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Insights into the Oxygen Evolution Reaction on Graphene-Based Single-Atom Catalysts from First-Principles-Informed Microkinetic Modeling

MetadataDetails
Publication Date2023-03-31
JournalACS Catalysis
AuthorsMichael Rebarchik, Saurabh Bhandari, Thomas Kropp, Manos Mavrikakis
InstitutionsUniversity of Wisconsin–Madison, UniversitĂ© Bourgogne Franche-ComtĂ©
Citations30

Single-atom transition metals embedded in nitrogen-doped graphene have emerged as promising electrocatalysts due to their high activity and low material cost. These materials have been shown to catalyze a variety of electrochemical reactions, but their active sites under reaction conditions remain poorly understood. Using first-principles density functional theory calculations, we develop a pH-dependent microkinetic model to evaluate the relative performance of transition metal catalysts embedded in fourfold N-substituted double carbon vacancies in graphene for the oxygen evolution reaction. We find that reaction pathways involving intermediates co-adsorbed on the metal site are preferred on all transition metals. These pathways lead to enhancements in catalytic activity and broaden the activity peak when compared with purely thermodynamics-based predictions. Furthermore, these findings demonstrate the importance of investigating reaction pathways on graphene-based catalysts and other two-dimensional (2D) materials that involve metal active centers decorated by spectator intermediate species.