Electrochemical reactions at the electrode/solution interface: Theory and applications to water electrolysis and oxygen reduction

Abstract

Theoretical simulations on complex electrochemical processes have been developed on the basis of the understanding in electrochemistry, which has benefited from quantum mechanics calculations. This article reviews the recent progress on the theory and applications in electrocatalysis. Two representative reactions, namely water electrolysis and oxygen reduction, are selected to illustrate how the theoretical methods are applied to electrocatalytic reactions. The microscopic nature of these electrochemical reactions under the applied potentials is described and the understanding of the reactions is summarized. The thermodynamics and kinetics of the electrochemical reactions affected by the interplay of the electrochemical potential, the bonding strength and the local surface structure are addressed at the atomic level. density functional theory, electrode/solution interface, water electrolysis, oxygen reduction reaction, review

Oxygen electrocatalysts for water electrolyzers and reversible fuel cells: status and perspective

“…On the other hand, it has been found that the surface local structure relevant to the stepped surface site greatly contributes to electrocatalytic activity. 131,132 That is, the stepped surface site such as Pt (211) can accommodate more oxygen species (O and OH) because atomic oxygen on the (111) surface moves to the (211) surface to form superoxy-type species. 132 Therefore, the utilization of more active sites by effectively modifying the surface structure as well as the binding energy of oxygen species are of great importance for the enhancement in oxygen kinetics.…”

Hydrogen production by alkaline water electrolysis

“…52,111,112 Considering that electrode reactions are the major causes of energy losses, the exact mechanism of the electrochemical processes has been pursued consistently for years, [113][114][115][116] to allow designing of highly efficient electrolytic cells, necessarily with better electrocatalysts. 117 However, the conventional theories in electrochemistry, 52 such as the Gouy-Chapman theory, the Nernst equation, and the Butler-Volmer model, do not fully allow the atomic-level understanding of the HER/OER at the electrolytic cell.…”

Silver nanostructures synthesis via optically induced electrochemical deposition

“…In an electrochemical reduction system, the kinetics at the interface between the electrode and bulk solution plays a pivotal role in the formation of the final products2930. In our OED system, at the interface between the illuminated solid α-Si:H substrate (namely, the virtual electrode) and bulk solution, a thin electric double layer (EDL, typically several nanometers) provides the voltage potential, reactive species, and environment for the overall reaction.…”