Synergistic leveraging confinement effects and mass transfer of CeO₂ for carbon dioxide to dimethyl carbonate conversion with methanol

Carbon dioxide serves as the main gas causing the greenhouse effect but is also a crucial carbon source in C1 chemistry for synthesizing high value‐added chemicals. In this study, we developed a porous CeO 2 material with hollow spherical architecture by employing adjustable polystyrene microspheres and tetrapropylammonium hydroxide as dual templates. This strategy created a high amount of oxygen vacancies and a synergistic combination of confinement effects and enhanced mass transfer properties, resulting in exceptional catalytic performance for the direct synthesis of dimethyl carbonate (DMC) from CO 2 and methanol. CeO 2 ‐282, with a diameter of 282 nm, had an outstanding DMC yield of 20.9 mmol g −1 cat at 140°C and 3.5 MPa for 12 h. Density functional theory calculation revealed that spatial confinement reduces the energy barrier of the rate‐determining step, as evidenced by comparative simulations in confined versus unrestricted environments.