Carbon mineralization pathways in interfacial adsorbed water nanofilms

Abstract Carbon mineralization in humidified carbon dioxide offers a promising route to mitigate anthropogenic emissions in a world stressed by water security. Despite its technological importance, our understanding of carbonation in water-poor environments lags, as traditional dissolution-precipitation pathways struggle to explain the adsorbed water nanofilm-mediated reactivity. Here, we utilize in operando X-ray diffraction (XRD) and advanced molecular simulations to investigate nanoconfined reactions driving forsterite carbonation, the magnesium-rich olivine. By examining magnesium ion dissolution and transport in atomistic simulations of the forsterite-water-carbon dioxide interface and comparing these with the in operando XRD activation energies, we identify both processes as rate-limiting at saturation. Our simulations reveal a mechanistic view of interfacial carbonation, where dissolution and precipitation are mediated by anomalous quasi two-dimensional diffusion. The transport process involves intermittent diffusive hopping in the desorbed state, separated by crawling events that are spatially short but temporally long. This understanding transcends carbon mineralization, with implications for understanding the transport of contaminants in geosystems, the design of multifunctional materials, water desalination, and molecular recognition systems.