Atomically Dispersed Iron Metal Site in a Porphyrin-Based Metal−Organic Framework for Photocatalytic Nitrogen Fixation

The rational design of photocatalysts for efficient nitrogen (N₂) fixation at ambient conditions is important for revolutionizing ammonia production and quite challenging because the great difficulty lies in the adsorption and activation of the inert N₂. Inspired by a biological molecule, chlorophyll, featuring a porphyrin structure as the photosensitizer and enzyme nitrogenase featuring an iron (Fe) atom as a favorable binding site for N₂ via π-backbonding, here we developed a porphyrin-based metal-organic framework (PMOF) with Fe as the active center as an artificial photocatalyst for N₂ reduction reaction (NRR) under ambient conditions. The PMOF features aluminum (Al) as metal node imparting high stability and Fe incorporated and atomically dispersed by residing at each porphyrin ring promoting the adsorption and the activation of N₂, termed Al-PMOF(Fe). Compared with the pristine Al-PMOF, Al-PMOF(Fe) exhibits a substantial enhancement in NH₃ yield (635 μg g^-1_cat.) and production rate (127 μg h^-1 g^-1_cat.) of 82% and 50%, respectively, on par with the best-performing MOF-based NRR catalysts. Three cycles of photocatalytic NRR experimental results corroborate a stable photocatalytic activity of Al-PMOF(Fe). The combined experimental and theoretical results reveal that the Fe-N site in Al-PMOF(Fe) is the active photocatalytic center that can mitigate the difficulty of the rate-determining step in photocatalytic NRR. The possible reaction pathways of NRR on Al-PMOF(Fe) were established. Our study of porphyrin-based MOF for the photocatalytic NRR will provide insight into the rational design of catalysts for artificial photosynthesis.