Confining and Highly Dispersing Single Polyoxometalate Clusters in Covalent Organic Frameworks by Covalent Linkages for CO2 Photoreduction

Single clusters have attracted extensive research interest in the field of catalysis. However, achieving a highly uniform dispersion of a single-cluster catalyst is challenging. In this work, for the first time, we present a versatile strategy for uniformly dispersed polyoxometalates (POMs) in covalent organic frameworks (COFs) through confining POM cluster into the regular nanopores of COF by a covalent linkage. These COF-POM composites combine the properties of light absorption, electron transfer, and suitable catalytic active sites; as a result, they exhibit outstanding catalytic activity in artificial photosynthesis: that is, CO₂ photoreduction with H₂O as the electron donor. Among them, TCOF-MnMo₆ achieved the highest CO yield (37.25 μmol g^-1 h^-1 with ca. 100% selectivity) in a gas-solid reaction system. Furthermore, a mechanism study based on density functional theory (DFT) calculations demonstrated that the photoinduced electron transfer (PET) process occurs from the COF to the POM, and then CO₂ reduction and H₂O oxidation occur on the POM and COF, respectively. This work developed a method for a uniform dispersion of POM single clusters into a COF, which also shows the potential of using COF-POM functional materials in the field of photocatalysis.