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

TY - JOUR

T1 - Ab Initio Cyclic Voltammetry on Cu(111), Cu(100) and Cu(110) in Acidic, Neutral and Alkaline Solutions

AU - Bagger, Alexander

AU - Arán-Ais, Rosa M.

AU - Halldin Stenlid, Joakim

AU - Campos Dos Santos, Egon

AU - Arnarson, Logi

AU - Jensen, Kim Degn

AU - Escudero‐Escribano, María

AU - Roldan Cuanya, Beatriz

AU - Rossmeisl, Jan

PY - 2019/11/19

Y1 - 2019/11/19

N2 - Electrochemical reactions depend on the electrochemical interface between the electrode 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 we use 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 electrolytes. The results have been validated by direct comparison to experimental cyclic voltammograms. The alkaline (NaOH) cyclic voltammograms are described by H* and OH*, while in neutral medium (KHCO3) the CO * species are dominating and in acidic (KCl) the Cl* species prevail. An almost one-to-one mapping is observed from simulation to experiments giving an atomistic understanding of the interface structure of the Cu facets. Atomistic understanding of the interface at relevant eletrolyte conditions will further allow realistic modelling of electrochemical reactions of importance for future eletrocatalytic studies.

AB - Electrochemical reactions depend on the electrochemical interface between the electrode 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 we use 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 electrolytes. The results have been validated by direct comparison to experimental cyclic voltammograms. The alkaline (NaOH) cyclic voltammograms are described by H* and OH*, while in neutral medium (KHCO3) the CO * species are dominating and in acidic (KCl) the Cl* species prevail. An almost one-to-one mapping is observed from simulation to experiments giving an atomistic understanding of the interface structure of the Cu facets. Atomistic understanding of the interface at relevant eletrolyte conditions will further allow realistic modelling of electrochemical reactions of importance for future eletrocatalytic studies.

U2 - 10.1002/cphc.201900509

DO - 10.1002/cphc.201900509

M3 - Journal article

C2 - 31430013

SN - 1439-4235

VL - 20

SP - 3096

EP - 3105

JO - ChemPhysChem

JF - ChemPhysChem

IS - 22

ER -