Chlorine intercalation in graphitic carbon nitride for efficient photocatalysis

•Cl intercalated g-C3N4 is obtained via pyrolysis of melamine and excessive NH4Cl.•Cl intercalation endows g-C3N4 with multiple superiorities.•It shows significantly enhanced photoreduction and photooxidation performance.•The Cl intercalation advantages are confirmed by experiments and DFT calculations.

Metal-free graphitic carbon nitride (g-C3N4) shows tremendous potentials in energy and environmental domains. Nonetheless, amelioration on the crystal configuration, electronic structure and microstructure of g-C3N4 for high-performing visible-light photocatalysis is still challenging and anticipated. Here we report the development of chlorine (Cl) intercalated g-C3N4 via co-pyrolysis of melamine and excessive ammonium chloride (excessive is very pivotal). This protocol renders not only Cl intercalation in the interlayer of g-C3N4, but also a homogeneous porous structure, thereby endowing g-C3N4 with multiple superiority effects, including significantly promoted charge migration by establishing interlayer pathway, up-shifted conduction-band level, narrowed band gap as well as enhanced surface area. The as-prepared Cl intercalated mesoporous g-C3N4 parades outstanding photocatalytic performance for water splitting into H2, CO2 reduction, liquid and air contaminants removal. The most enhanced photocatalytic performance was obtained at Cl-C3N4-3 for H2 evolution activity, which shows a 19.2-fold increase in contrast to pristine g-C3N4, accompanying with a high apparent quantum efficiency of 11.9% at 420 ± 15 nm. Experimental and DFT calculations results co-disclose that the aforementioned advantageous factors account for the profoundly boosted photooxidation and photoreduction capabilities of g-C3N4 under visible light. The present work may furnish a bottom-up tactic for integrally advancing g-C3N4, and also hold huge promise to be extended to other layered materials for photochemical or photoelectrochemical applications.

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