Biphase Pd Nanosheets with Atomic-Hybrid RhO x /Pd Amorphous Skins Disentangle the Activity-Stability Trade-Off in Oxygen Reduction Reaction

• Published in: Advanced materials (Weinheim) 2024-06, Vol.36 (24), p.e2314252
• Main Authors: Lyu, Zixi, Cai, Junlin, Zhang, Xia-Guang, Li, Huiqi, Huang, Hongpu, Wang, Shupeng, Li, Tianyu, Wang, Qiuxiang, Xie, Zhaoxiong, Xie, Shuifen
• Format: Article
• Language: English
• ISSN: 0935-9648; 1521-4095
• DOI: 10.1002/adma.202314252

The activity-stability trade-off relationship of oxygen reduction reaction (ORR) is a tricky issue that strikes the electrocatalyst population and hinders the widespread application of fuel cells. Here neoteric biphase Pd nanosheets that are structured with ultrathin two-dimensional crystalline Pd inner cores and ≈1 nm thin atomic-hybrid RhO /Pd amorphous skins, named c/a-Pd@PdRh NSs, for disentangling this trade-off dilemma for alkaline ORR are developed. The superthin amorphous skins significantly amplify the quantity of flexibly low-coordinated atoms for electrocatalysis. An in situ selected oxidation of the top-surface Rh dopants creates atomically hybrid RhO /Pd disorder surfaces. Detailed energy spectra and theoretical simulation confirm that these RhO /Pd interfaces can arouse a surface charge redistribution, causing significant electron deficiency and lowered d-band center for surface Pd. Meanwhile, anticorrosive Rh/RhO species can thermodynamically passivate the neighboring Pd atoms from oxidative dissolution. Thanks to these amplified interfacial effects, the biphase c/a-Pd@PdRh NSs simultaneously exhibit a superhigh ORR activity (5.92 A mg , 22.8 times that of Pt/C) and an outstanding long-lasting stability after 100k cycles of accelerated durability test, showcasing unprecedented electrocatalysts for breaking the activity-stability trade-off relationship of ORR. This work paves a bran-new strategy for designing high-performance electrocatalysts through creating modulated amorphous skins on low-dimensional nanomaterials.