Achieving delafossite analog by in situ electrochemical self-reconstruction as an oxygen-evolving catalyst

Abstract

Development of novel and robust oxygen evolution reaction (OER) catalysts with well-modulated atomic and electronic structure remains a challenge. Compared to the well-known metal hydroxides or (oxyhydr)oxides with lamellar structure, delafossites (ABO2) are characterized by alternating layers of A cations and edge-sharing BO2 octahedra, but are rarely used in OER due to their poor electron conductivity and intrinsic activity. Here, we propose a delafossite analog by mutation of metal oxyhydroxide and delafossite based on first-principles calculations. Modulation on the electronic structure due to distortion of the original crystal field of the BO2 layers is calculated to enhance electron conductivity and catalytic activity. Inspired by the theoretical design, we have experimentally realized the delafossite analog by electrochemical self-reconstruction (ECSR). Operando X-ray absorption spectroscopy and other experimental techniques reveal the formation of delafossite analog with Ag intercalated into bimetallic cobalt-iron (oxyhydr)oxide layers from a metastable precursor through amorphization. Benefitting from the featured local electronic and geometric structures, the delafossite analog shows superior OER activity, affording a current density of 10 mA⋅cm-2 at an overpotential of 187 mV and an excellent stability (300 h) in alkaline conditions.