Beyond Metal Sites: Global Aromatic Resonance as the Key Descriptor for Multi‐Atom Electrocatalysts
Zirui Wang, Yaxin Cheng, Xing Chen, Jixuan Yang, Xinyu Ye, Zhiyuan Xia, Ting Wang, Yuanmiao Sun, Hui‐Ming ChengABSTRACT
Multi‐atom catalysts exhibit complex intermetallic and metal‐ligand interactions. Traditional local descriptors fail to capture the global electronic characteristics, limiting the rational design of efficient electrocatalysts. Herein, an aromatic resonance ( A R ) index is introduced as a global descriptor to assess the catalytic performance of multi‐atom catalysts, with the electrochemical carbon monoxide reduction reaction as a representative case study. Unlike local descriptors, A R index quantitatively describes the dynamic “electronic buffer” formed by the π‐electron delocalization network within the ligand framework, showing a clear linear relationship with the Gibbs free energy change of a potential‐determining step (PDS). Mechanistic insights reveal that decreased A R index disrupts global delocalization, enhances metal‐ligand coupling, and promotes C─O bond activation. Guided by A R , Cu 2 TiN 6 @graphene is identified as the optimal catalyst, with a PDS of 0.17 eV and a kinetic barrier of 0.64 eV. This work provides an effective global perspective for understanding structure‐performance relationships in complex multi‐atom electrocatalysts.