Precise Layer‐by‐Layer Assembly of Dual Quantum Dots Artificial Photosystems Enabling Solar Water Oxidation

Abstract Quantum dots (QDs) colloidal nanocrystals are attracting enduring interest by scientific communities for solar energy conversion due to generic physicochemical merits including substantial light absorption coefficient, quantum confinement effect, enriched catalytically active sites, and tunable electronic structure. However, photo‐induced charge carriers of QDs suffer from ultra‐short charge lifespan and poor stability, rendering controllable vectorial charge modulation and customizing robust and stable QDs artificial photosystems challenging. Herein, tailor‐made oppositely charged transition metal chalcogenides quantum dots (TMCs QDs) and MXene quantum dots (MQDs) are judiciously harnessed as the building blocks for electrostatic layer‐by‐layer assembly buildup on the metal oxides (MOs) framework. In these exquisitely designed LbL assembles MOs/(TMCs QDs/MQDs) n heterostructured photoanodes, TMCs QDs layer acts as light‐harvesting antennas, and MQDs layer serves as electron‐capturing mediator to relay cascade electrons from TMCs QDs to the MOs substrate, thereby yielding the spatially ordered tandem charge transport chain and contributing to the significantly boosted charge separation over TMCs QDs and solar water oxidation efficiency of MOs/(TMCs QDs/MQDs) n photoanodes. The relationship between interface configuration and charge transfer characteristics is unambiguously unlocked, by which photoelectrochemical mechanism is elucidated. This work would provide inspiring ideas for precisely mediating interfacial charge transfer pathways over QDs toward solar energy conversion.