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O‐, N‐Atoms‐Coordinated Mn Cofactors within a Graphene Framework as Bioinspired Oxygen Reduction Reaction Electrocatalysts
Author(s) -
Yang Yang,
Mao Kaitian,
Gao Shiqi,
Huang Hao,
Xia Guoliang,
Lin Zhiyu,
Jiang Peng,
Wang Changlai,
Wang Hui,
Chen Qianwang
Publication year - 2018
Publication title -
advanced materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.707
H-Index - 527
eISSN - 1521-4095
pISSN - 0935-9648
DOI - 10.1002/adma.201801732
Subject(s) - catalysis , graphene , cofactor , manganese , electrocatalyst , transition metal , materials science , oxygen reduction reaction , redox , active site , oxygen , metal , atom (system on chip) , inorganic chemistry , nanotechnology , combinatorial chemistry , crystallography , chemistry , enzyme , electrochemistry , organic chemistry , electrode , metallurgy , computer science , embedded system
Manganese (Mn) is generally regarded as not being sufficiently active for the oxygen reduction reaction (ORR) compared to other transition metals such as Fe and Co. However, in biology, manganese‐containing enzymes can catalyze oxygen‐evolving reactions efficiently with a relative low onset potential. Here, atomically dispersed O and N atoms coordinated Mn active sites are incorporated within graphene frameworks to emulate both the structure and function of Mn cofactors in heme–copper oxidases superfamily. Unlike previous single‐metal catalysts with general M‐N‐C structures, here, it is proved that a coordinated O atom can also play a significant role in tuning the intrinsic catalytic activities of transition metals. The biomimetic electrocatalyst exhibits superior performance for the ORR and zinc–air batteries under alkaline conditions, which is even better than that of commercial Pt/C. The excellent performance can be ascribed to the abundant atomically dispersed Mn cofactors in the graphene frameworks, confirmed by various characterization methods. Theoretical calculations reveal that the intrinsic catalytic activity of metal Mn can be significantly improved via changing local geometry of nearest coordinated O and N atoms. Especially, graphene frameworks containing the Mn‐N 3 O 1 cofactor demonstrate the fastest ORR kinetics due to the tuning of the d electronic states to a reasonable state.