Metal substitution in the metalloporphyrin linker of metal−organic framework PCN-601 for photocatalytic CO₂ reduction

Abstract Metalloporphyrinic metal–organic framework PCN-601 exhibits high photocatalytic performance for CO 2 reduction. The photoreduction site was speculated to be the Ni atoms in nodes and thus single porphyrin centers are not effectively utilized. In this study, we applied Kohn–Sham density functional theory investigate effect of metal (Fe, Co, or Cu) substitution Ni-porphyrin linker on Our results show that properties Ni-porphyrin-based PCN-601, including photoexcitation, visible-light absorption, vacuum-aligned energy level, adsorption strength configuration, can further optimized by Fe linker. addition, Co-porphyrin-based is also found a promising candidate though its absorption relatively weak comparison with Fe- Ni-based analogs.