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Five key concepts linking vacancies, structure, and oxygen evolution reaction activity in cobalt-based

Kenneth Crossley¹, Thomas J Schmidt^1,2, Emiliana Fabbri¹

¹PSI Center for Energy and Environmental Science, 5232 Villigen PSI, Switzerland. emiliana.fabbri@psi.ch.

Chemical Communications (Cambridge, England)

|July 16, 2025

Summary

Cation and oxygen vacancies significantly influence cobalt-based electrocatalysts for the oxygen evolution reaction (OER). Engineering these vacancies is key to optimizing catalyst activity and understanding reaction mechanisms.

Area of Science:

Materials Science
Electrochemistry
Catalysis

Background:

Cobalt-based materials are crucial electrocatalysts for the oxygen evolution reaction (OER).
Surface reconstruction and reaction mechanisms critically impact OER catalyst performance.
Vacancies, specifically cation and oxygen vacancies, are increasingly recognized as key factors influencing catalyst behavior.

Purpose of the Study:

To review the multifaceted roles of cation and oxygen vacancies in cobalt-based OER electrocatalysts.
To elucidate how these vacancies dictate surface reconstruction, reaction pathways, and overall catalytic activity.
To examine the facet-dependent nature of vacancy effects and explore strategies for vacancy quantification.

Main Methods:

Literature review focusing on five key concepts related to vacancies in cobalt-based OER electrocatalysts.
Analysis of how cation and oxygen vacancies influence reactant adsorption and surface reconstruction.
Examination of the transition between the adsorbate evolution mechanism (AEM) and lattice oxygen evolution mechanism (LOEM) driven by vacancies.

Main Results:

Cation and oxygen vacancies initiate reactant adsorption, promoting active surface reconstruction.
Vacancies can shift the OER mechanism from AEM to LOEM, impacting efficiency.
The observed effects of vacancies are strongly dependent on the specific crystallographic facet of the catalyst.

Conclusions:

Rigorous quantification of oxygen vacancies is essential for identifying OER mechanism steering thresholds.
Vacancy engineering holds significant potential for unlocking enhanced performance in OER electrocatalysts.
Critical examination of oxygen vacancy quantification strategies is needed to advance the field.

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