The 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.
Keywords: CO2 photoreduction; compositional heterogeneity; metal-organic frameworks; seamless hetero-interface; single-particle catalyst.
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