Atomically Dispersed Metal Catalysts for Oxygen Reduction Reaction: Two‐Electron vs. Four‐Electron Pathways

Developing eco-friendly electrochemical devices for electrosynthesis, fuel cells (FCs), and metal-air batteries (MABs) requires precisely designing the electronic pathway in the oxygen reduction reaction (ORR) process. Understanding the principle of developing low-cost, highly active, and stable catalysts helps to reduce the usage of noble metals in ORR. Atomically dispersed metal catalysts (ADMCs) emerge as promising alternatives to replace commercial noble metals due to their high utilization of active metal atoms, high intrinsic activity, and controllable coordination environments. In this review, the research tendency and reaction mechanisms in ORR are first summarized. The basic principles concerning the geometric size and chemical coordination of two-electron ORR (2e^- ORR) catalysts were then discussed, aiming to outline the evolution of material design from 2e^- ORR to four-electron ORR (4e^- ORR). Subsequently, recent advances in ADMCs primarily investigated for the 4e^- ORR are well-documented. These advances encompass studies on M-N-C coordination, light heteroatom doping, dual-metal atoms-based coordination, and interaction between nanoparticle (NPs)/nanoclusters (NCs) and atomically dispersed metals (ADMs). Finally, the setups for 2/4e^- ORR applications, key challenges, and opportunities in the future design of ADMCs for the ORR are highlighted.