Orbital Level Understanding of Adsorbate-Surface Interactions in Metal Nanocatalysis


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Virginia Tech


We develop a theoretical framework for a priori estimation of catalytic activity of metal nanoparticles using geometry-based reactivity descriptors of surface atoms and kinetic analysis of reaction pathways at various types of active sites. We show that orbitalwise coordination numbers 𝐶𝑁α (α = 𝑠 or 𝑑) can be used to predict chemical reactivity of a metal site (e.g., adsorption energies of critical reaction intermediates) by being aware of the neighboring chemical environment, outperforming their regular (𝐶𝑁) and generalized (𝐶̅𝑁̅) counterparts with little added computational cost. Here we include two examples to illustrate this method: CO oxidation on Au (5𝑑¹⁰6𝑠¹) and O₂ reduction on Pt (5𝑑⁹6𝑠¹). We also employ Bayesian learning and the Newns-Anderson model to advance the fundamental understanding of adsorbate-surface interactions on metal nanocatalysts, paving the path toward adsorbate-specific tuning of catalysis.



density functional theory, reactivity descriptor, chemisorption models, Bayesian learning