Steering sp‐Carbon Content in Graphdiynes for Enhanced Two‐Electron Oxygen Reduction to Hydrogen Peroxide

Compared to sp2‐hybridized graphene, graphdiynes (GDYs) composed of sp and sp2 carbon are highly promising as efficient catalysts for electrocatalytic oxygen reduction into oxygen peroxide because of the high catalytic reactivity of the electron‐rich sp‐carbon atoms. The desired catalytic capacity of GDY, such as catalytic selectivity and efficiency, can theoretically be achieved by strategically steering the sp‐carbon contents or the topological arrangement of the acetylenic linkages and aromatic bonds. Herein, we successfully tuned the electrocatalytic activity of GDYs by regulating the sp‐to‐sp2 carbon ratios with different organic monomer precursors. As the active sp‐carbon atoms possess electron‐sufficient π orbitals, they can donate electrons to the lowest unoccupied molecular orbital (LUMO) orbitals of O2 molecules and initiate subsequent O2 reduction, GDY with the high sp‐carbon content of 50 at% exhibits excellent capability of catalyzing O2 reduction into H2O2. It demonstrates exceptional H2O2 selectivity of over 95.0% and impressive performance in practical H2O2 production, Faraday efficiency (FE) exceeding 99.0%, and a yield of 83.3 nmol s–1 cm–2. Our work holds significant importance in effectively steering the inherent properties of GDYs by purposefully adjusting the sp‐to‐sp2 carbon ratio and highlights their immense potential for research and applications in catalysis and other fields.