Reconstruction of Highly Dense Cu−N4Active Sites in Electrocatalytic Oxygen Reduction Characterized by Operando Synchrotron Radiation

The emerging star of single atomic site (SAS) catalyst has been regarded as the most promising Pt-substituted electrocatalyst for oxygen reduction reaction (ORR) in anion-exchange membrane fuel cells (AEMFCs). However, the metal loading in SAS directly affects the whole device performance. Herein, we report a dual nitrogen source coordinated strategy to realize high dense Cu-N₄ SAS with a metal loading of 5.61 wt% supported on 3D N-doped carbon nanotubes/graphene structure wherein simultaneously performs superior ORR activity and stability in alkaline media. When applied in H₂ /O₂ AEMFC, it could reach an open-circuit voltage of 0.90 V and a peak power density of 324 mW cm^-2 . Operando synchrotron radiation analyses identify the reconstruction from initial Cu-N₄ to Cu-N₄ /Cu-nanoclusters (NC) and the subsequent Cu-N₃ /Cu-NC under working conditions, which gradually regulate the d-band center of central metal and balance the Gibbs free energy of *OOH and *O intermediates, benefiting to ORR activity.