Efficient Polyethylene Furanoate Synthesis From CO ₂ and 5‐(Hydroxymethyl)furfural

The sustainable synthesis of polyethylene furanoate (PEF) from waste‐derived CO ₂ and 5‐(hydroxymethyl)furfural (HMF) is limited by kinetic mismatches, pH incompatibility, and stoichiometric imbalances in conventional cascade electrolysis systems. Herein, we propose a reaction‐pair recombination strategy that decouples key redox steps and selectively reintegrates them within a three‐cell cascade system. This configuration enables simultaneous generation of ethylene glycol (EG) and furandicarboxylic acid (FDCA) at industrial‐level current densities with Faradaic efficiencies of 71.5% and 87.1%, respectively, achieving a near‐optimal EG:FDCA ratio of 3:1. During a stable operation period of 25 h, the three‐cell cascade system exhibited a bis(2‐hydroxyethyl) furan‐2,5‐dicarboxylate (BHEF) productivity of 28.4 mmol L ⁻¹ h ⁻¹ and a PEF production rate of 2.1 g day ⁻¹ . Compared with the conventional routes, the new pathway achieves nearly 50‐fold higher energy efficiency and a low global warming potential of 0.83 g _CO2‐eq per gram of PEF, providing a sustainable platform for waste valorization into high‐value polymers.