In Situ High Selectivity Contact‐Electroreduction of CO2 to Methanol Using an Imine‐Mediated Metal‐Free Vitrimer Catalyst

Metal catalysts for the CO₂ reduction reaction (CO₂RR) face challenges such as high cost, limited durability, and environmental impact. Although various structurally diverse and functional metal‐free catalysts have been developed, they often suffer from slow kinetics, low selectivity, and nonrecyclability, significantly limiting their practical applications. In this study, we introduce a recyclable nonmetallic polymer material (vitrimer) as a catalyst for a new platform in contact‐electrocatalysis. This approach harnesses the contact charges generated between water droplets and vitrimer to drive CO₂RR, achieving methanol selectivity exceeding 90%. The imine groups within the vitrimer play a dual role, facilitating CO₂ adsorption and enriching friction‐generated electrons, thereby mediating efficient electron transfer between the imine groups and CO₂ to promote CO₂RR. After 84 h of CO₂RR, the system achieved a methanol production rate of 13 nmol·h⁻¹, demonstrating the excellent stability of the method. Moreover, the vitrimer retains its high‐performance electrocatalytic activity even after recycling. Mechanistic studies reveal that, compared to traditional metal catalysts, the N─O bond in the imine, which adsorbs the key intermediate *OCH₃, breaks more readily to produce methanol, resulting in enhanced product selectivity and yield. This efficient and environmentally friendly contact‐electroreduction strategy for CO₂ offers a promising pathway toward a circular carbon economy by leveraging natural water droplet‐based contact‐electrochemistry.