A simple but efficient strategy to improve the ability
of adsorptive
denitrogenation (ADN) of MIL-101(M101) was studied by the in situ
encapsulation of phosphomolybdic acid (PMA) and the subsequent purification
of the as-synthesized product by the NH4F solution. After
the NH4F treatment, the vast majority of PMA was removed,
loss of organic ligand (BDC) was observed, and the fluorination of
the hydroxyl group in the M101 structure occurred. The ADN activities
of the Cr-MOF matrix composites before and after fluorination were
studied in detail. The rest of PMA interacts strongly with M101 and
assists the ADN activity. Coordination unsaturated metal sites (CUS)
in M101 are formed after fluorination and also contribute to ADN activity.
Further, fluoride anions replace most of the hydroxide groups in M101,
which can promote the ADN of quinoline (QUI) and indole (IND) through
an acid–base interaction and N-atom coordination with the CUS
in M101. P-M101-F 5% exhibits the highest adsorptive capacity and
excellent regeneration ability. Special emphasis in this work is placed
on structure modulation (including PMA doping, CUS creation, and fluorination)
of M101 for enhancing ADN activity, which provides a useful scaffold
for future research in the rational design of MOF-based ADN catalysts.