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

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.