Lanthanum-Promoted Electrocatalyst for the Oxygen Evolution Reaction: Unique Catalyst or Oxide Deconstruction?

A conventional performance metric for electrocatalysts that promote the oxygen evolution reaction (OER) is the current density at a given overpotential. However, the assumption that increased current density at lower overpotentials indicates superior catalyst design is precarious for OER catalysts in the working environment, as the crystalline lattice is prone to deconstruction and amorphization, thus greatly increasing the concentration of catalytic active sites. We show this to be the case for La³⁺ incorporation into Co₃O₄. Powder X-ray diffraction (PXRD), Raman spectroscopy and extended X-ray absorption fine structure (EXAFS) reveal smaller domain sizes with decreased long-range order and increased amorphization for La-modified Co₃O₄. This lattice deconstruction is exacerbated under the conditions of OER as indicated by operando spectroscopies. The overpotential for OER decreases with increasing La³⁺ concentration, with maximum activity achieved at 17% La incorporation. HRTEM images and electron diffraction patterns clearly show the formation of an amorphous overlayer during OER catalysis that is accelerated with La³⁺ addition. O 1s XPS spectra after OER show the loss of lattice-oxide and an increase in peak intensities associated with hydroxylated or defective O-atom environments, consistent with Co(O)_<i>x</i>(OH)_<i>y</i> species in an amorphous overlayer. Our results suggest that improved catalytic activity of oxides incorporated with La³⁺ ions (and likely other metal ions) is due to an increase in the number of terminal octahedral Co(O)_<i>x</i>(OH)_<i>y</i> edge sites upon Co₃O₄ lattice deconstruction, rather than enhanced intrinsic catalysis.