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 ZrO(OH)(BDC), HBDC 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 Qui and 1176 mg·g Ind, while MIL-140(Zr)-DHTZ adsorbs 619 mg·g Qui and 511 mg·g Ind. The lower adsorption capacities of MIL-140(Zr)-DHTZ compared to UiO-66(Zr)-DHTZ are related to its lower surface area (783 m·g versus 330 m·g). 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.