Naphthalene Diimide-Based Donor–Acceptor–Donor Small Molecules as Metal-Free Organocatalysts for Photocatalytic CO₂ Reaction

The application of organic small molecules as metal-free photocatalysts for light-driven photoreduction of carbon dioxide (CO2) has seldom been explored. This work developed four naphthalene diimide (NDI)-derived donor–acceptor–donor small molecules with different numbers of thiophene units, namely, NDI-2T, NDI-TT, NDI-4T, and NDI-6T, as metal-free photocatalysts to catalyze the reduction of CO2 under irradiation with an air mass 1.5G solar simulator at one-sun intensity. The structure–property relationship was investigated by exploring the effects of the electron-donating ability of the donor units on the optical properties, redox potential, electron–hole distribution, and exciton lifetime. NDI-6T exhibited the most red-shifted absorption, longest exciton lifetime, and strongest electron–hole separation. However, the large upshift in oxidation potential because of the elevated electron-donating ability of the hexathiophene unit significantly reduced the driving force for catalyst regeneration, leading to poor catalytic performance. Alternatively, NDI-4T possessed proper redox potentials, reduced charge-transfer resistance, and excellent photocurrent intensity; therefore, it effectively converted CO2 to a single product of CO in the presence of water as an electron donor without a sacrificial reagent or cocatalyst with a product yield of 168.6 μmol gcat–1 24 h–1, which was considerably higher than those of NDI-TT (111.9 μmol gcat–1 24 h–1), NDI-2T (88.4 μmol gcat–1 24 h–1), and NDI-6T (40.5 μmol gcat–1 24 h–1). This study provides a practical guideline for the molecular design of conjugated organic molecules as promising photocatalysts for CO2 photoreduction.