C-S cleavage of dibenzothiophenes with or without steric hindrance by the interface between PtSx and ZnO

Desulfurization plays a critical role in refining crude oil to produce fuel and the manufacture of fine chemicals. However, its low efficiency becomes a great challenge for the present desulfurization if only the C-S cleavage is considered a promising approach to reducing hydrogen consumption under atmospheric pressure. Accordingly, we investigate the critical factors necessary to achieve high C-S cleavage of dibenzothiophenes under mild conditions of 0.1 MPa and H2/oil = 100. The mechanism of reactive adsorption desulfurization of dibenzothiophenes with or without steric hindrance at atmospheric pressure on Pt/ZnO is proposed by studying the adsorption model of active metal sites, the Pt efficiency in C-S cleavage influenced by the steric hindrance and the structural evolution of Pt active centers in the presence of sulfur adsorption/deposition. Based on both experimental and DFT results, we report C-S cleavage of dibenzothiophenes with (TOF = 15 h-1) or without steric hindrance (TOF = 128 h-1) that can be highly efficiently fractured (99.9%) by the interface between PtSx and ZnO. This work has great practical significance for developing atmospheric industrial adsorbents for ultra deep reactive adsorption desulfurization.

Automated summary

This study investigates the C-S cleavage mechanism of dibenzothiophenes with or without steric hindrance under mild conditions. The reactive adsorption desulfurization mechanism on Pt/ZnO is proposed based on the adsorption model, Pt efficiency, and structural evolution of Pt active centers. By utilizing the interface between PtSx and ZnO, highly efficient cleavage of dibenzothiophenes (99.9% fracture) is achieved with or without steric hindrance (TOF = 15 h-1 or TOF = 128 h-1). This work has significant practical implications for the development of atmospheric industrial adsorbents for ultra deep reactive adsorption desulfurization.