Unifying Scaling Relations and Multiple Reaction Mechanisms for Screening Transition Metal-Doped Co₃O₄ for Oxygen...

Area of Science:

• Materials Science
• Electrochemistry
• Computational Chemistry

Background:

• High-throughput screening is crucial for discovering new oxygen-evolution reaction (OER) catalysts.
• Descriptor-based frameworks combined with mechanistic analysis are needed for efficient catalyst development.
• Cobalt oxide (Co3O4) is a promising material for OER catalysis, but its activity can be tuned by doping.

Purpose of the Study:

• To develop a unified methodology for analyzing dopant effects on OER activity in Co3O4.
• To investigate the influence of various dopants (Cr, Mn, Fe, Ni, Cu, V) on Co3O4 OER performance.
• To establish a transferable theoretical framework for quantifying dopant effects in electrocatalysis.

Main Methods:

• Utilized density functional theory (DFT) calculations to model doped Co3O4 (001) facet.
• Developed a mechanistically resolved, potential-dependent volcano approach accounting for adsorption free energy uncertainty.
• Compared theoretical predictions with experimental results from synthesized Co3O4 nanoparticle catalysts.

Main Results:

• Identified Cr, Fe, Ni, and V as promising dopants enhancing OER activity in Co3O4.
• Chromium (Cr) exhibited the strongest OER promoting effect among all evaluated dopants.
• Theoretical predictions showed good qualitative agreement with experimental OER activity trends.

Conclusions:

• The developed theoretical model provides a transferable framework for analyzing dopant effects in electrocatalysis.
• Surface-enriched, Cr-doped Co3O4 nanoparticles confirmed the predicted increase in OER activity.
• This approach accelerates catalyst discovery by quantifying dopant effects and considering uncertainty.