Engineering zirconium-based UiO-66 for effective chemical conversion of d-xylose to lactic acid in aqueous condition

Abstract

Utilizing metal–organic frameworks (MOFs) as heterogeneous catalysts is an interesting and important application due to their well-controlled catalytic sites and well-defined porous structures. In this study we apply, for the first time, Zr-based UiO-66 for the catalytic hydrothermal conversion of D-xylose to lactic acid (LA). The reactions are catalyzed by the coordinatively unsaturated Zr⁴⁺, as Lewis acid sites, and the hydroxide ion (OH⁻) located at the defect sites. The catalytic performances of UiO-66 catalysts synthesized through a modulator-free approach (UiO-66) and an acetic acid modulator-assisted approach (UiO-66(AA)) are distinct due to the different concentrations of local defects. The UiO-66 catalyst possessing a higher defect concentration exhibits a superior LA yield of 1.17 mol from 1 mol of xylose. However, the UiO-66(AA) catalyst with higher crystallinity shows better selectivity for LA over furfural, a side product from the competitive pathway. The enhanced LA yield and excellent selectivity can be achieved by the removal of AA from UiO-66(AA) resulting in a novel MOF catalyst (UiO-66(AA)*) which provides more accessible catalytic sites with retained crystallinity. This work highlights that the structural engineering of MOF catalysts is crucial for the fine-tuning of their catalytic properties.