High‐performance Photoelectrochemical Hydrogen Production Using Asymmetric Quantum Dots

Abstract Solar‐driven photoelectrochemical (PEC) reactions using colloidal quantum dots (QDs) as photoabsorbers have shown great potential for the production of clean fuels. However, the low H2 evolution rate, consistent with low values of photocurrent density, and their limited operational stability are still the main obstacles. To address these challenges, the heterostructure engineering of asymmetric capsule‐shaped CdSe/CdxZn1‐xSe QDs with broad absorption and efficient charge extraction compared to pure‐shell QDs is reported. By engineering the shell composition from pure ZnSe shells into CdxZn1‐xSe gradient shells, the electron transfer rate increased from 4.0 × 107 s −1 to 32.7 × 107 s −1 . Moreover, the capsule‐shaped architecture enables more efficient spatial carrier separation, yielding a saturated current density of average of 25.4 mA cm −2 under AM 1.5 G one sun illumination. This value is the highest ever observed for QDs‐based devices and comparable to the best‐known Si‐based devices, perovskite‐based devices, and metal oxide‐based devices. Furthermore, PEC devices based on heterostructured QDs maintained 96% of the initial current density after 2 h and 82% after 10 h under continuous illumination, respectively. The results represent a breakthrough in hydrogen production using heterostructured asymmetric QDs.