Metal-Organic Framework-Derived Bamboo-like Nitrogen-Doped Graphene Tubes as an Active Matrix for Hybrid Oxygen-Reduction Electrocatalysts

• Published in: Small (Weinheim an der Bergstrasse, Germany) Vol. 11; no. 12; pp. 1443 - 1452
• Main Authors: Li, Qing, Pan, Hengyu, Higgins, Drew, Cao, Ruiguo, Zhang, Guoqi, Lv, Haifeng, Wu, Kangbing, Cho, Jaephil, Wu, Gang
• Format: Journal Article
• Language: English
• Published: Germany Blackwell Publishing Ltd 25-03-2015; Wiley Subscription Services, Inc
• Subjects: Catalysis; Catalysts; Construction; electrocatalysts; Fuel cells; Graphene; graphene tubes; Metal-organic frameworks; nanocomposites; Nanoparticles; Nanotechnology; Nitrogen; oxygen reduction; Platinum; Pt nanoparticles; Stability; Tubes; Pt nanoparticles; electrocatalysts; nanocomposites; graphene tubes; oxygen reduction
• ISSN: 1613-6810; 1613-6829
• DOI: 10.1002/smll.201402069

In this work, large size (i.e., diameter > 100 nm) graphene tubes with nitrogen‐doping are prepared through a high‐temperature graphitization process of dicyandiamide (DCDA) and Iron(II) acetate templated by a novel metal–organic framework (MIL‐100(Fe)). The nitrogen‐doped graphene tube (N‐GT)‐rich iron‐nitrogen‐carbon (Fe‐N‐C) catalysts exhibit inherently high activity towards the oxygen reduction reaction (ORR) in more challenging acidic media. Furthermore, aiming to improve the activity and stability of conventional Pt catalysts, the ORR active N‐GT is used as a matrix to disperse Pt nanoparticles in order to build a unique hybrid Pt cathode catalyst. This is the first demonstration of the integration of a highly active Fe‐N‐C catalyst with Pt nanoparticles. The synthesized 20% Pt/N‐GT composite catalysts demonstrate significantly enhanced ORR activity and H2‐air fuel cell performance relative to those of 20% Pt/C, which is mainly attributed to the intrinsically active N‐GT matrix along with possible synergistic effects between the non‐precious metal active sites and the Pt nanoparticles. Unlike traditional Pt/C, the hybrid catalysts exhibit excellent stability during the accelerated durability testing, likely due to the unique highly graphitized graphene tube morphologies, capable of providing strong interaction with Pt nanoparticles and then preventing their agglomeration.
An iron‐containing metal–organic framework, MIL‐100(Fe), is employed to prepare a new oxygen‐reduction non‐precious metal catalyst containing bamboo‐like nitrogen‐doped graphene tubes (diameter > 100 nm). The highly active graphene tubes are further integrated with Pt nanoparticles in order to build a hybrid electrocatalyst, exhibiting significantly improved activity and stability compared to conventional Pt/C catalysts in acid electrolyte.