Overcoming Site Heterogeneity In Search of Metal Nanocatalysts

Site heterogeneity
of metal nanocatalysts poses grand challenges
for catalyst design from first principles. To accelerate catalyst
discovery, it is of pivotal importance to develop an approach that
efficiently maps catalytic activity of nanoparticles onto geometry-based
descriptors while considering the geometric strain and metal ligand
of an active site. We demonstrate that there exist linear correlations
between orbitalwise coordination numbers CNα and
free formation energies of oxygen species (e.g., *OH and *OOH) at
Pt sites. Kinetic analysis along with herein developed structure–activity
relationships accurately predicts the activity trend of pure Pt nanoparticles
(∼1–7 nm) toward oxygen reduction. Application of the
approach to a search of Pt nanoalloys leads to several Pt monolayer
core–shell nanostructures with enhanced oxygen reduction activity
and reduced cost. The approach presented here facilitates a transition
from traditional single-crystal models to nanoparticles in theory-guided
catalyst discovery.