Rational confinement engineering of MOF‐derived carbon‐based electrocatalysts toward CO2 reduction and O2 reduction reactions

Abstract The goal of global carbon peak and neutrality gives an impetus to the utilization of clean energy (e.g., fuel cell) and carbon dioxide (CO 2 ) at a large scale, where the oxygen reduction reaction (ORR) and CO 2 reduction reaction (CO 2 RR) are the key reactions via the sustainable system, respectively. As a main precursor for fabricating affordable carbon‐based electrocatalysts with uniformly dispersed active centers and tailorable performances for ORR and CO 2 RR, metal organic frameworks (MOFs) have captured a surge of interest in recent years. Despite the facilitated development of MOF‐derived carbon‐based electrocatalysts by many investigations, it is still plagued by high overpotential and unsatisfied life span, which are greatly determined by the efficient and alterable confinement effect on synthesis and performance. In this review, firstly, the confined synthetic strategies (doping engineering, defect engineering, geometric engineering, etc.) of MOF‐derived carbon‐based electrocatalysts with multi‐sized active centers (atom, atomic clusters and nanoparticles (NPs)) are systematically summarized; secondly, the confinement effect on the interaction of ORR and CO 2 RR intermediates, as well as the catalytic durability and activity, was discussed from chemical and physical aspects. In the end, the review discusses the remaining challenges and emerging research topics in the future, including support upgradation and catalyst innovation, high selectivity and effective confinement synthesis, in situ and operando characterization techniques, theoretical investigation, and artificial intelligence (AI) assistant. The new understanding and insights into these aspects will guide the rational confinement concept of MOF‐derived carbon‐based electrocatalysts for ORR and CO 2 RR with optimized performances in terms of confinement engineering and are believed to be helpful for filling the existing gaps between scientific communities and practical use.