The electrochemical measurements were carried out with a PalmSens Muti EmStat3+ potentiostat, whereas the PEC measurements were carried out with a Ivium CompactStat potentiostat and a Newport Oriel 67005 solar light simulator equipped with an Air Mass 1.5 Global (AM 1.5G) solar filter. All experiments were carried out in a two compartment H cell separated by a bipolar membrane in reverse bias. For the electrochemical experiments in the aqueous system, the catholyte typically consisted of the capture solution (resulting from CO2 capture from pure CO2 or flue gas or air as previously described) with added 0.1 M K2SO4 and the14oluteion was purged with N2 containing 2% CH4 as an internal standard for 15 min. The anolyte consisted of 0.1 M K2SO4 purged with N2 containing 2% CH4 for 15 min, with the working, counter and the reference electrodes being CoPcNH2@MWCNT, Pt mesh, and an Ag/AgCl (sat. NaCl) electrode, respectively. For the glycolic capture solutions, the catholyte typically consisted of the capture solution with added 20% v/v MeCN co-solvent and 0.15 M TBABF4 supporting electrolyte, whereas the anolyte was 0.6 M NaOH, 0.15 M TBABF4 in 20% v/v MeCN in EG solvent mixture (both catholyte and anolyte were purged with N2 containing 2% CH4 for 15 min prior to experiment), and the working, counter and reference electrodes were CoPcNH2@MWCNT, Ni foam|Cu26Pd74 and Ag/AgNO3 (in 0.1 M n-Bu4NPF6 in MeCN) electrode, respectively. The potentials recorded with the Ag/AgCl (sat. NaCl) and Ag/AgNO3 (in 0.1 M n-Bu4NPF6 in MeCN) reference electrodes were converted to the RHE and Fc/Fc + scales, respectively, as per following equations: