Role of the Pyridinyl Radical in the Light-Driven Reduction of Carbon Dioxide: A First-Principles Study

The reduction of carbon dioxide to fuels or chemical feedstocks with solar energy is one of the grand goals of current chemistry. In recent years, electrochemical, photoelectrochemical, and photochemical experiments provided hints of an unexpected catalytic role of the pyridine molecule in the reduction of carbon dioxide to formic acid or methanol. In particular, it has been suggested that the 1-pyridinyl radical (PyH) may be able to reduce carbon dioxide to the hydroxy-formyl radical. However, extensive theoretical studies of the thermodynamics and kinetics of the reaction called this interpretation of the experimental observations into question. Using ab initio computational methods, we investigated the photochemistry of the hydrogen-bonded PyH···CO₂ complex. Our results reveal that carbon dioxide can be reduced to the hydroxy-formyl radical by a proton-coupled electron-transfer (PCET) reaction in excited states of the PyH···CO₂ complex. In contrast to the ground-state PCET reaction, which exhibits a substantial barrier, the excited-state PCET reaction is barrierless but requires the passage through two conical intersections. Our results provide a tentative explanation of the catalytic role of the PyH radical in the reduction of CO₂ with the qualification that the absorption of a photon by PyH is necessary.