Poly(triazine imide)/LiCl (PTI) is a crystalline, layered, carbon nitride that can be synthesized via a condensation reaction of melamine at high temperatures in a LiCl/KCl eutectic flux. Its structure consists of triazine units (C3N3) linked through imide bridges, thereby forming intralayer cavities containing Li cations and charge balanced by interlayer chloride anions. The incorporation of molecular dopants, e.g., 6-aminouracil and other pyrimidine-based molecules, into its structure has been investigated for the impact on its photocatalytic properties. Molecular dopants were added in stoichiometric amounts during the preparation of PTI and the resulting products were characterized by powder X-ray diffraction, UV-Vis diffuse reflectance and FT-IR spectroscopy. The inclusion of dopants yielded a control over the band gap from 3.15 eV down to 1.5 eV and was dependent on the dopant structure and its concentration. Further, photocatalytic activities for CO2 reduction were measured under 390 nm light irradiation as suspended powders in an aqueous bicarbonate solution, showing the formation of formate, dihydrogen, and potentially other products such as acetate. Results will be presented on their quantum yields as a function of the photocatalytic testing conditions.

Flux-based synthesis of poly(triazine imide) and modifications with molecular dopants for band gap tunability and photocatalytic CO2 reduction

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ACS Fall 2022

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