Spectroscopic Investigations of Complex Electronic Interactions by Elemental Doping and Material Compositing of Cobalt Oxide for Enhanced Oxygen Evolution Reaction Activity

Abstract Doping and compositing are two universal design strategies used to engineer the electronic state of a material and mitigate its disadvantages. These two strategies are extensively applied to design efficient electrocatalysts for water splitting. Using cobalt oxide (CoO) as a model catalyst, it is proven that the oxygen evolution reaction (OER) performance can be progressively improved, first by Fe‐doping to form Fe‐CoO solid solution, and further by the addition of CeO₂ to produce a Fe‐CoO/CeO₂ composite. X‐ray absorption spectroscopy (XAS) reveals that distinct electronic interactions are induced by the processes of doping and compositing. Fe‐doping of CoO can break down the structural symmetry, changing the electronic structure of both Co and O species at the surface and decreasing the flat‐band potential (V_fb). In comparison, subsequent compositing of Fe‐CoO with CeO₂ induces negligible electronic changes in the Fe‐CoO (as seen in ex situ characterizations), but significantly modifies the oxidative transformations of both Co and Fe under OER conditions. The spectroscopic investigations reveal that Fe‐doping and CeO₂ compositing play different roles in modifying the electronic properties of CoO in its pristine state and during OER catalysis, in return, providing useful guidance for the design of more efficient electrocatalysts using these two strategies.