The Design of Supramolecular Assemblies with Metal Salt as Precursors Enables The Growth of Stable Polymeric Carbon Nitride Photoanodes

Abstract Polymeric carbon nitrides (CN) have gained significant interest as photoanodes in photoelectrochemical cells (PEC). A widely researched approach for synthesizing CN films with controlled optical and photoelectrochemical properties relies on using supramolecular assemblies as the precursors for thermal polymerization over a transparent conductive substrate. However, the formation of supramolecular assemblies is highly dependent on the temperature and solubility in a given solvent, limiting the full potential of this method. Moreover, the intercalation of metal ions is challenging due to the use of polar solvents. Here, this study shows a new way of synthesizing supramolecular assemblies with metal ions using a solvothermal approach. The solvent, monomer composition, salt quantity, reaction temperature, and film thickness are varied in this study. As a result, well‐attached, uniform CN films with good optoelectronic properties are achieved. The synthesized photoactive CN films exhibit very low onset potentials and reach ≈0.13, ≈0.15, and 0.30 ± 0.01 mA cm −2 photocurrents in 0.1 m phosphate buffer (neutral) solution, 0.1 m KOH(aq) (basic) solution, and 0.1 m KOH solution containing 10 vol.% triethanolamine as the hole scavenger, respectively.