Oxygen Isotope Labeling Experiments Reveal Different Reaction Sites for the Oxygen Evolution Reaction on Nickel and Nickel Iron Oxides.

Abstract

Nickel iron oxide is considered a benchmark nonprecious catalyst for the oxygen evolution reaction (OER). However, the nature of the active site in nickel iron oxide is heavily debated. Here we report direct spectroscopic evidence for the different active sites in Fe‐free and Fe‐containing Ni oxides. Ultrathin layered double hydroxides (LDHs) were used as defined samples of metal oxide catalysts, and 18O‐labeling experiments in combination with in situ Raman spectroscopy were employed to probe the role of lattice oxygen as well as an active oxygen species, NiOO−, in the catalysts. Our data show that lattice oxygen is involved in the OER for Ni and NiCo LDHs, but not for NiFe and NiCoFe LDHs. Moreover, NiOO− is a precursor to oxygen for Ni and NiCo LDHs, but not for NiFe and NiCoFe LDHs. These data indicate that bulk Ni sites in Ni and NiCo oxides are active and evolve oxygen via a NiOO− precursor. Fe incorporation not only dramatically increases the activity, but also changes the nature of the active sites.