Dihydrotetrazine-Functionalized Zirconium-Based Metal–Organic Frameworks for High-Capacity Oil Denitrogenation

High structural stability, dual organic-inorganic nature, and tunability in chemical functionality are promising characteristics of zirconium-based metal-organic frameworks (Zr-MOFs). These properties assist Zr-MOFs in extending their applications in various fields, especially adsorptive removal of pollutants. In this work, two well-known Zr-MOFs (UiO-66(Zr) and MIL-140(Zr) with the formula Zr₆O₄(OH)₄(BDC)₆, H₂BDC is benzene 1,4-dicarboxylic acid) were synthesized and decorated with a dihydrotetrazine functional group through postsynthesis linker exchange (PSLE). Two dihydrotetrazine (DHTZ)-functionalized frameworks, UiO-66(Zr)-DHTZ and MIL-140(Zr)-DHTZ, were applied for the removal of quinoline (Qui) and indole (Ind) from the model oil. The results of adsorption experiments at room temperature display that these functionalized Zr-MOFs have significantly improved removal capacities for Qui (875% for UiO-66(Zr)-DHTZ and 303% for MIL-140(Zr)-DHTZ) and Ind (722% for UiO-66(Zr)-DHTZ and 257% for MIL-140(Zr)-DHTZ). Mechanistic studies based on X-ray photoelectron (XPS) and Fourier-transform infrared (FT-IR) spectroscopies reveal that there is a specific kind of host-guest interaction between dihydrotetrazine and nitrogen-containing compounds (NCCs). UiO-66(Zr)-DHTZ adsorbs 1426 mg·g^-1 Qui and 1176 mg·g^-1 Ind, while MIL-140(Zr)-DHTZ adsorbs 619 mg·g^-1 Qui and 511 mg·g^-1 Ind. The lower adsorption capacities of MIL-140(Zr)-DHTZ compared to UiO-66(Zr)-DHTZ are related to its lower surface area (783 m²·g^-1 versus 330 m²·g^-1). The recyclability of the frameworks goes up to five cycles without any significant decrease in the removal capacity. These results indicate that dihydrotetrazine-functionalized Zr-MOFs are highly stable platforms with superior adsorption capacity compared to basic and neutral NCCs.