Origins of enhanced oxygen reduction activity of transition metal nitrides

Zeng, Rui; Li, Huiqi; Shi, Zixiao; Xu, Lang; Meng, Jinhui; Xu, Weixuan; Wang, Hongsen; Li, Qihao; Pollock, Christopher J.; Lian, Tianquan; Mavrikakis, Manos; Muller, David A.; Abruña, Héctor D.

doi:10.1038/s41563-024-01998-7

Title: Origins of enhanced oxygen reduction activity of transition metal nitrides

Journal Article · Tue Sep 03 00:00:00 UTC 2024 · Nature Materials

DOI: https://doi.org/10.1038/s41563-024-01998-7 · OSTI ID:3011387

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^[2]; Meng, Jinhui ^[3]; Xu, Weixuan ^[1];

^[1]; Li, Qihao ^[1];

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Cornell Univ., Ithaca, NY (United States)
Univ. of Wisconsin, Madison, WI (United States)
Emory Univ., Atlanta, GA (United States)

Transition metal nitride (TMN-) based materials have recently emerged as promising non-precious-metal-containing electrocatalysts for the oxygen reduction reaction (ORR) in alkaline media. However, the lack of fundamental understanding of the oxide surface has limited insights into structure–(re)activity relationships and rational catalyst design. Here, in this work, we demonstrate how a well-defined TMN can dictate/control the as-formed oxide surface and the resulting ORR electrocatalytic activity. Structural characterization of MnN nanocuboids revealed that an electrocatalytically active Mn₃O₄ shell grew epitaxially on the MnN core, with an expansive strain along the [010] direction to the surface Mn₃O₄. The strained Mn₃O₄ shell on the MnN core exhibited an intrinsic activity that was over 300% higher than that of pure Mn₃O₄. A combined electrochemical and computational investigation indicated/suggested that the enhancement probably originates from a more hydroxylated oxide surface resulting from the expansive strain. This work establishes a clear and definitive atomistic picture of the nitride/oxide interface and provides a comprehensive mechanistic understanding of the structure–reactivity relationship in TMNs, critical for other catalytic interfaces for different electrochemical processes.

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Research Organization:: Cornell Univ., Ithaca, NY (United States); Energy Frontier Research Centers (EFRC) (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; SC0019445

OSTI ID:: 3011387

Journal Information:: Nature Materials, Journal Name: Nature Materials Journal Issue: 12 Vol. 23; ISSN 1476-4660; ISSN 1476-1122

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

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