Hierarchically Ordered Pore Engineering of Metal−Organic Framework‐based Materials for Electrocatalysis

Abstract Ordered pore engineering that embeds uniform pores with periodic alignment in electrocatalysts opens up a new avenue for achieving further performance promotion. Hierarchically ordered porous metal–organic frameworks (HOP‐MOFs) possessing multilevel pores with ordered distribution are the promising precursors for the exploration of ordered porous electrocatalysts, while the scalable acquisition of HOP‐MOFs with editable components and adjustable pore size regimes is critical. This review presents recent progress on hierarchically ordered pore engineering of MOF‐based materials for enhanced electrocatalysis. The synthetic strategies of HOP‐MOFs with different pore size regimes, including the self‐assembly guided by reticular chemistry, surfactant, nanoemulsion, and nanocasting, are first introduced. Then the applications of HOP‐MOFs as the precursors for exploring hierarchically ordered porous electrocatalysts are summarized, selecting representatives to highlight the boosted performance. Especially, the intensification of molecule and ion transport integrated with optimized electron transfer and site exposure over the hierarchically ordered porous derivatives are emphasized to clarify the directional transfer and integration effect endowed by ordered pore engineering. Finally, the remaining scientific challenges and an outlook of this field are proposed. It is hoped that this review will guide the hierarchically ordered pore engineering of nanocatalysts for boosting the catalytic performance and promoting the practical applications.