Effective visible‐light CO 2 photoreduction over (metallo)porphyrin‐based metal–organic frameworks to achieve useful hydrocarbons

Metal–organic frameworks (MOFs) have proved to be particularly appropriate for CO 2 conversion. In the present work, we report metalloporphyrin‐based MOFs, PCN‐222(M) (M = Fe, Co, Ni, and Cu), which promote photocatalytic CO 2 conversion to valuable chemicals. These ultra‐highly stable frameworks are constructed from Zr 6 clusters and metalloporphyrin linkers. Metalloporphyrinic MOF has been synthesized and employed as a visible‐light photocatalyst for carbon dioxide to form formate. The effect of metalloporphyrinic PCN‐222(M) on CO 2 reduction has been studied. Remarkably, PCN‐222(M) is highly efficient in visible light‐driven CO 2 reduction into formate ion compared with the nonmetal porphyrinic PCN‐222. Metal ions of porphyrinic linkers play a great role in CO 2 sorption, light harvesting, bandgap, photoluminescence (pL) intensity, and charge transfer, which influence CO 2 reduction. CO 2 adsorption and activation over metal ions of porphyrinic linkers play a significant part in the improvement of the conversion efficiency; the product obtained was characterized by gas chromatography/mass spectrometry (GC/MS) and ion mobility spectrometry (IMS) analyses. The reaction mechanism has been discussed in detail.