Photo‐ / Photothermal‐ / Electro‐Driven Catalytic CO₂ Conversion Into Dimethyl Carbonate

Abstract Dimethyl carbonate (DMC), an important and environmentally friendly chemical intermediate has found widespread application in various industrial processes. In this review, we summarize the recent progress in the photo‐ / photothermal‐ / electro‐fixing of CO 2 into DMC, focusing on the mechanisms of electron transfer, multistep chemical reaction pathways, and the design of active sites of catalysts. This review highlights the characteristics and advantages of photothermal catalysis in the conversion of CO 2 to DMC by comparing the challenges posed by the high energy consumption required for thermocatalytic processes under high‐pressure conditions and the limited efficiency of photocatalysis. Advances in photothermal catalysis are discussed, particularly focusing on metal‐semiconductor composites and defect engineering strategies. Furthermore, this review systematically addresses the structure‐activity relationships of catalysts for the direct synthesis of DMC from CO 2 and methanol, leveraging in situ characterization techniques and density functional theory (DFT). Finally, the future challenges and potential opportunities for enhancing CO 2 utilization via DMC production are outlined, emphasizing the significance of these advancements for sustainable chemical processes.