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 · Nat Commun · 2021

basic_science · Level V

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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 <sup>57</sup>Fe Mössbauer spectroscopy and X-ray absorption spectroscopy (XAS) are able to clearly identify Fe<sup>4+</sup> in mixed-metal Co-Fe oxides. The highest Fe<sup>4+</sup> 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<sub>x</sub> films in 1 M KOH, tracks the absolute concentration of Fe<sup>4+</sup>. The results reported herein suggest an important role for the formation of the Fe<sup>4+</sup> redox state in activating cobaltate OER catalysts at high iron loadings.