Structured Growth of Metal-Organic Framework MIL-53(Al) from Solid Aluminum Carbide Precursor.

The conventional synthesis of metal-organic frameworks (MOFs) through soluble metal-salt precursors provides little control over the growth of MOF crystals. The use of alternative metal precursors would provide a more flexible and cost-effective strategy for direction- and shape-controlled MOF synthesis. Here, we demonstrate for the first time the use of insoluble metal-carbon matrices to foster directed growth of MOFs. Aluminum carbide was implemented as both the metal precursor and growth-directing agent for the generation of MIL-53(Al). A unique needle-like morphology of the MOF was grown parallel to the bulk surface in a layer-by-layer manner. Importantly, the synthesis scheme was found to be transferrable to the production of different linker analogues of the MOF and other topologies. Given the variety of metal carbides available, these findings can be used as a blueprint for controlled, efficient, and economical MOF syntheses and set a new milestone toward the industrial use of MOFs at large-scale.