Converting greenhouse gases into valuable products has become a promising approach for achieving a carbon-neutral economy and sustainable development. However, the conversion efficiency depends on the energy yield of the substrate. In this study, we developed an electro-biocatalytic system by integrating electrochemical and microbial processes to upcycle CO into a valuable product (ectoine) using renewable energy. This system initiates the electrocatalytic reduction of CO to methane, an energy-dense molecule, which then serves as an electrofuel to energize the growth of an engineered methanotrophic cell factory for ectoine biosynthesis. The scalability of this system was demonstrated using an array of ten 25 cm electrochemical cells equipped with a high-performance carbon-supported isolated copper catalyst. The system consistently generated methane at the cathode under a total partial current of approximately -37 A (~175 mmol h) and O at the anode under a total partial current of approximately 62 A (~583 mmol h). This output met the requirements of a 3-L bioreactor, even at maximum CH and O consumption, resulting in the high-yield conversion of CO to ectoine (1146.9 mg L). This work underscores the potential of electrifying the biosynthesis of valuable products from CO, providing a sustainable avenue for biomanufacturing and energy storage.

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