Residence times of nanoconfined CO2 in layered aluminosilicates

Abstract

Nanoconfinement of CO₂ in layered aluminosilicates contributes to the capture and release of this greenhouse gas in soils. In this work, we show that the residence times of CO₂ in montmorillonite are lowered by 15 min for each 1 °C increment in temperature during venting. Molecular simulations showed that activation energies of release are no more than half of the experimentally derived value of 34 kJ mol⁻¹. This raised the possibility of additional processes limiting CO₂ mobility in real materials, including (chemi)sorption at reactive sites or frayed edges or defects. The residence times (∼1616 min at −50 °C to ∼6 min at 60 °C) for some of the driest (∼1.4 mmol H₂O per g) montmorillonites that can be produced at ambient temperatures are readily lowered by inclusion of additional water. They are, in turn, prolonged again as the water content and interlayer spacing become smaller through venting. These efforts showed that soil-building clay minerals will lose their propensity to dynamically exchange CO₂ as temperatures continue to rise, yet they may retain CO₂ more efficiently in cold seasons as soils will become depleted in moisture content.