Abstract:In the present work, a novel photocatalytic fuel cell (PFC) system involving a dual heterojunction photoelectrodes, viz. polyaniline/TiO 2 nanotubes (PANI/TiO 2 NTs) photoanode and CuO/Co 3 O 4 nanorods (CuO/Co 3 O 4 NRs) photocathode, has been designed. Compared to TiO 2 NTs electrode of PFC, the present heterojunction design not only enhances the visible light absorption but also offers the higher efficiency in degrading Rhodamine B-a model organic pollutant. The study includes an evaluation of the dual performance of the photoelectrodes as well. Under visible-light irradiation of 3 mW cm −2 , the cell composed of the photoanode PANI/TiO 2 NTs and CuO/Co 3 O 4 NRs photocathode forms an interior bias of +0.24 V within the PFC system. This interior bias facilitated the transfer of electrons from the photoanode to photocathode across the external circuit and combined with the holes generated therein along with a simultaneous power production. In this manner, the separation of electron/hole pair was achieved in the photoelectrodes by releasing the holes and electrons of PANI/TiO 2 NTs photoanode and CuO/Co 3 O 4 NRs photocathode, respectively. Using this PFC system, the degradation of Rhodamine B in aqueous media was achieved to an extent of 68.5% within a reaction duration of a four-hour period besides a simultaneous power generation of 85 µA cm −2 .