title: Oxygen Reduction on Ag(100) in Alkaline Solutions--A Theoretical Study.
abstract: Silver is much more reactive to oxygen than gold; nevertheless, in alkaline solutions, the rates of oxygen reduction on both metals are similar. To explain this phenomenon, the first, rate-determining step of oxygen reduction on Ag(100) is determined by a combination of DFT, molecular dynamics, and electrocatalysis theory. In vacuum, oxygen is adsorbed on Ag(100), but in the electrochemical environment, the adsorption energy is offset by the loss of hydration energy as the molecule approaches the surface. As a result, the first electron transfer should take place in an outer-sphere mode. Previously, the same mechanism for oxygen reduction on Au(100) has been predicted, and these calculations have been repeated by using a more advanced version of the electrocatalysis theory discussed herein to confirm previous conclusions. The theoretical results compare well with experimental data.
authors.affiliation: Institute of Theoretical Chemistry, Ulm University, 89069, Ulm, Germany.
authors.forename: Aleksej
authors.initials: A
authors.lastname: Goduljan
authors.affiliation: Institute of Theoretical Chemistry, Ulm University, 89069, Ulm, Germany.
authors.forename: Leandro Moreira
authors.initials: LM
authors.lastname: de Campos Pinto
authors.affiliation: Institute of Theoretical Chemistry, Ulm University, 89069, Ulm, Germany.
authors.forename: Fernanda
authors.initials: F
authors.lastname: Juarez
authors.affiliation: Institute of Theoretical Chemistry, Ulm University, 89069, Ulm, Germany.|Facultad de Matemática, Astronoma y Fsica, IFEG-CONICET, Universidad Nacional de Córdoba, Córdoba, Argentina.
authors.forename: Elizabeth
authors.initials: E
authors.lastname: Santos
authors.affiliation: Institute of Theoretical Chemistry, Ulm University, 89069, Ulm, Germany.
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Schmickler
keywords: density functional calculations; electrochemistry; electron transfer; oxygen; silver