Identifying the Intrinsic Relationship between the Restructured Oxide Layer and Oxygen Evolution Reaction Performance on the Cobalt Pnictide Catalyst.

Cobalt pnictides show good catalytic activity and stability on oxygen evolution reaction (OER) behaviors in a strong alkaline solution. Identifying the intrinsic composition/structure-property relationship of the oxide layer on the cobalt pnictides is critical to design better and cheaper electrocatalysts for the commercial viability of OER technologies. In this work, the restructured oxide layer on the cobalt pnictides and its effect on the activity and mechanism for OER is systematically analyzed. In-situ electrochemical impedance spectroscopy (EIS) and near edge x-ray absorption fine structure (NEXAFS) spectra indicate that a higher OER performance of cobalt pnictides than Co3 O4 is attributed to the more structural disorder and oxygen defect sites in the cobalt oxide layer evolved from cobalt pnictides. Using angle resolved x-ray photoelectron spectroscopy (AR-XPS) further demonstrates that the oxygen defect sites mainly concentrate on the subsurface of cobalt oxide layer. The current study demonstrated promising opportunities for further enhancing the OER performance of cobalt-based electrocatalysts by controlling the subsurface defects of the restructured active layer.