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2019-9-13-PtNi-slab-CEWithStrain_Final-ChemRxiv-v3.pdf (3.59 MB)

Computationally Generated Maps of Surface Structures and Catalytic Activities for Alloy Phase Diagrams

revised on 13.09.2019, 00:08 and posted on 13.09.2019, 14:41 by Liang Cao, Le, Niu, Tim Mueller

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 two 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.


Email Address of Submitting Author


Johns Hopkins University



ORCID For Submitting Author


Declaration of Conflict of Interest

The authors declare no competing financial interests.

Version Notes

v1 submitted on 06/23/2019 v2 submitted on 06/25/2019 v3 submitted on 09/12/2019