Microscopic Kinetics Pathway of Salt Crystallization in Graphene Nanocapillaries

The fundamental understanding of crystallization, in terms of microscopic kinetic and thermodynamic details, remains a key challenge in the physical sciences. Here, by using in situ graphene liquid cell transmission electron microscopy, we reveal the atomistic mechanism of NaCl crystallization from solutions confined within graphene cells. We find that rock salt NaCl forms with a peculiar hexagonal morphology. We also see the emergence of a transitory graphitelike phase, which may act as an intermediate in a two-step pathway. With the aid of density functional theory calculations, we propose that these observations result from a delicate balance between the substrate-solute interaction and thermodynamics under confinement. Our results highlight the impact of confinement on both the kinetics and thermodynamics of crystallization, offering new insights into heterogeneous crystallization theory and a potential avenue for materials design.

Automated summary

In this study, the atomistic mechanism of NaCl crystallization from solutions confined within graphene cells was revealed using in situ graphene liquid cell transmission electron microscopy. The research highlighted the impact of confinement on both the kinetics and thermodynamics of crystallization, offering new insights into heterogeneous crystallization theory and a potential avenue for materials design. The findings were attributed to a delicate balance between the substrate-solute interaction and thermodynamics under confinement, as suggested by density functional theory calculations.