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In this work, the effect of ion-selective membranes on the detailed carbon balance was systematically analyzed for high-rate CO reduction in GDE-type flow electrolyzers. By using different ion-selective membranes, we show nearly identical catalytic selectivity for CO reduction, which is primarily due to a similar local reaction environment created at the cathode/electrolyte interface the introduction of a catholyte layer. In addition, based on a systematic exploration of gases released from electrolytes and the dynamic change of electrolyte speciation, we demonstrate the explicit discrepancy in carbon balance paths for the captured CO at the cathode/catholyte interface reaction with OH when using different ion-selective membranes: (i) the captured CO could be transported through an anion exchange membrane in the form of CO , subsequently releasing CO along with O in the anolyte, and (ii) with a cation exchange membrane, the captured CO would be accumulated in the catholyte in the form of CO , while (iii) with the use of a bipolar membrane, the captured CO could be released at the catholyte/membrane interface in the form of gaseous CO.

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