Harnessing the Synergistic Interplay between Atomic-Scale Vacancies and Ligand Effect to Optimize the Oxygen Reduction Activity and Tolerance Performance

• Published in: Angewandte Chemie International Edition p. e202414989
• Main Authors: Ye, Shenghua, Chen, Wenda, Ou, Zhijun, Zhang, Qinghao, Zhang, Jie, Li, Yongliang, Ren, Xiangzhong, Ouyang, Xiaoping, Zheng, Lirong, Yan, Xueqing, Liu, Jianhong, Zhang, Qianling
• Format: Journal Article
• Language: English
• Published: Germany 28-10-2024
• Subjects: Ligand effect; Strain effect; Platinum; Oxygen reduction reaction; Defects
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202414989

Defect engineering is an effective strategy for regulating the electrocatalysis of nanomaterials, yet it is seldom considered for modulating Pt-based electrocatalysts for the oxygen reduction reaction (ORR). In this study, we designed Ni-doped vacancy-rich Pt nanoparticles anchored on nitrogen-doped graphene (Vac-NiPt NPs/NG) with a low Pt loading of 3.5 wt . % and a Ni/Pt ratio of 0.038 : 1. Physical characterizations confirmed the presence of abundant atomic-scale vacancies in the Pt NPs induces long-range lattice distortions, and the Ni dopant generates a ligand effect resulting in electronic transfer from Ni to Pt. Experimental results and theoretical calculations indicated that atomic-scale vacancies mainly contributed the tolerance performances towards CO and CH
OH, the ligand effect derived from a tiny of Ni dopant accelerated the transformation from *O to *OH species, thereby improved the ORR activity without compromising the tolerance capabilities. Benefiting from the synergistic interplay between atomic-scale vacancies and ligand effect, as-prepared Vac-NiPt NPs/NG exhibited improved ORR activity, sufficient tolerance capabilities, and excellent durability. This study offers a new avenue for modulating the electrocatalytic activity of metal-based nanomaterials.