Recent Advances in Metal‐Organic Framework‐Based Nanomaterials for Electrocatalytic Nitrogen Reduction

Abstract The production of ammonia under moderate conditions is of environmental and sustainable importance. The electrochemical nitrogen reduction reaction (E‐NRR) method has been intensively investigated in the recent decades. Nowadays, the further development of E‐NRR is largely hindered by the lack of competent electrocatalysts. Metal‐organic frameworks (MOFs) are considered as the next‐generation catalysts for E‐NRR, featuring their tailorable structures, abundant active sites and favorable porosity. To present a comprehensive review on both the fundamental and advanced development in MOFs catalyst‐based E‐NRR field, this paper first introduces the basic principles of E‐NRR, including the reaction mechanism, major apparatus components, performance criteria, and ammonia detection protocols. Next, the synthesis and characterization methods for MOFs and their derivatives are discussed. In addition, a reaction mechanism study via density functional theory calculations is also presented. After that, the recent advancement of MOF‐based catalysts in the E‐NRR field as well as the modification approaches on MOFs for E‐NRR optimization is elaborated. Finally, the current challenges and outlook of MOF catalyst‐based E‐NRR field are emphasized.