Green and scalable synthesis of nitro- and amino-functionalized UiO-66(Zr) and the effect of functional groups on the oxidative desulfurization performance

Abstract

Nitro- and amino-functionalized UiO-66(Zr) have great potential in some applications. In general, the synthesis is carried out with the addition of modulator and solvent, and the yields of the obtained samples are about 0.3 g per 80 mL autoclave. In this study, we report that they can be facilely prepared under environmentally friendly conditions. The characterization results show that these materials possess high surface area and rich porosity similar to the conventional samples. Importantly, the synthesis was scalable up to 12 g of product per 80 mL autoclave, which is 40 times that prepared by the conventional route. In addition, the effect of functional groups on the catalytic performance of UiO-66(Zr) was systematically investigated. It was found that nitro-functionalized UiO-66(Zr) exhibited much better catalytic performance than UiO-66(Zr) and amino-functionalized UiO-66(Zr) in the oxidative desulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene. Such an outstanding catalytic performance can be attributed to the introduction of the electron-withdrawing groups in organic linkers, which enhanced the ability of UiO-66(Zr) to gain electrons.