Synthesis of defected UIO‐66 with boosting the catalytic performance via rapid crystallization

Abstract Due to environmental and health concerns, it is very important to develop high activity oxidative desulfurization (ODS) catalyst for petroleum purification. Recently, defect engineering of metal organic frameworks (MOFs) to generate a large number of unsaturated catalytic active sites is a very promising approach. Defective MOF has good research value as ODS catalyst. Here, UIO‐66 with lots of defects can be prepared by rapid crystallization using concentrated hydrochloric acid as a modulator. The prepared UIO‐66 material has good industrial applicability due to its low synthesis temperature (100°C), short synthesis time (20–30 min), large‐scale preparation, and excellent catalytic performance (dibenzothiophene can be entirely removed in 6 min under the optimal catalytic conditions [25‐mg catalyst, 60°C, O/S 7.5]). The obtained material exhibits not only extraordinary ODS activity of 37.6 mmol h −1 g −1 but also good cycle stability for the removal of DBT (in 7 cycles without significant loss of activity, greater than 90.2%). And for large space volume 4,6‐DMDBT, it also shows excellent catalytic performance. The ODS mechanism of defect UIO‐66 for DBT is explored, and it proves that hydroxyl radicals and superoxide radicals are generated and play a critical role in ODS reaction. The excellent catalytic performance of defect UIO‐66 gives mainly the credit to the abundant defect sites, large specific surface area, and pore volume.