Molecular insights into the performance of promoters for carbon dioxide hydrate

Hydrate-based CO₂ storage is a cost-effective and environmentally friendly approach to reduce carbon emission, and the addition of hydrate promoters has shown a promising avenue for enhancing CO₂ hydrate formation. In this work, the promotion mechanism and promotion performance of five different hydrate promoters (denoted as DIOX, CP, THF, THP, and CH) were investigated and compared by first-principles calculations and molecular dynamics simulations. The results show that the hydrate promoters prefer to singly occupy 5¹²6⁴ cages of the sII hydrate, and CO₂ molecules can singly occupy 5¹² cage or multiply occupy 5¹²6⁴ cages. The cohesive energy density indicates that the optimum CO₂ storage capacity can reach up to ∼28 wt%. The stabilization effects of hydrate promoters on the hydrate stability should follow the order of CP > CH > DIOX > THF ≈ THP. The hydrate promoters can increase the water-water interactions, and the molecular diffusivity shows that the dynamic stability of the hydrates is THP ≈ CH > CP > DIOX > THF. Further, the hydrate promoters can accelerate the hydrate formation kinetics, which reduce the induction time and increase the nucleation and growth process.