Reactivity of Monoethanolamine at the Air-Water Interface and Implications for CO 2 Capture.

The development of CO 2 -capture technologies is key to mitigating climate change due to anthropogenic greenhouse gas emissions. These cover a number of technologies designed to reduce the level of CO 2 emitted into the atmosphere or to eliminate CO 2 from ambient air. In this context, amine-based sorbents in aqueous solutions are broadly used in most advanced separation techniques currently implemented in industrial applications. It has been reported that the gas/liquid interface plays an important role in the early stages of the capture process, but how the interface influences the chemistry is still a matter of debate. With the help of first-principles molecular dynamics simulations, we show that monoethanolamine (MEA), a prototypical sorbent molecule, has a weak affinity for the air-water interface, where in addition it exhibits a lower nucleophilicity compared to bulk solution. The change in reactivity is due to the combination of structural and electronic factors, namely, the shift of the conformational equilibrium and the stabilization of the N-atom lone pair. Based on these results, strategies for improving the efficiency of alkanolamine sorbents are proposed.