β-Nickel oxyhydroxide (β-NiOOH) is a promising electrocatalyst for the oxygen evolution reaction (OER), which is the more difficult half-reaction involved in water splitting. In this study, we revisit the OER activities of the two most abundant crystallographic facets of pristine β-NiOOH, the (0001) and (1010) facets, which expose 6-fold-lattice-oxygen-coordinated and 5-fold-lattice-oxygen-coordinated Ni sites, respectively. To this end, we model various active sites on these two facets using hybrid density functional theory, which includes a fraction of the exact nonlocal Fock exchange in the electronic description of the system. By evaluating thermodynamic OER overpotentials, we show that the two active sites considered on each crystallographic facet demonstrate OER activities remarkably different from each other. However, the lowest OER overpotentials calculated for the two facets were found to be similar to each other and comparable to the overpotential for the 4-fold-lattice-oxygen-coordinated Ni site on the (1211) facet of β-NiOOH previously examined in J. Am. Chem. Soc. 2019, 141, 1, 693-705. This finding shows that all of the low-index facets investigated so far could be responsible for the experimentally observed OER activity of pristine β-NiOOH. However, the lowest overpotential active sites on these three crystallographic facets operate via different mechanisms, underscoring the importance of considering multiple OER pathways and intermediates on each crystallographic facet of a potential electrocatalyst. Specifically, our work demonstrates that consideration of previously overlooked active sites, transition-metal-ion oxidation states, reaction intermediates, and lattice-oxygen-stabilization are critical to reveal the lowest overpotential OER pathways on pristine β-NiOOH.
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry