Catalytic Activity Maps for Alloy Nanoparticles.

To enable rational design of alloy nanoparticle catalysts, we develop an approach to generate catalytic activity maps of alloy nanoparticles on a grid of particle size and composition. The catalytic activity maps are created by using a quaternary cluster expansion to explicitly predict adsorbate binding energies on alloy nanoparticles of varying shape, size, and atomic order while accounting for interactions among the adsorbates. This cluster expansion is used in kinetic Monte Carlo simulations to predict activated nanoparticle structures and turnover frequencies on all surface sites. We demonstrate our approach on Pt-Ni octahedral nanoparticle catalysts for the oxygen reduction reaction (ORR), revealing that the specific activity is predicted to be optimized at an edge length of larger than 5.5 nm and a composition of about PtNi and the mass activity is predicted to be optimized at an edge length of 3.3-3.8 nm and a composition of about PtNi.