Semiconductor quantum dot-sensitized rainbow photocathode for effective photoelectrochemical hydrogen generation [Chemistry]

The present study reports the fabrication of CdSe quantum dot (QD)-sensitized photocathodes on NiO-coated indium tin oxide (ITO) electrodes and their H₂-generating ability upon light irradiation. A well-established spin-coating method was used to deposit CdSe QD stock solution onto the surface of NiO/ITO electrodes, thereby leading to the construction of various CdSe QD-sensitized photocathodes. The present report includes the construction of rainbow photocathodes by spin-coating different-sized QDs in a sequentially layered manner, thereby creating an energetically favorable gradient for charge separation. The resulting rainbow photocathodes with forward energetic gradient for charge separation and subsequent electron transfer to a solution-based hydrogen-evolving catalyst (HEC) exhibit good light-harvesting ability and enhanced photoresponses compared with the reverse rainbow photocathodes under white LED light illumination. Under minimally optimized conditions, a photocurrent density of as high as 115 μA⋅cm⁻² and a Faradaic efficiency of 99.5% are achieved, which is among the most effective QD-based photocathode water-splitting systems.