Electronic Phosphide-Support Interactions in Carbon-Supported Molybdenum Phosphide Catalysts Derived from Metal-Organic Frameworks.

Interfacial interaction in carbon-supported catalysts can offer geometric, electronic, and compositional effects that can be utilized to regulate catalytically active sites, while this is far from being systematically investigated in carbon-supported phosphide catalysts. Here, we proposed a novel concept of electronic phosphide-support interaction (EPSI), which was confirmed by using molybdenum phosphide (MoP) supported on nitrogen-phosphorus codoped carbon (NPC) as a model catalyst (MoP@NPC). Such a strong EPSI could not only stabilize MoP in a low-oxidation state under environmental conditions but also regulate its electronic structure, leading to reduced dissociation energy of the oxygen-containing intermediates and enhancing the catalytic activity for oxidative desulfurization. The removal of dibenzothiophene over the MoP@NPC was as high as 100% with a turnover frequency (TOF) value of 0.0027 s -1 , which was 33 times higher than that of MoP without EPSI. This work will open new avenues for the development of high-performance supported phosphide catalysts.