Atomically Permeated MoP‐WO_x Core‐Shell Catalysts for Efficient and Selective Oxidation of Thiophenic Sulfides in Fuels via Direct Electron Transfer Mechanism

Abstract

Heterogeneous interfaces designed rationally in catalysts can induce geometrical, compositional, and electronic effects that can be applied to modulate catalytically active sites and consequently accelerate reaction kinetics. Here, a core‐shell heterostructure catalyst consisting of crystalline molybdenum phosphide (MoP) cores and amorphous tungsten oxide (WOx) shells on porous carbon nanosheets (PCN) is developed for oxidative desulfurization (ODS) of fuels. The strongly coupled core‐shell heterogeneous interface triggers a distinctive atomic permeation effect that induces substantial electron transfer from MoP to WOx and subsequent generation of electron‐rich W sites, consequently optimizing the adsorption of intermediates and substrates. The resulting catalyst (WOx@MoP/PCN) demonstrates a turnover frequency as high as 768.1 h−1 for ODS at 60 °C, exceeding that of almost all the state‐of‐the‐art ODS catalysts by 1–2 orders of magnitude. Moreover, a novel surface oxidation pathway based on direct electron transfer is identified in the WOx@MoP/PCN‐H2O2 system, which bypasses the formation of reactive oxygen species, consequently endowing the system with a moderate redox potential. Thus, WOx@MoP/PCN exhibits unprecedented selectivity, achieving 100% removal of thiophenic sulfides from real diesel with minimal consumption of oxidant.