Electrochemically Assisted Self-Assembly Technique for the Fabrication of Mesoporous Metal-Organic Framework Thin Films: Composition of 3D Hexagonally Packed Crystals with 2D Honeycomb-like Mesopores.

In this work, we introduce a novel and general strategy for the environmentally friendly fabrication of mesoporous metal-organic framework (mMOF) thin films via the electrochemically assisted self-assembly (EASA) technique. Implementation of this procedure as a one-step, additive-free, and versatile protocol leads to the in situ simultaneous synthesis and deposition of mesoporous architectures of MOFs at room temperature under green conditions without the need for any base, pretreatment, or chemical modification of the underlying surface. Our procedure provides a controllable method for the synthesis of mMOF thin films (modified electrodes) consisting of hollow three-dimensional hexagonally packed crystals with two-dimensional honeycomb-like mesopores in the walls of the cavities, which grow perpendicularly onto any of the conducting surface. The resulting modified electrodes show enhanced electron transfer properties and better mass transfer performance along with the appropriate signal suitable for electrochemical sensing applications. This work can be a breakthrough and provide a new perspective for the modification and functionalization of the surface with any type of mMOF by the electrochemically driven cooperative (soft-templating) mechanism.