Optimizing the Performance of Low-Loaded Electrodes for CO 2 -to-CO Conversion Directly from Capture Medium: A Comprehensive Parameter Analysis.

Gas-fed reactors for CO 2 reduction processes are a solid technology to mitigate CO 2 accumulation in the atmosphere. However, since it is necessary to feed them with a pure CO 2 stream, a highly energy-demanding process is required to separate CO 2 from the flue gasses. Recently introduced bicarbonate zero-gap flow reactors are a valid solution to integrate carbon capture and valorization, with them being able to convert the CO 2 capture medium (i.e., the bicarbonate solution) into added-value chemicals, such as CO, thus avoiding this expensive separation process. We report here a study on the influence of the electrode structure on the performance of a bicarbonate reactor in terms of Faradaic efficiency, activity, and CO 2 utilization. In particular, the effect of catalyst mass loading and electrode permeability on bicarbonate electrolysis was investigated by exploiting three commercial carbon supports, and the results obtained were deepened via electrochemical impedance spectroscopy, which is introduced for the first time in the field of bicarbonate electrolyzers. As an outcome of the study, a novel low-loaded silver-based electrode fabricated via the sputtering deposition technique is proposed. The silver mass loading was optimized by increasing it from 116 μg/cm 2 to 565 μg/cm 2 , thereby obtaining an important enhancement in selectivity (from 55% to 77%) and activity, while a further rise to 1.13 mg/cm 2 did not provide significant improvements. The tremendous effect of the electrode permeability on activity and proficiency in releasing CO 2 from the bicarbonate solution was shown. Hence, an increase in electrode permeability doubled the activity and boosted the production of in situ CO 2 by 40%. The optimized Ag-electrode provided Faradaic efficiencies for CO close to 80% at a cell voltage of 3 V and under ambient conditions, with silver loading of 565 μg/cm 2 , the lowest value ever reported in the literature so far.