PEC measurements
were carried out in a sealed two-compartment cell (Vsolution = 40 cm3) where the compartments were
separated by a Nafion117 membrane. The working electrode was a PEDOT
or PEDOT/nanocarbon modified GC (A = 4 cm2), a Pt sheet was applied as a counter and a Ag/AgCl/3 M NaCl as
a reference electrode while the applied potential was −0.9
V during the measurements. The electrodes were pretreated at the same
potential for 300 s without illumination. The 0.1 M Na2SO4 electrolyte was saturated with Ar prior to the measurements
(constant bubbling for 30 min). During the reaction, gas samples were
taken at 30, 60, 90, and 120 min via an online detection system, which
was coupled to the cathode compartment of the cell. Products in the
gas phase were separated with a ShinCarbon ST column and analyzed
with a Shimadzu GC-2010 Plus gas chromatograph equipped with a barrier
discharge ionization (BID) detector. The optimized parameters were
the following: carrier gas, helium; oven program, Tstart = 35 °C (2.5 min), ΔTramp = 20 °C min–1, Tend = 270 °C (3 min); injection temperature T = 150 °C; linear velocity was controlled by the pressure pstart = 250 kPa (2.5 min), Δpramp = 15 kPa min–1, pend = 400 kPa (7.5 min); and the split ratio was 10.