Integration of Plasmonic Ag(I) Clusters and Fe(II) Porphyrinates into Metal‐Organic Frameworks for Efficient Photocatalytic CO2 Reduction Coupling with Photosynthesis of Pure H2O2

Abstract Efficient photocatalytic CO 2 reduction coupled with the photosynthesis of pure H 2 O 2 is a challenging and significant task. Herein, using classical CO 2 photoreduction site iron porphyrinate as the linker, Ag(I) clusters were spatially separated and evenly distributed within a new metal–organic framework (MOF), namely Ag 27 TPyP‐Fe . With water as electron donors, Ag 27 TPyP‐Fe exhibited remarkable performances in artificial photosynthetic overall reaction with CO yield of 36.5 μmol g −1 h −1 and ca . 100 % selectivity, as well as H 2 O 2 evolution rate of 35.9 μmol g −1 h −1 . Since H 2 O 2 in the liquid phase can be more readily separated from the gaseous products of CO 2 photoreduction, high‐purity H 2 O 2 with a concentration up to 0.1 mM was obtained. Confirmed by theoretical calculations and the established energy level diagram, the reductive iron(II) porphyrinates and oxidative Ag(I) clusters within an integrated framework functioned synergistically to achieve artificial photosynthesis. Furthermore, photoluminescence spectroscopy and photoelectrochemical measurements revealed that the robust connection of Ag(I) clusters and iron porphyrinate ligands facilitated efficient charge separation and rapid electron transfer, thereby enhancing the photocatalytic activity.