Issue 8, 2023

Single Cu–N4 sites enable atomic Fe clusters with high-performance oxygen reduction reactions

Abstract

Atomically dispersed Fe–N4 catalysts have proven to be promising alternatives to commercial Pt/C for the oxygen reduction reaction. Most reported Fe–N4 catalysts suffer from inferior O–O bond-breaking capabilities due to superoxo-like O2 adsorption, though the isolated dual-atomic metal site strategy is extensively adopted. Atomic Fe clusters show greater promise for promoting O–O bond cleavage by undergoing peroxo-like O2 adsorption. However, the excessively strong binding strength between Fe clusters and oxygenated intermediates sacrifices the activity. Here, we first report a Fex/Cu–N@CF catalyst with atomic Fe clusters functionalized by adjacent single Cu–N4 sites anchored on a porous carbon nanofiber membrane. Theoretical calculation indicates that the single Cu–N4 sites can modulate the electronic configuration of Fe clusters to reduce the O2* protonation reaction free energy which ultimately enhances the electrocatalytic performance. In particular, the Cu–N4 sites can increase the overlap between the d orbitals of Fe and p orbitals of O to accelerate O–O cleavage in OOH*. As a result, this unique atomic catalyst exhibits a half potential (E1/2) of 0.944 V in alkaline medium, exceeding that of commercial Pt/C, whereas its acidic performance E1/2 = 0.815 V is comparable to that of Pt/C. This work shows the great potential of single atoms for improvements in atomic cluster catalysts.

Graphical abstract: Single Cu–N4 sites enable atomic Fe clusters with high-performance oxygen reduction reactions

Supplementary files

Article information

Article type
Paper
Submitted
15 Mar 2023
Accepted
04 Jul 2023
First published
06 Jul 2023

Energy Environ. Sci., 2023,16, 3576-3586

Single Cu–N4 sites enable atomic Fe clusters with high-performance oxygen reduction reactions

S. Wu, S. Jiang, S. Liu, X. Tan, N. Chen, J. Luo, S. H. Mushrif, K. Cadien and Z. Li, Energy Environ. Sci., 2023, 16, 3576 DOI: 10.1039/D3EE00840A

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