Large‐Scale Atomic Strain Defects on Palladium Surfaces for Enhanced Oxygen Reduction and Zinc–Air Batteries

Abstract Designing nano‐electrocatalysts rich in surface defects is critical to improve their catalytic performance. However, prevailing synthesis techniques rely heavily on complex procedures that compromise defect extensiveness and uniformity, casting a high demand for methods capable of synthesizing large‐scale crystalline defects. An innovative design strategy is herein proposed that induces ample strain/dislocation defects during the growth of palladium (Pd), which is well‐known as a good oxygen reduction reaction (ORR) catalyst. The controlled defect engineering on Pd core is achieved by the tensile stress exerted from an intentionally applied Fe₃O₄ skin layer during synthesis, which changes the surface free energy of Pd to stabilize the defect presence. With such large‐scale crystalline defects, this Pd catalyst exhibits significantly higher ORR activity than commercial Pt/C, enabling its promising future in zinc–air battery catalysis. Additionally, the protective Fe₃O₄ skin covering the catalyst also enhances its catalytic stability. Theoretical calculations show that the superior catalytic property of such defect‐engineered Pd is associated with the correspondingly modified adsorption energy of *O intermediates onto its surface, which further improves the reaction rate and thus boosts ORR kinetics. Findings here are expected to provide a paradigm for designing efficient and stable metal catalysts with plentiful large‐scale strain defects.