Clay nanoflakes and organic molecules synergistically promoting CO₂ hydrate formation

Carbon dioxide (CO₂) reduction is an urgent challenge worldwide due to the dramatically increased CO₂ concentration and concomitant environmental problems. Geological CO₂ storage in gas hydrate in marine sediment is a promising and attractive way to mitigate CO₂ emissions owning to its huge storage capability and safety. However, the sluggish kinetics and unclear enhancing mechanisms of CO₂ hydrate formation limit the practical application of hydrate-based CO₂ storage technologies. Here, we used vermiculite nanoflakes (VMNs) and methionine (Met) to investigate the synergistic promotion of natural clay surface and organic matter on CO₂ hydrate formation kinetics. Induction time and t₉₀ in VMNs dispersion with Met were shorter by one to two orders of magnitude than Met solution and VMNs dispersion. Besides, CO₂ hydrate formation kinetics showed significant concentration-dependence on both Met and VMNs. The side chains of Met can promote CO₂ hydrate formation by inducing water molecules to form a clathrate-like structure. However, when Met concentration exceeded 3.0 mg/mL, the critical amount of ammonium ions from dissociated Met distorted the ordered structure of water molecules, inhibiting CO₂ hydrate formation. Negatively charged VMNs can attenuate this inhibition by adsorbing ammonium ions in VMNs dispersion. This work sheds light on the formation mechanism of CO₂ hydrate in the presence of clay and organic matter which are the indispensable constituents of marine sediments, also contributes to the practical application of hydrate-based CO₂ storage technologies.