NDLI: Structural and mechanistic basis for the high activity of Fe–N

Content Provider	Royal Society of Chemistry (RSC)
Author	McCool, Geoff Ghoshal, Shraboni Jaouen, Frédéric Liang, Wentao Jia, Qingying Sougrati, Moulay-Tahar Yuan, Xianxia Ma, Zi-Feng Halevi, Barr Ma, Chunrong Mukerjee, Sanjeev McKinney, Samuel Li, Jingkun
Copyright Year	2016
Abstract	The development of efficient non-platinum group metal (non-PGM) catalysts for oxygen reduction reaction (ORR) is of paramount importance for clean and sustainable energy storage and conversion devices. The major bottleneck in developing Fe–N–C materials as the leading non-PGM catalysts lies in the poor understanding of the nature of active sites and reaction mechanisms. Herein, we report a scalable metal organic framework-derived Fe–N–C catalyst with high ORR activity demonstrated in practical H2/air fuel cells, and an unprecedented turnover frequency (TOF) in acid in rotating disk electrode. By characterizing the catalyst under both ex situ and operando conditions using combined microscopic and spectroscopic techniques, we show that the structures of active sites under ex situ and working conditions are drastically different. Resultantly, the active site proposed here, a non-planar ferrous Fe–N4 moiety embedded in distorted carbon matrix characterized by a high Fe2+/3+ redox potential, is in contrast with those proposed hitherto derived from ex situ characterizations. This site reversibly switches to an in-plane ferric Fe–N4 moiety poisoned by oxygen adsorbates during the redox transition, with the population of active sites controlled by the Fe2+/3+ redox potential. The unprecedented TOF of the active site is correlated to its near-optimal Fe2+/3+ redox potential, and essentially originated from its favorable biomimetic dynamic nature that balances the site-blocking effect and O2 dissociation. The porous and disordered carbon matrix of the catalyst plays pivotal roles for its measured high ORR activity by hosting high population of reactant-accessible active sites.
Starting Page	2418
Ending Page	2432
Page Count	15
File Format	HTM / HTML PDF
ISSN	17545692
Volume Number	9
Issue Number	7
Journal	Energy & Environmental Science
DOI	10.1039/c6ee01160h
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Redox Sustainable energy Acid Rotating disk electrode Active site Carbon Extracellular matrix Oxygen Biomimetics Dissociative
Content Type	Text
Resource Type	Article
Subject	Environmental Chemistry Pollution Renewable Energy, Sustainability and the Environment Nuclear Energy and Engineering

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