High Capacity Oil Denitrogenation Over Azine and Tetrazine Decorated Metal-Organic Frameworks: Critical Roles of Hydrogen-Bonding

In this work, we demonstrate that rational decoration of pore walls of the metal–organic frameworks (MOFs) with azine and dihydro-tetrazine functions is a very practical strategy for high capacity removal of both neutral and basic nitrogen-containing compounds (NCCs) from model oil. Its performance is even much better than the MOFs with high surface area, open metal sites, and different functional groups such as amine, hydroxyl, carboxy, and sulfonate. For this aim, a number of isostructure functional MOFs (FMOFs) have been synthesized. Among them, TMU-5 (with formula [Zn(OBA)(BPDH)0.5]n·1.5DMF, where H2OBA = 4,4′-oxybis(benzoic acid) and BPDH = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene) and TMU-34 (with formula [Zn(OBA)(H2DPT)0.5]n·DMF H2DPT = 3,6-di(pyridin-4-yl)-1,4-dihydro-1,2,4,5-tetrazine) show high affinity toward neutral and basic NCCs, respectively. Dihydro-tetrazine-decorated TMU-34 shows good affinity toward basic NCCs [pyridine (PYD) and quinoline (QUI)] because of hydrogen bonding of dihydro...