Highly selective oxygen reduction to H2O2 on π-d conjugated coordination polymers: The effect of coordination atoms

•Ni CCPs with different coordination structures (NiN2O2 and NiN4) were fabricated.•NiN2O2 exerts an H2O2 evolution rate of 374 mmol g−1 h−1 with a selectivity of 91 %.•A coordination atoms-dependent performance for H2O2 evolution has been demonstrated.•The NiN2O2 based gas-diffusion electrode realized high-flux H2O2 production.•The energy barrier for *OOH formation and hydrogenation are optimized in NiN2O2.