Tensile properties of structural I clathrate hydrates: Role of guest-host hydrogen bonding ability

Clathrate hydrates (CHs) are one of the most promising molecular structures in applications of gas capture and storage, and gas separations. Fundamental knowledge of mechanical characteristics of CHs is of crucial importance for assessing gas storage and separations at cold conditions, as well as understanding their stability and formation mechanisms. Here, the tensile mechanical properties of structural I CHs encapsulating a variety of guest species (CH4, NH3, H2S, CH2O, CH3OH, and CH3SH) that have different abilities to form hydrogen (H-) bonds with water molecule are explored by classical molecular dynamics (MD) simulations. All investigated CHs are structurally stable clathrate structures. Basic mechanical properties of CHs including tensile limit and Young's modulus are dominated by the H-bonding ability of host-guest molecules and the guest molecular polarity. CHs containing small CH4, CH2O and H2S guest molecules that possess weak H-bonding ability are mechanically robust clathrate structures and mechanically destabilized via brittle failure on the (101) plane. However, those entrapping CH3SH, CH3OH, and NH3 that have strong H-bonding ability are mechanically weak molecular structures and mechanically destabilized through ductile failure as a result of gradual global dissociation of clathrate cages.

Automated summary

Mechanical properties of clathrate hydrates are influenced by the ability of host-guest molecules to form hydrogen bonds and the polarity of guest molecules, with structures containing guests with weak hydrogen bonding ability exhibiting brittle failure, while structures entrapping guests with strong hydrogen bonding ability showing ductile failure.