A Method for Obtaining Liquid-Solid Adsorption Rates from Molecular Dynamics Simulations: Applied to Methanol on Pt(111) in H2O.

Adsorption is an important step in heterogeneous catalysis as it predetermines how many reactant molecules can participate in a surface reaction per unit time. While the rate of adsorption processes is well studied in gas-solid adsorption in both theory and experiment, such rates are still not well studied for liquid-solid adsorption. This is partly because the ever-changing configurations of liquid-phase solvent molecules impede the ability to study a molecule approaching a surface from a liquid phase by either experiment or theory. In this work, we develop a method using molecular dynamics (MD) simulations to study the rate of adsorption in liquid-solid adsorption processes. Specifically, we use MD to model the diffusion of a methanol molecule in aqueous solvent and its adsorption to a Pt(111) surface. We find that by approximating the solute motion as following the same displacement rates as a random walk model, the adsorbed and non-adsorbed states of the methanol molecule near the Pt(111) surface can be discerned and quantified. In particular, this methodology enables extracting a sticking coefficient and a macroscopically relatable adsorption rate. This method can be applied to arbitrary types of reactants and surfaces, as well as different liquid environments, thus providing a general tool for predicting quantitative adsorption rates of liquid-solid adsorption systems.