Unveiling the hidden reaction kinetic network of carbon dioxide in supercritical aqueous solutions

TL;DR

This study uses advanced simulations and machine learning to uncover detailed reaction pathways and intermediates of CO$_2$ in supercritical water, revealing new stable species and mechanisms especially under nanoconfinement.

Contribution

It introduces a novel combination of ab initio molecular dynamics and unsupervised learning to automatically identify complex reaction pathways and intermediates of CO$_2$ in supercritical water, including under nanoconfinement.

Findings

Discovery of a stable pyrocarbonate intermediate in nanoconfined water.

Identification of pyrocarbonic acid formation in supercritical water.

Revealed different proton transfer mechanisms in bulk versus nanoconfined solutions.

Abstract

Dissolution of CO$_2$ in water followed by the subsequent hydrolysis reactions is of great importance to the global carbon cycle, and carbon capture and storage. Despite enormous previous studies, the reactions are still not fully understood at the atomistic scale. Here, we combined ab initio molecular dynamics simulations with Markov state models to elucidate the reaction mechanisms and kinetics of CO$_2$ in supercritical water both in the bulk and nanoconfined states. The integration of unsupervised learning with first-principles data allows us to identify complex reaction coordinates and pathways automatically instead of a priori human speculation. Interestingly, our unbiased modelling found a novel pathway of dissolving CO$_2$(aq) under graphene nanoconfinement, involving the pyrocarbonate anion (C$_2$O$_5^{2-}$(aq)) as an intermediate state. The pyrocarbonate anion was previously hypothesized to have a fleeting existence in water; however our study reveals that it is a crucial reaction intermediate and stable carbon species in the nanoconfined solutions. We even observed the formation of pyrocarbonic acid (H$_2$C$_2$O$_5$(aq)), which was unknown in water. The unexpected appearance of pyrocarbonates is related to the superionic behavior of the confined solutions. We also found that carbonation reactions involve collective proton transfer along transient water wires, which exhibits concerted behavior in the bulk solution but proceeds stepwise under nanoconfinement. Our study highlights the importance of large oxocarbons in aqueous carbon reactions, with great implications for the deep carbon cycle and the sequestration of CO$_2$.