Density Functional Theory Methods for Electrocatalysis
Electrocatalysis involves catalytic reactions occurring in electrochemical systems, where bond breaking and forming on the catalyst surface are coupled with electron and ion transfer. Electrocatalytic reactions occur in fuel cells, with examples such as hydrogen oxidation, methanol oxidation, and oxygen reduction as well as in electrolysis cells, with examples such as hydrogen evolution, water splitting, and carbon dioxide reduction. Density functional theory (DFT) can be used in a similar manner to its application to non-electrochemical catalytic reactions however, additional complexities arise owing to the electrochemical nature of the catalytic interface. As in typical heterogeneous catalysis, the electrocatalyst is generally a supported nanoparticle, and all of the same challenges in developing appropriate and computationally tractable model systems (use of low-index plane surfaces or small particles as models, for example) apply to electrocatalytic systems.