Metal-Organic Frameworks (MOFs) are porous, crystalline materials constructed from organic linkers and metal nodes that have myriad potential applications in gas separations, storage, and catalysis. However, the sustainable and controlled synthesis of MOFs remains a "black box" in many cases, making it challenging to prepare MOFs with a well-defined crystallite size distribution on large scale. Here, we discuss several findings en route to sustainable and scalable strategies to prepare MOFs. First, we demonstrate that high-concentration synthesis produces kinetic intermediates during the synthesis of MOF-74 materials. These intermediates possess structural features that the thermodynamic MOF does not, such as solid-state photoluminesence, and can be used as precursors to produce high-quality MOF nanocrystals. We extend this strategy to the mechanochemical synthesis of MOF-74 analogues using exogenous organic base, as well as to the controlled synthesis of MOF-74 analogues by slow addition of exogenous base. Our strategies provide new avenues to prepare MOFs in a controlled manner on large scale.

Opening the black box: New strategies for the synthesis of metal-organic frameworks

ACS Spring Meeting 2021

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