Molecule Confined Isolated Metal Sites Enable the Electrocatalytic Synthesis of Hydrogen Peroxide

The direct synthesis of hydrogen peroxide (H₂ O₂ ) through the two-electron oxygen reduction reaction is a promising alternative to the industrial anthraquinone oxidation process. Selectivity to H₂ O₂ is however limited by the four-electron pathway during oxygen reduction. Herein, it is reported that aminoanthraquinone confined isolated metal sites on carbon supports selectively steer oxygen reduction to H₂ O₂ through the two-electron pathway. Confining isolated NiNx sites under aminoanthraquinone increases the selectivity to H₂ O₂ from below 55% to above 80% over a wide potential range. Spectroscopy characterization and density functional theory calculations indicate that isolated NiNx sites are confined within a nanochannel formed between the molecule and the carbon support. The confinement reduces the thermodynamic barrier for OOH* desorption versus further dissociation, thus increasing the selectivity to H₂ O₂ . It is revealed how tailoring noncovalent interactions beyond the binding site can empower electrocatalysts for the direct synthesis of H₂ O₂ through oxygen reduction.