Ab Initio Cyclic Voltammetry on Cu(111), Cu(100) and Cu(110) in Acidic, Neutral and Alkaline Solutions

Electrochemical reactions depend on the electrochemical interface; between the catalytic surfaces and the electrolytes. To control and advance electrochemical reactions there is a need to develop realistic simulation models of the electrochemical interface to understand the interface from an atomistic point-of-view. Here we present a method for obtaining thermodynamic realistic interface structures, a procedure to derive specific coverages and to obtain ab initio simulated cyclic voltammograms. As a case study, the method and procedure is applied in a matrix study of three Cu facets in three different electrolyte. The results are validated by a direct comparison with experimental cyclic voltammograms. The alkaline (NaOH) electrolyte CV are described by H* and OH*, while neutral (KHCO3) the CO3* species are present and in acidic (KCl) the Cl* species dominate. An almost one-to-one mapping is observed from simulation to experiments giving an atomistic understanding of the interface structure of the Cu facets. The strength of atomistic understanding the interface at electrolyte conditions will allow realistic investigations of electrochemical reactions in future studies.