). Electrodes were prepared by first immobilizing CoPcNH2 on multi-walled carbon nanotubes (MWCNT) through π-π stacking, followed by drop-casting the composite on a graphite foil substrate (CoPcNH2@MWCNT; Figures ). Electrochemical reduction of aqueous captured CO2 solutions were then explored in a two-compartment, three-electrode configuration with the fabricated CoPcNH2@MWCNT electrode, a Ag/AgCl (sat. NaCl) electrode, and a Pt mesh as the working, reference, and counter (water oxidation) electrode, respectively. The catholyte was CO2 captured solutions with 0.1 M K2SO4 (supporting electrolyte; pH 7.8-8.3), the anolyte was 0.1 M K2SO4 (pH 7.6), and the compartments were separated by a bipolar membrane. Cyclic voltammetry (CV) scans in a TEA (1 M) captured CO2 medium in this setup showed an onset potential of -0.4 V vs. the reversible hydrogen electrode (RHE; Figures ). Subsequent controlled potential electrolysis (CPE) at different potentials (1 h) produced only CO and H2 as products (Figure ). The formed bicarbonate C-O bond during CO2 capture is thus cleaved during reduction, regenerating the amine. An optimum CO faradaic efficiency (FECO) of 46.2±2.0 % was obtained at -0.7 V vs. RHE (Figure ). CPE with the primary and secondary amine (MEA and DEA) captured CO2 solutions at this potential resulted in lower FECO of 10.2±1.7 and 16.5±1.5%, respectively (Figure ). Control experiments without an amine did not capture CO2 and consequently, produced no CO during CPE, confirming the role of amine in the CCU process (Figure ).