Detection of high-valent iron species in alloyed oxidic cobaltates for catalysing the oxygen evolution reaction

Li, Nancy; Hadt, Ryan G.; Hayes, Dugan; Chen, Lin X.; Nocera, Daniel G.

doi:10.1038/s41467-021-24453-6

Title: Detection of high-valent iron species in alloyed oxidic cobaltates for catalysing the oxygen evolution reaction

Journal Article · 08 July 2021 · Nature Communications

DOI: https://doi.org/10.1038/s41467-021-24453-6 · OSTI ID:1806590

Li, Nancy;

;

Abstract Iron alloying of oxidic cobaltate catalysts results in catalytic activity for oxygen evolution on par with Ni-Fe oxides in base but at much higher alloying compositions. Zero-field ⁵⁷ Fe Mössbauer spectroscopy and X-ray absorption spectroscopy (XAS) are able to clearly identify Fe ⁴⁺ in mixed-metal Co-Fe oxides. The highest Fe ⁴⁺ population is obtained in the 40–60% Fe alloying range, and XAS identifies the ion residing in an octahedral oxide ligand field. The oxygen evolution reaction (OER) activity, as reflected in Tafel analysis of CoFeO _x films in 1 M KOH, tracks the absolute concentration of Fe ⁴⁺ . The results reported herein suggest an important role for the formation of the Fe ⁴⁺ redox state in activating cobaltate OER catalysts at high iron loadings.

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Research Organization:: Harvard Univ., Cambridge, MA (United States); Harvard University, Cambridge, MA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0017619

OSTI ID:: 1806590

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 12; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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