Defect‐Derived Catalysis Mechanism of Electrochemical Reactions in Two‐Dimensional Carbon Materials

In the past decades, remarkable progress has been achieved in the exploration of electrocatalysts with high activity, long durability, and low cost. Among these, defective graphene (DG)‐based catalysts are considered as one of the most potential substitutes for precious metal‐based electrocatalysts. DG‐based catalysts contain abundant active centers with different configurations resulting from their extraordinary high‐structural tunability. Herein, an overview on recent advancements in developing four kinds of DG‐based catalysts is presented: 1) heteroatoms‐doped graphene; 2) intrinsic DG (vacancy and topological defect); 3) nonmetal atoms or/and metal species‐modified intrinsic DG (heterogeneous species and intrinsic defects co‐tuned DG); and 4) DG‐based van der Waals‐type multilayered heterostructures. In particular, the synergistic effects between various defects are discussed, and the origin of catalytic activity is reviewed. Meanwhile, the established defect‐derived catalytic mechanism is summarized, which is beneficial for the rational design and fabrication of high‐performance electrocatalysts for practical energy‐related applications. Finally, challenges and future research directions on defect engineering in noble metal‐free materials for electrocatalysis are proposed.