Linking Composition, Structure and Thickness of CoOOH layers to Oxygen Evolution Reaction Activity by Correlative Microscopy

Abstract

The role of β-CoOOH crystallographic orientations in catalytic activity for the oxygen evolution reaction (OER) remains elusive. We combine correlative electron backscatter diffraction/scanning electrochemical cell microscopy with X-ray photoelectron spectroscopy, transmission electron microscopy, and atom probe tomography to establish the structure-activity relationships of various faceted β-CoOOH formed on a Co microelectrode under OER conditions. We reveal that ≈6 nm β-CoOOH(01 $\bar{1}$ 0), grown on [ $\bar{1}2\bar{1}$ 0]-oriented Co, exhibits higher OER activity than ≈3 nm β-CoOOH(10 $\bar{1}$ 3) or ≈6 nm β-CoOOH(0006) formed on [02 $\bar{2}1]$ - and [0001]-oriented Co, respectively. This arises from higher amounts of incorporated hydroxyl ions and more easily reducible Co^III -O sites present in β-CoOOH(01 $\bar{1}$ 0) than those in the latter two oxyhydroxide facets. Our correlative multimodal approach shows great promise in linking local activity with atomic-scale details of structure, thickness and composition of active species, which opens opportunities to design pre-catalysts with preferred defects that promote the formation of the most active OER species.

Keywords: Atom Probe Tomography; Cobalt Oxyhydroxide; Identical Location Microscopy; Scanning Electrochemical Cell Microscopy; Water Splitting.