The development of a general method for the facile synthesis of hierarchical porous metal-organic frameworks (H-MOFs) with tunable porosities is important because of their widespread applications. Herein, through the ingenious use of different neutral organic amines as templates, we report the development of a green and versatile method to synthesize three H-MOFs (Cu-BTC, ZIF-8, and ZIF-90) with tunable morphologies and porosities. The selected neutral amine template molecules deprotonated organic ligands and facilitated the formation of H-MOFs while guiding the formation of meso- and macropores. These high quality as-synthesized H-MOFs possessed micro-, meso-, and macropore hierarchical structures and high thermal stability after the amine templates were removed by simple washing and drying. The as-prepared Cu-BTC H-MOFs exhibited more than 2 times higher activity than conventional microporous Cu-BTC in catalyzing Henry reaction. Our facile strategy establishes a green and general route to synthesize a large variety of H-MOFs for various applications, particularly when large molecules or biomolecules are involved.

由于其广泛的应用，开发一种易于合成具有可调孔隙率的多层多孔金属有机骨架（H-MOF）的通用方法非常重要。在本文中，通过巧妙地使用不同的中性有机胺作为模板，我们报告了一种绿色通用方法的发展，该方法可合成具有可调形态和孔隙度的三种H-MOF（Cu-BTC，ZIF-8和ZIF-90）。选定的中性胺模板分子使有机配体去质子化并促进H-MOF的形成，同时指导中孔和大孔的形成。在通过简单的洗涤和干燥除去胺模板后，这些高质量的合成H-MOF具有微孔，中孔和大孔层次结构，并且具有很高的热稳定性。所制备的Cu-BTC H-MOF在催化亨利反应中表现出比常规微孔Cu-BTC高两倍以上的活性。我们的简便策略建立了一条绿色的通用路线，可以合成用于各种应用的多种H-MOF，尤其是在涉及大分子或生物分子时。