Carbonic anhydrase (CA) is a zinc-containing metalloprotein, in which the Zn active center plays the key role to transform CO into carbonate. Inspired by nature, herein we used metal-organic frameworks (MOFs) to mimic CA for CO conversion, on the basis of the structural similarity between the Zn coordination in MOFs and CA active center. The biomimetic activity of MOFs was investigated by detecting the hydrolysis of para-nitrophenyl acetate, which is a model reaction used to evaluate CA activity. The biomimetic materials (e.g., CFA-1) showed good catalytic activity, and excellent reusability, and solvent and thermal stability, which is very important for practical applications. In addition, ZIF-100 and CFA-1 were used to mimic CA to convert CO gas, and exhibited good efficiency on CO conversion compared with those of other porous materials (e.g., MCM-41, active carbon). This biomimetic study revealed a novel CO treatment method. Instead of simply using MOFs to absorb CO, ZIF-100 and CFA-1 were used to mimic CA for in situ CO conversion, which provides a new prospect in the biological and industrial applications of MOFs.

Highly efficient removal of trace propyne (C3H4) (propyne <1000 ppm) from propylene (C3H6) is an essential and challenging industrial process due to the high molecular similarity of C3H4 and C3H6.

Selective separation of propyne/propadiene mixture to obtain pure propadiene (allene), an essential feedstock for organic synthesis, remains an unsolved challenge in the petrochemical industry, thanks mainly to their similar physicochemical properties. We herein introduce a convenient and energy-efficient physisorptive approach to achieve propyne/propadiene separation using microporous metal-organic frameworks (MOFs). Specifically, HKUST-1, one of the most widely studied high surface area MOFs that is available commercially, is found to exhibit benchmark performance (propadiene production up to 69.6 cm3/g, purity > 99.5%) as verified by dynamic breakthrough experiments. Experimental and modeling studies provide insight into the performance of HKUST-1 and indicate that it can be attributed to a synergy between thermodynamics and kinetics that arises from abundant open metal sites and cage-based molecular traps in HKUST-1.

Integrating photocatalysis and biocatalysis to fabricate photobiocatalysts for asymmetric catalysis is of great significance but remains challenging. In this work, we build a photoenzymatic platform for asymmetric catalysis using rationally designed photocatalytic porphyrinic covalent organic frameworks (COFs) as mesoporous solid carriers to immobilize wheat germ lipase (WGL). The formed WGL@COFs photobiocatalysts show high enzymatic activity and good operational stability. Attributed to the proximity effect of photocatalysts and enzymes in one system, WGL@COFs exhibit good performance and reusability for an enantioselective Mannich reaction under visible light irradiation. Notably, this asymmetric reaction with the formation of C­(sp3)–C­(sp3) bonds cannot be achieved by WGL or COFs independently. Furthermore, various characterization techniques unveil the catalytic mechanism (singlet oxygen as the main pathway of asymmetric catalysis). This work creates a general and efficient strategy using COFs as photocatalytic platforms for enzyme immobilization to fabricate photobiocatalysts that realize highly efficient photoenzymatic asymmetric catalysis.