Regulated Dual Defects of Bridging Organic and Terminal Inorganic Ligands in Iron‐based Metal‐Organic Framework Nodes for Efficient Photocatalytic Ammonia Synthesis

Engineering advantageous defects to construct well‐defined active sites in catalysts is promising but challenging to achieve efficient photocatalytic NH3 synthesis from N2 and H2O due to the chemical inertness of N2 molecule. Here, we report defective Fe‐based metal‐organic framework (MOF) photocatalysts via a non‐thermal plasma‐assisted synthesis strategy, where their NH3 production capability is synergistically regulated by two types of defects, namely, bridging organic ligands and terminal inorganic ligands (OH− and H2O). Specially, the optimized MIL‐100(Fe) catalysts, where there are only terminal inorganic ligand defects and coexistence of dual defects, exhibit the respective 1.7‐ and 7.7‐fold activity enhancement comparable to the pristine catalyst under visible light irradiation. As revealed by experimental and theoretical calculation results, the dual defects in the catalyst induce the formation of abundant and highly accessible coordinatively unsaturated Fe active sites and synergistically optimize their geometric and electronic structures, which favors the injection of more d‐orbital electrons in Fe sites into the N2 π* antibonding orbital to achieve N2 activation and the formation of a key intermediate *NNH in the reaction. This work provides a guidance on the rational design and accurate construction of porous catalysts with precise defective structures for high‐performance activation of catalytic molecules. The regulated dual defects of bridging organic ligands and terminal ligands of hydroxyls (OH−) and H2O induce the formation of exposed coordinatively unsaturated Fe centers as active sites in a Fe‐based MOF catalyst, resulting in the efficient activation of inert N2 molecules and thus the enhanced photocatalytic NH3 production.