Au Nanoparticle-Anchored Hollow Nanospheres of a Single-Atomized Porphyrin-Covalent Organic Framework Hybrid for Boosting Photoreduction of CO2 under Solar Irradiation

Recent decades have seen a surge of interest in the photoreduction of carbon dioxide to fuels, and significant efforts have been made to develop efficient visible-light-driven photocatalysts. Nonetheless, efficient conversion of CO2 with selectivity has proven to be a persistent challenge. Here, a hybrid plasmonic covalent organic framework (COF) is developed by combining a hollow porphyrin-based COF with a cobalt (Co) single atom decorated with plasmonic Au nanoparticles (COF-366-Co(H)/Au) to greatly enhance photoreduction of CO2. The photocatalytic redox processes in this hybrid system are driven toward generation of CO by the plasmon-induced energetic electron transfer, improved light harvesting, and efficient surface reactions. The COF-366-Co(H)/Au shows excellent activity, producing CO at a rate of up to 1200 μmol g–1 h–1 with a selectivity of ca. 98%. The COF-366-Co(H)/Au exhibits an AQY of 0.5% at 420 nm, which is one of the notable values reported in the literature. This approach demonstrates the use of hollow COFs in tandem with single-atom and plasmonic nanoparticles toward solar-to-fuel conversion.