Facilitated Photocatalytic CO2Reduction in Aerobic Environment on a Copper‐Porphyrin Metal–Organic Framework

Abstract

AbstractHerein, we fabricated a π–π stacking hybrid photocatalyst by combining two two‐dimensional (2D) materials: g‐C3N4and a Cu‐porphyrin metal–organic framework (MOF). After an aerobic photocatalytic pretreatment, this hybrid catalyst exhibited an unprecedented ability to photocatalytically reduce CO2to CO and CH4under the typical level (20 %) of O2in the air. Intriguingly, the presence of O2did not suppress CO2reduction; instead, a fivefold increase compared with that in the absence of O2was observed. Structural analysis indicated that during aerobic pretreatment, the Cu node in the 2D‐MOF moiety was hydroxylated by the hydroxyl generated from the reduction of O2. Then the formed hydroxylated Cu node maintained its structure during aerobic CO2reduction, whereas it underwent structural alteration and was reductively devitalized in the absence of O2. Theoretical calculations further demonstrated that CO2reduction, instead of O2reduction, occurred preferentially on the hydroxylated Cu node.