Toward Realistic Models of the Electrocatalytic Oxygen Evolution Reaction

Area of Science:

• Electrochemistry
• Computational Chemistry
• Materials Science

Background:

• The oxygen evolution reaction (OER) is crucial for converting renewable electricity into fuels and chemicals.
• OER is kinetically limited, requiring significant overpotential due to its complex multi-step mechanism.
• Understanding OER mechanisms is vital for improving catalyst performance.

Purpose of the Study:

• To review advances in understanding the electrocatalytic oxygen evolution reaction (OER) mechanisms.
• To organize the review by the increasing complexity of OER modeling approaches.
• To assess the role and evolution of computational methods in OER mechanistic studies.

Main Methods:

• Review of phenomenological models based on experimental data.
• Analysis of early ab initio simulation studies of OER mechanisms.
• Examination of advanced ab initio simulations that relax previous assumptions (e.g., electric field, electrolyte, kinetics).

Main Results:

• Phenomenological models provide a foundational understanding of OER.
• Early ab initio simulations offered insights but relied on simplifying assumptions.
• Relaxing assumptions in ab initio models (e.g., including electric fields, electrolytes, and kinetics) enhances mechanistic accuracy.
• Comparison with experimental data validates different modeling approaches.

Conclusions:

• Computational modeling, particularly advanced ab initio simulations, plays an increasingly critical role in deciphering OER mechanisms.
• Addressing remaining challenges in modeling is essential for future OER catalyst development.
• The integration of experimental and computational approaches is key to overcoming OER complexity.