Photoelectrochemical Behavior of PEDOT/Nanocarbon Electrodes: Fundamentals and Structure–Property Relationships

[Image: see text] In this study, we investigated the photoelectrochemical behavior of poly(3,4-ethylenedioxythiophene) (PEDOT)/carbon nanotube (CNT) and PEDOT/graphene nanocomposite photoelectrodes for the first time. Electrodeposition allowed control of both the composition and the morphology (as demonstrated by both transmission and scanning electron microscopy images) and also ensured an intimate contact between the PEDOT film and the nanocarbon scaffold. The effect of CNT and graphene on the photoelectrochemical behavior of the nanocomposite samples was studied by linear sweep photovoltammetry, incident photon-to-charge-carrier conversion efficiency measurements, and long-term photoelectrolysis coupled with gas-chromatographic product analysis. We demonstrated that the nanocarbon framework facilitated efficient charge carrier transport, resulting in a 4-fold increase in the measured photocurrents for the PEDOT/CNT electrode, compared to the bare PEDOT counterpart. The presented results contribute to the better understanding of the enhanced photoelectrochemical behavior of organic semiconductor/nanocarbon electrode assemblies and might encourage other researchers to study these intriguing hybrid materials further.