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Title: Octahedral spinel electrocatalysts for alkaline fuel cells
Designing high-performance nonprecious electrocatalysts to replace Pt for the oxygen reduction reaction (ORR) has been a key challenge for advancing fuel cell technologies. Here, we report a systematic study of 15 different AB 2 O 4 /C spinel nanoparticles with well-controlled octahedral morphology. The 3 most active ORR electrocatalysts were MnCo 2 O 4 /C, CoMn 2 O 4 /C, and CoFe 2 O 4 /C. CoMn 2 O 4 /C exhibited a half-wave potential of 0.89 V in 1 M KOH, equal to the benchmark activity of Pt/C, which was ascribed to charge transfer between Co and Mn, as evidenced by X-ray absorption spectroscopy. Scanning transmission electron microscopy (STEM) provided atomic-scale, spatially resolved images, and high-energy-resolution electron-loss near-edge structure (ELNES) enabled fingerprinting the local chemical environment around the active sites. The most active MnCo 2 O 4 /C was shown to have a unique Co-Mn core–shell structure. ELNES spectra indicate that the Co in the core is predominantly Co 2.7+ while in the shell, it is mainly Co 2+ . Broader Mn ELNES spectra indicate less-ordered nearest oxygen neighbors. Co in the shell occupies mainly tetrahedral sites, which are likely candidates as the active sites for the ORR. Such microscopic-level investigation probes the heterogeneous electronic structure at the single-nanoparticle level, and may provide a more rational basis for the design of electrocatalysts for alkaline fuel cells.  more » « less
Award ID(s):
1719875
NSF-PAR ID:
10149149
Author(s) / Creator(s):
; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Proceedings of the National Academy of Sciences
Volume:
116
Issue:
49
ISSN:
0027-8424
Page Range / eLocation ID:
24425 to 24432
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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