Identification of Catalytic Sites for Oxygen Reduction in Metal/Nitrogen‐Doped Carbons with Encapsulated Metal Nanoparticles

• Published in: Angewandte Chemie International Edition Vol. 59; no. 4; pp. 1627 - 1633
• Main Authors: Chen, Ming‐Xi, Zhu, Mengzhao, Zuo, Ming, Chu, Sheng‐Qi, Zhang, Jing, Wu, Yuen, Liang, Hai‐Wei, Feng, Xinliang
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 20.01.2020
• Edition: International ed. in English
• Subjects: Active sites; Ammonium chloride; Catalysts; Catalytic activity; Chemical reduction; encapsulated nanoparticles; Encapsulation; Fe-N-C; fuel cells; Fuel technology; Graphene; Heterogeneity; Metals; Nanoparticles; Nitrogen; Oxygen; oxygen reduction reaction (ORR); Oxygen reduction reactions; Platinum; Proton exchange membrane fuel cells; Temperature; active sites; fuel cells; encapsulated nanoparticles; Fe-N-C; oxygen reduction reaction (ORR)
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201912275

The development of metal‐N‐C materials as efficient non‐precious metal (NPM) catalysts for catalysing the oxygen reduction reaction (ORR) as alternatives to platinum is important for the practical use of proton exchange membrane fuel cells (PEMFCs). However, metal‐N‐C materials have high structural heterogeneity. As a result of their high‐temperature synthesis they often consist of metal‐Nx sites and graphene‐encapsulated metal nanoparticles. Thus it is hard to identify the active structure of metal‐N‐C catalysts. Herein, we report a low‐temperature NH4Cl‐treatment to etch out graphene‐encapsulated nanoparticles from metal‐N‐C catalysts without destruction of co‐existing atomically dispersed metal‐Nx sites. Catalytic activity is much enhanced by this selective removal of metallic nanoparticles. Accordingly, we can confirm the spectator role of graphene‐encapsulated nanoparticles and the pivotal role of metal‐Nx sites in the metal‐N‐C materials for ORR in the acidic medium. ORR inspiring: With a low‐temperature NH4Cl treatment graphene‐encapsulated nanoparticles (NPs) are etched out of metal‐N‐C catalysts. Removing these metallic NPs greatly enhances the catalytic oxygen reduction reaction (ORR) activity allowing the real catalytic centres to be identified.