Atomic-Level Observation of Potential-Dependent Variations at the Surface of an Oxide Catalyst during Oxygen Evolution Reaction.

Understanding the intricate details of the surface atomic structure and composition of catalysts during the oxygen evolution reaction (OER) is crucial for developing catalysts with high stability in water electrolyzers. While many notable studies highlight surface amorphization and reconstruction, systematic analytical tracing of the catalyst surface as a function of overpotential remains elusive. Heteroepitaxial (001) films of chemically stable and lattice-oxygen-inactive LaCoO3 are thus utilized as a model catalyst to demonstrate a series of atomic-resolution observations of the film surface at different anodic potentials. The first key finding is that atoms at the surface are fairly dynamic even at lower overpotentials. Angstrom-scale atomic displacements within the perovskite framework are identified below a certain potential level. Another noteworthy feature is that amorphization (or paracrystallization) with no long-range order is finally induced at higher overpotentials. In particular, surface analyses consistently support that the oxidation of lattice oxygen is coupled with amorphous phase formation at the high potentials. Theoretical calculations also reveal an upward shift of oxygen 2p states toward the Fermi level, indicating enhanced lattice oxygen activation when atom displacement occurs more extensively. This study emphasizes that the degradation behavior of OER catalysts can distinctively vary depending on the overpotential level.

Elucidating intrinsic contribution of d-orbital states to oxygen evolution electrocatalysis in oxides.

Although numerous studies on oxide catalysts for an efficient oxygen evolution reaction have been carried out to compare their catalytic performance and suggest new compositions, two significant constraints have been overlooked. One is the difference in electronic conduction behavior between catalysts (metallic versus insulating) and the other is the strong crystallographic surface orientation dependence of the catalysis in a crystal. Consequently, unless a comprehensive comparison of the oxygen-evolution catalytic activity between samples is made on a crystallographically identical surface with sufficient electron conduction, misleading interpretations on the catalytic performance and mechanism may be unavoidable. To overcome these limitations, we utilize both metallic (001) LaNiO3 epitaxial thin films together with metal dopants and semiconducting (001) LaCoO3 epitaxial thin films supported with a conductive interlayer. We identify that Fe, Cr, and Al are beneficial to enhance the catalysis in LaNiO3 although their perovskite counterparts, LaFeO3, LaCrO3, and LaAlO3, with a large bandgap are inactive. Furthermore, semiconducting LaCoO3 is found to have more than one order higher activity than metallic LaNiO3, in contrast to previous reports. Showing the importance of facilitating electron conduction, our work highlights the impact of the near-Fermi-level d-orbital states on the oxygen-evolution catalysis performance in perovskite oxides.

Atomic-Level Manipulations in Oxides and Alloys for Electrocatalysis of Oxygen Evolution and Reduction.

As chemical reactions and charge-transfer simultaneously occur on the catalyst surface during electrocatalysis, numerous studies have been carried out to attain an in-depth understanding on the correlation among the surface structure and composition, the electrical transport, and the overall catalytic activity. Compared with other catalysis reactions, a relatively larger activation barrier for oxygen evolution/reduction reactions (OER/ORR), where multiple electron transfers are involved, is noted. Many works over the past decade thus have been focused on the atomic-scale control of the surface structure and the precise identification of surface composition change in catalyst materials to achieve better conversion efficiency. In particular, recent advances in various analytical tools have enabled noteworthy findings of unexpected catalytic features at atomic resolution, providing significant insights toward reducing the activation barriers and subsequently improving the catalytic performance. In addition to summarizing important surface issues, including lattice defects, related to the OER and ORR in this Review, we present the current status and discuss future perspectives of oxide- and alloy-based catalysts in terms of atomic-scale observation and manipulation.