ReaxFF Molecular Dynamics Study on the Influence of Temperature on Adsorption, Desorption, and Decomposition at the...

The reaction dynamics of a liquid-solid interface with the example of an acetic acid/water solution interacting with a ZnO(101̅0) surface was investigated using ReaxFF reactive force field-based molecular dynamics. The interactions were studied over a broad temperature range to assess the kinetics and reaction pathways. Two different acetic acid dissociation mechanisms are observed in the simulations: (1) deprotonation to surface cation, which produces a terminal hydroxyl and (2) deprotonation to a bridging hydroxyl, which results in water production. An increase in temperature promotes the dissociation of acetic acids and its adsorption to surface at first, but as the temperature increase continues, the surface coverage by acetates decreases due to evaporation from the surface or decomposition. The acetate decomposition starts with a nucleophilic attack of oxygen to methyl carbon and results in the production of carbon dioxide, which is consistent with experimental findings in the literature. The coverage of the surface by water molecules decreases as the system is heated up, which is also observed in other molecular dynamics studies. At elevated temperatures, acetate molecules are more stable than water molecules or bridging hydroxyls on the surface. These simulations validate the ReaxFF method for the water/organic mixture and metal oxide surface interactions and provide insights into structure and reactivity of aqueous solvents on metal oxide surfaces at elevated temperatures. Adsorption trends that are observed in this study are consistent with phenomenological Langmuir models. The reaction of acetic acid decomposition to smaller molecules such as CO₂ and CH₂O agrees with experimental observations. Understanding the details of these dynamic surface reactions are critical to understand important new cold sintering processes that utilize transient liquid and solid reactions, and the latter could be used to predict solvent selection for cold sintering.