Acid and Base Resistant Zirconium Polyphenolate-Metalloporphyrin Scaffolds for Efficient CO 2 Photoreduction.

A series of zirconium polyphenolate-decorated-(metallo) porphyrin metalorganic frameworks (MOFs), ZrPP-n (n = 1, 2), featuring infinite ZrIV-oxo chains linked via polyphenolate groups on four peripheries of eclipse-arranged porphyrin macrocycles, are successfully constructed through a top-down process from simulation to synthesis. These are the unusual examples of Zr-MOFs (or MOFs in general) based on phenolic porphyrins, instead of commonly known carboxylate-based types. Representative ZrPP-1 not only exhibits strong acid resistance (pH = 1, HCl) but also remains intact even when immersed in saturated NaOH solution (approximate to 20 m), an exceptionally large range of pH resistance among MOFs. The metallation at the porphyrin core gives rise to materials with enhanced sorption and catalytic properties. In particular, ZrPP-1-Co, with precise and uniform distribution of active centers, exhibits not only high CO2 trapping capability (approximate to 90 cm(3) g(-1) at 1 atm, 273 K, among the highest in Zr-MOFs) but also high photocatalytic activity for reduction of CO2 into CO (approximate to 14 mmol g(-1) h(-1)) and high selectivity over CH4 (> 96.4%) without any cocatalyst under visible-light irradiation ( lambda > 420 nm). Given the strong chemical resistance under extreme alkali conditions, these catalysts can be recycled without appreciable loss of activity. The possible mechanism for photocatalytic reduction of CO2-to-CO over ZrPP-1-Co is also proposed.