Metal–Organic Frameworks Derived from Zero-Valent Metal Substrates: Mechanisms of Formation and Modulation of Properties

The replicative construction of metal–organic frameworks (MOFs) templated with solvent-insoluble solid substrates is of marked importance, as it allows for the assembly of 2D and 3D macro- and mesoscopic architectures with properties that are challenging to attain by the conventional solution-based synthesis approach. This work reports an in situ and direct construction of MOFs from zero-valent metal substrates via a green hydrothermal oxidation–MOF construction chemistry without the use of any additional metal source, chemical reagents, or acidification of solvent, and elucidates the zero-valent metal derived formation mechanisms of MOFs and their structure modulation to 1D nanofibers (NFs), 2D film, and 3D core–shell microstructures. Through modulation of the competing surface oxidation-dissolution and MOF crystallization kinetics, Al@MIL-53 core–shell microstructures and MIL-53 (Al) NFs are obtained that exhibit unique morphologies and marked properties superior to the conventional MIL-53 (Al) powders. The generality of zero-valent metal-templated synthesis of MOFs is demonstrated with formation of MIL-53 (Al), HKUST-1, and ZIF-7 polycrystalline films on Al, Cu, and Zn metal meshes, elucidating the significance of the approach utilizing solid metal substrate that can be easily processed into various shapes, architectures, and compositions.