CO Mineralization by MgO Nanocubes in Nanometric Water Films.

Water films formed by the adhesion and condensation of air moisture on minerals can trigger the formation of secondary minerals of great importance to nature and technology. Magnesium carbonate growth on Mg-bearing minerals is not only of great interest for CO capture under enhanced weathering scenarios but is also a prime system for advancing key ideas on mineral formation under nanoconfinement. To help advance ideas on water film-mediated CO capture, we tracked the growth of amorphous magnesium carbonate (AMC) on MgO nanocubes exposed to moist CO gas. AMC was identified by its characteristic vibrational spectral signature and by its lack of long-range structure by X-ray diffraction. We find that AMC (MgCO·2.3-2.5HO) grew in sub-monolayer (ML) to 4 ML thick water films, with formation rates and yields scaling with humidity. AMC growth was however slowed down as AMC nanocoatings blocked water films access to the reactive MgO core. Films could however be partially dissolved by exposure to thicker water films, driving AMC growth for several more hours until nanocoatings blocked the reactions again. These findings shed new light on a potentially important bottleneck for the efficient mineralization of CO using MgO-bearing products. Notably, this study shows how variations in the air humidity affect CO capture by controlling water film coverages on reactive minerals. This process is also of great interest in the study of mineral growth in nanometrically thick water films.