Octahedral spinel electrocatalysts for alkaline fuel cells

Yang, Yao; Xiong, Yin; Holtz, Megan E.; Feng, Xinran; Zeng, Rui; Chen, Gary; DiSalvo, Francis J.; Muller, David A.; Abruña, Héctor D.

doi:10.1073/pnas.1906570116

Octahedral spinel electrocatalysts for alkaline fuel cells

Journal Article · Thu Nov 14 00:00:00 EST 2019 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1906570116· OSTI ID:1574556

Yang, Yao; Xiong, Yin; Holtz, Megan E.; Feng, Xinran; Zeng, Rui; Chen, Gary; DiSalvo, Francis J.; ;

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.

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Research Organization:: Cornell Univ., Ithaca, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Alkaline-Based Energy Solutions (CABES)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019445

OSTI ID:: 1574556

Alternate ID(s):: OSTI ID: 1767727

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 49 Vol. 116; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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25 ENERGY STORAGE
alkaline fuel cells
catalysis (heterogeneous)
charge transport
electrocatalysis
electron energy-loss spectroscopy
hydrogen and fuel cells
materials and chemistry by design
membranes
oxygen reduction reaction
scanning transmission electron microscopy
spinel oxides
synthesis (novel materials)
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Octahedral spinel electrocatalysts for alkaline fuel cells

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