AbstractElectrocatalytic and photocatalytic nitrogen fixation have become new ways to achieve green nitrogen reduction because of their environmentally friendly and cost‐effective characteristics. At present, there has been an increasing curiosity about using metal‐organic frameworks (MOFs) for photocatalysis and electrocatalysis. However, electrocatalytic and photocatalytic ammonia production is still not practical for practical applications. Having a thorough understanding of nitrogen fixation is necessary for the advancement of practical applications and the development of highly efficient catalysts in the future. The catalytic nitrogen fixation activity of MOF itself is limited. By adjusting the exposure of active sites through low‐temperature calcination and solvent addition, the photogenerated carrier recombination is inhibited, and the adsorption and activation of N2 are enhanced, improving its performance in nitrogen fixation applications. This review examines the reported photocatalysts, electrocatalysts, and photoelectrocatalysts based on MOFs and their associated materials. The underlying mechanism for photocatalysis and electrocatalysis is elucidated. Additionally, an inclusive survey of MOFs and related materials as catalysts for nitrogen reduction reaction (NRR) is presented, with representative examples discussed. Finally, the research progress of MOF‐based catalytic nitrogen fixation materials is summarized and prospected.
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