Study of Direct Synthesis of DMC from CO₂ and Methanol on CeO₂: Theoretical Calculation and Experiment

Abstract

Rare earth metal oxides are known to have good catalytic effectiveness in the direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol. In this work, we screened ceria (CeO2) catalysts by analyzing their capacity for CO2 adsorption. The effects of the crystal surface morphology and oxygen vacancy on the catalytic performance of the ceria catalyst were studied by using density functional theory (DFT). The results show that the (110) surface and higher oxygen vacancy content can better promote the synthesis of DMC and that the rod-shaped CeO2 catalyst has a better catalytic effect. The oxygen vacancy content on the catalyst was improved by freeze-drying and confirmed by thermogravimetric analysis, Raman spectroscopy, and electron paramagnetic resonance. The freeze-dried CeO2 (CeO2-FD) then showed a higher catalytic performance. The conversion rate of methanol and the yield of DMC were 33.95% and 584 mmol g–1cat, respectively, under mild conditions (140 °C and 1 MPa).

Efficient Visible‐Light‐Assisted Synthesis of Dimethyl Carbonate from CO2 and Methanol by Ce–Metal Organic Framework‐Derived CeO2 Nanoparticles

“…[ 10,18,27 ] As can be seen from Figure 2c, the O 1 s XPS spectra of CeO 2 –C can be fitted with three peaks located at approximately 529.8, 531.5, and 532.6 eV, corresponding to lattice oxygen (O L ), oxygen vacancy (O V ), and chemisorbed oxygen species (O C ), respectively. [ 7,11 ] The peaks of O v and O c for CeO 2 –M – 5 appear slightly shifted to higher binding energy, which could be attributed to the increase in content of OCe 3+ bond. [ 28 ] The O V concentration is 6.6% and 18.9%, respectively, which corresponds to CeO 2 –C and CeO 2 –M–5 (consistent with the result of Ce 3+ ).…”

“…In the traditional thermo‐catalytic route, the synthesis of DMC from CO 2 and methanol requires significant energy input, but the yield of DMC is still very low. [ 11 ] Moreover, the effective activation of CO 2 is the key rate‐control step in the process. As a consequence, it is necessary to improve the effective activation of CO 2 to quickly break the reaction equilibrium to promote the formation of DMC via the construction of a reasonable reaction system.…”

Engineering the Microstructure at Co Single-Atom Sites by Co Nanoparticles Core for Enhanced Formic Acid Selective Dehydrogenation

“…All thermal corrections are obtained by frequency calculations of VASP followed by VASPKIT data processing at the temperature of 383 K, and the detailed calculation method of thermodynamic correction is shown in the Supporting Information. The transition states (TSs) are determined by a constrained optimization scheme. − …”

The Emergence of the Ubiquity of Cerium in Heterogeneous Oxidation Catalysis Science and Technology

“…The growth in the development and application of cerium-containing materials since about 1980 has truly been remarkable. Cerium has been applied to many of the major fields of fundamental and applied catalysis and continues to be exploited for its redox and defect structural properties in many emerging technology applications as well, including CO 2 conversion [169], advanced fuel cell technologies [170], biomimetic catalysis [171], and the manufacture of sustainable aviation fuels [172,173]. The application of cerium oxide to catalysis, which started as a redox promoter and then as an "inert" support for metal catalysts, has grown into a dynamic field of rational catalyst design based on the increased understanding of cerium's unique redox properties, structural versatility, and agency as a catalyst constituent.…”