Optimizing the Intermediates Adsorption by Manipulating the Second Coordination Shell of Ir Single Atoms for Efficient Water Oxidation

The precise regulation of single‐atom catalysts (SACs) with the desired local chemical environment is vital to elucidate the relationship between the SACs structure and the catalytic performance. The debate on the effect of the local coordination environment is quite complicated even for the SACs with the same composition and chemical nature, calling for increased attention on the regulation of second coordination shell. For oxide‐supported SACs, it remains a significant challenge to precisely manipulate the second coordination shell of single atoms supported on oxides due to the structural robustness of oxides. Here, Ir single atoms are anchored on NiO supports via different bonding strategies, resulting in the diverse Ir‐O‐Ni coordination numbers for Ir sites. Specifically, Ir1/NiO, Ir1‐NiO, and Ir1@NiO SACs with increasing Ir‐O‐Ni coordination numbers of 3, 4, and 5 were synthesized, respectively. We found that the activity of the three samples towards oxygen evolution reaction (OER) exhibited a volcano‐shaped relationship with the Ir‐O‐Ni coordination number, with Ir1‐NiO showing the lowest overpotential of 225 mV at 10 mA cm‐2. Mechanism investigations indicate that the moderate coordination number of Ir‐O‐Ni in Ir1‐NiO creates the higher occupied Ir dz2 orbital, weakening the adsorption strength for *OOH intermediates and thereby enhancing the OER activity.