Computationally generated maps of surface structures and catalytic activities for alloy phase diagrams

Abstract

Significance Designing new alloy catalysts is challenging because of the large number of ways the atoms in an alloy can be arranged. We have developed a method that allows researchers to rapidly predict the near-surface atomic arrangement and catalytic properties of an alloy, making it possible to identify the conditions under which alloys should be synthesized to create the best catalysts. We demonstrate our approach by providing evidence that the Pt3Ni(111) surface, one of the best catalysts for an important reaction in fuel cells, likely draws its excellent catalytic properties from the formation of an alloy phase in which the Pt and Ni atoms are well-ordered. These results will facilitate the rational design of new alloy catalysts. To facilitate the rational design of alloy catalysts, we introduce a method for rapidly calculating the structure and catalytic properties of a substitutional alloy surface that is in equilibrium with the underlying bulk phase. We implement our method by developing a way to generate surface cluster expansions that explicitly account for the lattice parameter of the bulk structure. This approach makes it possible to computationally map the structure of an alloy surface and statistically sample adsorbate binding energies at every point in the alloy phase diagram. When combined with a method for predicting catalytic activities from adsorbate binding energies, maps of catalytic activities at every point in the phase diagram can be created, enabling the identification of synthesis conditions likely to result in highly active catalysts. We demonstrate our approach by analyzing Pt-rich Pt–Ni catalysts for the oxygen reduction reaction, finding 2 regions in the phase diagram that are predicted to result in highly active catalysts. Our analysis indicates that the Pt3Ni(111) surface, which has the highest known specific activity for the oxygen reduction reaction, is likely able to achieve its high activity through the formation of an intermetallic phase with L12 order. We use the generated surface structure and catalytic activity maps to demonstrate how the intermetallic nature of this phase leads to high catalytic activity and discuss how the underlying principles can be used in catalysis design. We further discuss the importance of surface phases and demonstrate how they can dramatically affect catalytic activity.