Instantaneous CO2 hydrate nucleation enabled by liable cluster solutions for efficient carbon capture and storage

초록

Clathrate hydrates offer a promising route for carbon capture and storage due to their high CO2 storage density, environmental compatibility, and potential for energy-efficient operation. However, the long and stochastic induction time associated with hydrate nucleation remains a major barrier to industrial implementation. Here, we report a liable cluster solution, generated through a controlled freeze-thaw process of dilute THF/water/L-methionine solutions, that dramatically accelerates CO2 hydrate nucleation and growth under quiescent conditions. Across 180 CO2 hydrate nucleation experiments performed under various THF concentrations and temperatures, the liable cluster solution nearly eliminated the induction time, greatly outperforming typical THF + L-methionine solutions and the freeze-thaw-treated L-methionine solutions. Mechanistic analyses using in-situ Raman spectroscopy reveal the immediate formation of sII THF-CO2 hydrate after pressurization, followed by sequential growth of sI CO2 hydrate. FTIR measurements indicate enhanced water structuring in the liable cluster state, suggesting a favorable entropic contribution that acts in concert with the strong enthalpic driving force arising from early sII hydrate formation. Kinetic experiments further demonstrate the practical value of the liable cluster approach, showing rapid CO2 uptake and high storage capacity, reaching 147 mmol CO2/mol H2O (84.7% of theoretical maximum) within 30 min. These results establish the liable cluster strategy as a highly effective and industrially viable platform for hydrate-based CO2 storage. © 2026 Elsevier B.V.

키워드