Theory and experiments join forces to characterize the electrocatalytic interface

Mononuclear Fe in N-doped carbon: computational elucidation of active sites for electrochemical oxygen reduction and oxygen evolution reactions

“…27,28 The simulation of the environment of electrocatalysts, including description of the solvent, the electrolyte and the applied potential, is also indispensable for a better understanding of electrocatalytic processes. 29 Beside the CHE method, a more detailed approach, named surface charging (SC), 30 can be applied to model electrocatalysis. In this approach, the influence of the solvent and of the applied potential are taken into consideration, which are especially important for studying adsorbates with large dipole moments.…”

Real-Time Characterization of the Fine Structure and Dynamics of an Electrical Double Layer at Electrode–Electrolyte Interfaces

“…Electrochemistry is central to a plethora of fields including energy conversion and storage, biochemistry, sensors, and corrosion, and it is concerned with the dynamic structure and processes at the electrode–electrolyte interface. For the knowledge-based development of these areas, a fundamental understanding of the corresponding electrode–electrolyte interfaces, particularly of the interface structure and dynamics on the molecular scale, is greatly demanded. − As first realized by Helmholtz, an electrified electrode surface repels ions with the same sign and attracts those with the opposite charge from the electrolyte, resulting in a depletion or enrichment of ions in the electrical double layer at the electrode–electrolyte interface . However, for systems involving the chemisorption of species from electrolytes on electrode surfaces, which is ubiquitous and has been of great concern in electrochemistry, this classical double layer theory is challenged and far away from fully describing the structure and dynamics at the interface.…”

Atomistic modeling of electrocatalysis: Are we there yet?

“…[270][271][272][273][274][275] Alternative operando (potential dependent) spectroscopies give also precious information about the surface state under operating conditions. 276,277 Reproducing (and interpreting) such data from first principles brings methods one step further toward validation. Nevertheless, most of these techniques do not directly probe the electrochemical reactivity.…”

“…In this respect, electrochemical scanning tunneling microscopy is most valuable, since it gives a direct depiction of the atomistic structure 270–275 . Alternative operando (potential dependent) spectroscopies give also precious information about the surface state under operating conditions 276,277 . Reproducing (and interpreting) such data from first principles brings methods one step further toward validation.…”