▎ 摘　　要

The predicted maximal activity of subnanometer to nanometer scale transition metal alloy/intermetallic catalyst nanoparticles (TMNP) supported on graphene for the electrochemical oxygen reduction reaction (ORR) is investigated. VdW corrected DFT calculations are performed for size-selected TMNP supported on graphene (metal-decorated graphene) through generation and analysis of thermodynamic scaling relations. Based on these results, a Volcano Plot analysis is performed. Through screening of the best possible sub-nanometer catalysts, size and composition permutations of candidate alloy/intermetallic NP are further screened for predicted catalyst activity for the ORR. Results from this study indicate it can be possible to shift ORR catalyst performance of subnanometer to nanometer sized alloy/intermetallic particles-even those containing the highly noble metals-much closer to the predicted Volcano Plot maximum than is previously seen using models of single crystal surface catalysts (pure metals or alloy/intermetallics). Based on the results from this analysis, future considerations for modifying the support-catalyst pairing to additionally shift the activity closer to the Volcano maximum are suggested.