Does a Thermoneutral Electrocatalyst Correspond to the Apex of a Volcano Plot for a Simple Two-Electron Process?

Area of Science:

• Electrocatalysis
• Materials Science
• Chemical Kinetics

Background:

• Volcano analyses are standard for evaluating electrocatalyst performance.
• The apex of the volcano curve typically represents ideal thermoneutral binding of reaction intermediates per Sabatier's principle.
• Recent findings suggest a shift, with optimal catalysts exhibiting endergonic binding at zero overpotential.

Purpose of the Study:

• To investigate the implications of a right-shifted volcano curve apex.
• To redefine the optimum catalyst requirements in light of new experimental observations.
• To analyze how kinetic effects and applied overpotential influence catalyst performance and Sabatier's principle.

Main Methods:

• Theoretical analysis and viewpoint discussion.
• Focus on two-electron electrochemical processes.
• Inclusion of kinetic factors and applied overpotential in catalyst assessment.

Main Results:

• The traditional definition of an optimum catalyst based on thermoneutral binding may be insufficient.
• Endergonic binding of intermediates can lead to enhanced catalytic activity under specific conditions.
• Kinetic effects and overpotential significantly alter the position of the volcano curve apex.

Conclusions:

• The definition of an optimum electrocatalyst needs revision to incorporate kinetic effects and overpotential.
• Sabatier's principle requires modification when applied to real-world electrocatalytic systems.
• This viewpoint provides a framework for understanding and designing more efficient electrocatalysts.