Molecular dynamics study of aqueous uranyl in hydrophilic mesoporous confinement: the case of slit-like pore in amorphous silica

Patsahan,; Holovko, M.

doi:10.5488/cmp.10.2.143

Cited by 11 publications

(16 citation statements)

References 13 publications

(20 reference statements)

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“…Interactions of uranyl with water and mineral surfaces have consequently been the object of numerous investigations. [2][3][4][5][6][7][8][9][10][11][12] Quartz is of major interest due to the abundance of silicate minerals in the environment. Interactions in mildly acidic to circumneutral and oxidizing conditions are of particular relevance in these systems given the ability of deprotonated silanols (oxo groups) to bind with the equatorial shell of uranyl species.…”

Section: Introductionmentioning

confidence: 99%

Crystallographic controls on uranyl binding at the quartz/water interface

Boily

Rosso

2011

Phys. Chem. Chem. Phys.

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Molecular dynamics methods were used to simulate UO(2)(OH)(2)(0) binding to pairs of oxo sites (O(S)) on three low-index planes of α-SiO(2) in contact with water. Differences in binding site distributions on the (001), (010) and (101) planes produced distinct sets of stable U inner-sphere species. Steric constraints prevented bidentate coordination to the (001) surface, resulting in a mononuclear monodentate complex, [UO(2)(OH)(2)(H(2)O)(n)O(S)] (90% for n=1 and 10% for n=2 over 5 ns production runs). Binuclear bidentate coordination, [UO(2)(OH)(2)(H(2)O)(n)(O(S))(2)], was however favored on the (010) (99% for n=0 and 1% for n=1) and the (101) (72% for n=0 and 28% for n=1) planes. These results underscore a predominant four-coordinated equatorial shell for U when complexed to the quartz/water interface. Potential of mean force calculations uncovered a diversity of metastable outer- and inner-sphere complexes at local energy minima up to ∼0.4 nm from the surface. These calculations point to important differences in both energetic requirements and mechanisms for the approach of UO(2)(OH)(2)(0) to different quartz surfaces. Binding strengths are affected by binding site distribution, steric freedom, U hydration and OH orientation, and increase in the order (001) (3.7 kJ mol(-1)) < (101) (5.6 kJ mol(-1)) < (010) (6.5 kJ mol(-1)). A general binding mechanism involves (1) formation of monodentate outer-sphere complexes, (2) removal of oxo-bound waters, (3) formation of one (monodentate), then two (bidentate) direct U-O(S) bonds (inner-sphere), and (4) expulsion of excessive waters from the equatorial shell of U.

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Section: Introductionmentioning

confidence: 99%

Crystallographic controls on uranyl binding at the quartz/water interface

Boily

Rosso

2011

Phys. Chem. Chem. Phys.

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“…[74] Furthermore, the rough LPS is calculated to display greater affinity for the uranyl ion than Na + and Ca 2 + . The adsorption of aqueous uranyl onto solid materials involved in the contamination of soils has stimulated several MD studies at the a-quartz surface, [75] in mesoporous confinement like slit-like pores of amorphous silica [76] or the external surface of clays (i.e., montmorillonite, beidellite, or pyrophillite). [77] These studies provide stimulating microscopic views of the uranyl environment in such heterogeneous media.…”

Section: Modeling Uranyl In Other Complex Systems: Biomolecules and Amentioning

confidence: 99%

Insights into Uranyl Chemistry from Molecular Dynamics Simulations

Bühl¹,

Wipff²

2011

ChemPhysChem

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First-principles and purely classical molecular dynamics (MD) simulations for complexes of the uranyl ion (UO(2)(2+)) are reviewed. Validation of Car-Parrinello MD simulations for small uranyl complexes in aqueous solution is discussed. Special attention is called to the mechanism of ligand-exchange reactions at the uranyl centre and to effects of solvation and hydration on coordination and structural properties. Large-scale classical MD simulations are surveyed in the context of liquid-liquid extraction, with uranyl complexes ranging from simple hydrates to calixarenes, and nonaqueous phases from simple organic solvents and supercritical CO(2) to ionic liquids.

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“…Many studies for electrolytes confined in a slit considered only a single slit in equilibrium with a bulk in the GC ensemble [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32]. The behavior of fluids near surfaces attracted the attention of many workers [33][34][35]. Electrolytes are especially interesting due to the forming DLs.…”

Section: Introductionmentioning

confidence: 99%

Selective adsorption of ions in charged slit-systems

Valiskó

Henderson

Boda³

2013

Condens. Matter Phys.

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We study the selective adsorption of various cations into a layered slit system using grand canonical Monte Carlo simulations. The slit system is formed by a series of negatively charged membranes. The electrolyte contains two kinds of cations with different sizes and valences modelled by charged hard spheres immersed in a continuum dielectric solvent. We present the results for various cases depending on the combinations of the properties of the competing cations. We concentrate on the case when the divalent cations are larger than the monovalent cations. In this case, size and charge have counterbalancing effects, which results in interesting selectivity phenomena.

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Molecular dynamics study of aqueous uranyl in hydrophilic mesoporous confinement: the case of slit-like pore in amorphous silica

Cited by 11 publications

References 13 publications

Crystallographic controls on uranyl binding at the quartz/water interface

Crystallographic controls on uranyl binding at the quartz/water interface

Insights into Uranyl Chemistry from Molecular Dynamics Simulations

Selective adsorption of ions in charged slit-systems

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