Engineering the Interfacial Structure of Heavy Metal‐Free Colloidal Heterostructured Quantum Dots for High‐Efficiency Photoelectrochemical Water Oxidation without Co‐Catalyst

Solar‐driven photoelectrochemical (PEC) water splitting cell fabricated using colloidal quantum dots (QDs) is deemed as low‐cost and high‐efficiency solar‐to‐fuel conversion systems for future carbon neutrality. However, current QDs‐based PEC technologies are still hindered by several critical restrictions including the sluggish water oxidation kinetics and the frequent use of highly toxic QDs (e.g., Pb, Cd‐chalcogenides) as well as co‐catalysts, thus limiting their prospective commercial developments. Herein, the optoelectronic properties of heavy metal‐free InP/ZnSe core/shell QDs are tailored by introducing the interfacial GaP layers with variable thicknesses. As‐prepared InP/GaP/ZnSe core/shell QDs are used to sensitize TiO 2 film as photoanodes for PEC water oxidation, showing an unprecedented photocurrent density of 4.1 mA cm −2 at 1.23 V versus reversible hydrogen electrode with excellent durability under one sun AM 1.5 G illumination. It is demonstrated that engineering the thickness of the interfacial GaP layer enables optimized optical properties and can introduce appropriate intermediate energy levels to promote the charge extraction from the InP core to the ZnSe shell for enhanced PEC water oxidation efficiency. This study paves the way for interfacial engineering of “green” core/shell QDs to realize cost‐effective, environment‐friendly, high‐performance, and co‐catalyst‐free QDs‐based PEC water splitting system.