Quantum Dot-Sensitized Photoreduction of CO₂ in Water with Turnover Number > 80,000

Abstract

Climate change and global energy demands motivate the search for sustainable transformations of carbon dioxide (CO₂) to storable liquid fuels. Photocatalysis is a pathway for direct conversion of CO₂ to CO, one step within light-powered reaction networks that could, if efficient enough, transform the solar energy conversion landscape. To date, the best performing photocatalytic CO₂ reduction systems operate in nonaqueous solvents, but technologically viable solar fuels networks will likely operate in water. Here we demonstrate catalytic photoreduction of CO₂ to CO in pure water at pH 6-7 with an unprecedented combination of performance parameters: turnover number (TON(CO)) = 72,484-84,101, quantum yield (QY) = 0.96-3.39%, and selectivity (<i>S</i>_CO) > 99%, using CuInS₂ colloidal quantum dots (QDs) as photosensitizers and a Co-porphyrin catalyst. At higher catalyst concentration, the system reaches QY = 3.53-5.23%. The performance of the QD-driven system greatly exceeds that of the benchmark aqueous system (926 turnovers with a quantum yield of 0.81% and selectivity of 82%), due primarily to (i) electrostatic attraction of the QD to the catalyst, which promotes fast multielectron delivery and colocalization of protons, CO₂, and catalyst at the source of photoelectrons, and (ii) termination of the QD's ligand shell with free amines, which capture CO₂ as carbamic acid that serves as a reservoir for CO₂, effectively increasing its solubility in water, and lowers the onset potential for catalytic CO₂ reduction by the Co-porphyrin. The breakthrough efficiency achieved in this work represents a nonincremental step in the realization of reaction networks for direct solar-to-fuel conversion.