Bioelectrocatalytic Cofactor Regeneration Coupled to CO(2) Fixation in a Redox‐Active Hydrogel for Stereoselective C−C Bond Formation

The sustainable capture and conversion of carbon dioxide (CO(2)) is key to achieving a circular carbon economy. Bioelectrocatalysis, which aims at using renewable energies to power the highly specific, direct transformation of CO(2) into value added products, holds promise to achieve this goal. However, the functional integration of CO(2)‐fixing enzymes onto electrode materials for the electrosynthesis of stereochemically complex molecules remains to be demonstrated. Here, we show the electricity‐driven regio‐ and stereoselective incorporation of CO(2) into crotonyl‐CoA by an NADPH‐dependent enzymatic reductive carboxylation. Co‐immobilization of a ferredoxin NADP(+) reductase and crotonyl‐CoA carboxylase/reductase within a 2,2′‐viologen‐modified hydrogel enabled iterative NADPH recycling and stereoselective formation of (2S)‐ethylmalonyl‐CoA, a prospective intermediate towards multi‐carbon products from CO(2), with 92±6 % faradaic efficiency and at a rate of 1.6±0.4 μmol cm(−2) h(−1). This approach paves the way for realizing even more complex bioelectrocatalyic cascades in the future.