Electride‐Sponsored Radical‐Controlled CO 2 Reduction to Organic Acids: A Computational Design

Converting CO 2 into high‐value chemicals has been regarded as an important solution for a sustainable low‐carbon economy. In this work, we have theoretically designed an innovative strategy for the absorption and activation of CO 2 by the electride N3Li, that is, 1,3,5(2,6)‐tripyridinacyclohexaphane (N3) intercalated by lithium. DFT computations showed that the interaction of CO 2 with N3Li leads to the catalytic complex N3Li(η 2 ‐O 2 C), which can initiate the radical‐controlled reduction of another CO 2 to form organic acids through radical reactions in the gas phase. The CO 2 reduction consists of four steps: (1) The formation of N3Li(η 2 ‐O 2 C) through the combination of N3Li and CO 2 , (2) hydrogen abstraction from RH (R=H, CH 3 , and C 2 H 5 ) by N3Li(η 2 ‐O 2 C) to form the radical R . and N3Li(η 2 ‐O 2 C)H, (3) the combination of CO 2 and the radical R . to form RCOO . , and (4) intermolecular hydrogen transfer from the intermediate N3Li(η 2 ‐O 2 C)H to RCOO . . In the whole reaction process, the CO 2 moiety in the complex N3Li(η 2 ‐O 2 C) maintains a certain radical character at the carbon atom of CO 2 and plays a self‐catalyzing role. This work represents the first example of electride‐sponsored radical‐controlled CO 2 reduction, and thus provides an alternative strategy for CO 2 conversion.