The E1/2 of the Fc/Fc + couple was determined as 0.41 V vs. Ag/AgNO3 (in 0.1 M n-Bu4NPF6 in MeCN) by cyclic voltammetry (50 mV s -1 ) in a single compartment three-electrode configuration with glassy carbon as the working electrode, Pt mesh as the counter electrode and Ag/AgNO3 (in 0.1 M n-Bu4NPF6 in MeCN) as the reference electrode, using an electrolyte containing 5 mM ferrocene and 0.15 M TBABF4 in 20% v/v MeCN in EG media. The dark CV scans for the Ni foam|Cu26Pd74 were taken in a three electrode twocompartment setup with Pt mesh as the counter electrode and Ag/AgCl (sat. NaCl) or Ag/AgNO3 (in 0.1 M n-Bu4NPF6 in MeCN) as the reference electrode for aqueous and glycolic systems, respectively (scan rate 10 mV s -1 ). Similarly, the CV scans of the assembled photocathode (PVK|CoPcNH2@MWCNT) were recorded in a three-electrode system in both aqueous TEA captured and glycolic NaOH captured CO2 medium under chopped (5 s on, 5 s off), continuous or no simulated solar illumination (1 sun), with Ni foam|Cu26Pd74 counter electrode, and Ag/AgCl (sat. NaCl) or Ag/AgNO3 (in 0.1 M n-Bu4NPF6 in MeCN) as the reference electrode for aqueous and glycolic systems, respectively, at a scan rate of 10 mV s -1 . The Newport Oriel 67005 solar light simulator was calibrated to 1 sun (100 mW cm -2 ) using a Newport light meter before each experiment. The working potentials of both cathode and anodes under solar illumination (without any external voltage) were determined from CV overlaps.