Insight into Surface Electronic Effects on Pd Nanostructures as Efficient Electrocatalysts.

Although the unique properties of nanomaterials have endowed enzyme-mimic catalysts with broad applications, the development of catalysts still relies on trial-and-error strategies without predictive indicators. Surface electronic structures have rarely been studied in enzyme-mimic catalysts. Herein, we present a platform for understanding the impact of surface electronic structures on electrocatalysis toward H 2 O 2 decomposition, using the Pd icosahedra (Pd ico), Pd octahedra (Pd oct) and Pd cubic nanocrystals as electrocatalysts. The electronic properties on Pd were modulated with a correlation of surface orientation. We revealed the relationship between the electronic properties and electrocatalytic performance, in which the surface electron accumulation can boost the electrocatalytic activity of the enzyme-mimic catalysts. As a result, the Pd icodimer exhibits the highest electrocatalytic and sensing efficiency. This work offers new perspectives for the investigation of structure-activity relationships and provides an effective knob for utilizing the surface electronic structures to boost the catalytic performance for enzyme-mimics.