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DOE OSTI · 1617782

A Method for Obtaining Liquid–Solid Adsorption Rates from Molecular Dynamics Simulations: Applied to Methanol on Pt(111) in H 2 O

Zhang, Xiaohong·Savara, Aditya·Getman, Rachel B.
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Abstract

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.

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Zhang, Xiaohong, Savara, Aditya, Getman, Rachel B.. 2020-03-05. A Method for Obtaining Liquid–Solid Adsorption Rates from Molecular Dynamics Simulations: Applied to Methanol on Pt(111) in H 2 O. https://doi.org/10.1021/acs.jctc.9b01249

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