70 pm upwards from the cube center. 'Ibis apparently leads to much stronger bonding of cesium compared to potassium. Once taken up into the outermost cube cages on the surface of the crystallites cesium ions are not able to penetrate further since they are much larger than the electron window between the cubes. Furthermore, they are not able to return to the solution phase either leading to a practically irreversible sorption.Peer reviewe

Effect of layer charge on the crystalline swelling of Na+, K+ and Ca2+ montmorillonites : DFT and molecular dynamics studies

The swelling and cation exchange properties of montmorillonite are fundamental in a wide range of applications ranging from nanocomposites to catalytic cracking of hydrocarbons. The swelling results from several factors and, though widely studied, information on the effects of a single factor at a time is lacking. In this study, density functional theory (DFT) calculations were used to obtain atomic-level information on the swelling of montmorillonite. Molecular dynamics (MD) was used to investigate the swelling properties of montmorillonites with different layer charges and interlayer cationic compositions. Molecular dynamics calculations, with CLAYFF force field, consider three layer charges (-1.0, -0.66 and -0.5 e per unit cell) arising from octahedral substitutions and interlayer counterions of Na, K and Ca. The swelling curves obtained showed that smaller layer charge results in greater swelling but the type of the interlayer cation also has an effect. The DFT calculations were also seen to predict larger d values than MD. The formation of 1, 2 and 3 water molecular layers in the interlayer spaces was observed. Finally, the data from MD calculations were used to predict the self-diffusion coefficients of interlayer water and cations in different montmorillonites and in general the coefficient increased with increasing water content and with decreasing layer charge.Peer reviewe

Radium sorption on biotite; surface complexation modeling study

The sorption of Ra on Olkiluoto biotite in the context of deep geological disposal of spent nuclear fuel was studied with isotherm batch sorption experiments. Ba was used as an analog for Ra in the experiments and modeling studies. A wide concentration range of Ra/Ba was used in the isotherm studies (2.6 x 10(-9) M to 1 x 10(-3) M) in addition to four different Olkiluoto reference groundwaters with salinity types ranging from fresh to saline. Experimental results show that both in the fresh and saline reference groundwaters, the distribution coefficients of Ra tend to decrease in the higher isotherm concentrations of Ba. With one reference groundwater, the distribution coefficients increased with the concentration of Ba due to significant coprecipitation of Ra. With the fresh reference groundwaters, the distribution coefficients of Ra were consistently approximately one order of magnitude lower than in the saline reference groundwater. A PHREEQC multi-site complexation model coupled with an optimization tool in Python was used to interpret the experimental Ra sorption results. Molecular modeling with CASTEP code implemented into Materials Studio was used to update the PHREEQC model with more realistic biotite sorption site density data. It was observed that while the multi-site model predicts the sorption of Ra well in lower isotherm concentrations, auxiliary reactions of Ra disrupt the model in high Ba isotherm concentrations. The experimental and modeled distribution coefficient data of Ra on biotite can be used in the safety case calculations of the deep geological disposal of spent nuclear fuel in Finland and Sweden.Peer reviewe

Multi-site surface complexation modelling of Se(IV) sorption on biotite

A surface complexation model of Se(IV) sorption on biotite with one type of strong sorption sites and two types of weak sorption sites were developed based on experimental data obtained from titration, sorption edge and sorption isotherm experiments. Titration data was collected using a batch-wise manner together with back-titration to calibrate the effect of mineral dissolution in 0.01 M KClO4 background electrolytes from pH 3 to 11 in an inert atmosphere glovebox. Further calibrations of the titration curve include proton exchange and cation exchange in which the calculations of cation occupancies on biotite surfaces were taken into account. The sorption edge measurements were determined by measuring the sorption of 10(-9) M total Se with a radioactive Se-75 tracer on converted biotite in 0.01 M KClO4 solution from pH 3 to 11. Se sorption was observed to be strongly dependent on pH. Surface complexation modelling was performed by deriving a set of optimized parameters that can fit titration, sorption edge and sorption isotherm (at pH similar to 7.7) experimental data. A CASTEP code implemented into Materials Studio was used to calculate the site densities and site types on the biotite surfaces. Weak sorption sites with site densities of 3.2 sites/nm(2) and 1.4 sites/nm(2) were derived from the codes and used in the sorption model. A computer code that coupled PHREEQC with Python was developed for the fitting and optimizing processes. The model was validated by sorption data at pH similar to 9.5. The results show that the model can provide quantitative predicts of Se(IV) sorption in groundwater conditions of a deep geological repository and help improve the performance assessments by giving more convincing estimates of the release of radionuclides towards aquifers and biosphere.Peer reviewe

The sorption and diffusion of 133Ba in crushed and intact granitic rocks from the Olkiluoto and Grimsel in-situ test sites

Peer reviewe

Molecular Layer Deposition Using Ring-Opening Reactions : Molecular Modeling of the Film Growth and the Effects of Hydrogen Peroxide

Published under an ACS AuthorChoice licenseNovel coating materials are constantly needed for current and future applications in the area of microelectronics, biocompatible materials, and energy-related devices. Molecular layer deposition (MLD) is answering this cry and is an increasingly important coating method for organic and hybrid organic-inorganic thin films. In this study, we have focused on hybrid inorganic-organic coatings, based on trimethylaluminum, monofunctional aromatic precursors, and ring-opening reactions with ozone. We present the MLD processes, where the films are produced with trimethylaluminum, one of the three aromatic precursors (phenol, 3-(trifluoromethyl) phenol, and 2-fluoro-4-(trifluoromethyl)benzaldehyde), ozone, and the fourth precursor, hydrogen peroxide. According to the in situ Fourier-transform infrared spectroscopy measurements, the hydrogen peroxide reacts with the surface carboxylic acid group, forming a peroxyacid structure (C(O)-O-OH), in the case of all three processes. In addition, molecular modeling for the processes with three different aromatic precursors was carried out. When combining these modeling results with the experimental research data, new interesting aspects of the film growth, reactions, and properties are exploited.Peer reviewe

Sorption of Se species on mineral surfaces, part I : Batch sorption and multi-site modelling

The sorption behavior of Se(IV) on Grimsel granodiorite and its main minerals, plagioclase, K-feldspar, quartz and biotite, were investigated in Grimsel groundwater simulant in a large Se concentration range (from 1.66 x 10(-10) M to 1 x 10(-3) M). Experimental results show that the distribution coefficients (K-d values) of Se (IV) on the rock and mineral samples increased with the decreasing of Se(IV) concentration. The sorption of Se (IV) on biotite has the largest K-d value in low concentration area (<10(-7) M) stabilizing between 0.0595 +/- 0.0097 m(3)/Kg and 0.0713 +/- 0.0164 m(3)/Kg. The Kd value of Se(IV) on K-feldspar was the second largest (0.0154 +/- 0.0019 m(3)/Kg in 10(-9) M) while the sorption on quartz was negligible. The sorption behavior of Se(IV) on Grimsel granodiorite followed the same trend as plagioclase, the most abundant mineral in Grimsel granodiorite, with K-d values of 0.0078 +/- 0.0010 m(3)/Kg for Grimsel granodiorite and 0.0085 +/- 0.0016 m(3)/Kg for plagioclase, when Se(IV) concentration was 10(-9) M. HPLC-ICP-MS results show that all the Se(IV) remained in + IV oxidation state after more than 1 month experimental time and speciation modelling proved that the main species in Grimsel groundwater simulant were HSeO3- and SeO32-. Multi-site surface complexation modelling was performed by PHREEQC with the help of molecular modelling techniques which was performed with the CASTEP code implemented into Materials Studio. The modelling results predict that there are three kinds of sorption sites on the surface of biotite mineral, with sorption site densities differing in three magnitudes.Peer reviewe