A Database of Solution Additives Promoting Mg2+ Dehydration and the Onset of MgCO3 Nucleation

Formed via aqueous carbonation of Mg²⁺ ions, the crystallization of magnesite (MgCO₃) is a promising route to carbon capture and reuse, albeit limited by the slow precipitation of MgCO₃. Although magnesite is naturally abundant, forming at low temperature conditions, its industrial production is an energy-intensive process due to the temperatures required to prevent the formation of hydrated phases. The principal difficulty in aqueous conditions arises from the very strong Mg²⁺···H₂O interaction, with high barriers to Mg²⁺ dehydration. Using atomistic simulations, we have investigated the influence of 30 additive anions (X ^n-, n = 1-3), ranging from simple halides to more complex molecules, on the first two steps of MgCO₃ aggregation from solution, as follows: Mg²⁺ dehydration and subsequent prenucleative Mg²⁺···CO₃ ^2- pairing. We have computed the thermodynamic stabilities of solvent shared ion pairs (Mg²⁺···H₂O···X ^n-) and contact ion pairs (Mg²⁺···X ^n-) to reveal the propensity of solution additives to inhibit or promote Mg²⁺···CO₃ ^2- formation. We have determined the stabilization of undercoordinated hydrated Mg²⁺ states with a vacant coordination site to which CO₃ ^2- can bind, subsequently initiating MgCO₃ nucleation or Mg²⁺ incorporation into the crystal lattice. Extensive molecular dynamics simulations of electrolyte solutions containing Na₂CO₃ with different sources of Mg²⁺ (i.e., MgCl₂, MgSO₄, and Mg(CH₃COO)₂) further show that the degree of dehydration of Mg²⁺ and the structure of prenucleation MgCO₃ clusters change depending on the counterion identity. Through a fundamental understanding of the role of solution additives in the mechanism of Mg²⁺ dehydration, our results help to rationalize previously reported experimental observation of the effect of solvation environments on the growth of magnesite. This understanding may contribute to identifying the solution composition and conditions that could promote the low-temperature CO₂ conversion into MgCO₃ at industrially relevant scales.