Solvent-Free Synthesis of ZIFs: A Route toward the Elusive Fe(II) Analogue of ZIF-8

Herein we report the synthesis of an elusive metal-organic framework, the iron(II) analogue of ZIF-8 with the formula Fe(2-methylimidazolate)(2), here denoted as MUV-3. The preparation of this highly interesting porous material, inaccessible by common synthetic procedures, occurs in a solvent-free reaction upon addition of an easily detachable template molecule, yielding single crystals of MUV-3. This methodology can be extended to other metals and imidazolate derivatives, allowing the preparation of ZIF-8, ZIF-67, and the unprecedented iron(II) ZIFs Fe(2-ethylimidazolate)(2) and Fe(2-methylbenzimidazolate)(2). The different performance of MUV-3 toward NO sorption, in comparison to ZIF-8, results from the chemisorption of NO molecules, which also causes a gate-opening behavior. Finally, the controlled pyrolysis of MUV-3 results in a N-doped graphitic nanocomposite that exhibits extraordinary performance for the oxygen evolution reaction (OER), with low overpotential at different current densities (316 mV at 10 mA cm(-2)), low Tafel slope (37 mV per decade), high maximum current density (710 mA cm(-2) at 2.0 V vs RHE), and great durability (15 h).