Freeze-dried dicyandiamide-derived g-C3N4 as an effective photocatalyst for H2 generation

Hydrogen (H2) is viewed as a clean, green, and sustainable energy source. The photocatalytic H2 evolution using light-activated photocatalyst under light irradiation is attractive to convert light into chemical energy in a feasible way. In the present work, photocatalysis of H2 generation was explored, using graphitic carbon nitride (g-C3N4) synthesized from freeze-dried dicyandiamide (DICY). The DICY underwent rapid dissolution-recrystallization during the freeze-drying process, enabling more complete polymerization of the heptazine units of g-C3N4 than occurred in the same compound synthesized from untreated DICY. After loading with Pt as a cocatalyst, and under light irradiation (metal halide lamp) in the presence of triethanolamine, g-C3N4 synthesized from freeze-dried DICY (DCN) showed an increased H2 evolution rate (∼20 μmol h‒1) compared with that using g-C3N4 derived from untreated DICY (CN) (12 μmol h‒1). In addition, DCN had a higher H2 generation rate than CN under light of different wavelengths (400, 450, and 550 nm). The improved activity of DCN could be attributed to inhibition of charge recombination (evidenced by photoluminescence), fast charge transfer (evidenced by electrochemical impedance spectra and photocurrent measurements), and a suitable energy bandgap (evidenced by Mott-Schottky and UV–vis measurements) resulting from better-polymerized heptazine rings (evidenced by nuclear magnetic resonance spectroscopy). In summary, DCN prepared in this study could be used as a visible-light activated and effective metal-free material for photocatalytic H2 generation.