Precursor-Engineering Coupled Microwave Molten-Salt Strategy Enhances Photocatalytic Hydrogen Evolution Performance of g-C N Nanostructures.

A precursor-engineering strategy coupled with a microwave molten-salt process (PE-MWMS) is developed to synthesize graphitic carbon nitride (g-C N ) with an isotype triazine/heptazine-based g-C N heterojunction as a photocatalyst for the hydrogen evolution reaction (HER) under visible light illumination. Four hybrid precursor combinations-thiourea/melamine, thiourea/dicyandiamide, urea/melamine, and urea/dicyandiamide-are used to synthesize g-C N heterojunctions by the PE-MWMS process. Control experiments indicate that the precursor components and microwave treatment have a great effect on the HER performance of the g-C N samples. Samples synthesized with the optimal molar ratios of thiourea/melamine (2:1), thiourea/dicyandiamide (2:1), urea/melamine (3:1), and urea/dicyandiamide (3:1), exhibit the highest HER rates of 3135, 2519, 2844, and 2565 μmol g  h , respectively. The amounts of heptazine and triazine units in the g-C N samples can be easily adjusted by changing the ratios of the hybrid precursors and play a decisive role in improving the photocatalytic HER activity. Because of the unique composition and microstructure, the efficient separation of electron-hole pairs, the broadened photo-absorption edges, and the narrowed band gaps, the as-obtained triazine/heptazine-based g-C N nanostructures exhibit promising activity for HER application.