Porphyrin-based metal–organic framework catalysts for photoreduction of CO2: understanding the effect of node connectivity and linker metalation on activity

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Abstract
Three zirconium–porphyrin based MOFs with different linker connectivity, PCN-222, PCN-223 and PCN-224, and their Zn(II) ion metalated analogues, were prepared and used as catalysts for the photoreduction of CO2 under visible-light irradiation. Before metalation with Zn2+ in the porphyrin linkers, the lowest linker-connected PCN-224 (6-fold) exhibited a higher formate yield rate of 45.2 μmol g−1 h−1 compared to PCN-222 and PCN-223. However, after the incorporation of Zn2+ into the porphyrin, PCN-222-Zn showed the highest formate yield rate of 120.2 μmol g−1 h−1. The density functional theory (DFT) computational results revealed that the catalytic activity correlated with the CO2 adsorption affinity. The CO2 adsorption energy on PCN-222-Zn (294.4 kJ mol−1) was the highest among all of the samples. The overall catalytic performance was affected by the Zr6-oxo cluster connectivity and the introduced dual reaction sites when the porphyrin linkers were metalated with Zn(II) ions.
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  • Huizhou University

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