Structure of the active sites on H3PO4/ZrO2 catalysts for dimethyl carbonate synthesis from methanol and carbon dioxide

The catalytic properties of H3PO4/ZrO2 catalysts for dimethyl carbonate (DMC) synthesis from CH3OH and CO2 were investigated. The modification of ZrO2 with H3PO4 promoted the activity for selective DMC formation. The characterization of H3PO4/ZrO2 catalysts was performed by means of BET, XRD, (31)p NIAS NMR, LRS, DRIFT, and NH3-TPD. From the characterization results, it was determined that ZrO2 had Lewis acid sites and did not have Bronsted acid sites. The presence of Bronsted acid sites as well as Lewis acid sites was observed on H3PO4/ZrO2 (P/Zr = 0.05). The acidity of the Bronsted sites is weak, and the site's structure is a bridged OH. Furthermore, this Bronsted site is formed by the interaction between tetragonal Zr and P. In the reaction scheme of DMC formation, the Bronsted acid site can contribute to CH3OH activation and to the enhancement of the catalytic activity.