Locally Varying Surface Binding Affinity on Pd-Au Nanocrystals Enhances Electrochemical Ethanol Oxidation Activity.

Abstract

Noble metal nanocrystals face challenges in effectively catalyzing electrochemical ethanol oxidation reaction (EOR)-represented multistep, multielectron transfer processes due to the linear scaling relationship among binding energies of intermediates, impeding independent optimization of individual elemental steps. Herein, we develop noble metal nanocrystals with a range of local surface binding affinities in close proximity to overcome this challenge. Experimentally, this is demonstrated by applying tensile strain to a Pd surface and decorating it with discrete Au atoms, forming a diversity of binding sites with varying affinities in close proximity for guest molecules, as evidenced by CO probing and density functional theory calculations. Such a surface enables reaction intermediates to migrate between different binding sites as needed for each elemental step, thereby reducing the energy barrier for the overall EOR when compared to reactions at a single site. On these tailored surfaces, we attain specific and mass activities of 32.7 mA cm^-2 and 47.8 A mg_Pd^-1 in EOR, surpassing commercial Pd/C by 10.9 and 43.8 times, respectively, and outperforming state-of-the-art Pd-based catalysts. These results highlight the promise of this approach in improving a variety of multistep, multielectron transfer reactions, which are crucial for energy conversion applications.