Breaking the short-range proximity requirement in quantum dot/molecular catalyst hybrids for CO2 reduction via long-range hot electron sensitization

Abstract

The efficient light-driven fuel production from homogeneous photocatalytic systems is one promising avenue towards an alternative energy economy. However, electron transfer from a conventional photosensitizer to a catalyst is short-range and necessitates spatial proximity between them. Here we show that energetic hot electrons generated by Mn-doped semiconductor quantum dots (QDs) allow for long-range sensitization of Ni(cyclam)-based molecular catalysts, enabling photocatalytic reduction of CO₂ to CO without requiring chemical linkages between the QDs and catalyst molecules. Our results demonstrate the potential of hot electron sensitization in simplifying the design of hybrid catalyst systems while improving photocatalytic activity.