Abstract: Supported Cu₂(OH)₃Cl catalysts were prepared by the slurry impregnantion method and used in MeOH oxidative carbonylation to dimethyl carbonate (DMC). The catalytic activity of Cu₂(OH)₃Cl supported on various supports was higher than that of supported CuCl₂, and active carbon (AC) was the suitable support because of its larger specific surface area. Cu₂(OH)₃Cl/AC (w(Cu) = 18.71%) exhibited excellent catalytic performance. MeOH conversion, DMC selectivity, and DMC space time yield were 6.93%, 67.3%, and 139.13 mg/(g·h), respectively, and the catalyst was more stable. The supported catalysts were characterized by CO-temperature programmed desorption, X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy, showing that the higher dispersion of Cu₂(OH)₃Cl in Cu₂(OH)₃Cl/AC was getting worse and transformed to CuCl₂ and CuO during the reaction, resulting in the decrease of catalytic activity. The unique Cu^Ⅱ species in the fresh catalyst transferred into Cu^I species partially during the reaction.

Key words: methanol, oxidative carbonylation, dimethyl carbonate, copper chloride hydroxide, supported catalyst, active carbon