Insights into a New Formation Mechanism of Robust Cu/SiO2 Catalysts for Low-Temperature Dimethyl Oxalate Hydrogenation Induced by a Chelating Ligand of EDTA

Abstract

The Cu/SiO2 catalyst has been widely used in dimethyl oxalate (DMO) hydrogenation due to its low cost and high efficiency. However, the reaction temperature of DMO hydrogenation is higher than the Hüttig temperature of Cu, and the smaller Cu particles are easier to agglomerate. Therefore, there is much interest in constructing a catalyst with a small particle size and strong stability. In the present work, the effect of introducing EDTA on Cu/SiO2 catalysts is systematically investigated. It not only was beneficial to form smaller copper nanoparticles (CuNPs) but also to enhance the stability of Cu species by introducing a suitable amount of EDTA. Furthermore, the surface Cu species were more evenly dispersed, and the number of active sites was increased with the introduction of EDTA; subsequently, the synergistic effect between Cu+ and Cu0 was enhanced. The best performance of 0.08E-Cu/SiO2 had been achieved in the DMO hydrogenation to ethylene glycol (EG), and the DMO conversion and EG selectivity reached 99.9% and 97.7%, respectively. Above all, the 0.08E-Cu/SiO2 catalyst exhibited a high level of stability during the 1200 h life test at 180 °C.