Title: In situ Spectroscopic Insight into the Origin of the Enhanced Performance of Bimetallic nanocatalysts towards ORR

Authors: Ya-Hao Wang, Jia-Bo Le, Wei-Qiong LI, Jie Wei, Petar Radjenovic, Hua Zhang, Xiao-Shun Zhou, Jun Cheng, Zhong-Qun Tian, Jian-Feng Li

Abstract: 

It is vital to understand the oxygen reduction reaction (ORR) mechanism at the molecular level for the rational design and synthesis of high activity fuel cell catalysts. Surface enhanced Raman spectroscopy (SERS) is a powerful technique capable of detecting the bond vibrations of surface species in the low wavenumber range, however using it to probe practical nanocatalysts remains extremely challenging. Herein, shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS) was used to investigate ORR processes on the surface of novel bimetallic Pt3Co nanocatlyst satellite structures. Direct spectroscopic evidence of *OOH suggests that ORR undergoes an associative mechanism on Pt3Co in both acidic and basic environments. Density functional theory (DFT) calculations show that the weak *O adsorption arises from electronic effect on the Pt3Co surface and accounts for enhanced ORR activity. This work shows SHINERS is a promising technique for the real‐time observation of catalytic processes.

Full-Link: https://onlinelibrary.wiley.com/doi/10.1002/anie.201908907