Chapter 5: Density Functional Theory Methods for Electrocatalysis

Electrochemical reactions occur at electrode surfaces in fuel cell and electrolysis applications. Their reaction mechanisms involve both chemical and electrochemical elementary steps. Increased computational power and advances in density functional theory (DFT) have enabled atomistic-level insights into the mechanisms of catalytic reactions. A number of approaches exist to extend DFT methods to consider electrocatalytic reactions. This chapter introduces the basic principles of the electrochemical interface and highlights the challenges of modeling electrocatalysis using DFT methods. The review of available DFT-based electrochemical models will show the reader approaches and approximations made to overcome those challenges. Finally, examples of selected models, ranging from the simplest linear free energy approach to more sophisticated double-layer representation will guide the reader step-by-step through how to apply DFT calculations to electrocatalytic systems.