Radiation‐Synthesized Metal–Organic Frameworks with Ligand‐Induced Lewis Pairs for Selective CO2 Electroreduction

Abstract The electrochemical activation of inert CO 2 molecules through C─C coupling reactions under ambient conditions remains a significant challenge but holds great promise for sustainable development and the reduction of CO 2 emission. Lewis pairs can capture and react with CO 2 , offering a novel strategy for the electrosynthesis of high‐value‐added C2 products. Herein, an electron‐beam irradiation strategy is presented for rapidly synthesizing a metal–organic framework (MOF) with well‐defined Lewis pairs (i.e., Cu‐ N pyridinic ). The synthesized MOFs exhibit a total C2 product faradic efficiency of 70.0% at −0.88 V versus RHE. In situ attenuated total reflection Fourier transform infrared and Raman spectra reveal that the electron‐deficient Lewis acidic Cu sites and electron‐rich Lewis basic pyridinic N sites in the ligand facilitate the targeted chemisorption, activation, and conversion of CO 2 molecules. DFT calculations further elucidate the electronic interactions of key intermediates in the CO 2 reduction reaction. The work not only advances Lewis pair‐site MOFs as a new platform for CO 2 electrochemical conversion, but also provides pioneering insights into the underlying mechanisms of electron‐beam irradiated synthesis of advanced nanomaterials.