A concentrated CO2 stream (99.995%) was first used to develop and optimize the PEC system. Different amines, including industrially-relevant monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA) and diazabicyclo[2,2,2]octane (DABCO) were employed for CO2 capture in aqueous medium at ambient temperature. The capture was done by purging concentrated CO2 through 1 M amine solution for 2 h (flowrate: 30 mL min -1 ). The solution was further purged with N2 (15 min) to remove any physically dissolved CO2 (Figure ). C nuclear magnetic resonance ( 13 C-NMR) spectra of the post-capture solutions revealed that under these conditions, MEA and DEA captured 0.75±0.07 and 0.77±0.10 mol CO2 per mol amine, respectively, as bicarbonate and carbamate species. In contrast, the tertiary amines TEA and DABCO captured CO2 only as bicarbonate salts (0.60±0.05 and 0.85±0.08 mol CO2 per mol amine, respectively, after 2 h; Scheme 1, eq 1-2; Figure ). Other than amines, aqueous and organic solutions of NaOH were also used for efficient CO2 capture (Scheme 1, eq 3). When concentrated CO2 was purged through an aqueous 1 M NaOH solution (2 h), NaHCO3 was formed quantitatively. Similarly, 1 M NaOH solution in organic EG captured 0.96±0.02 mol CO2 per mol NaOH as sodium glycol carbonate upon CO2 purging (Scheme 1, eq 4; Figure ). The CO2 captured species thus obtained were subsequently for conversion.