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

Efficient photocatalytic CO₂ reduction coupled with the photosynthesis of pure H₂O₂ is a challenging and significant task. Herein, using classical CO₂ photoreduction site iron porphyrinate as the linker, Ag(I) clusters were spatially separated and evenly distributed within a new metal-organic framework (MOF), namely Ag₂₇TPyP-Fe. With water as electron donors, Ag₂₇TPyP-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 H₂O₂ evolution rate of 35.9 μmol g^-1 h^-1. Since H₂O₂ in the liquid phase can be more readily separated from the gaseous products of CO₂ photoreduction, high-purity H₂O₂ 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.