Defect-Mediated Synergistic Effect of POM/UiO-66(Zr) Host-Guest Catalysts for Robust Deep Desulfurization at Ambient Temperature.

Abstract

Stable platforms of host-guest catalysts are indispensable in the field of heterogeneous catalysis, however, clarifying the specific effect of host remains challenging. Herein, polyoxometalate (POM) is encapsulated in three types of UiO-66(Zr) with different controlled densities of defects by the aperture opening and closing strategy at ambient-temperature. It is found that catalytic activity of POM for oxidative desulfurization (ODS) at room temperature is turned on when encapsulated in the defective UiO-66(Zr), and the sulfur oxidation efficiency shows an obvious increasing trend (from 0.34 to 10.43 mmol g-1 h-1 ) with the increased concentration of defects in UiO-66(Zr) host. The as-prepared catalyst with the most defective host displays ultrahigh performance which removed 1000ppm sulfur with exceptionally diluted oxidant at room-temperature within 25min. The turnover frequency can reach 620.0 h-1 at 30°C, which surpassed all the reported MOFs based ODS catalysts. A substantial guest/host synergistic effect mediated by the defective sites in UiO-66(Zr) is responsible for the enhancement. Density functional theory calculations reveal that OH/OH2 capped on the open Zr sites of host UiO-66(Zr) can decompose H2 O2 to OOH group and enables the formation of WVI -peroxo intermediates that determine the ODS activity.