Impact of Aspect Ratio on Charge Carrier Dynamics and Efficiency Enhancement in CdSe/CdS Dot-in-Rod Nanostructures for Photocatalytic Hydrogen Evolution

We demonstrated that the aspect ratio (AR)-tunable CdSe/CdS dot-in-rod (DiR) nanostructures with quasi-type-II band structure were successively synthesized using the hot injection method. When the AR of CdSe/CdS DiR was tuned from 10 to 37, the exciton localization efficiency along the longitudinal CdS rod shell decreased from 57.9 to 15.1%, resulting in a 5-fold improvement in the efficiency of photocatalytic hydrogen (H2) evolution. The optimal CdSe/CdS DiR exhibited the highest H2 evolution rate of 2.11 mmol·g–1·h–1 at an AR of 29 without any cocatalyst assistance. In situ transient absorption spectroscopy was employed to investigate the interfacial charge carrier dynamics of CdSe/CdS DiR during practical photocatalytic H2 evolution. The findings indicated that the half-life of delocalized electrons on the conduction band along the longitudinal CdS rod shell increases from 11.5 to 20.1 μs as the AR increased, demonstrating that the AR-dependent charge carrier dynamics significantly influences the photoactivity of CdSe/CdS DiR. This study provides valuable and novel insights into the tunability of charge carrier dynamics through AR manipulation in one-dimensional semiconductor nano-heterostructures for solar fuel generation.