Extending the π-conjugation of g-C₃N₄ by incorporating aromatic carbon for photocatalytic H₂ evolution from aqueous solution

This study details the synthesis of high-activity g-C₃N₄ catalysts for H₂ generation from a triethanolamine aqueous solution under visible light. We anneal a mixture of urea and NH₄Cl to obtain g-C₃N₄ nanosheets, which are subsequently solvated with ethanol molecules and annealed to form aromatic carbon-doped g-C₃N₄. The results of analyses conducted using X-ray photoelectron, Fourier-transform infrared, and carbon-13 nuclear magnetic resonance spectroscopies demonstrated that annealing the ethanol molecules leads to the grafting of aromatic heterocycles on the g-C₃N₄ nanosheets and substitution of nitrogen with carbon. The grafted aromatic heterocycles and doped carbon atoms extend the π-conjugation system in g-C₃N₄ to reduce the band gap and facilitate the separation of photogenerated charges. The carbon-incorporating also preserve the crystallinity of g-C₃N₄ during high-temperature annealing, which facilitates the suppression of the recombination of photogenerated charges at defect sites. The developed aromatic carbon-doped g-C₃N₄ effectively catalyzes H₂ generation from the aqueous solution, achieving apparent quantum yields of 14% and 2.2% under 420 and 550 nm monochromatic irradiation, respectively, whereas urea-derived g-C₃N₄ reached only 3.4% and 0.1%. The proposed strategy of extending the π-conjugation system is promising for promoting the activity of carbon-nitride photocatalysts.