Solar light-driven selective photoelectrochemical CO2 reduction to CO in aqueous media using Si nanowire arrays decorated with Au and Au-based metal nanoparticles

To address recent energy and environmental issues, such as global warming and resource depletion, significant interest has been shown in carbon dioxide (CO2) fixation based on photoelectrochemical processes under solar light irradiation. The present paper describes the applicability of gold nanoparticles-decorated silicon nanowire arrays (Au/SiNW) as photoelectrodes to promote CO2 reduction. The decoration with Au nanoparticles of SiNW was performed by an electroless plating utilizing surface hydrogen-terminated silicon groups, generated during the nanowire formation process. Au/SiNW exhibits efficient photoelectrochemical performance for CO2 reduction to produce CO selectively in an aqueous medium under simulated solar light irradiation owing to its vertically aligned nanowire structure and Au nanoparticles as cocatalysts. The former provides high specific surface area and light trapping effect, and the latter induces selective interaction with CO2. Moreover, a unique two-steps method for Au decoration that consists of photo-assisted deposition of copper nanoparticles and the following electroless plating to replace Cu atoms to Au ones achieves more uniform decoration of SiNW with highly dispersed core-shell structured Cu@Au nanoparticles. The resulting photoelectrode, termed Cu@Au/SiNW, shows improved selectivity toward CO production and gives a good Faradic efficiency of 72% in an aqueous medium.