Strongly Electron‐Accepting Lattice Oxygen of CeO 2 for Highly Efficient Dimethyl Carbonate Synthesis from CO 2 and Methanol

Abstract Converting CO 2 and green methanol to dimethyl carbonate (DMC) has both theoretical and practical value in carbon neutrality and MeOH upgrading, but its efficiency is far from the application requirement due to the thermodynamic non‐spontaneous process limitation and high kinetic barrier in CO 2 and methoxy coupling. Herein, the strongly electron‐accepting lattice oxygen was introduced onto CeO 2 via a hydroxylation‐induced Pt spontaneous redispersion strategy. The introduction of strongly electron‐accepting lattice oxygen enabled the highly reactive *CO intermediate formation, which triggered a novel thermodynamically favorable *CH 3 O–*CO coupling to DMC synthesis. In addition, the lattice oxygen modification also markedly regulated the electron distribution of catalyst, thereby optimizing the adsorption strength of CO 2 and methanol and thus reducing the entire reaction barrier of *CH 3 O–CO 2 coupling to DMC via a rate‐determining‐step shifting. Benefiting from these advantages, Pt 1 /CeO 2 –SO sample achieved a DMC yield of 62.1 mmol g −1 —six‐fold higher than reported conventional catalyst under similar conditions. This work revealed the key role of strongly electron‐accepting lattice oxygen in the innovative DMC synthesis pathway, with potential applications in developing more efficient synthetic routes for methanol upgrading and CO 2 resource utilization.