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-tetrazine (−NH)···(N) basic NCCs. TMU-34 can adsorb about 619 and 632 mg g^–1 PYD and QUI, respectively. On the other hand, azine-methyl-functionalized TMU-5 shows very high affinity to neutral NCCs [pyrrole (PRR) and indole (IND)] owing to strong hydrogen bonding of azine-methyl (Me–CN–NC–Me)···(NH) neutral NCCs. TMU-5 can adsorb 518 and 578 mg g^–1 PRR and IND, respectively. These numbers are among the best reported data in this area and even reveal higher significance of the host–guest interaction when we consider moderate surface of these FMOFs. These results have been achieved by our “application-directed cavity functionalization” approach through decoration of MOF structures by suitable organic functional groups for specific purposes.