Electrolyte Design Using “Porous Water” for High‐purity Carbon Monoxide Electrosynthesis from Dilute Carbon Dioxide

Electrosynthesis of high-purity carbon monoxide (CO) from captured carbon dioxide (CO₂) remains energy-intensive due to the unavoidable CO₂ regeneration and post-purification stages. Here, we propose a direct high-purity CO electrosynthesis strategy employing an innovative electrolyte, termed porous electrolyte (PE), based on "porous water". Zeolite nanocrystals within PE provide permanent pores in the liquid phase, enabling physical CO₂ adsorption through an intraparticle diffusion model, as demonstrated by molecular dynamics simulations and in situ spectral analysis. Captured CO₂ spontaneously desorbs under applied reductive potential, driven by the interfacial CO₂ concentration gradient, and is subsequently reduced electrochemically. The high CO₂ concentration in PE enhances mass transfer, and surface ion exchange between Si-OH groups and K⁺ ions on the zeolite surface generates a stronger interfacial electric field, promoting electron transfer steps. This optimized kinetics for mass and electron transfer confers heightened intrinsic activity toward CO₂ electroreduction. The PE-based electrolysis system demonstrated superior CO Faradaic efficiency and partial current density compared to the conventional CO₂-fed system. A circular system using PE and a Ni-N/C cathode realized continuous production of high-purity CO (97.0 wt %) from dilute CO₂ (15 %) and maintained >90.0 wt % under 150 mA cm^-2, with significantly reduced energy consumption and costs.