Fluxionality of Subnano Clusters Reshapes the Activity Volcano of Electrocatalysis

The Sabatier activity volcano provides intuitive guide for catalyst design, but also imposes fundamental limitations on the composition and maximal activity of catalysts. We show that the ORR activity volcano is shifted and reshaped by the potential-dependent fluxionality of subnano cluster catalysts. Fluxionality causes the typically under-binding Ag/Au to gain optimal activity in the cluster form, and surpass Pt/Pd. Furthermore, isomerization of clusters as a function of the potential breaks linear scaling relationships, enabling surpassing the volcano apex relative to the bulk. The effect is likely general for fluxional cluster catalysts.

Automated summary

The research discovered that the potential-dependent fluxionality of subnano cluster catalysts can shift and reshape the ORR activity volcano, allowing Ag/Au to exhibit optimal activity in cluster form and surpass Pt/Pd. This effect is likely applicable to other fluxional cluster catalysts.