Unmasking the Critical Role of the Ordering Degree of Bimetallic Nanocatalysts on Oxygen Reduction Reaction by In Situ Raman Spectroscopy.

Precise control and accurate understanding of the ordering degree of bimetallic nanocatalysts (BNs) are challenging yet crucial to acquire advanced materials for the oxygen reduction reaction (ORR). AuCu BNs with various ordering degrees were synthesized to evaluate the influence of ordering degree on the ORR at a molecular level using in situ Raman spectroscopy. The activity of AuCu BNs was improved by over 2 times after a disorder‐to‐order transition, making the performance of highly ordered AuCu BNs exceed that of benchmark Pt/C. Direct Raman spectroscopic evidence of key intermediate (*OH) demonstrates that the active site is the combination site of Au and Cu. Moreover, two distinct *OH species are observed on the ordered and disordered structure, and the ordered site is more beneficial for ORR due to its lower affinity to *OH. This work deepens the understanding on the important role of ordering degree on BNs and enables the design of improved catalysts. [ABSTRACT FROM AUTHOR]