High-Performance Chlorine-Doped Cu2O Catalysts for the Ethynylation of Formaldehyde

Abstract

The in situ formed Cu+ species serve as active sites in the ethynylation of formaldehyde. The key problem that needs to be solved in this process is how to avoid excessive reduction of Cu2+ to inactive metallic Cu, which tends to decrease the catalytic activity. In this work, Cl−-modified Cu2O catalysts with different Cl content were prepared by co-precipitation. The characterization results demonstrated that Cl− remained in the lattice structure of Cu2O, inducing the expansion of the Cu2O lattice and the enhancement of the Cu–O bond strength. Consequently, the reduction of Cu+ to Cu0 was effectively prevented in reductive media. Moreover, the activity and stability of Cu2O were significantly improved. The Cl− modification increased the yield of 1,4-butynediol (BD) from 73% to 94% at a reaction temperature of 90 °C. More importantly, the BD yield of Cl− modified Cu2O was still as high as 86% during the ten-cycle experiment, whereas the BD yield of Cu2O in the absence of Cl− decreased sharply to 17% at the same reaction conditions. This work provides a simple strategy to stabilize Cu+ in reductive media.