MOFs‐Derived N‐Doped Carbon‐Encapsulated Metal/Alloy Electrocatalysts to Tune the Electronic Structure and Reactivity of Carbon Active Sites†

Abstract Despite progress over the past few years in developing efficient low‐cost catalysts, precious metals are still the best catalysts for hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). However, the natural scarcity and high cost greatly hamper their large‐scale commercialization. The combination of graphene shell with metal core could tune the electronic structure of carbon active sites. Recently, nitrogen doped graphene encapsulated metal or alloy (M@NG) has emerged as novel and fascinating electrocatalysts. In this review, we focus on some recent advances in designing M@NG electrocatalysts for HER, OER and ORR through tuning electronic structure and activity of carbon active sites. We have summarized some facile and universal strategy for synthesizing various M@NG via direct annealing of metal‐organic frameworks (MOFs). With elaborated MOFs precursor design, careful control over the nitrogen doping level, metal element types and alloy structure, the electronic structure of carbon active sites can be rationally tuned to optimize activity for different electrochemical reactions. We hope this review can provide new insights into the design of M@NG with high catalytic activity.