Recent Advances in ZIF-Derived Atomic Metal-N-C Electrocatalysts for Oxygen Reduction Reaction: Synthetic Strategies, Active Centers, and Stabilities

Exploring highly active, stable electrocatalysts with earth-abundant metal centers for the oxygen reduction reaction (ORR) is essential for sustainable energy conversion. Due to the high cost and scarcity of platinum, it is a general trend to develop metal-N-C (M-N-C) electrocatalysts, especially those prepared from the zeolite imidazolate framework (ZIF) to replace/minimize usage of noble metals in ORR electrocatalysis for their amazingly high catalytic efficiency, great stability, and readily-tuned electronic structure. In this review, the most pivotal advances in mechanisms leading to declined catalytic performance, synthetic strategies, and design principles in engineering ZIF-derived M-N-C for efficient ORR catalysis, are presented. Notably, this review focuses on how to improve intrinsic ORR activity, such as M-N-x-C-y coordination structures, doping metal-free heteroatoms in M-N-C, dual/multi-metal sites, hydrogen passivation, and edge-hosted M-N-x. Meanwhile, how to increase active sites density, including formation of M-N complex, spatial confinement effects, and porous structure design, are discussed. Thereafter, challenges and future perspectives of M-N-C are also proposed. The authors believe this instructive review will provide experimental and theoretical guidance for designing future, highly active ORR electrocatalysts, and facilitate their applications in diverse ORR-related energy technologies.

Automated summary

This review highlights the significance of exploring highly active and stable electrocatalysts with earth-abundant metal centers for the oxygen reduction reaction (ORR). The focus is on the synthetic strategies and design principles of metal-N-C (M-N-C) electrocatalysts derived from zeolite imidazolate framework (ZIF) for efficient ORR catalysis. The review discusses methods to improve intrinsic ORR activity, such as coordination structures, doping metal-free heteroatoms, and edge-hosted structures, as well as strategies to increase active site density, including formation of M-N complexes and porous structure design.