Interfacial Reactivity and Speciation Emerging from Na-Montmorillonite Interactions with Water and Formic Acid at 200 °C: Insights from Reactive Molecular Dynamics Simulations, Infrared Spectroscopy, and X‑ray Scattering Measurements

Reactive organic fluid–mineral interactions at elevated temperatures contribute to the evolution of planetary matter. One of the less studied but important transformations in this regard involves the reactions of formic acid with naturally occurring clays such as sodium montmorillonite. To advance a mechanistic understanding of these interactions, we use ReaxFF reactive molecular dynamics (MD) simulations in conjunction with infrared (IR) spectroscopy and X-ray scattering experiments to investigate the speciation behavior of water–formic acid mixtures on sodium montmorillonite interfaces at 473 K and 1 atm. Using a newly developed reactive force field, we show that the experimental IR spectra of unreacted and reacted mixtures can be accurately reproduced by ReaxFF/MD. We further benchmark the simulation predictions of sodium carbonate and bicarbonate formation in the clay interlayers using small-angle and wide-angle X-ray xcattering measurements. Subsequently, leveraging the benchmarked force field, we interrogate the pathway of speciation reactions with emphasis on carbonate, formate, and hydroxide groups, elucidating the energetics, transition states, intermediates, and preferred products. We also delineate the differences in reactivities and catalytic effects of clay edges, facets, and interlayers owing to their local chemical environments, which have far reaching consequences in their speciation behavior. The experimental and simulation approaches described in this study and the transferable force fields can be applied translationally to advance the science of clay–fluid interactions for several applications including subsurface fluid storage and recovery and clay–pollutant dynamics.