Carbonation of MgOSingle Crystals: Implications forDirect Air Capture of CO₂

Direct air capture (DAC) may be feasible to remove carbon dioxide (CO₂) from the atmosphere at the gigaton scale, holding promise to become a major contributor to climate change mitigation. Mineral looping using magnesium oxide (MgO) is potentially an economical, efficient, and sustainable pathway to gigaton-scale DAC. The hydroxylation and carbonation of MgO determine the efficiency of the looping process, but their rates and mechanisms remain uncertain. In this work, MgO single crystals were reacted in air or CO₂ at varying humidities and characterized by X-ray scattering, microscopy, and vibrational spectroscopy. Results show that the hydroxylation formed a brucite (Mg(OH)₂)-like layer immediately after crystal cleaving. Concurrently, the carbonation formed hydrated magnesium carbonate phases, including barringtonite (MgCO₃·2H₂O) and nesquehonite (MgCO₃·2H₂O), in the layer. Rapid initial growth of the layer is also manifested in short-range bending/warping of nanocrystallites, resulting in multiple orientations of the same phases on the surface. The layer growth slowed down over time, indicating surface passivation. The formation of barringtonite and nesquehonite with 1:1 CO₃/Mg ratio indicates an efficient carbonation when compared to other magnesium carbonate phases of lower ratio. Our results are essential for understanding surface passivation mechanisms and tackling the passivation issue of mineral looping DAC technology.