A series of zirconium polyphenolate-decorated-(metallo)porphyrin metal-organic frameworks (MOFs), ZrPP-n (n = 1, 2), featuring infinite Zr -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 CO trapping capability (≈90 cm g at 1 atm, 273 K, among the highest in Zr-MOFs) but also high photocatalytic activity for reduction of CO into CO (≈14 mmol g h ) and high selectivity over CH (>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 CO -to-CO over ZrPP-1-Co is also proposed.

Traditional semiconducting metal oxide-based gas sensors are always limited on low surface areas and high operating temperatures. Considering the high surface area and high stability of zeolitic imidazolate framework (ZIF), ZIF-67 (surface area of 1832.2 m(2) g(-1)) was first employed as a promising formaldehyde gas sensor at a low operating temperature (150 °C), and the gas sensor could detect formaldehyde as low as 5 ppm. This work develops a new promising application approach for porous metal-organic frameworks.