Air-Steam Etched Construction of Hierarchically Porous Metal-Organic Frameworks

The introduction of mesoporosity into the microporous metal-organic frameworks(MOFs)is expected to expand their applications.Herein,we report a green and facile method to obtain hierarchically porous MOF structures by using an air-steam etching process.By virtue of the protonation reaction between the imidazole moiety and water vapor,the protonated imidazole related linkers leave the framework,resulting in the formation of mesopores in the zeolitic imidazolate frameworks(ZIFs),as exemplified by ZIF-8.Given the mild etching process,the materials'structural integrity and crystallinity are well maintained.Accordingly,the hierarchical porous ZIF-8 exhibited enhanced performance in the dye removal as well as CO_(2) cycloaddition reaction with epichlorohydrin in comparison with microporous ZIF-8,owing to the accelerated mass transfer arising from mesoporous structures.Remarkably,the proposed steam etching approach is generally applicable,which can be readily extended to other ZIFs,such as ZIF-14,ZIF-69,and ZIF-71,thus representing a powerful strategy to construct hierarchically porous MOF materials.

Pore engineering of ZIF-8 with ionic liquids for membrane-based CO_(2)separation:bearing functional group effect

CO_(2)separation performance of polymer membranes can be significantly enhanced by selecting porous fillers with high CO_(2)affinity.Ionic liquids incorporation has been recognized as an effective strategy for improving the separation ability of pristine porous fillers.However,the influence of the specific functional groups of ILs in IL@MOF composites on separation performance of MMMs still remains unclear.Herein,we designed three microenvironment-tuned IL@ZIF-8 composites in which the three ILs contain different functional groups(-CH3,–SO3H,and–NH2).Molecular simulation results showed that the NH2-IL@ZIF-8 has a commendable CO_(2)adsorption capacity and CO_(2)/CH4 adsorptive selectivity,and the results were well confirmed by the following experimental data.More importantly,the prepared NH2-IL@ZIF-8 based MMMs also exhibit superior CO_(2)separation performance among the three IL@ZIF-8 based MMMs owning to its high CO_(2)affinity.Thus,this work can provide guidance for designing IL@MOF composites for MMMs fabrication towards gas separation,and the research mode combining molecular simulation prediction and experimental verification can afford valuable reference for material development in membrane separation field.