Highly polarized carbon nano-architecture as robust metal-free catalyst for oxygen reduction in polymer electrolyte membrane fuel cells

• Published in: Nano energy 2018-07, Vol.49, p.23-30
• Main Authors: Zhu, Jianbing, Xiao, Meiling, Song, Ping, Fu, Jing, Jin, Zhao, Ma, Liang, Ge, Junjie, Liu, Changpeng, Chen, Zhongwei, Xing, Wei
• Format: Article
• Language: English
• Subjects: Active site; Metal-free catalyst; Oxygen reduction reaction; Polymer electrolyte membrane fuel cell
• ISSN: 2211-2855
• DOI: 10.1016/j.nanoen.2018.04.021

Metal-free electrocatalysts have eluded widespread adoption in polymer electrolyte membrane fuel cells due to their far inferior catalytic activity than most non-precious metal-N-C counterparts (M-Nx-C) for oxygen reduction reaction (ORR), despite their distinct advantages over the M-Nx-C catalysts, including lower cost and higher durability. Herein, we develop a rational bottom-up engineering strategy to improve the ORR performance of a metal-free catalyst by constructing a three-dimensional ultrathin N, P dual-doped carbon nanosheet. The resultant catalyst represents unprecedented ORR performance with an onset potential of 0.91 V, half-wave potential of 0.79 V. Impressively, a maximum power output at 579 mW cm−2 is generated in the fuel cell test, the best among reported metal-free catalysts and outperforms most of the M-Nx-C catalysts. The outstanding catalytic performance results from the highly active polarized carbon sites which are induced by selective graphitic nitrogen and phosphorous dual doping. Our findings provide new directions for the exploration of alternatives to Pt and bring a renew interests in the metal-free catalysts. The ORR performance of metal-free electrocatalysts in acid media was successfully boosted by using electronic modulation and nanostructure engineering strategy simultaneously. The resultant NPC catalyst featured with 3D porous nanosheet structure represents unprecedented ORR performance with an onset potential of 0.91 V and half-wave potential of 0.79 V in acid medium, the best among reported metal-free catalysts. [Display omitted] •The synthesized catalyst exhibits the best ORR performance among metal-free catalysts in acidic medium.•Graphitic N and P polarize the adjacent carbon atoms, making them catalytically active to ORR.•Optimized 3D porous structure guarantees activity manifestation of these active sites.