Polyoxometalates encapsulated into hollow double-shelled nanospheres as amphiphilic nanoreactors for an effective oxidative desulfurization

Abstract

Although some catalytic hollow nanoreactors have been fabricated in the past, the encapsulated active species focus on metal nanoparticles, and a method for polyoxometalate (POM)-containing hollow nanoreactors has seldom been developed. Herein, we report a synthetic strategy towards POM-based amphiphilic nanoreactors, where the hollow mesoporous double-shelled SiO₂@C nanospheres were used to encapsulate Keggin-type H₃PMo₁₂O₄₀ (PMo₁₂). The outer hydrophobic carbon shell was beneficial for the enrichment of the organic substrate around the nanoreactor and simultaneously prevented the deposition of POMs on the outer surface of the nanoreactor. The inner hydrophilic silica cavity was modified by two types of organosilanes, which not only created an amphiphilic cavity environment but also acted as an anchor to mobilize PMo₁₂. As the POM nanoreactor had the hydrophilic@hydrophobic SiO₂@C shell and an amphiphilic cavity, both dibenzothiophene (DBT) and H₂O₂ could smoothly diffuse into the nanosized cavity, where the DBT was effectively oxidized (conversion: >99%) by the immobilized PMo₁₂ under mild conditions. Importantly, the control experiments indicated that the confined effect of nanoreactor, amphiphilic SiO₂@C double-shell, unique cavity environment, and mesoporous channels accounted for an excellent catalytic performance. Moreover, the nanoreactor was robust and could be reused for five cycles without loss of activity.