Non-Nernstian Effects in Theoretical Electrocatalysis

Area of Science:

• * Electrocatalysis and sustainable chemistry.
• * Theoretical and computational chemistry.
• * Surface science and interfacial phenomena.

Background:

• * Electrocatalysis is key to sustainable chemistry, offering energy efficiency and reduced emissions.
• * Theoretical understanding has evolved from Nernstian predictions to include second-order field effects.
• * Non-Nernstian field effects, involving species-electric field interactions, are increasingly recognized.

Purpose of the Study:

• * To review and elucidate non-Nernstian field effects in electrocatalysis.
• * To provide theoretical and computational strategies for understanding and exploiting these effects.
• * To bridge the gap between theoretical predictions and experimental observations.

Main Methods:

• * Comprehensive literature review of theoretical and computational studies.
• * Analysis of energetic contributions to capacitive and faradaic processes.
• * Discussion of strategies for theoretical modeling and experimental validation.

Main Results:

• * Clear distinction established between Nernstian and non-Nernstian electrocatalytic effects.
• * Non-Nernstian effects are shown to significantly influence reactivity and catalyst performance.
• * Theoretical frameworks for incorporating field effects are outlined.

Conclusions:

• * Non-Nernstian effects are critical for accurate mechanistic analysis and catalyst screening.
• * Exploiting these effects can lead to more efficient and selective electrocatalysts.
• * Experimental methods are proposed to isolate and validate non-Nernstian contributions.