Understanding Advanced Transition Metal‐Based Two Electron Oxygen Reduction Electrocatalysts from the Perspective of Phase Engineering

Abstract Non‐noble transition metal (TM)‐based compounds have recently become a focal point of extensive research interest as electrocatalysts for the two electron oxygen reduction (2e− ORR) process. To efficiently drive this reaction, these TM‐based electrocatalysts must bear unique physiochemical properties, which are strongly dependent on their phase structures. Consequently, adopting engineering strategies toward the phase structure has emerged as a cutting‐edge scientific pursuit, crucial for achieving high activity, selectivity, and stability in the electrocatalytic process. This comprehensive review addresses the intricate field of phase engineering applied to non‐noble TM‐based compounds for 2e− ORR. First, the connotation of phase engineering and fundamental concepts related to oxygen reduction kinetics and thermodynamics are succinctly elucidated. Subsequently, the focus shifts to a detailed discussion of various phase engineering approaches, including elemental doping, defect creation, heterostructure construction, coordination tuning, crystalline design, and polymorphic transformation to boost or revive the 2e− ORR performance (selectivity, activity, and stability) of TM‐based catalysts, accompanied by an insightful exploration of the phase‐performance correlation. Finally, the review proposes fresh perspectives on the current challenges and opportunities in this burgeoning field, together with several critical research directions for the future development of non‐noble TM‐based electrocatalysts.