Mechanistic Investigations of a Hydrogen-Evolving Cobalt Diimine-Dioxime Complex in an Oxygen Environment: Roles of Secondary Coordination Sphere, Bronsted Acid, and Axial Ligand.

ABSTRACT: The concept of a secondary coordination sphere (SCS) has been widely adopted in designing molecular electrocatalysts to promote energy-conversion reactions, such as the hydrogen-evolution reaction (HER) or the reduction of carbon dioxide. The role of SCS in the oxygen-tolerant properties of molecular electrocatalysts is less explored. An HER electrocatalyst, the cobalt diimine-dioxime complex, is one of the metal complexes designed by the concept of SCS to facilitate HER and retain its reactivity in an oxygen environment. Nevertheless, the mechanism underlying its oxygen tolerance remains unclear. This study revealed that in the presence of molecular oxygen, the oxygen reduction reaction (ORR) predominates over the hydrogen evolution reaction (HER) for this cobalt complex. Further investig

SUBMITTER: Tsai YS 

PROVIDER: S-EPMC11898077 | biostudies-literature | 2025 Mar

REPOSITORIES: biostudies-literature