Engineering 3d‐2p‐4f Gradient Orbital Coupling to Enhance Electrocatalytic Oxygen Reduction

The development of highly efficient and economical materials for the oxygen reduction reaction (ORR) plays a key role in practical energy conversion technologies. However, the intrinsic scaling relations exert thermodynamic inhibition on realizing highly active ORR electrocatalysts. Herein, a novel and feasible gradient orbital coupling strategy for tuning the ORR performance through the construction of Co 3d-O 2p-Eu 4f unit sites on the Eu2O3-Co model is proposed. Through the gradient orbital coupling, the pristine ionic property between Eu and O atoms is assigned with increased covalency, which optimizes the e(g) occupancy of Co sites, and weakens the O(sic)O bond, thus ultimately breaking the scaling relation between *OOH and *OH at Co-O-Eu unit sites. The optimized model catalyst displays onset and half-wave potential of 1.007 and 0.887 V versus reversible hydrogen electrode, respectively, which are higher than those of commercial Pt/C and most Co-based catalysts ever reported. In addition, the catalyst is found to possess superior selectivity and durability. It also reveals better cell performance than commercial noble-metal catalysts in Zn-air batteries in terms of high power/energy densities and long cycle life. This study provides a new perspective for electronic modulation strategy by the construction of gradient 3d-2p-4f orbital coupling.