Adsorbate-assisted migration of the metal atom in atomically dispersed catalysts: An ab initio molecular dynamics...

We present a phenomenological study of dynamical evolution of the active site in atomically dispersed catalysts in the presence of reaction intermediates associated with CO oxidation and low-temperature water-gas shift reaction. Using picosecond ab initio molecular dynamics, we probe the initiation of adsorbate-induced diffusion of atomically dispersed platinum on rutile TiO₂(110). NVT trajectories spanning 5 ps at 500 K reveal that the dynamical stability of the metal atom is governed by its local coordination to the support and adsorbate. Adsorbates that bind the strongest to Pt typically also lead to the fastest diffusion of the metal atom, and all adsorbates weaken Pt-support interactions, resulting in higher diffusion coefficients compared to bare Pt. We note, however, the absence of quantitative correlations between adsorption characteristics (Pt Bader charge, adsorbate binding energy) and ensemble-averaged quantities (diffusion coefficients). A recurring structural motif identified in several trajectories is a near-linear coordination between support oxygen, Pt, and specific adsorbates. These geometries, on account of enhanced metal support interactions, stabilize Pt and inhibit migration over picosecond timescales. We also identify hydrogen bonding events between the adsorbate and support for OH-containing groups. In the case of OH-bound Pt, for instance, we believe that short-lived H-bonds between OH and support promote Pt migration in the beginning of the NVT trajectory, while the subsequent formation of a near-linear geometry stabilizes the Pt atom despite the continued formation of short-lived hydrogen bonds. These observations are consistent with prior studies that report stabilization of isolated metal atoms in the presence of hydroxyl groups.