Metal‐Tuned Acetylene Linkages in Hydrogen Substituted Graphdiyne Boosting the Electrochemical Oxygen Reduction

Different from graphene with the highly stable sp 2 ‐hybridized carbon atoms, which shows poor controllability for constructing strong interactions between graphene and guest metal, graphdiyne has a great potential to be engineered because its high‐reactive acetylene linkages can effectively chelate metal atoms. Herein, a hydrogen‐substituted graphdiyne (HsGDY) supported metal catalyst system through in situ growth of Cu 3 Pd nanoalloys on HsGDY surface is developed. Benefiting from the strong metal‐chelating ability of acetylenic linkages, Cu 3 Pd nanoalloys are intimately anchored on HsGDY surface that accordingly creates a strong interaction. The optimal HsGDY‐supported Cu 3 Pd catalyst (HsGDY/Cu 3 Pd‐750) exhibits outstanding electrocatalytic activity for the oxygen reduction reaction (ORR) with an admirable half‐wave potential (0.870 V), an impressive kinetic current density at 0.75 V (57.7 mA cm −2 ) and long‐term stability, far outperforming those of the state‐of‐the‐art Pt/C catalyst (0.859 V and 15.8 mA cm −2 ). This excellent performance is further highlighted by the Zn–air battery using HsGDY/Cu 3 Pd‐750 as cathode. Density function theory calculations show that such electrocatalytic performance is attributed to the strong interaction between Cu 3 Pd and CC bonds of HsGDY, which causes the asymmetric electron distribution on two carbon atoms of CC bond and the strong charge transfer to weaken the shoulder‐to‐shoulder π conjugation, eventually facilitating the ORR process.