Acid and Base Resistant Zirconium Polyphenolate‐Metalloporphyrin Scaffolds for Efficient CO₂ Photoreduction

A series of zirconium polyphenolate-decorated-(metallo)porphyrin metal-organic 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 (≈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 (≈90 cm³ g⁻¹ at 1 atm, 273 K, among the highest in Zr-MOFs) but also high photocatalytic activity for reduction of CO₂ into CO (≈14 mmol g⁻¹ h⁻¹ ) and high selectivity over CH₄ (>96.4%) without any cocatalyst under visible-light irradiation (λ > 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.