Rational Design of Dot‐on‐Rod Nano‐Heterostructure for Photocatalytic CO₂ Reduction: Pivotal Role of Hole Transfer and Utilization

Abstract Inspired by green plants, artificial photosynthesis has become one of the most attractive approaches toward carbon dioxide (CO₂) valorization. Semiconductor quantum dots (QDs) or dot‐in‐rod (DIR) nano‐heterostructures have gained substantial research interest in multielectron photoredox reactions. However, fast electron–hole recombination or sluggish hole transfer and utilization remains unsatisfactory for their potential applications. Here, the first application of a well‐designed ZnSe/CdS dot‐on‐rods (DORs) nano‐heterostructure for efficient and selective CO₂ photoreduction with H₂O as an electron donor is presented. In‐depth spectroscopic studies reveal that surface‐anchored ZnSe QDs not only assist ultrafast (≈2 ps) electron and hole separation, but also promote interfacial hole transfer participating in oxidative half‐reactions. Surface photovoltage (SPV) spectroscopy provides a direct image of spatially separated electrons in CdS and holes in ZnSe. Therefore, ZnSe/CdS DORs photocatalyze CO₂ to CO with a rate of ≈11.3 µmol g⁻¹ h⁻¹ and ≥85% selectivity, much higher than that of ZnSe/CdS DIRs or pristine CdS nanorods under identical conditions. Obviously, favored energy‐level alignment and unique morphology balance the utilization of electrons and holes in this nano‐heterostructure, thus enhancing the performance of artificial photosynthetic solar‐to‐chemical conversion.