Spatial Heterogeneity and Strong Coupling of FeII/FeIII in an Individual Metal‐Organic Framework Nanoparticle for Efficient CO2 Photoreduction

Abstract

AbstractThe synthesis and characterization of an FeII/FeIII metal‐organic framework (MOF) nanocrystal with spatial heterogeneity that arises from the non‐uniform distribution of different valence states is disclosed. The FeII/FeIII‐Ni Prussian blue analog (PBA) delivers superior photocatalytic performance in the selective CO2 reduction reaction thanks to the strong FeII/FeIII coupling, with CO yield up to 12.27 mmol g−1 h−1 and 90.6% selectivity under visible‐light irradiation. Density functional theory calculation and experimental studies prove that the spatial heterogeneity of FeII/FeIII in the individual MOF nanocrystal not only directs and expedites the charge transfer within a catalyst particle but also creates the heterogeneity of catalytically‐active Ni sites for efficient CO2 photoreduction. The current findings add to a growing literature of materials with compositional heterogeneity and provide a reference for future research.