Correlation of urea precipitation temperature with phase formation, morphology, and catalytic activity for CO2 conversion of CeO2

Abstract

This study proposes a simple method for tailoring the morphology and activity of cerium oxide (CeO<inf>2</inf>) catalysts in converting carbon dioxide (CO<inf>2</inf>) and methanol to green organic carbonate, dimethyl carbonate (DMC), to utilize and reduce CO<inf>2</inf> emissions. CeO<inf>2</inf> was prepared by urea precipitation at 85, 105, and 125 °C for 2 h, then calcining at 600 °C for 2 h. The phase structure and morphology of CeO<inf>2</inf> correlated with the urea hydrolysis rate. A low degree of supersaturation at 85 °C led to heterogeneous precipitation of cerium oxycarbonate (Ce<inf>2</inf>O(CO<inf>3</inf>)<inf>2</inf>.H<inf>2</inf>O) and CeO<inf>2</inf> with spherical morphology, while a higher degree of supersaturation at 105 °C and 125 °C resulted in homogeneous precipitation of single-phase Ce<inf>2</inf>O(CO<inf>3</inf>)<inf>2</inf>.H<inf>2</inf>O with spindle and elongated octahedral morphology, respectively. The spindle-shaped CeO<inf>2</inf> prepared at 105 °C with a predominant surface (111) facet showed the highest catalytic activity, with a DMC yield of 18.81 mmol.g<inf>cat</inf>⁻¹. The enhanced catalytic efficiency of spindle-shaped CeO<inf>2</inf> was due to the high concentration of surface-active defect sites of exposed cerium cations and oxygen vacancies, which optimized the number of acid–base sites in adsorbing and activating CO<inf>2</inf> and methanol to produce DMC.