Synergistic Ni–MoO3 Redox Catalysis in MIL‐101(Cr) for Efficient H2O2 Activation and Ultra‐Deep Desulfurization

In this study, a novel Ni–MoO 3 @MIL‐101(Cr) composite catalyst was synthesized via a one‐step hydrothermal method for the oxidative desulfurization (ODS) of dibenzothiophene (DBT). The catalyst combines the high specific surface area of MIL‐101(Cr) with the redox properties of Ni–MoO 3 , providing an effective synergy between adsorption and catalytic oxidation. The incorporation of Ni as a promoter significantly enhances catalytic activity, enabling complete sulfur removal (∼100%) under mild conditions (50 °C) within 60 min. Structural characterizations (scanning electron microscopy, X‐ray diffraction, and SAED) reveal that the catalyst retains its nanosheet–nanorod morphology and crystalline MoO 3 phase after repeated use, with only a slight decrease in the crystallinity of the MIL‐101(Cr) framework. Mechanistic analyses using X‐ray photoelectron spectroscopy, Raman, and temperature‐programmed reduction demonstrate that surface oxygen vacancies and Lewis acid sites promote ODS activity, while highly dispersed Ni–MoO 3 species facilitate H 2 O 2 activation and Mo 6+ /Mo 5+ redox cycling, leading to efficient generation of reactive oxygen species. The catalyst also exhibits excellent stability, maintaining 98.7% DBT conversion after five cycles. These results demonstrate that the strong Ni–Mo synergistic effect and efficient oxygen activation make Ni–MoO 3 @MIL‐101(Cr) a robust and highly efficient catalyst for deep fuel desulfurization. This study presents a significant advancement in the field of oxidative desulfurization by developing a synergistic Ni–MoO 3 redox catalytic system confined within the porous MIL‐101(Cr) framework. Unlike conventional catalysts, the designed material effectively enhances H 2 O 2 activation through cooperative interactions between Ni and Mo species, enabling rapid and ultra‐deep removal of refractory sulfur compounds under mild conditions. The integration of redox‐active sites with a high‐surface‐area MOF support not only improves catalytic efficiency but also ensures excellent stability and recyclability. This work provides new insights into the rational design of bimetallic catalysts for green fuel purification and offers a promising strategy for achieving sustainable and energy‐efficient desulfurization processes.