The inhibition of the proton donor ability of bicarbonate promotes the electrochemical conversion of CO2 in bicarbonate solutions

•Integrated CO2 capture and conversion via electrochemical conversion of bicarbonate proposed.•The bicarbonate reduction mechanism involves a CO2-mediated step, with CO2 being the substrate.•Bicarbonate promote the hydrogen evolution reaction (HER), thus making the process inefficient.•By using cationic surfactants, HER is inhibited while CO2 reduction (CO2R) is promoted.•A bicarbonate solution acts as a carbon pool enabling CO2 to be stored up to saturation levels (2.2 M).