Combined Effect of Catholyte Gap and Cell Voltage on Syngas Ratio in Continuous CO₂/H₂O Co-electrolysis

Electrochemical devices are constructed for continuous syngas (CO + H₂) production with controlled selectivity between CO₂ and proton reduction reactions. The ratio of CO to H₂, or the faradaic efficiency toward CO generation, was mechanically manipulated by adjusting the space volume between the cathode and the polymer gas separator in the device. In particular, the area added between the cathode and the ion-conducting polymer using 0.5 M KHCO₃ catholyte regulated the solution acidity and proton reduction kinetics in the flow cell. The faradaic efficiency of CO production was controlled as a function of the distance between the polymer separator and cathode in addition to that manipulated by the electrode potential. Further, the electrochemical CO₂ reduction device using Au NPs presented a stable operation for more than 23 h at different H₂:CO production levels, demonstrating the functional stability of the flow cell utilizing the mechanical variable as an important operational factor.