Nanoconfinement facilitates reactions of carbon dioxide in supercritical water

Abstract

The reactions of CO ₂ in water under extreme pressure-temperature conditions are of great importance to the carbon storage and transport below Earth’s surface, which substantially affect the carbon budget in the atmosphere. Previous studies focus on the CO ₂(aq) solutions in the bulk phase, but underground aqueous solutions are often confined to the nanoscale, and nanoconfinement and solid-liquid interfaces may substantially affect chemical speciation and reaction mechanisms, which are poorly known on the molecular scale. Here, we apply extensive ab initio molecular dynamics simulations to study aqueous carbon solutions nanoconfined by graphene and stishovite (SiO ₂) at 10 GPa and 1000 ~ 1400 K. We find that CO ₂(aq) reacts more in nanoconfinement than in bulk. The stishovite-water interface makes the solutions more acidic, which shifts the chemical equilibria, and the interface chemistry also significantly affects the reaction mechanisms. Our findings suggest that CO ₂(aq) in deep Earth is more active than previously thought, and confining CO ₂ and water in nanopores may enhance the efficiency of mineral carbonation.

Abstract

Aqueous CO ₂under nanoconfinement is of great importance to the carbon storage and transport in Earth. Here, the authors apply ab initio molecular dynamics simulations to study the effects of confinement and interfaces, and show that that CO(aq) reacts more in nanoconfinement than in bulk.