Danfei Fu, Hao Yang, Zhongjie Yang
ABSTRACT Renewable electricity‐driven electrocatalytic nitrate reduction for ammonia production is not only beneficial for the treatment of nitrogen‐containing wastewater but also facilitates the recovery of valuable resources. Metal‐organic frameworks (MOFs)‐based electrocatalysts have been extensively investigated as promising nitrate reduction reaction (NO 3 − RR) catalysts due to their structural and compositional tunability, as well as their highly dispersed active sites. Herein, the recent research advances made in MOFs and their‐derived electrocatalysts for NO 3 − RR are reviewed. In the discussions, an attempt is made to highlight the advantages of MOFs and their derivatives in NO 3 − RR, focusing on key aspects including catalyst design strategies, reaction mechanisms, and approaches for enhancing catalytic performance. First, microstructure regulation enhances the catalytic activity of MOFs and their derivatives, and structure–activity relationships are analyzed for NO 3 − RR. Then, by integrating theoretical calculations and advanced in situ characterization, we thoroughly summarized the key intermediates, rate‐determining steps, and electron/proton transfer mechanisms in the NO 3 − RR reaction pathway. Finally, we provide insights into future directions and prospects regarding the design, synthesis, and evaluation of MOFs‐based electrocatalysts for enhanced NO 3 − RR.