Spectroscopic Verification of Adsorbed Hydroxy Intermediates in the Bifunctional Mechanism of the Hydrogen Oxidation Reaction
Yaohui Wang, Xiao‐Ting Wang, Huajie Ze, Xia‐Guang Zhang, Petar M. Radjenovic, Yue‐Jiao Zhang, Jin‐Chao Dong, Zhong‐Qun Tian, Jian‐Feng Li
Abstract
Abstract Elucidating hydrogen oxidation reaction (HOR) mechanisms in alkaline conditions is vital for understanding and improving the efficiency of anion‐exchange‐membrane fuel cells. However, uncertainty remains around the alkaline HOR mechanism owing to a lack of direct in situ evidence of intermediates. In this study, in situ electrochemical surface‐enhanced Raman spectroscopy (SERS) and DFT were used to study HOR processes on PtNi alloy and Pt surfaces, respectively. Spectroscopic evidence indicates that adsorbed hydroxy species (OH ad ) were directly involved in HOR processes in alkaline conditions on the PtNi alloy surface. However, OH ad species were not observed on the Pt surface during the HOR. We show that Ni doping promoted hydroxy adsorption on the platinum‐alloy catalytic surface, improving the HOR activity. DFT calculations also suggest that the free energy was decreased by hydroxy adsorption. Consequently, tuning OH adsorption by designing bifunctional catalysts is an efficient method for promoting HOR activity.