Surface Stoichiometry Control of Colloidal Heterostructured Quantum Dots for High‐Performance Photoelectrochemical Hydrogen Generation

Abstract Manipulating the separation and transfer behaviors of charges has long been pursued for promoting the photoelectrochemical (PEC) hydrogen generation based on II–VI quantum dot (QDs), but remains challenging due to the lack of effective strategies. Herein, a facile strategy is reported to regulate the recombination and transfer of interfacial charges through tuning the surface stoichiometry of heterostructured QDs. Using this method, it is demonstrated that the PEC cells based on CdSe‐(Se_xS_1−x)₄‐(CdS)₂ core/shell QDs with a proper S_surface/Cd_surface ratio exhibits a remarkably improved photocurrent density (≈18.4 mA cm⁻² under one sun illumination), superior to the PEC cells based on QDs with Cd‐rich or excessive S‐rich surface. In‐depth electrochemical and spectroscopic characterizations reveal the critical role (hole traps) of surface S atoms in suppressing the recombination of photogenerated charges, and further attribute the inferior performance of excessive S‐rich QDs to the impeded charge transfer from QDs to TiO₂ and electrolyte. This work puts forward a simple surface engineering strategy for improving the performance of QDs PEC cells, providing an efficient method to guide the surface design of QDs for their applications in other optoelectronic devices.