Nanotechnology

Electrode

Organic chemistry

Enzyme

Cofactor

Combinatorial chemistry

Electrocatalyst

Active site

Atom (system on chip)

Crystallography

Transition metal

Catalysis

Physical chemistry

Embedded system

Inorganic chemistry

Chemistry

Metallurgy

Materials science

Graphene

Computer science

Metal

Oxygen reduction reaction

Electrochemistry

Manganese

Oxygen

Redox

Advanced Materials

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-N3 O1 cofactor demonstrate the fastest ORR kinetics due to the tuning of the d electronic states to a reasonable state.

O‐, N‐Atoms‐Coordinated Mn Cofactors within a Graphene Framework as Bioinspired Oxygen Reduction Reaction Electrocatalysts