A Dynamically Stabilized Single‐Nickel Electrocatalyst for Selective Reduction of Oxygen to Hydrogen Peroxide

On‐location electrochemical generation of H 2 O 2 is of great current interest. Herein, selective two‐electron reduction of O 2 to H 2 O 2 by a single [Ni II (H 2 O) 6 ] 2+ cation that is dynamically associated with a negatively charged metal–organic layer (MOL) by hydrogen bonding and coulombic interactions is reported. In contrast, Ni II centers covalently immobilized on the MOL reduce O 2 to H 2 O in a four‐ electron process. Oxygen adsorption by [Ni II (H 2 O) 6 ] 2+ followed by two‐electron reduction generates neutral [Ni II (H 2 O) 4 (OH)(OOH)] 0 , which momentarily disconnects from the negatively charged MOL to avoid the injection of additional electrons. Release of H 2 O 2 from [Ni II (H 2 O) 4 (OH)(OOH)] 0 regenerates [Ni II (H 2 O) 6 ] 2+ , which regains affinity to the MOL. Such dynamically associated Ni II single‐metal electrocatalysts ensure high selectivity and represent a new strategy for generating selective catalysts for electrochemical production of important chemicals.