Morphology Tailoring of Pt Nanocatalysts for the Oxygen Reduction Reaction: The Paradigm of Pt 13

Understanding the relationship between the morphology of Pt nanocatalysts and their catalytic performance towards the oxygen reduction reaction (ORR) is important for their applications as electrocatalysts. In this work, using density functional theory calculations, we investigate structural properties, ORR activity, and CO tolerance of five morphological forms of the Pt 13 cluster. Four of these are low‐energy, lower symmetry conformations (Pt 13−1 and Pt 13−4 have C S symmetry, Pt 13−2 and Pt 13−3 are of C 2 v symmetry) and the fifth (Pt 13−5 ) is a higher energy, icosahedral structure. Our results indicate that of the five considered, Pt 13−1 and Pt 13−2 possesses the best, overall comparable, combination of catalytic characteristics—activity and CO tolerance—relevant to the ORR. Computational characterization of morphology‐dependent catalytic properties of sub‐nano and nanosized particles herein can inform the design and synthesis of nanocatalysts with superior targeted functionalities.