Hydrogen storage is a key enabling technology required for attaining a hydrogen-based economy. Fundamental research can reveal the underlying principles controlling hydrogen uptake and release by storage materials, and also aid in characterizing and designing novel storage materials. New ideas for hydrogen storage materials come from exploiting the properties of hydrophobic hydration, which refers to water s ability to stabilize, by its mode of association, specific structures under specific conditions. Although hydrogen was always considered too small to support the formation of solid clathrate hydrate structures, exciting new experiments show that water traps hydrogen molecules at conditions of low temperatures and moderate pressures. Hydrogen release is accomplished by simple warming. While these experiments lend credibility to the idea that water could form an environmentally attractive alternative storage compound for hydrogen fuel, which would advance our nation s goals of attaining a hydrogen-based economy, much work is yet required to understand and realize the full potential of clathrate hydrates for hydrogen storage. Here we undertake theoretical studies of hydrogen in water to establish a firm foundation for predictive work on clathrate hydrate H{sub 2} storage capabilities. Using molecular simulation and statistical mechanical theories based in part on quantum mechanical descriptions of molecular interactions, we characterize the interactions between hydrogen and liquid water in terms of structural and thermodynamic properties. In the process we validate classical force field models of hydrogen in water and discover new features of hydrophobic hydration that impact problems in both energy technology and biology. Finally, we predict hydrogen occupancy in the small and large cages of hydrogen clathrate hydrates, a property unresolved by previous experimental and theoretical work.
We report on our studies of the structural properties of a hydrogen molecule dissolved in liquid water. The radial distribution function, coordination number and coordination number distribution are calculated using different representations of the interatomic forces within molecular dynamics (MD), Monte Carlo (MC) and ab initio molecular dynamics (AIMD) simulation frameworks. Although structural details differ in the radial distribution functions generated from the different force fields, all approaches agree that the average and most probable number of water molecules occupying the inner hydration sphere around hydrogen is 16. Furthermore, all results exclude the possibility of clathrate-like organization of water molecules around the hydrophobic molecular hydrogen solute.
Water is the critical natural resource of the new century. Significant improvements in traditional water treatment processes require novel approaches based on a fundamental understanding of nanoscale and atomic interactions at interfaces between aqueous solution and materials. To better understand these critical issues and to promote an open dialog among leading international experts in water-related specialties, Sandia National Laboratories sponsored a workshop on April 24-26, 2005 in Santa Fe, New Mexico. The ''Frontiers of Interfacial Water Research Workshop'' provided attendees with a critical review of water technologies and emphasized the new advances in surface and interfacial microscopy, spectroscopy, diffraction, and computer simulation needed for the development of new materials for water treatment.
We used molecular dynamics simulations to study the adsorption of aqueous uranyl species (UO22+) onto clay mineral surfaces in the presence of sodium counterions and carbonato ligands. The large system size (10 000 atoms) and long simulation times (10 ns) allowed us to investigate the thermodynamics of ion adsorption, and the atomistic detail provided clues for the observed adsorption behavior. The model system consisted of the basal surface of a low-charge Na-montmorillonite clay in contact with aqueous uranyl carbonate solutions with concentrations of 0.027 M, 0.081 M, and 0.162 M. Periodic boundary conditions were used in the simulations to better represent an aqueous solution interacting with an external clay surface. Uranyl adsorption tendency was found to decrease as the aqueous uranyl carbonate concentration was increased, while sodium adsorption remained constant. The observed behavior is explained by physical and chemical effects. As the ionic strength of the aqueous solution was increased, electrostatic factors prevented further uranyl adsorption once the surface charge had been neutralized. Additionally, the formation of aqueous uranyl carbonate complexes, including uranyl carbonato oligomers, contributed to the decreased uranyl adsorption tendency.