For heterogeneous catalysis, it is well established that scaling relationships between the adsorption energies of intermediates limit the performance of a catalysts, including nitrogen reduction reaction (NRR), CO2 reduction reaction (CO2RR), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) . Taking OER and ORR on transition metal surfaces as examples, the universal scaling relationship between the adsorption energies of key intermediates(*OH, *O, and *OOH), represented by ΔG*O = 2ΔG*OH and ΔG*OOH = ΔG*OH + 3.2, set a theoretical limit of the overpotential at 370 mV for the most active metal . Highly active singlesites in SACs cannot be free from these scaling relations as well . It mainly originates from the homogeneity of the adsorption of intermediates, meaning that the adsorption site and pattern of different intermediates are not changed during the reaction process . Meanwhile, enzymes and molecular catalysts can break the homogeneity of adsorption and bypass the limit with the help of the secondary coordination ligands, by selectively tunning the adsorption of intermediates or even changing the mechanism from water nucleophilic attack (WNA), where water attacks a metal oxo speices, to coupling two metal-oxo entities (I2M), where two metal oxyl radicals form the O-O bond. Craig et al. found that the intramolecular H-bonding between *OOH and the coordinating ligands in Ru complexes could selectively stabilize *OOH intermediate and result to a lower value of ΔG*OOH -ΔG*OH, which is favorable for OER . Matheu et al. showed that H-bonding between dangling carboxylate group and *OOH can boost the kinetics of the *O to *OOH step in the WNA mechanism . Theoretical investigations have also predicted that the second coordination sphere could modulate the binding energy of the crucial *O intermediate . More drastic effect can be found when the secondary interactions change the mechanism of OER. For example, Zhang et al. reported that the carboxylate groups in Ru(tda)(py)2(tda = (2,2′:6′,2″-terpyridine)-6,6″-dicarboxylate, py = pyridine), can work as an oxide relay in catalytic water oxidation, which will replace the OOH intermediate with a per-carboxylate species . Therefore, identifying the secondary coordination effects (SCE) in SACs by means of theoretical computation may help us sort out how to leverage it to alter scaling relations in heterogeneous catalysis towards improved activities.