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Title: Octahedral spinel electrocatalysts for alkaline fuel cells

Abstract

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. Suchmore » 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.« less

Authors:
; ; ; ; ; ; ; ORCiD logo; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1574556
Grant/Contract Number:  
SC0019445
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 116 Journal Issue: 49; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Yang, Yao, Xiong, Yin, Holtz, Megan E., Feng, Xinran, Zeng, Rui, Chen, Gary, DiSalvo, Francis J., Muller, David A., and Abruña, Héctor D. Octahedral spinel electrocatalysts for alkaline fuel cells. United States: N. p., 2019. Web. doi:10.1073/pnas.1906570116.
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Yang, Yao, Xiong, Yin, Holtz, Megan E., Feng, Xinran, Zeng, Rui, Chen, Gary, DiSalvo, Francis J., Muller, David A., & Abruña, Héctor D. Octahedral spinel electrocatalysts for alkaline fuel cells. United States. doi:10.1073/pnas.1906570116.
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Yang, Yao, Xiong, Yin, Holtz, Megan E., Feng, Xinran, Zeng, Rui, Chen, Gary, DiSalvo, Francis J., Muller, David A., and Abruña, Héctor D. Thu . "Octahedral spinel electrocatalysts for alkaline fuel cells". United States. doi:10.1073/pnas.1906570116.
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@article{osti_1574556,
title = {Octahedral spinel electrocatalysts for alkaline fuel cells},
author = {Yang, Yao and Xiong, Yin and Holtz, Megan E. and Feng, Xinran and Zeng, Rui and Chen, Gary and DiSalvo, Francis J. and Muller, David A. and Abruña, Héctor D.},
abstractNote = {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.},
doi = {10.1073/pnas.1906570116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 49,
volume = 116,
place = {United States},
year = {2019},
month = {11}
}
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DOI:  10.1073/pnas.1906570116
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