Control Over Nitrogen Dopant Sites in Palladium Metallene for Manipulating Catalytic Activity and Stability in the Oxygen Reduction Reaction

• Published in: Advanced functional materials 2024-11, Vol.34 (48), p.n/a
• Main Authors: Zeng, Tiantian, Niu, Mang, Xu, Binghui, Yuan, Weiyong, Guo, Chun Xian, Cao, Dapeng, Li, Chang Ming, Zhang, Lian Ying, Zhao, Xiu Song
• Format: Article
• Language: English
• Subjects: Atomic properties; Atomic structure; atomic vacancy doping; Catalytic activity; Chemical reduction; Control stability; Dopants; Doping; Electronic structure; interstitial doping; Light elements; Nitrogen; nitrogen dopant; oxygen reduction reaction; Oxygen reduction reactions; Palladium; palladium metallene
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.202408264

Doping light elements in Pt‐group metals is an effective approach toward improving their catalytic properties for oxygen reduction reaction (ORR). However, it is challenging to control dopant sites and to establish the correlation between the doping site and the catalytic property. In this paper, this success is demonstrated in controlling N doping sites in Pd metallene to manipulate electrocatalytic properties toward ORR. A Pd metallene sample with N dopant predominantly located at the atomic vacancy site (V‐N‐Pd metallene) exhibits two times higher mass activity in ORR than a Pd metallene sample with N dopant mainly occupied the interstitial site (I‐N‐Pd metallene). However, the I‐N‐Pd metallene shows improved durability than the V‐N‐Pd metallene, with only a 4 mV decay in half‐wave potential after 20 000 cycles. Computational calculation results reveal that the significantly enhanced ORR activity of V‐N‐Pd metallene arises from the atomic vacancy‐doped N, which modulates the electronic structure of Pd metallene to weaken the adsorption energy of intermediate O* species. This work provides guidelines for manipulating catalytic properties by controlling the doping sites of light elements in metal nanostructures. This study reports that the ORR activity and stability of N‐doped Pd metallene can be manipulated by controlling the N doping sites, of which the V‐N‐Pd metallene exhibits two times higher mass activity in the ORR than I‐N‐Pd metallene, whereas the latter shows improved durability than the former with only a 4 mV decay in half‐wave potential after 20 000 cycles.